ACS Publications. Most Trusted. Most Cited. Most Read
The Role of Isostatic Pressing in Large-Scale Production of Solid-State Batteries
More

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:ACS Energy Lett. 2022, 7, 11, 3936-3946
  • Open Access
Focus Review

The Role of Isostatic Pressing in Large-Scale Production of Solid-State Batteries
Click to copy article linkArticle link copied!

Open PDFSupporting Information (3)

ACS Energy Letters

Cite this: ACS Energy Lett. 2022, 7, 11, 3936–3946
Click to copy citationCitation copied!
https://doi.org/10.1021/acsenergylett.2c01936
Published October 18, 2022

Copyright © 2022 The Authors. Published by American Chemical Society. This publication is licensed under

CC-BY-NC-ND 4.0 .

Abstract

Click to copy section linkSection link copied!
High Resolution Image
Download MS PowerPoint Slide

Scalable processing of solid-state battery (SSB) components and their integration is a key bottleneck toward the practical deployment of these systems. In the case of a complex system like a SSB, it becomes increasingly vital to envision, develop, and streamline production systems that can handle different materials, form factors, and chemistries as well as processing conditions. Herein, we highlight isostatic pressing (ISP) as a versatile processing platform for large-scale production of the currently most promising solid electrolyte materials. We briefly summarize the development of ISP techniques as well as the processing methods and windows accessible. Subsequently, we discuss recent reports on SSBs that leverage ISP techniques and their impact on the electrochemical performance of the systems. Finally, we also provide a techno-economic analysis for implementing ISP at scale along with some key perspectives, challenges, and future directions for large-scale production of SSB components and integration.

This publication is licensed under

CC-BY-NC-ND 4.0 .
  • cc licence
  • by licence
  • nc licence
  • nd licence
Copyright © 2022 The Authors. Published by American Chemical Society

Subjects

what are subjects
Solid-state batteries (SSBs) are promising energy storage alternatives that can achieve high energy densities by enabling Li metal anodes and high-voltage cathodes. (1,2) When combined with long cycle life, improved safety, and low cost (<$100/kWh), the value proposition of solid-state lithium metal batteries becomes more and more relevant. There are, however, significant materials and processing challenges that disrupt the materialization of working SSBs at present. (3−5) Recent reviews make it clear that the energy and power densities of the reported SSBs fall short in comparison with those of the state-of-the-art Li-ion batteries. The technical barriers to be addressed in the long term include achieving areal capacities in the range of 3–10 mAh cm–2, with less than 10% excess Li anode and more than 70% active material loading, in solid-state composite cathodes that are assembled against thin electrolytes which can withstand current densities higher than 1 mA cm–2 and yet enable higher Coulombic efficiencies. Cell design calculations show that solid electrolytes with <100 μm thicknesses and Li metal anodes with <50 μm thickness are necessary to achieve energy densities comparable to or higher than those of the state-of-the-art lithium-ion batteries. (4−6) The processability and integration of thick composite cathodes, thin solid electrolytes, and thin lithium metal anodes into cell configurations in scalable fashions are of utmost significance to improve the value proposition of near-market SSBs.
An ideal SSB cell is a dense, thin, tri-layer assembly with conformal interfaces. (1,3) Generating these dense, thin multi-layer systems required for practical SSBs is typically not possible with conventional processing approaches for a variety of reasons. (7−9) Indeed, each component of the SSB has a multitude of issues that need to be tackled to engineer high-performance cells (Figure 1a). (4,10,11) The sheer variety of materials and their properties independent of the solid electrolytes make development of a consistent processing platform almost impossible to achieve. (2,12,13) For example, garnet solid electrolytes typically undergo dual-step sintering for achieving the cubic phase and densification of the pellets along with an additional sintering step in Ar to remove the Li2CO3 impurities. (14,15) The sintering temperatures for garnets are typically in excess of 1000 °C, with hold-times of 10 h or longer. In contrast, sulfide, argyrodites, and anti-perovskite materials are synthesized at lower temperatures of 100–400 °C and are generally processed into cells at room temperature and under uniaxial loading. (16−19) Most of the processing routes described are strictly for small-scale pellet preparation. So far, a large-scale roll-to-roll kind of processing is typically only demonstrated on hybrid electrolytes that leverage the slot-die processing of polymer dispersions to make larger form factor materials. (20,21,37)

Figure 1

Figure 1. (a) Current challenges in processing and integration of solid-state batteries. (b) Uneven density distribution by single uniaxial pressing in rigid die for cylinder. (c) Schematic diagram of a pressure vessel cavity into which the sample is inserted and subjected to isostatic pressure and temperature conditions, and temperature and pressure ranges for CIP (blue), WIP (green), and HIP (orange) techniques.

High Resolution Image
Download MS PowerPoint Slide
Conventional pressing methods are used for a broad number of applications to compact, form, integrate, and densify materials for further fabrication and use. (22) Powder metallurgy processing commonly applies conventional pressing methods consisting of uniaxial press-and-sinter to create solid parts of various geometries from raw powder. (23,24) Most solid electrolyte (SE) materials and components are processed using these approaches. The compaction mechanisms are material and process dependent but typically consist of loose particle restacking and deformation at points of contact as pressure increases. This method poses significant challenges for SSB materials and components as it invariably leads to high variation in density throughout the compact due to friction at die walls resulting in non-uniform properties (Figure 1b). (25,26) Although improved density uniformity is possible with use of lubricants and additional punches, the application window is limited.

The solid-state battery community needs to start envisioning pathways to streamline and scale-up the processing of promising solid electrolytes from pellet scale to form factors that are more practical.

The SSB community needs to start envisioning pathways to streamline and scale-up the processing of promising solid electrolytes from pellet scale to form factors that are more practical. Application of high formation pressures and temperatures over sustained time is an underlying requirement for processing most materials under study. In this regard, isostatic pressing (ISP) is a technique that has inherent versatility to cover the processing conditions required for most promising SE materials as well as the capability to achieve large-scale production. ISP can be employed for generating the thin, dense SE layers needed for practical SSBs. Furthermore, it can also provide a pathway toward integration of the cathode, solid electrolyte, and anode layers into a dense, tri-layer system for practical applications. Herein, we discuss an overview of the ISP technology along with recent experimental results in the SSB domain that leverage ISP techniques to achieve superior electrochemical performance. We also provide a techno-economic analysis to evaluate the viability of using ISP for large-scale production of SSB components and assemblies. Finally, we provide some perspectives from the research and instrumentation viewpoints for increasing the penetration of ISP in the SSB manufacturing ecosystem.

ISP Processing Pathways and Their Application to SSBs

Click to copy section linkSection link copied!
Isostatic pressing is a technique that applies pressure uniformly in all directions on the compact or container being pressed. (27,28) The process fundamentals are based on Pascal’s law, in which a pressure change exerted on a fluid in an enclosed vessel will be transmitted undiminished to all portions of the fluid, surfaces, and walls within the vessel. Depending on the processing parameters, the fluid can be a gas or liquid. This processing route provides a path to eliminate the frictional forces hindering conventional pressing techniques due to die wall interaction thereby improving the average density for a given applied pressure as well as the uniformity that can be achieved. (29−31) The resultant density and uniformity of the sample depend on the optimization of three key variables: time, temperature, and pressure of the ISP cycle. (27)
There are three main categories of isostatic pressing: (1) cold isostatic pressing (CIP), (2) warm isostatic pressing (WIP), and (3) hot isostatic pressing (HIP), with a common thread between these techniques being the use of a pressure vessel. A typical ISP process involves loading of the sample inside the pressure vessel, which is then elevated to the required process temperature and pressure using appropriate process control systems followed by a hold and a relaxation process to ambient conditions (Figure 1c). CIP, WIP, and HIP are primarily differentiated by the process conditions (T and P) that are accessible within the technique (Figure 1c, Table 1). Beyond the pressure vessel, CIP and WIP are relatively simple systems consisting of various valves, intensifiers, pumps, and a control panel. Due to the elevated temperatures involved in HIP, the equipment is more complex, requiring additional subsystems to ensure safe and reliable operation. CIP can offer ISP capabilities up to 600 MPa (87 000 psi) dependent on equipment design and size. (27) Liquid consisting of water and an additive such as oil is generally used as the pressure medium. WIP can be performed in standard CIP vessels offering similar pressing capabilities (Figure S2). The pressurizing medium is heated externally and circulated into the pressure vessel. Elevated temperatures up to 150 °C (302 °F) with good temperature uniformity are possible with utilizing high-temperature oil and compatible bag material. WIP cycle time is extended relative to that of CIP due to the heating of the circulating media, with one cycle every 10–20 min being feasible, dependent on temperature uniformity requirements. It is important to note here that handling of reactive materials like Li metal, sulfides, and argyrodites requires careful selection of the pressure medium to eliminate any potential chemical reactivity. Also, handling of Li metal within ISP equipment is not established; however, it is expected that, with proper optimization of the experimental conditions, Li metal anodes can be processed using CIP/WIP techniques. Standard HIP processing equipment offers capabilities up to 200 MPa (30 000 psi) and high temperatures up to 2000 °C with great temperature uniformity and accuracy. Due to the elevated temperatures required, inert argon gas is commonly used as the pressure medium to protect both the workpieces and the furnace during operation. The gas is supplied to the HIP vessel from a gas storage system and delivered from a compressor(s) through a series of valves under high pressure. (28,32) Due to the high compressibility of gas relative to liquid, processing time is significantly increased, typically requiring hours instead of minutes. However, recent advancements in vessel design and cooling strategies have enabled uniform rapid cooling (URC), significantly reducing process time. Production rates are dependent on several factors such as applied pressure, vessel size, level of automation, and pump capacity but can achieve one operation cycle per minute or faster. The size of the vessel is dependent on product size and volume needs, with an vessel inner diameter of up to 3 m and length up to 5 m (Figure S1).
Table 1. Standard Processing Capabilities of Isostatic Pressing Equipmenta
ISP techniqueCIPWIPHIP
pressure mediumliquid - waterliquid - oil/watergas - argon/nitrogen
standard temperature rating (°C/°F)20/68150/3022000/3632
standard pressure rating (MPa/ksi)600/87500/72.5207/30
cycle timeo++++
equipment costo++++
a

Qualitative values are represented by o, +, and +++, where o < + < +++.

Currently, there is an absence of consensus with regard to how SSBs are going to be scaled up for production due to the variety of materials, architectures, and components as well as design philosophies. Primarily, the form factors prevalent in the literature are pouch cells, cylindrical cells, and prismatic cells (Figure 2a). Within these cell configurations, the underlying architectures are identical: the tri-layer anode|solid electrolyte|cathode films supported on current collectors. We anticipate that ISP will primarily be used for compaction of densification of individual components, viz. thin SE films as well as these tri-layer cell assemblies, to enable improved performance.

Currently, there is an absence of consensus with regard to how solid-state batteries are going to be scaled up for production due to the variety of materials, architectures, and components as well as design philosophies.

It is anticipated that batch processing of stacked sheets of solid electrolyte or wound spools of the SE films can be processed using ISP to generate the required dense thin films (Figure 2b). For full cells, we anticipate that tri-layer assemblies and pouch cells as well as cylindrical geometries are compatible for ISP, with the latter preferred as this ensures pressure uniformity across all the surfaces of the samples undergoing the ISP treatment as well as allows for higher packing fraction of the container volume resulting in higher throughput. Ultimately, ISP offers a more efficient and effective alternative to consolidate internal voids and defects for maximum uniformity and density, achieving intimate contact between particles without geometrical limitations, all while preserving the shape of an object. Over conventional routes, ISP enables the production of larger components, increases allowable length–diameter ratios, and provides superior material properties.

Figure 2

Figure 2. ISP integration pathways into SSB manufacturing. (a) Possible packaging of SSB systems and the underlying tri-layer architectures. (b) ISP configurations of the components and assemblies envisioned for large-scale production.

High Resolution Image
Download MS PowerPoint Slide

Critical Survey of ISP Implementations in SSB Field

Click to copy section linkSection link copied!
Isostatic pressing has seen limited application in the SSB field thus far. To date, the majority of the implementation of ISP techniques is for densification of green pellets prior to their sintering (Supporting Information). As discussed earlier, for a given material system, high densities can only be achieved through careful optimization of the time–temperature–pressure dependence of the ISP cycle. However, no such study is reported for any SE material in the literature. In contrast, most reports utilize an average isostatic pressure of 200–250 MPa for the CIP cycle. The choice of this processing pressure is most likely arbitrary. As such, there is no correlation between the reported density of the pellet and the ISP conditions (Figure S3). This primarily indicates that the ISP conditions that are being used are largely un-optimized. No reports of WIP for SE densification were available to the best of the authors’ knowledge, while only a few reports of HIP treatment were identified (Figure 3a). The phase purity of the solid electrolytes is typically not impacted by the ISP treatments (Figure 3b) as no additional peaks from decomposition products or Li loss are seen for LLZO, even after a HIP treatment. (33) Additionally, carefully tuning the processing conditions with garnets can help minimize/eliminate the need for mother powder during sintering that currently constitutes a significant amount of material waste for LLZO materials. (34) After the HIP treatment, the opaque pellet turns translucent, as shown in the inset in Figure 3b. (33) This typically is indicative of larger grain sizes and high densities, both of which result in improved transport and electrochemical properties. It should be noted that the relative intensities of certain reflections are modulated after the HIP process. This suggests that the grain growth during ISP might lead to certain preferred orientations.

Overall, the demonstrations here showcase that the application of isostatic pressing to the soft solid electrolyte material families can enable processing of these materials with a high degree of local microstructural control that is imperative for durable solid-state batteries.

Recent work has shown that cathode particles with certain crystallographic orientations perform better compared to polycrystalline counterparts in SSBs. (35) The ability to control and grow preferred orientations during the sintering/integration process can have significant benefits for the performance of batteries. This aspect of ISP has not been utilized by the community thus far but is expected to yield high-performance battery systems. It should be noted here that the available literature data suggests almost all the SE densification work with ISP is carried out for garnet or NASICON-type crystalline materials. This is counter-intuitive, as one would assume that softer electrolytes like sulfide and argyrodites can benefit enormously from these densification strategies. Further work is needed to explore ISP processing techniques for materials like sulfides and halides. Earlier work has conclusively shown that local microstructural differences occurring in the solid electrolyte due to uniaxial pressing can catastrophically impact the SSB cell. (17,57) As a proof of concept on the applicability of ISP techniques to these electrolytes, CIP and WIP processing was carried out on anti-perovskite solid electrolytes (Figure 3). As can be seen from the scanning electron microscopy (SEM) images (Figure 3c–e), the cross-sectional morphologies of the anti-perovskite materials processed with conventional uniaxial pressing and ISP techniques are completely distinct. Uniaxial pressing leads to materials with some porosity and distinct grain boundaries, both of which can limit the electrochemical performance of the material. (58−63) Overall, both ISP techniques lead to improved density compared to the green pellet; however, WIP shows additional formation of small rod-like crystals (Figure 3d,e). We also carried out synchrotron tomography on the CIP and WIP processed materials. From the synchrotron tomography data sets, it was observed that the uniaxially pressed pellet results in a porosity of ∼12%, while the CIP pellet shows an average porosity of ∼1.8% and the WIP pellet shows a porosity of 0.15%. CIP and WIP, therefore, lead to an order of magnitude reduction of porosity and highly dense solid electrolytes that are vital for high-performance SSBs. Overall, the demonstrations here showcase that the application of ISP to the soft SE material families can enable processing of these materials with a high degree of local microstructural control that is imperative for durable SSBs. It should be noted that the densification mechanism in ISP is strongly dependent on the materials’ properties. For metallic-like components, ISP relies on creep diffusion to achieve high density, while for polycrystalline ceramic-like materials the densification is governed by the grain growth mechanism. As such, there is no strict definition of a “critical temperature” at/above which densification occurs. However, it is necessary to carefully optimize the time–temperature–pressure correlation for each material system to optimize the densification process. Further, some studies have also indicated that ISP treatment of the solid electrolytes can improve their mechanical properties. (64) HIP-processed LLTO showed an average Young’s modulus of ∼223 MPa, compared to 192 MPa obtained by conventional sintering approaches. Further work on the impact of ISP processing conditions on the surface mechanics of the solid electrolyte is going to be vital toward designing resilient interfaces for SSBs.

Figure 3

Figure 3. (a) Compilation of isostatic pressing parameters used in the SSB literature for densification and integration of solid electrolytes and cells, respectively. Largely CIP is the primary technique that is leveraged within the SSB community. Shaded markers indicate either HIP or WIP cycles. The color of the markers indicates the solid electrolyte material family (pink markers, LLZO; yellow markers, Na-based NASICONs; green markers, sulfides; gray marker, hybrid electrolyte). The data for this figure are collected from refs (33,34,36−56). (b) XRD patterns and optical images of LLZO before and after the HIP treatment. The scale bars represent 10 mm. Data adapted from ref (33). SEM images of anti-perovskite solid electrolytes processed under (c) uniaxial loading conditions, (d) CIP conditions, and (e) WIP conditions. The scale bars in all the SEM images are 10 μm. (f, g) Tomographic reconstruction slices and pore volume visualization of the anti-perovskites processed under CIP and WIP conditions along with the measured porosity. The sub-volume investigated for porosity evaluation and visualized here is 300 × 300 × 300 μm3.

High Resolution Image
Download MS PowerPoint Slide
We also looked at the available literature in terms of ionic conductivities as well as full cells and symmetric cells that were processed using ISP. We note that the aim of this compilation is (1) to showcase that ISP techniques can be used for multiple material systems and (2) to visualize the spread of the data set when it comes to transport properties and cycling behavior when ISP techniques are employed. The literature data does not always report the impact of ISP versus standard conditions, which makes it difficult to provide an explicit comparison for each case. Figure 4a displays the compilation of ionic conductivities of solid electrolytes that underwent cold isostatically pressed (CIP) or hot isostatically pressed (HIP) pelleting as a function of inverse temperature. As mentioned above, most of the pellet densification processes are carried out for garnet and NASICON-type materials. It is discernible from Figure 4a that the conductivity data are very promising in terms of the magnitude of conductivity. However, even within the same material family, there is a large variance in the reported conductivity data due to the lack of optimization of the CIP and HIP processes. Apart from the intrinsic crystal structure and defect chemistry, the practical ionic conductivity of a particular solid electrolyte depends on the pressure, temperature, and time involved in densification. These three parameters need to be optimized to get optimum sample density. It is anticipated that the conductivity variance reported in Figure 4a is probably due to non-optimization of sample processing parameters and thereby sub-optimal densification.

Figure 4

Figure 4. (a) Compilation of ionic conductivity data sets from literature that leveraged ISP processing methods for solid electrolyte densification. The marker colors represent different material families (garnet, Na-solid electrolytes, and Li-based NASICONs). The data are adapted from refs (33,38,39,41,43,51,53,55,65−67). (b) Discharge polarization curves and (c) capacity retention profiles from solid-state battery cells that were integrated into tri-layer configurations using ISP processes. The corresponding solid electrolyte system is indicated in the legend. The data for (b) and (c) are adapted from refs (37,43,44,50,56,68−71).

High Resolution Image
Download MS PowerPoint Slide
The reported data shows pellet densities ranging from 85 to 100%, formed using ISP techniques for a range of processing pressures (Figure S3). Figure 4b exhibits the discharge profiles of various solid electrolyte|electrode assemblies integrated using an ISP process. The reports are promising in terms of interfacial resistances and the discharge capacity. Most of the cells exhibit practical discharge capacity as obtained from the conventional liquid electrolyte-based cell. Apart from the densification of electrolyte pellet/film, CIP/HIP helps to form a better interfacial contact between the electrolyte and electrode interfaces. The reduced contact impedance assists in obtaining practical discharge capacity. The discharge polarization curves also indicate that ISP processes do not generate secondary phases, indicating minimal reactivity between the electrolyte and electrode due to the high pressures. The retention behaviors of various SSB full cells that were integrated using ISP processes are shown in Figure 4c. The full cell and symmetric cells are processed with a comparatively wider range of materials. The reported data display excellent cycling stability, in some cases for close to 1000 cycles. (69) This work also highlighted the ameliorating influence of WIP in enhancing the density of the layers, interfacial adhesion of the cathode|solid electrolyte, uniformity of lithium deposition, and structural integrity of the solid electrolyte. Compared to this, uniaxial pressing would result in non-uniform density that would contribute to accelerated failures of solid electrolyte. Overall, the results thus far indicate that an optimized ISP process would be a great tool for the fabrication of high-performance and durable SSB components and cells.

Technoeconomic Analysis for Large-Scale Production of SSB Materials and Assemblies

Click to copy section linkSection link copied!
Large-scale adoption and production are crucial to drive SSB to a cost basis that is feasible when compared to that of conventional Li-ion batteries. (4) However, at the current nascent stage of manufacturing readiness level for most of the SE material families, it is difficult to accurately predict the techno-economics of a given processing pathway. (8,11) We carry out a preliminary analysis for processing costs associated with ISP considering its employment in two distinct stages of the SSB manufacturing process: (1) SE laminate formation and (2) tri-layer cell integration. Several projections of anticipated electric vehicle (EV) sales in the coming two decades suggest over 50 million EVs coming to the world market by 2040 (Figure S4). (72) The techno-economic projections included here assume that all those EVs are built with solid-state battery packs (Figure 5a). Additionally, we assume that all SE fabrication and cell integration are carried out using ISP processing. Assuming a pack and cell configuration (4 mAh cm–2 cathode loading, N/P ratio 0.2, SE thickness 75 μm, cell thickness 500 μm), we projected the required SE volume as well as the tri-layer cell volume for meeting the requirements of the expected EVs up to 2040 (Figure 5c). Detailed information regarding the projection calculation is available in the Excel sheet included in Supporting Information. It should be noted here that due to the inherent process of ramp–hold–release in all the ISP configurations (CIP/WIP/HIP), these are essentially batch processes. The typical configurations and costs of the CIP/WIP/HIP instruments are highlighted in Figure 5b. The metrics for the dimensions and cycle times as well as costs are adapted from Quintus’ internal design parameters which they envision for the SSB processing equipment. Further details on the metrics can be found in the Supporting Information. These metrics represent the state-of-the-art instruments with the largest sample handling volumes for large-scale production. Due to the geometry of the instruments, cylindrical form factors are preferred compared to planar configurations. For this analysis, we assume spools/rolls of SE films and/or tri-layer films on some backing substrate being fed to the ISP instrument for processing. The volume available for actual materials is defined by the product of packing fraction and the total volume measured from the dimensions. The packing fraction considers the volume taken up by the sealing/backing/holding materials and is assumed to be 0.6. Note that this packing fraction is a conservative estimate and there is an opportunity for significant improvement. Cost per cycle mentioned in Figure 5 reflects a number that incorporates capital expenditure over a 10-year time frame. Correspondingly, we calculate the cost of processing solid electrolyte (Figure 5c) as well as of cell integration (Figure 5d) considering various ISP cycle and their combinations. Based on the cycles/year metric, we also predicted that roughly 8–15 HIP/WIP/CIP units will be required to handle the SE processing and cell integration. Based on these calculations, it is estimated that the running cost of ISP for cell integration is ∼$1–20K/GWh based on the type of technique used. We understand that very different ISP cycles might be required depending on the materials chemistry involved, which can influence these results. However, these calculations provide an initial estimate of the scale of processing costs to meet the EV demands in the near future.

Figure 5

Figure 5. (a) Overview of the protocol used for techno-economic analysis carried out here. (b) Typical features of a state-of-the-art CIP/WIP/HIP instrument commercially available today. Dimensions reflect the volume of the largest sample that can be accommodated within the instrument. Packing fraction represents the fraction of the available volume which will occupied by the material of interest. Cycles assumed are detailed in the Supporting Information. Cost per cycle and cost per volume are in U.S. dollars. (c) Projected volumes of solid electrolyte and cells that need to be processed to cater to the expected EV demands in the next 20 years. For details see the Supporting Information. Projected processing cost for (d) solid electrolyte processing and (e) cell integration considering different ISP protocols.

High Resolution Image
Download MS PowerPoint Slide

Perspectives and Future Directions

Click to copy section linkSection link copied!
As discussed earlier, the major roadblock in the successful commercial deployment of all-solid-state batteries is the availability of a reliable, adaptable, and versatile large-scale manufacturing approach for solid-state architectures. Effectively addressing this challenge would leapfrog present-day battery technology into the next decades by enabling energy-dense SSBs to meet the burgeoning demands of portable electronics, grid storage, EV, and even eVTOL applications. Herein, our team comprehensively discussed and highlighted isostatic pressing as a potential pathway toward this goal of large-scale production of SSBs and their components.

As we continue to innovate on materials and interfaces within the solid-state battery, it is crucial to keep a lens on the manufacturing aspects of these systems.

Despite the versatility and easy adaptability of this manufacturing approach to cater to the needs of SSBs with varying form factors, battery chemistries, and configurations, continuous R&D efforts to address several underlying challenges in implementation of ISP have to be systematically undertaken to realize the true potential of this manufacturing approach. To this extent, we have also summarized some key perspectives, challenges, and future directions in ISP for SSB manufacturing as follows: (i) Employing and optimizing ISP techniques for SSB components and cells will not only be crucial for large-scale production but also afford key technological advantages that can improve the performance of SSBs. Briefly, this was highlighted by the ability to achieve high-density materials (>99%), the ability to control crystallographic orientations, and the ability to achieve conformal and resilient interfaces. (ii) We have shown the characteristic differences between key ISP processes─CIP, WIP, and HIP─and their application to SSB materials and cell integration. (iii) The techno-economic model discussed here provides a reference point for the scale of processing costs associated with SSB components and cells to meet the future EV demands. It drives home the crucial point that component and cell productions for SSBs become viable only with economies of scale. As we continue to innovate on materials and interfaces within the SSB, it is crucial to keep a lens on the manufacturing aspects of these systems. ISP processing is one of the key avenues toward achieving this goal.

Supporting Information

Click to copy section linkSection link copied!

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.2c01936.

  • Anti-perovskite solid electrolyte preparation and characterization details, including Figures S1–S5 (PDF)

  • Excel sheet summarizing the referenced experimental data from literature (XLSX)

  • Excel sheet that includes the techno-economic model for ISP (XLSX)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

Click to copy section linkSection link copied!
  • Corresponding Authors
  • Authors
    • Marm Dixit - Electrification & Energy Infrastructure Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States;  Orcidhttps://orcid.org/0000-0002-9599-9288
    • Ruhul Amin - Electrification & Energy Infrastructure Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States;  Orcidhttps://orcid.org/0000-0002-0054-3510
    • James Shipley - Quintus Technologies AB, Quintusvägen 2, SE-721 66 Västerås, Sweden
    • Richard Eklund - Quintus Technologies AB, Quintusvägen 2, SE-721 66 Västerås, Sweden
    • Nitin Muralidharan - Electrification & Energy Infrastructure Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States;  Orcidhttps://orcid.org/0000-0001-6042-5295
    • Lisa Lindqvist - Quintus Technologies, Lewis Center, Ohio 43035, United States
    • Anton Fritz - Quintus Technologies AB, Quintusvägen 2, SE-721 66 Västerås, Sweden
    • Rachid Essehli - Electrification & Energy Infrastructure Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
    • Mahalingam Balasubramanian - Electrification & Energy Infrastructure Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States;  Orcidhttps://orcid.org/0000-0002-3988-3125
  • Author Contributions

    M.D. and C.B. contributed equally.

  • Notes
    The authors declare no competing financial interest.

Biographies

Click to copy section linkSection link copied!
Download MS PowerPoint Slide

Marm Dixit is a Weinberg Distinguished Staff Fellow at the Oak Ridge National Laboratory. Marm was awarded the ECS Toyota Young Investigator Fellowship 2021, and ECS student travel grant on two occasions. He received his Ph.D. in Mechanical Engineering from Vanderbilt University.

Download MS PowerPoint Slide

Chad Beamer has a M.S. from The Ohio State University in material science. He spent time with GE Aviation and Bodycote early in his career and currently works for Quintus Technologies. There he manages the Application Center, educates on isostatic pressing technologies, and leads development efforts within both academia and industry.

Download MS PowerPoint Slide

Ruhul Amin is a staff scientist at ORNL with expertise in simulation and experimental studies on transport properties and interfacial kinetics with more than 18 years of experience in the battery field. He is a recipient of several awards and has published over 80 peer-reviewed articles and several patents.

Download MS PowerPoint Slide

James Shipley is Manager for Business Development at Quintus Technologies, working with isostatic processing with a focus on additive manufacturing, castings, powder near net shape, and metal injection molding for all manner of alloys and materials.

Download MS PowerPoint Slide

Richard Eklund has been managing applied product development and manufacturing of heavy engineered equipment for over 30 years. At Quintus Technologies he is responsible for the development of the product program for warm isostatic pressing.

Download MS PowerPoint Slide

Nitin Muralidharan is currently a R&D Associate Staff Scientist in the Emerging and Solid-State Batteries Group. His research portfolio includes development of cobalt-free cathodes, solid-state batteries, and mechano-electrochemistry. He received his Ph.D. in Interdisciplinary Materials Science from the Vanderbilt University, Nashville, Tennessee.

Download MS PowerPoint Slide

Lisa Lindqvist has a M.S. in computational mechanics from Luleå University of Technology in Sweden. She joined Quintus Technologies after graduating in 2021 and works with stress analyses of the equipment at the time of writing.

Download MS PowerPoint Slide

Anton Fritz has a M.S. from Luleå University of Technology in Aerospace Engineering. In 2018 he started his career at Quintus Technologies as a young graduate. Today his main topics are fluid mechanics and CFD simulation. He is also involved in several R&D projects.

Download MS PowerPoint Slide

Rachid Essehli is a R&D Staff with 15 years of experience in synthesis of new compounds, both glassy and crystalline forms, and a strong background in characterization of materials by X-ray diffraction. He works on the material synthesis, engineering and characterization of materials for Li-ion, beyond Li-ion, and solid-state batteries.

Download MS PowerPoint Slide

Mahalingam Balasubramanian received his Ph.D. in physics from the University of Connecticut. He is currently a Distinguished Scientist and Lead of the Emerging and Solid-State Battery Group in the Electrification and Energy Infrastructures Division at Oak Ridge National Laboratory.

Download MS PowerPoint Slide

Ilias Belharouak is a Distinguished Scientist and the Head of Electrification and Energy Storage at the Oak Ridge National Laboratory and an Adjunct Professor at the University of Tennessee Knoxville. He holds Ph.D. and M.S. degrees in Materials Science and Solid-State Chemistry from the Bordeaux 1 University, Bordeaux, France.

Acknowledgments

Click to copy section linkSection link copied!

This research at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) under contract DE-AC05-00OR22725, was sponsored by Laboratory Directed Research and Development (LDRD) Program at Oak Ridge National Laboratory, and the Office of Energy Efficiency and Renewable Energy (EERE) Vehicle Technologies Office (VTO) (Director: David Howell) Applied Battery Research subprogram (Program Manager: Peter Faguy). M.D. was also supported by Alvin M. Weinberg Fellowship at the Oak Ridge National Laboratory. SEM micrography and EDS work reported here was conducted at the Center for Nanophase Materials Sciences (CNMS), which is a U.S. DOE, Office of Science User Facility at Oak Ridge National Laboratory. This research also used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. The authors would like to thank Pavel Shevchenko and Francesco de Carlo for their help with the tomography experiments.

References

Click to copy section linkSection link copied!

This article references 72 other publications.

  1. 1
    Janek, J.; Zeier, W. G. A Solid Future for Battery Development. Nat. Energy 2016, 1, 16141,  DOI: 10.1038/nenergy.2016.141
    Google Scholar
    There is no corresponding record for this reference.
  2. 2
    Manthiram, A.; Yu, X.; Wang, S. Lithium Battery Chemistries Enabled by Solid-State Electrolytes. Nat. Rev. Mater. 2017, 2 (4), 103,  DOI: 10.1038/natrevmats.2016.103
    Google Scholar
    There is no corresponding record for this reference.
  3. 3
    Dixit, M. B.; Park, J.-S.; Kenesei, P.; Almer, J.; Hatzell, K. B. Status and Prospect of in Situ and Operando Characterization of Solid-State Batteries. Energy Environ. Sci. 2021, 14, 4672– 4711,  DOI: 10.1039/D1EE00638J
    Google Scholar
    3
    Status and prospect of in situ and operando characterization of solid-state batteries
    Dixit, Marm B.; Park, Jun-Sang; Kenesei, Peter; Almer, Jonathan; Hatzell, Kelsey B.
    Energy & Environmental Science (2021), 14 (9), 4672-4711CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
    Electrification of the transportation sector relies on radical re-imagining of energy storage technologies to provide affordable, high energy d., durable and safe systems. Next generation energy storage systems will need to leverage high energy d. anodes and high voltage cathodes to achieve the required performance metrics (longer vehicle range, long life, prodn. costs, safety). Solid-state batteries (SSBs) are promising materials technol. for achieving these metrics by enabling these electrode systems due to the underlying material properties of the solid electrolyte (viz. mech. strength, electrochem. stability, ionic cond.). Electro-chemo-mech. degrdn. in SSBs detrimentally impact the Coulombic efficiencies, capacity retention, durability and safety in SSBs restricting their practical implementation. Solid|solid interfaces in SSBs are hot-spots of dynamics that contribute to the degrdn. of SSBs. Characterizing and understanding the processes at the solid|solid interfaces in SSBs is crucial towards designing of resilient, durable, high energy d. SSBs. This work provides a comprehensive and crit. summary of the SSB characterization with a focus on in situ and operando studies. Addnl., perspectives on exptl. design, emerging characterization techniques and data anal. methods are provided. This work provides a thorough anal. of current status of SSB characterization as well as highlights important avenues for future work.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhs1CktrbO&md5=c8833cfa1785cbc3da687472752a1787
  4. 4
    Dixit, M.; Parejiya, A.; Essehli, R.; Muralidharan, N.; Haq, S. U.; Amin, R.; Belharouak, I. SolidPAC Is an Interactive Battery-on-Demand Energy Density Estimator for Solid-State Batteries. Cell Rep. Phys. Sci. 2022, 3 (2), 100756,  DOI: 10.1016/j.xcrp.2022.100756
    Google Scholar
    4
    SolidPAC is an interactive battery-on-demand energy density estimator for solid-state batteries
    Dixit, Marm; Parejiya, Anand; Essehli, Rachid; Muralidharan, Nitin; Haq, Shomaz Ul; Amin, Ruhul; Belharouak, Ilias
    Cell Reports Physical Science (2022), 3 (2), 100756CODEN: CRPSF5; ISSN:2666-3864. (Elsevier Inc.)
    Solid-state batteries hold the promise to be highly impactful next-generation technologies for high-energy and -power-d. rechargeable battery applications. It is crucial to identify the metrics that an emerging battery technol. should fulfil to achieve parity with conventional Li-ion batteries, primarily in terms of energy d. However, limited approaches exist today to assess and extrapolate the impact of battery designs and choices of cell components on the cell-level energy d. of a solid-state battery. Herein, we introduce the solid-state battery performance analyzer and calculator (SolidPAC), an interactive exptl. toolkit to enable the design of a solid-state battery for user-specified application requirements. The toolkit is flexible enough to assist the battery community in quantifying the impact of materials chem. and fractions, electrode thicknesses and loadings, and electron flows on cell energy d. and costs and in utilizing inverse engineering concepts to correlate the cell energy d. output to materials and cell design inputs.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xht1WjsrjL&md5=2488debf203c396065f2e4137d4c6519
  5. 5
    Randau, S.; Weber, D. A.; Kötz, O.; Koerver, R.; Braun, P.; Weber, A.; Ivers-Tiffée, E.; Adermann, T.; Kulisch, J.; Zeier, W. G.; Richter, F. H.; Janek, J. Benchmarking the Performance of All-Solid-State Lithium Batteries. Nat. Energy 2020, 5 (3), 259– 270,  DOI: 10.1038/s41560-020-0565-1
    Google Scholar
    5
    Benchmarking the performance of all-solid-state lithium batteries
    Randau, Simon; Weber, Dominik A.; Koetz, Olaf; Koerver, Raimund; Braun, Philipp; Weber, Andre; Ivers-Tiffee, Ellen; Adermann, Torben; Kulisch, Joern; Zeier, Wolfgang G.; Richter, Felix H.; Janek, Juergen
    Nature Energy (2020), 5 (3), 259-270CODEN: NEANFD; ISSN:2058-7546. (Nature Research)
    Increasing the specific energy, energy d., specific power, energy efficiency and energy retention of electrochem. storage devices are major incentives for the development of all-solid-state batteries. However, a general evaluation of all-solid-state battery performance is often difficult to derive from published reports, mostly due to the interdependence of performance measures, but also due to the lack of a basic ref. system. Here, we present all-solid-state batteries reduced to the bare min. of compds., contg. only a lithium metal anode, β-Li3PS4 solid electrolyte and Li(Ni0.6Co0.2Mn0.2)O2 cathode active material. We use this minimalistic system to benchmark the performance of all-solid-state batteries. In a Ragone-type graph, we compare literature data for thiophosphate-, oxide-, phosphate- and polymer-based all-solid-state batteries with our minimalistic cell. Using fundamental equations for key performance parameters, we identify research targets towards high energy, high power and practical all-solid-state batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXls1Ciurs%253D&md5=9c8e4a5f98bf58f87d9971ffbf1a5955
  6. 6
    Hatzell, K. B.; Chen, X. C.; Cobb, C.; Dasgupta, N. P.; Dixit, M. B.; Marbella, L. E.; McDowell, M. T.; Mukherjee, P.; Verma, A.; Viswanathan, V.; Westover, A.; Zeier, W. G. Challenges in Lithium Metal Anodes for Solid State Batteries. ACS Energy Lett. 2020, 5, 922– 934,  DOI: 10.1021/acsenergylett.9b02668
    Google Scholar
    6
    Challenges in Lithium Metal Anodes for Solid-State Batteries
    Hatzell, Kelsey B.; Chen, Xi Chelsea; Cobb, Corie L.; Dasgupta, Neil P.; Dixit, Marm B.; Marbella, Lauren E.; McDowell, Matthew T.; Mukherjee, Partha P.; Verma, Ankit; Viswanathan, Venkatasubramanian; Westover, Andrew S.; Zeier, Wolfgang G.
    ACS Energy Letters (2020), 5 (3), 922-934CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
    A review. In this Perspective, we highlight recent progress and challenges related to the integration of lithium metal anodes in solid-state batteries. While prior reports have suggested that solid electrolytes may be impermeable to lithium metal, this hypothesis has been disproven under a variety of electrolyte compns. and cycling conditions. Herein, we describe the mechanistic origins and importance of lithium filament growth and interphase formation in inorg. and org. solid electrolytes. Multimodal techniques that combine real and reciprocal space imaging and modeling will be necessary to fully understand nonequil. dynamics at these buried interfaces. Currently, most studies on lithium electrode kinetics at solid electrolyte interfaces are completed in sym. Li-Li configurations. To fully understand the challenges and opportunities afforded by Li-metal anodes, full-cell expts. are necessary. Finally, the impacts of operating conditions on solid-state batteries are largely unknown with respect to pressure, geometry, and break-in protocols. Given the rapid growth of this community and the diverse portfolio of solid electrolytes, we highlight the need for detailed reporting of exptl. conditions and standardization of protocols across the community.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXjtlWrsLo%253D&md5=118bf765db2b34bb743ca396b89b8a6c
  7. 7
    Schnell, J.; Knörzer, H.; Imbsweiler, A. J.; Reinhart, G. Solid versus Liquid─A Bottom-Up Calculation Model to Analyze the Manufacturing Cost of Future High-Energy Batteries. Energy Technology 2020, 8 (3), 1901237,  DOI: 10.1002/ente.201901237
    Google Scholar
    7
    Solid versus Liquid-A Bottom-Up Calculation Model to Analyze the Manufacturing Cost of Future High-Energy Batteries
    Schnell, Joscha; Knoerzer, Heiko; Imbsweiler, Anna Julia; Reinhart, Gunther
    Energy Technology (Weinheim, Germany) (2020), 8 (3), 1901237CODEN: ETNEFN; ISSN:2194-4296. (Wiley-VCH Verlag GmbH & Co. KGaA)
    All-solid-state batteries (ASSB) are promising candidates for future energy storage. However, only a little is known about the manufg. costs for industrial prodn. Herein, a detailed bottom-up calcn. is performed to est. the required investment and to facilitate comparison with conventional lithium-ion batteries (LIB). Results indicate that sulfide-based ASSBs can indeed be competitive if the material compatibility issues can be solved and prodn. is successfully scaled. In contrast, oxide-based ASSBs will probably not be able to compete if cost is the decisive factor. A sensitivity anal. with Monte Carlo simulation reveals that the inert gas atm. required for sulfide-based ASSBs contributes little to the overall cell costs, whereas the sintering step for oxide-based ASSBs is highly crit. The calcn. also indicates that inhouse manufg. of the lithium anode will be cheaper than purchasing the lithium foil externally if the cell producer has sufficient processing know-how. Finally, the aerosol deposition method is investigated, revealing that a deposition rate far above 1000 mm3 min-1 would be required to make the technol. economically feasible in ASSB prodn. The results of this study will help researchers and industry prioritize development efforts and push the scale-up of future high-energy batteries with improved performance.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXksVGlu7g%253D&md5=87a671fcc6929f61b16f3b000693fbc6
  8. 8
    Hatzell, K. B.; Zheng, Y. Prospects on Large-Scale Manufacturing of Solid State Batteries. MRS Energy Sustainability 2021, 8 (1), 33– 39,  DOI: 10.1557/s43581-021-00004-w
    Google Scholar
    There is no corresponding record for this reference.
  9. 9
    Schnell, J.; Günther, T.; Knoche, T.; Vieider, C.; Köhler, L.; Just, A.; Keller, M.; Passerini, S.; Reinhart, G. All-Solid-State Lithium-Ion and Lithium Metal Batteries – Paving the Way to Large-Scale Production. J. Power Sources 2018, 382, 160– 175,  DOI: 10.1016/j.jpowsour.2018.02.062
    Google Scholar
    9
    All-solid-state lithium-ion and lithium metal batteries - paving the way to large-scale production
    Schnell, Joscha; Guenther, Till; Knoche, Thomas; Vieider, Christoph; Koehler, Larissa; Just, Alexander; Keller, Marlou; Passerini, Stefano; Reinhart, Gunther
    Journal of Power Sources (2018), 382 (), 160-175CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    Challenges and requirements for the large-scale prodn. of all-solid-state lithium-ion and lithium metal batteries are herein evaluated via workshops with experts from renowned research institutes, material suppliers, and automotive manufacturers. Aiming to bridge the gap between materials research and industrial mass prodn., possible solns. for the prodn. chains of sulfide and oxide based all-solid-state batteries from electrode fabrication to cell assembly and quality control are presented. Based on these findings, a detailed comparison of the prodn. processes for a sulfide based all-solid-state battery with conventional lithium-ion cell prodn. is given, showing that processes for composite electrode fabrication can be adapted with some effort, while the fabrication of the solid electrolyte separator layer and the integration of a lithium metal anode will require completely new processes. This work identifies the major steps towards mass prodn. of all-solid-state batteries, giving insight into promising manufg. technologies and helping stakeholders, such as machine engineering, cell producers, and original equipment manufacturers, to plan the next steps towards safer batteries with increased storage capacity.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXjtlaqtbc%253D&md5=970ae25e087dd33eb2c03871e6bbaee8
  10. 10
    Dixit, M.; Muralidharan, N.; Parejiya, A.; Amin, R.; Essehli, R.; Belharouak, I. Current Status and Prospects of Solid-State Batteries as the Future of Energy Storage: Management and Applications of Energy Storage Devices. Intech Open 2021, 39– 61,  DOI: 10.5772/intechopen.98701
    Google Scholar
    There is no corresponding record for this reference.
  11. 11
    Albertus, P.; Anandan, V.; Ban, C.; Balsara, N.; Belharouak, I.; Buettner-Garrett, J.; Chen, Z.; Daniel, C.; Doeff, M.; Dudney, N. J.; Dunn, B.; Harris, S. J.; Herle, S.; Herbert, E.; Kalnaus, S.; Libera, J. A.; Lu, D.; Martin, S.; McCloskey, B. D.; McDowell, M. T.; Meng, Y. S.; Nanda, J.; Sakamoto, J.; Self, E. C.; Tepavcevic, S.; Wachsman, E.; Wang, C.; Westover, A. S.; Xiao, J.; Yersak, T. Challenges for and Pathways toward Li-Metal-Based All-Solid-State Batteries. ACS Energy Lett. 2021, 6 (4), 1399– 1404,  DOI: 10.1021/acsenergylett.1c00445
    Google Scholar
    11
    Challenges for and Pathways toward Li-Metal-Based All-Solid-State Batteries
    Albertus, Paul; Anandan, Venkataramani; Ban, Chunmei; Balsara, Nitash; Belharouak, Ilias; Buettner-Garrett, Josh; Chen, Zonghai; Daniel, Claus; Doeff, Marca; Dudney, Nancy J.; Dunn, Bruce; Harris, Stephen J.; Herle, Subramanya; Herbert, Eric; Kalnaus, Sergiy; Libera, Joesph A.; Lu, Dongping; Martin, Steve; McCloskey, Bryan D.; McDowell, Matthew T.; Meng, Y. Shirley; Nanda, Jagjit; Sakamoto, Jeff; Self, Ethan C.; Tepavcevic, Sanja; Wachsman, Eric; Wang, Chunsheng; Westover, Andrew S.; Xiao, Jie; Yersak, Thomas
    ACS Energy Letters (2021), 6 (4), 1399-1404CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
    A review. Solid-state batteries hold great promise for high-energy batteries for elec. vehicles and other applications. While the potential is great, success is contingent on solving crit. challenges in materials science, processing science, and fabrication of practical full cells. This focus article has outlined several key challenges in the hope that they will encourage and inspire solns. and the eventual realization of high-energy solid-state batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXmvVCmsLY%253D&md5=8de2940c82b1d2767d98def586dae92e
  12. 12
    Zheng, F.; Kotobuki, M.; Song, S.; Lai, M. O.; Lu, L. Review on Solid Electrolytes for All-Solid-State Lithium-Ion Batteries. J. Power Sources 2018, 389 (April), 198– 213,  DOI: 10.1016/j.jpowsour.2018.04.022
    Google Scholar
    12
    Review on solid electrolytes for all-solid-state lithium-ion batteries
    Zheng, Feng; Kotobuki, Masashi; Song, Shufeng; Lai, Man On; Lu, Li
    Journal of Power Sources (2018), 389 (), 198-213CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    All-solid-state (ASS) lithium-ion battery has attracted great attention due to its high safety and increased energy d. One of key components in the ASS battery (ASSB) is solid electrolyte that dets. performance of the ASSB. Many types of solid electrolytes have been investigated in great detail in the past years, including NASICON-type, garnet-type, perovskite-type, LISICON-type, LiPON-type, Li3N-type, sulfide-type, argyrodite-type, anti-perovskite-type and many more. This paper aims to provide comprehensive reviews on some typical types of key solid electrolytes and some ASSBs, and on gaps that should be resolved.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXnsFWjsLY%253D&md5=3cb31a091d2fff8bfc994dc6853179e2
  13. 13
    Quartarone, E.; Mustarelli, P. Electrolytes for Solid-State Lithium Rechargeable Batteries: Recent Advances and Perspectives. Chem. Soc. Rev. 2011, 40 (5), 2525,  DOI: 10.1039/c0cs00081g
    Google Scholar
    13
    Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives
    Quartarone, Eliana; Mustarelli, Piercarlo
    Chemical Society Reviews (2011), 40 (5), 2525-2540CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    This crit. review presents an overview of the various classes of Li+ conductors for use as electrolytes in lithium polymer batteries and all-solid state microbatteries. Initially, we recall the main models for ion transport and the structure-transport relationships at the basis of the obsd. cond. behaviors. Emphasis is then placed on the physico-chem. and functional parameters relevant for optimal electrolytes prepn., as well as on the techniques of choice for their evaluation. Finally, the state of the art of polymer and ceramic electrolytes is reported, and the most interesting strategies for the future developments are described (121 refs.).
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXkvVWjtLY%253D&md5=9492a31219e7b6c1e4b6221805b5c600
  14. 14
    Thangadurai, V.; Narayanan, S.; Pinzaru, D. Garnet-Type Solid-State Fast Li Ion Conductors for Li Batteries: Critical Review. Chem. Soc. Rev. 2014, 43 (13), 4714– 4727,  DOI: 10.1039/c4cs00020j
    Google Scholar
    14
    Garnet-type solid-state fast Li ion conductors for Li batteries: critical review
    Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana
    Chemical Society Reviews (2014), 43 (13), 4714-4727CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review. Batteries are electrochem. devices that store elec. energy in the form of chem. energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and elec. vehicles. Conventional LiBs use an org. polymer electrolyte, which exhibits several safety issues including leakage, poor chem. stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power d. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compds. are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion cond. of ∼10-6 at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion cond. of 10-3 S cm-1 at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chem. stable at higher temps. and voltages compared to polymer electrolytes. Here, we discuss the chem. compn.-structure-ionic cond. relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXpsVKisrg%253D&md5=cf00b77444023feaa2fc3faed1423c1e
  15. 15
    Alexander, G. v.; Indu, M. S.; Murugan, R. Review on the Critical Issues for the Realization of All-Solid-State Lithium Metal Batteries with Garnet Electrolyte: Interfacial Chemistry, Dendrite Growth, and Critical Current Densities Ionics; Springer Science and Business Media Deutschland GmbH, 2021; pp 4105– 4126.  DOI: 10.1007/s11581-021-04190-y o
    Google Scholar
    There is no corresponding record for this reference.
  16. 16
    Singh, N.; Horwath, J. P.; Bonnick, P.; Suto, K.; Stach, E. A.; Matsunaga, T.; Muldoon, J.; Arthur, T. S. The Role of Lithium Iodide Addition to Lithium Thiophosphate: Implications beyond Conductivity. Chem. Mater. 2020, 32, 7150– 7158,  DOI: 10.1021/acs.chemmater.9b05286
    Google Scholar
    16
    Role of Lithium Iodide Addition to Lithium Thiophosphate: Implications beyond Conductivity
    Singh, Nikhilendra; Horwath, James P.; Bonnick, Patrick; Suto, Koji; Stach, Eric A.; Matsunaga, Tomoya; Muldoon, John; Arthur, Timothy S.
    Chemistry of Materials (2020), 32 (17), 7150-7158CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    Because of their high cond. and potential to utilize lithium metal, lithium thiophosphate electrolytes have attracted significant attention to realize solid-state batteries for vehicle applications. However, lithium metal still presents many challenges in potentially maximizing the battery energy d. One important requirement is to limit the amt. of lithium metal during cell construction or to operate the cell under limited lithium conditions. Here, the interface between lithium thiophosphate and lithium iodide-doped lithium thiophosphate with lithium metal is investigated. Lithium iodide plays a protective role at the interface and enables improved lithium cycling. Operando transmission electron microscopy anal. reveals delamination and dead lithium at the interface as major challenges for solid-state batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFWgtrvL&md5=d9ae5b14873cc515acba79e1d4250740
  17. 17
    Dixit, M. B.; Singh, N.; Horwath, J. P.; Shevchenko, P. D.; Jones, M.; Stach, E. A.; Arthur, T. S.; Hatzell, K. B. In Situ Investigation of Chemomechanical Effects in Thiophosphate Solid Electrolytes. Matter 2020, 3 (6), 2138– 2159,  DOI: 10.1016/j.matt.2020.09.018
    Google Scholar
    There is no corresponding record for this reference.
  18. 18
    Homann, G.; Meister, P.; Stolz, L.; Brinkmann, J. P.; Kulisch, J.; Adermann, T.; Winter, M.; Kasnatscheew, J. High-Voltage All-Solid-State Lithium Battery with Sulfide-Based Electrolyte: Challenges for the Construction of a Bipolar Multicell Stack and How to Overcome Them. ACS Appl. Energy Mater. 2020, 3 (4), 3162– 3168,  DOI: 10.1021/acsaem.0c00041
    Google Scholar
    18
    High-Voltage All-Solid-State Lithium Battery with Sulfide-Based Electrolyte: Challenges for the Construction of a Bipolar Multicell Stack and How to Overcome Them
    Homann, Gerrit; Meister, Paul; Stolz, Lukas; Brinkmann, Jan Paul; Kulisch, Joern; Adermann, Torben; Winter, Martin; Kasnatscheew, Johannes
    ACS Applied Energy Materials (2020), 3 (4), 3162-3168CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    Solid electrolytes can be the key for the desired goal of increased safety and specific energies of batteries. On a cell and battery pack level, the all-solid nature and the absence of liq. electrolyte leakage are considered to enable safe and effective performance realization of the rechargeable Li metal electrode and bipolar cell stacking, resp. Well performing Li metal cells with high-energy/voltage pos. electrodes such as LiNi0.6Mn0.2Co0.2O2 (NMC622) can already be cycled when using a blend of the sulfidic solid electrolyte such as β-Li3PS4 (LPS) and Li salt in poly(ethylene)oxide (PEO). However, operation of a bipolar stack using these cell materials utilizing the common Al/Cu clad as bipolar plate results in an immediate short circuit, because of an ionic intercell connection via molten LiTFSI/PEO. Oversizing the area of the bipolar plates can prevent such a short circuit and indeed enables a partial charge of the stack, but after a certain time, the next cell failure is obsd., consisting of severe, sulfur caused, corrosion of copper which was used as metal substrate for the lithium anode. The exchange of the sulfide incompatible Cu collector by (also area-oversized) stainless steel can finally enable a failure-free performance of the bipolar cell stack, which performs similar to a single cell with regard to cycling stability.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXkvFyjsL4%253D&md5=ccb4220513f6ae0b37b7b418992be0c5
  19. 19
    Lau, J.; DeBlock, R. H.; Butts, D. M.; Ashby, D. S.; Choi, C. S.; Dunn, B. S. Sulfide Solid Electrolytes for Lithium Battery Applications. Adv. Energy Mater. 2018, 8 (27), 1800933,  DOI: 10.1002/aenm.201800933
    Google Scholar
    There is no corresponding record for this reference.
  20. 20
    Dixit, M. B.; Zaman, W.; Bootwala, Y.; Zheng, Y.; Hatzell, M. C.; Hatzell, K. B. Scalable Manufacturing of Hybrid Solid Electrolytes with Interface Control. ACS Appl. Mater. Interfaces 2019, 11 (48), 45087– 45097,  DOI: 10.1021/acsami.9b15463
    Google Scholar
    20
    Scalable Manufacturing of Hybrid Solid Electrolytes with Interface Control
    Dixit, Marm B.; Zaman, Wahid; Bootwala, Yousuf; Zheng, Yanjie; Hatzell, Marta C.; Hatzell, Kelsey B.
    ACS Applied Materials & Interfaces (2019), 11 (48), 45087-45097CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Hybrid solid electrolytes are promising alternatives for high energy d., metallic Li batteries. Scalable manufg. of multi-material electrolytes with tailored transport pathways can provide an avenue toward controlling Li stripping and deposition mechanisms in all solid state devices. A novel roll-to-roll compatible coextrusion device is demonstrated to study meso-structural control during manufg. Solid electrolytes with 25 wt.\% and 75wt.\% PEO-LLZO compns. were studied. The coextrusion head is demonstrated to effectively process multi-material films with strict compositional gradients in a single-pass. Av. manufg. variability of 5.75 ± 1.2μm is obsd. in the thickness across all the electrolytes manufd. Coextruded membrane with 1 mm stripes shows the highest room temp. cond. of 8.8 × 10-6 S cm-1 compared to the cond. of single material films (25%:1.2 × 10-6 S cm-1 , 75%:1.8 × 10-6 S cm-1 ). Distribution of relaxation times and effective mean field theory calcns. suggest that the interface generated between the two materials possess high ion-conducting properties. Computational simulations were used to further substantiate the influence of macro-scale interfaces on ion transport.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitFSqt7nL&md5=52b792eef365abb2a907505d9f5bc0f3
  21. 21
    Keller, M.; Varzi, A.; Passerini, S. Hybrid Electrolytes for Lithium Metal Batteries. J. Power Sources 2018, 392 (April), 206– 225,  DOI: 10.1016/j.jpowsour.2018.04.099
    Google Scholar
    21
    Hybrid electrolytes for lithium metal batteries
    Keller, Marlou; Varzi, Alberto; Passerini, Stefano
    Journal of Power Sources (2018), 392 (), 206-225CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    This perspective article discusses the most recent developments in the field of hybrid electrolytes, here referred to electrolytes composed of two, well-defined ion-conducting phases, for high energy d. lithium metal batteries. The two phases can be both solid, as e.g., two inorg. conductors or one inorg. and one polymer conductor, or, differently, one liq. and one inorg. conductor. In this latter case, they are referred as quasi-solid hybrid electrolytes. Techniques for the appropriate characterization of hybrid electrolytes are discussed emphasizing the importance of ionic conduction and interfacial properties. On this view, multilayer systems are also discussed in more detail. Investigations on Lewis acid-base interactions, activation energies for lithium-ion transfer between the phases, and the formation of an interphase between the components are reviewed and analyzed. The application of different hybrid electrolytes in lithium metal cells with various cathode compns. is also discussed. Fabrication methods for the feasibility of large-scale applications are briefly analyzed and different cell designs and configurations, which are most suitable for the integration of hybrid electrolytes, are detd. Finally, the specific energy of cells contg. different hybrid electrolytes is estd. to predict possible enhancement in energy with respect to the current lithium-ion battery technol.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXovFGltr4%253D&md5=cfd041bbb8d101d20355a231a7a018b8
  22. 22
    Mahmud, L. S.; Muchtar, A.; Somalu, M. R. Challenges in Fabricating Planar Solid Oxide Fuel Cells: A Review. Renewable Sustainable Energy Rev. 2017, 72, 105– 116,  DOI: 10.1016/j.rser.2017.01.019
    Google Scholar
    23
    Challenges in fabricating planar solid oxide fuel cells: A review
    Mahmud, L. S.; Muchtar, A.; Somalu, M. R.
    Renewable & Sustainable Energy Reviews (2017), 72 (), 105-116CODEN: RSERFH; ISSN:1364-0321. (Elsevier Ltd.)
    A review. Most technologies for fabricating solid oxide fuel cells (SOFCs) are adopted from ceramic-fabrication methods. Selecting an appropriate method of prepg. SOFC components is a main concern for many researchers because the method can strongly affect SOFC properties and performance. The method must be reproducible and highly controllable to improve SOFC performance and durability. SOFC fabrication methods have been customized to achieve high power outputs at low operation temps. and thus broaden the choice of material and reduce fabrication cost. This article provides an overview of planar SOFC fabrication methods. Planar SOFC fabrication methods such as uniaxial pressing, tape casting, screen printing, dip coating, and slurry spin coating are discussed because these methods are cost effective. This article also discusses the tech. parameters that can influence the processes of these methods and SOFC performance. The methods of prepg. the materials of SOFC components are discussed because these methods directly affect the fabrication process.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtlClsLw%253D&md5=068a1e72ebab99e053ccbdcdcbf8cf93
  23. 23
    Robertson, I. M.; Schaffer, G. B. Review of Densification of Titanium Based Powder Systems in Press and Sinter Processing. Powder Metallurgy 2010, 53 (2), 146– 162,  DOI: 10.1179/174329009X434293
    Google Scholar
    24
    Review of densification of titanium based powder systems in press and sinter processing
    Robertson, I. M.; Schaffer, G. B.
    Powder Metallurgy (2010), 53 (2), 146-162CODEN: PWMTAU; ISSN:0032-5899. (Maney Publishing)
    A review. The development of novel extractive metallurgy techniques for titanium offers the prospect of lower cost Ti powder and therefore wider application of Ti. This review is largely confined to coverage of the low cost press and sinter methods of powder metallurgy, consisting of cold pressing of mixed elemental powders followed by sintering without the application of external pressure. Cold die compaction, sintering behavior and densification are reviewed in detail. Some information on powders and cold isostatic pressing is included. Microstructure, mech. properties and applications are considered in less detail. The review deals mostly with the sintering of alloys, but there is some ref. to synthesis of intermetallic compds., such as the shape memory alloy NiTi and Ti aluminides for high temp. applications. Densification is discussed in terms of the four fundamental processing variables: compaction pressure, particle size, sintering temp., and sintering time. Other factors such as alloy compn., the form of alloying addn., type and impurity content of powders and heating rate are also considered.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXpt1ymt7w%253D&md5=68e1b11b17189b8f073b3654e7cb260a
  24. 24
    Hotza, D.; di Luccio, M.; Wilhelm, M.; Iwamoto, Y.; Bernard, S.; Diniz da Costa, J. C. Silicon Carbide Filters and Porous Membranes: A Review of Processing, Properties, Performance and Application. J. Membr. Sci. 2020, 610, 118193,  DOI: 10.1016/j.memsci.2020.118193
    Google Scholar
    25
    Silicon carbide filters and porous membranes: A review of processing, properties, performance and application
    Hotza, Dachamir; Di Luccio, Marco; Wilhelm, Michaela; Iwamoto, Yuji; Bernard, Samuel; Diniz da Costa, Joao C.
    Journal of Membrane Science (2020), 610 (), 118193CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)
    A review. Silicon carbide (SiC) filters and porous membranes is a growing industry with deployment for gas and liq. sepn. processes. In view of its importance, the research efforts into the development of SiC filters and membranes are of growing interest around the world. Therefore, this review paper is focused on the latest advancements in SiC and SiC composites used for the prepn. of substrates and thin films in filters and membranes. There is a multitude of methods used to prep. filters and membranes of different shapes (tubular, honeycomb, flat sheets and multi-channel), which are influenced by precursor mixt. and sintering conditions. In turn, these processing conditions affect porosity and pore size, which affects the transport and sepn. properties of SiC filters and membranes. SiC particles size and distribution allow for the precise control of pore size in membranes, leading to high gas sepn. factors. In addn., SiC has strong thermal stability properties that are very desirable for high temp. gas cleaning. Together with gas and liq. transport and sepn. properties, this review also addresses the potential applications in gas and liq. sepn. processes, coupled with thermal/chem. stability properties. Future challenges are highlighted towards further research efforts.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtVSjtrzM&md5=a429eff4a67a86f85a4e5f565e7340ad
  25. 25
    Song, J. -H; Evans, J. R. G. A Die Pressing Test for the Estimation of Agglomerate Strength. J. Am. Ceram. Soc. 1994, 77 (3), 806– 814,  DOI: 10.1111/j.1151-2916.1994.tb05369.x
    Google Scholar
    26
    A die pressing test for the estimation of agglomerate strength
    Song, Jin Hua; Evans, Julian R. G.
    Journal of the American Ceramic Society (1994), 77 (3), 806-14CODEN: JACTAW; ISSN:0002-7820.
    A die pressing test was developed for quick and inexpensive estn. of the agglomerate strength of ceramic powders. The crit. nominal pressure (pc) at which contact areas between agglomerates start to increase rapidly was found from the relationship between change in sample height and applied pressure in uniaxial single-ended die pressing. A quant. microscopic method was used for measuring the area fraction (ψ) of agglomerates which transmits the force through the assembly. A die pressing agglomerate strength, σd, is defined as σd = 0.7 pc/ψ. This strength was compared with the agglomerate tensile strength obtained from single agglomerate diametral compression tests and found to be 50% higher than the latter because of multipoint loading. A suggested guideline is that the mean agglomerate tensile strength is approx. 52% of pc detd. in a die pressing test for spherical agglomerates. In addn. to agglomerate tensile strength, the mean agglomerate size, the interior macropore structure of agglomerates, as well as the packing efficiencies between and inside agglomerates can be estd. by the procedure.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXit1CrsbY%253D&md5=41da21d1d1a5ef3b002579256d51adf8
  26. 26
    Mahesh, M. L. V.; Bhanu Prasad, V. v.; James, A. R. A Comparison of Different Powder Compaction Processes Adopted for Synthesis of Lead-Free Piezoelectric Ceramics. Eur. Phys. J. B 2016, 89 (4), 108,  DOI: 10.1140/epjb/e2016-60390-6
    Google Scholar
    There is no corresponding record for this reference.
  27. 27
    Attia, U. M. Cold-Isostatic Pressing of Metal Powders: A Review of the Technology and Recent Developments. Crit. Rev. Solid State Mater. Sci. 2021, 46 (6), 587– 610,  DOI: 10.1080/10408436.2021.1886043
    Google Scholar
    28
    Cold-isostatic pressing of metal powders: a review of the technology and recent developments
    Attia, Usama M.
    Critical Reviews in Solid State and Materials Sciences (2021), 46 (6), 587-610CODEN: CCRSDA; ISSN:1040-8436. (Taylor & Francis, Inc.)
    Cold-isostatic pressing (CIP) is a powder-based, near-net-shape technol. for the prodn. of metal and ceramic components. CIP has been commonly used for processing ceramics, but not as widely used for metals. Recent developments in process capability and powder metallurgy, however, have allowed CIP to be increasingly used in the manuf. of high-performance metal parts. Advantages such as solid-state processing, uniform microstructure, shape complexity, low tooling cost and process scalability have made CIP a viable processing route for metals. In addn., the potential to produce near-net-shape parts with minimal material waste has made the process more widely acceptable in niche applications, such as aerospace and automotive. This review assesses the state of the technol. in terms of capabilities and limitations, materials, tool design and fabrication, process modeling, post processing and assessment. The review also highlights challenges and research gaps in using CIP for producing metal parts, with a focus on potential areas of improvement and recent developments that address these challenges.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXkvFCrt7o%253D&md5=4c5b3769a19df40a45302e13f8b9bfee
  28. 28
    Bocanegra-Bernal, M. H. Hot Isostatic Pressing (HIP) Technology and Its Applications to Metals and Ceramics. J. Mater. Sci. 2004, 39 (21), 6399– 6420,  DOI: 10.1023/B:JMSC.0000044878.11441.90
    Google Scholar
    29
    Hot Isostatic Pressing (HIP) technology and its applications to metals and ceramics
    Bocanegra-Bernal, M. H.
    Journal of Materials Science (2004), 39 (21), 6399-6420CODEN: JMTSAS; ISSN:0022-2461. (Kluwer Academic Publishers)
    This review examines some of the components of this increasingly exploited technol. as well as the application of which will surely increase as a result of const. development in equipment design and extensive research in the field of ceramic and metal materials in general for the prodn. of fully dense and reliable parts. Newly developed high temp. HIP equipment can offer potential improvements to material properties relative to more conventional techniques as a possible soln. to the manuf. of ceramic and metal components for airframe and structural components where crit. and highly stressed applications are required. By the use the near net shape techniques, exotic materials can be used more cost effectively than machining from solid. Designers and manufacturers alike can make better products by introducing HIP to their prodn. route.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXosVyjtb4%253D&md5=5c89e8c43afa2e2308d4175cfca8e08f
  29. 29
    Radomir, I.; Geamăn, V.; Stoicănescu, M. Densification Mechanisms Made During Creep Techniques Applied to the Hot Isostatic Pressing. Procedia Soc. Behav Sci. 2012, 62, 779– 782,  DOI: 10.1016/j.sbspro.2012.09.131
    Google Scholar
    There is no corresponding record for this reference.
  30. 30
    Swinkels, F. B.; Wilkinson, D. S.; Arzt, E.; Ashby, M. F. Mechanisms of Hot-Isostatic Pressing. Acta Metall. 1983, 31 (11), 1829– 1840,  DOI: 10.1016/0001-6160(83)90129-3
    Google Scholar
    31
    Mechanisms of hot-isostatic pressing
    Swinkels, F. B.; Wilkinson, D. S.; Arzt, E.; Ashby, M. F.
    Acta Metallurgica (1983), 31 (11), 1829-40CODEN: AMETAR; ISSN:0001-6160.
    The hot-isostatic pressing of Pb, Sn, and polymethylmethacrylate [9011-14-7] powders was studied by using a rig enabling continuous measurement of d. The dominant mechanisms of densification were plastic yielding and power-low creep. Large discrepancies were found between the data and previous models for these mechanisms. Improved models, while still approx., include new phys. ideas and give a better description of the expts.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2cXhtFSkug%253D%253D&md5=d1546fc6027e74e70dcf6af283005643
  31. 31
    du Plessis, A.; Macdonald, E. Hot Isostatic Pressing in Metal Additive Manufacturing: X-Ray Tomography Reveals Details of Pore Closure. Addit. Manuf. 2020, 34, 101191,  DOI: 10.1016/J.ADDMA.2020.101191
    Google Scholar
    32
    Hot isostatic pressing in metal additive manufacturing: X-ray tomography reveals details of pore closure
    du Plessis, A.; Macdonald, E.
    Additive Manufacturing (2020), 34 (), 101191CODEN: AMDAD2; ISSN:2214-7810. (Elsevier B.V.)
    Hot isostatic pressing (HIP) of additively manufd. metals is a widely adopted and effective method to improve the d. and microstructure homogeneity within geometrically-complex metal structures fabricated with laser powder bed fusion (LPBF). The role of pores in the fatigue performance of additively manufd. metal parts is increasingly being recognized as a crit. factor and HIP post-processing is now heralded as a method to eliminate pores, esp. for high-criticality applications such as in the aerospace industry. In this work, X-ray tomog. was employed to provide insights into pore closure efficiency by HIP for an intentional and artificially-induced cavity as well as for a range of typical process-induced pores (lack of fusion, keyhole, contour pores, etc.) in coupon samples of Ti6Al4V. Subsequent heat treatments (annealing after HIP) in some cases resulted in internal pore reopening for previously closed internal pores as well as a new "blistering" effect obsd. for some near-surface pores, which the authors believe is reported for the first time. Implications of these results for quality control and HIP processing of LPBF parts are discussed. Finally, the utility of using HIP to consolidate intentionally-unmelted powder in order to improve prodn. rates of powder bed fusion has great potential and is preliminarily demonstrated.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFajsrbF&md5=ce3119b912d5e24e3d9e30b317de804f
  32. 32
    Loh, N. L.; Sia, K. Y. An Overview of Hot Isostatic Pressing. J. Mater. Process Technol. 1992, 30 (1), 45– 65,  DOI: 10.1016/0924-0136(92)90038-T
    Google Scholar
    There is no corresponding record for this reference.
  33. 33
    Sugata, S.; Saito, N.; Watanabe, A.; Watanabe, K.; Kim, J. D.; Kitagawa, K.; Suzuki, Y.; Honma, I. Quasi-Solid-State Lithium Batteries Using Bulk-Size Transparent Li7La3Zr2O12 Electrolytes. Solid State Ion 2018, 319, 285– 290,  DOI: 10.1016/j.ssi.2018.02.029
    Google Scholar
    There is no corresponding record for this reference.
  34. 34
    Huang, X.; Lu, Y.; Guo, H.; Song, Z.; Xiu, T.; Badding, M. E.; Wen, Z. None-Mother-Powder Method to Prepare Dense Li-Garnet Solid Electrolytes with High Critical Current Density. ACS Appl. Energy Mater. 2018, 1 (10), 5355– 5365,  DOI: 10.1021/acsaem.8b00976
    Google Scholar
    35
    None-Mother-Powder Method to Prepare Dense Li-Garnet Solid Electrolytes with High Critical Current Density
    Huang, Xiao; Lu, Yang; Guo, Haojie; Song, Zhen; Xiu, Tongping; Badding, Michael E.; Wen, Zhaoyin
    ACS Applied Energy Materials (2018), 1 (10), 5355-5365CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    Cubic Li-garnet Li7La3Zr2O12 (c-LLZO) is a promising Li+ ion conductor for applications as a ceramic solid electrolyte in next generation high safety Li batteries. The sintering temp. of c-LLZO is usually >1100°, where Li-loss is severe, esp. in conventional air ambient sintering method. Covering the green body with mother powder is often adopted for compensating the Li-loss. The mother powder having the same compn. as the green body cannot be repeatedly use, which raises the cost of the c-LLZO ceramics. A self-compensating Li-loss method without mother powder is proposed and studied to prep. high-quality c-LLZO ceramics. In this method, excess Li is added to c-LLZO green pellets to self-compensate Li-loss at high temp. The impact of different amts. of excess Li and crucible material, such as Pt, MgO, Al2O3, and ZrO2 was studied. With optimized such sintering method, Ta doped LLZO pellets with 10% excess Li can be well sintered inside low-cost MgO crucible without mother powder at 1250° for only 40 min and lab. scale prodn. is demonstrated. The ceramics have relative densities of ∼96%, conductivities of ∼6.47 × 10-4 S cm-1 and crit. c.d. of 1.15 mA cm-2 at 25°, which is fundamental for further researches on solid-state batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1Klt7bP&md5=e21cdaf524951aabd5a40620060e462d
  35. 35
    Zahiri, B.; Patra, A.; Kiggins, C.; Yong, A. X. B.; Ertekin, E.; Cook, J. B.; Braun, P. V. Revealing the Role of the Cathode-Electrolyte Interface on Solid-State Batteries. Nat. Mater. 2021, 20, 1392– 1400,  DOI: 10.1038/s41563-021-01016-0
    Google Scholar
    36
    Revealing the role of the cathode-electrolyte interface on solid-state batteries
    Zahiri, Beniamin; Patra, Arghya; Kiggins, Chadd; Yong, Adrian Xiao Bin; Ertekin, Elif; Cook, John B.; Braun, Paul V.
    Nature Materials (2021), 20 (10), 1392-1400CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)
    Interfaces have crucial, but still poorly understood, roles in the performance of secondary solid-state batteries. Here, using crystallog. oriented and highly faceted thick cathodes, we directly assess the impact of cathode crystallog. and morphol. on the long-term performance of solid-state batteries. The controlled interface crystallog., area and microstructure of these cathodes enables an understanding of interface instabilities unknown (hidden) in conventional thin-film and composite solid-state electrodes. A generic and direct correlation between cell performance and interface stability is revealed for a variety of both lithium- and sodium-based cathodes and solid electrolytes. Our findings highlight that minimizing interfacial area, rather than its expansion as is the case in conventional composite cathodes, is key to both understanding the nature of interface instabilities and improving cell performance. Our findings also point to the use of dense and thick cathodes as a way of increasing the energy d. and stability of solid-state batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhtFCms7bF&md5=a1ec4bc8b65aea7d9804fc9f8c6b121e
  36. 36
    Hou, M.; Qu, T.; Zhang, Q.; Yaochun, Y.; Dai, Y.; Liang, F.; Okuma, G.; Hayashi, K. Investigation of the Stability of NASICON-Type Solid Electrolyte in Neutral-Alkaline Aqueous Solutions. Corros. Sci. 2020, 177, 109012,  DOI: 10.1016/j.corsci.2020.109012
    Google Scholar
    37
    Investigation of the stability of NASICON-type solid electrolyte in neutral-alkaline aqueous solutions
    Hou, Minjie; Qu, Tao; Zhang, Qingkai; Yao, Yaochun; Dai, Yongnian; Liang, Feng; Okuma, Gaku; Hayashi, Katsuro
    Corrosion Science (2020), 177 (), 109012CODEN: CRRSAA; ISSN:0010-938X. (Elsevier Ltd.)
    The effects of aq. solns. with different pH values on the ionic cond. of Na3Zr2Si2PO12 (NASICON) are studied at room temp. The ionic cond. of NASCION reduced severely in the soln. with pH value of 7. The AC impedance method was used to study the changes of the bulk, grain boundary, and cracking surface resistances of the sample under different conditions. The electrolyte morphol., cell parameters, Na+ site occupancy fraction, and microscopic strain change were obtained by SEM and XRD data refinement. According to above anal., the degrdn. processes of hydration, grain refinement, and surface cracking were obsd. gradually, the corresponding corrosion mechanism of NASICON in aq. solns. was explained.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVCltrrF&md5=ad00ecee37705201fbdac25a10cd0bdb
  37. 37
    van den Broek, J.; Rupp, J. L. M.; Afyon, S. Boosting the Electrochemical Performance of Li-Garnet Based All-Solid-State Batteries with Li4Ti5O12 Electrode: Routes to Cheap and Large Scale Ceramic Processing. J. Electroceram. 2017, 38 (2–4), 182– 188,  DOI: 10.1007/s10832-017-0079-9
    Google Scholar
    38
    Boosting the electrochemical performance of Li-garnet based all-solid-state batteries with Li4Ti5O12 electrode: Routes to cheap and large scale ceramic processing
    van den Broek, Jan; Rupp, Jennifer L. M.; Afyon, Semih
    Journal of Electroceramics (2017), 38 (2-4), 182-188CODEN: JOELFJ; ISSN:1385-3449. (Springer)
    All-solid-state batteries based on fast Li+ conducting solid electrolytes such as Li7La3Zr2O12 (LLZO) give perspective on safe, non-inflammable, and temp. tolerant energy storage. Despite the promise, ceramic processing of whole battery assemblies reaching close to theor. capacities and finding optimal strategies to process large-scale and low cost battery cells remains a challenge. Here, we tackle these issues and report on a solid-state battery cell composed of Li4Ti5O12 / c-Li6.25Al0.25La3Zr2O12 / metallic Li delivering capacities around 70-75 Ah/kg with reversible cycling at a rate of 8 A/kg (for 2.5-1.0 V, 95°C). A key aspect towards the increase in capacity and Li+ transfer at the solid electrolyte-electrode interface is found to be the intimate embedding of grains and their connectivity, which can be implemented by the isostatic pressing of cells during their prepn. We suggest that simple adaptation of ceramic processing, such as the applied pressure during processing, strongly alters the electrochem. performance by assuring good grain contacts at the electrolyte-electrode interface. Among the garnet-type all-solid-state ceramic battery assemblies in the field, considerably improved capacities and cycling properties are demonstrated for Li4Ti5O12 / c-Li6.25Al0.25La3Zr2O12 / metallic Li pressed cells, giving new perspectives on cheap ceramic processing and up-scalable garnet-based all-solid-state batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlvFWrtro%253D&md5=6ac34f6d5945a246ac846f75122cdfeb
  38. 38
    Lu, J.; Li, Y. Conductivity and Stability of Li3/8Sr7/16–3x/2LaxZr1/4Ta3/4O3 Superionic Solid Electrolytes. Electrochim. Acta 2018, 282, 409– 415,  DOI: 10.1016/j.electacta.2018.06.085
    Google Scholar
    39
    Conductivity and stability of Li3/8Sr7/16-3x/2LaxZr1/4Ta3/4O3 superionic solid electrolytes
    Lu, Jiayao; Li, Ying
    Electrochimica Acta (2018), 282 (), 409-415CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
    Oxide solid electrolytes Li3/8Sr7/16-3x/2LaxZr1/4Ta3/4O3 (LSLZT, x = 0, 0.025, 0.05) with different A-site vacancy were synthesized using conventional solid-state reaction procedure at 1300°. Approx. single-phase perovskite-type was obtained which was analyzed by x-ray diffraction. Also, scanning electron microscope, a.c. impedance spectroscopy and potentiostatic polarization measurement methods were adopted to study the microstructure, Li+ conductivities and electronic conductivities of the samples, resp. Among these samples, the optimal compn. of Li3/8Sr7/16-3x/2LaxZr1/4Ta3/4O3 (x = 0.025) was selected with bulk cond. of 1.26 × 10-3 S cm-1, total cond. of 3.30 × 10-4 S cm-1, electronic cond. of 6.60 × 10-9 S cm-1 at 30° and activation energy of 0.28 eV. Also, the cyclic voltammogram anal. indicated the stability of this solid electrolyte at voltages >1.3 V against metallic Li. The solid electrolyte as a separator in LiFePO4/Li half-cell showed good cycle performance that comprises 98.7% of original values at 0.2 C charge-discharge rates after 50 cycles.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtFCmurjK&md5=d8b5578abc149913e8add5fb48ff67fa
  39. 39
    Reinacher, J.; Berendts, S.; Janek, J. Preparation and Electrical Properties of Garnet-Type Li6BaLa2Ta2O12 Lithium Solid Electrolyte Thin Films Prepared by Pulsed Laser Deposition. Solid State Ion 2014, 258, 1– 7,  DOI: 10.1016/j.ssi.2014.01.046
    Google Scholar
    There is no corresponding record for this reference.
  40. 40
    Shin, R. H.; Son, S. I.; Han, Y. S.; Kim, Y. do; Kim, H. T.; Ryu, S. S.; Pan, W. Sintering Behavior of Garnet-Type Li7La3Zr2O12-Li3BO3 Composite Solid Electrolytes for All-Solid-State Lithium Batteries. Solid State Ion 2017, 301, 10– 14,  DOI: 10.1016/j.ssi.2017.01.005
    Google Scholar
    There is no corresponding record for this reference.
  41. 41
    Huang, L.; Wen, Z.; Wu, M.; Wu, X.; Liu, Y.; Wang, X. Electrochemical Properties of Li1.4Al0.4Ti1.6(PO4)3 Synthesized by a Co-Precipitation Method. J. Power Sources 2011, 196 (16), 6943– 6946,  DOI: 10.1016/j.jpowsour.2010.11.140
    Google Scholar
    42
    Electrochemical properties of Li1.4Al0.4Ti1.6(PO4)3 synthesized by a co-precipitation method
    Huang, Lezhi; Wen, Zhaoyin; Wu, Meifen; Wu, Xiangwei; Liu, Yu; Wang, Xiuyan
    Journal of Power Sources (2011), 196 (16), 6943-6946CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    Sub-micron Li1.4Al0.4Ti1.6(PO4)3 (LATP) ceramic powder is synthesized by a co-pptn. method which can be applied for mass prodn. A pure Nasicon phase is confirmed by XRD and the primary particle size of the product is 200-500 nm. The sinterability of LATP is studied and the relative d. of 97% reached at a sintering temp. ≥900° for 6 h. The bulk Li ionic cond. of the sintered pellet is 2.19 × 10-3 S cm-1, and a total cond. of 1.83 × 10-4 S cm-1 is obtained.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXmvFyku7s%253D&md5=eefd37f74c45bc8190979804d04e704d
  42. 42
    He, M.; Cui, Z.; Han, F.; Guo, X. Construction of Conductive and Flexible Composite Cathodes for Room-Temperature Solid-State Lithium Batteries. J. Alloys Compd. 2018, 762, 157– 162,  DOI: 10.1016/j.jallcom.2018.05.255
    Google Scholar
    43
    Construction of conductive and flexible composite cathodes for room-temperature solid-state lithium batteries
    He, Minghui; Cui, Zhonghui; Han, Feng; Guo, Xiangxin
    Journal of Alloys and Compounds (2018), 762 (), 157-162CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
    Interfacial issues arising from the poor interface contact and poor interface stability between the stiff solid-state electrolytes (SSEs) and the electrodes have restricted the development of successful solid-state batteries (SSBs). Herein, we demonstrate that constructing flexible composite cathodes by introducing conductive frameworks consisting of succinonitrile and lithium salt significantly improves the contact performance and interface stability between garnet solid electrolyte and LiFePO4 cathode, enabling the resulted SSBs cycling steadily with high capacity even at room temp. The introduction of such flexible frameworks not only enables close contact between the cathode and the stiff SSE, but also bridges every electrode and electrolyte particles together forming interconnected three-dimensional ionic conductive paths, reducing the total resistance to one-half of the batteries without such frameworks. On the other hand, the network is flexible enough to accommodate the vol. change of LiFeO4 during cycling. These advantages endow that the SSBs of Li/SSE/LiFePO4 with the flexible composite cathodes demonstrate an initial discharge capacity of 149.8 mAh g-1 and the Coulombic efficiency of 99% after 100 cycles at 0.05 C under room temp. This method demonstrated here to integrate electrodes and stiff electrolytes by introducing flexible components will provides inspirations for people to construct high-performance room-temp. SSBs.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtVamtrbK&md5=46574b48a6e09888ba4aa4b7a8d6afdd
  43. 43
    Shen, L.; Yang, J.; Liu, G.; Avdeev, M.; Yao, X. High Ionic Conductivity and Dendrite-Resistant NASICON Solid Electrolyte for All-Solid-State Sodium Batteries. Mater. Today Energy 2021, 20, 100691,  DOI: 10.1016/j.mtener.2021.100691
    Google Scholar
    44
    High ionic conductivity and dendrite-resistant NASICON solid electrolyte for all-solid-state sodium batteries
    Shen, L.; Yang, J.; Liu, G.; Avdeev, M.; Yao, X.
    Materials Today Energy (2021), 20 (), 100691CODEN: MTEACH; ISSN:2468-6069. (Elsevier Ltd.)
    The low ionic cond. and poor dendrites suppression capability of Na3Zr2Si2PO12 solid electrolyte limit the practical application of all-solid-state sodium batteries. Herein, the optimized Na3.4Mg0.1Zr1.9Si2.2P0.8O12 electrolyte is obtained by simultaneously substituting the Zr4+ with Mg2+ and P5+ with Si4+ through solid-state reaction. The Na3.4Mg0.1Zr1.9Si2.2P0.8O12 electrolyte has superior room temp. ionic cond. of 3.6 x 10-3 S cm-1, which is 17 times higher than that of pristine Na3Zr2Si2PO122. No short circuit of the Na/Na3.4Mg0.1Zr1.9Si2.2P0.8O12/Na sym. battery is obsd. up to 2.0 mA cm-2, and the sym. battery displays stable sodium plating/stripping cycles for over 2000 h at 0.1 mA cm-2 and 300 h at 1.0 mA cm-2. The resultant Na3.4Mg0.1Zr1.9Si2.2P0.8O12 electrolyte is further employed in two all-solid-state sodium batteries. The Na3V2(PO4)3/Na3.4Mg0.1Zr1.9Si2.2P0.8O12/Na all-solid-state sodium battery maintains a discharge capacity of 93.3 mAh g-1 at 0.1C after 50 cycles, and the FeS2/Na3.4Mg0.1Zr1.9Si2.2P0.8O12/Na all-solid-state sodium battery delivers a discharge capacity of 173.1 mAh g-1 at 0.1C after 20 cycles, which are significantly enhanced compared with those based on pristine Na3Zr2Si2PO12 . This strategy provides an efficient method to prep. optimized NASICON solid electrolytes with high ionic cond. and excellent dendrites suppression capability and promotes the practical application of all-solid-state sodium batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXntFOltLg%253D&md5=69b4a1683b0593fd6ff0eddc739f005f
  44. 44
    Yang, J.; Huang, Z.; Zhang, P.; Liu, G.; Xu, X.; Yao, X. Titanium Dioxide Doping toward High-Lithium-Ion-Conducting Li1.5Al0.5Ge1.5(PO4)3 Glass-Ceramics for All-Solid-State Lithium Batteries. ACS Appl. Energy Mater. 2019, 2 (10), 7299– 7305,  DOI: 10.1021/acsaem.9b01268
    Google Scholar
    45
    Titanium Dioxide Doping toward High-Lithium-Ion-Conducting Li1.5Al0.5Ge1.5(PO4)3 Glass-Ceramics for All-Solid-State Lithium Batteries
    Yang, Jing; Huang, Zhen; Zhang, Peng; Liu, Gaozhan; Xu, Xiaoxiong; Yao, Xiayin
    ACS Applied Energy Materials (2019), 2 (10), 7299-7305CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    Developing solid electrolytes with high Li-ion cond. is crucial to realize high-performance all-solid-state Li batteries. The substitution of ions with larger ionic radius can enlarge the Li+ migration tunnels and therefore enhance the Li-ion cond. Ti4+ is employed to partially replace Ge4+ in Li2O-Al2O3-GeO2-P2O5 glass-ceramics electrolyte to improve its cond. The highest total Li-ion cond. of 1.07 × 10-3 S cm-1 at room temp. is obtained from Li1.5Al0.5Ge1.5(PO4)3-7.5% TiO2 sample sintered at 900° for 6 h. The bulk and grain boundary conductivities are 1.67 × 10-3 S cm-1 and 2.99 × 10-3 S cm-1, resp., which are superior than that of the pristine Li1.5Al0.5Ge1.5(PO4)3 counterpart. Both bulk and grain boundary conductivities of the sample have been significantly improved, which could be attributed to the increase of bottleneck sizes of the Li+ migration tunnels and the decrease of grain boundary area. All-solid-state Li batteries employing LiFePO4 as cathode and solid electrolyte as separator and ionic conductor are assembled. A reversible capacity of 132.3 mA-h g-1 is delivered after 200 cycles under a c.d. of 0.1 C with a capacity retention ratio of 91.1%, showing the solid electrolyte is ideal for all-solid-state Li-battery applications.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhslKgtbbF&md5=3975d93228925f489174f1af99bb6a44
  45. 45
    Uchida, Y.; Hasegawa, G.; Shima, K.; Inada, M.; Enomoto, N.; Akamatsu, H.; Hayashi, K. Insights into Sodium Ion Transfer at the Na/NASICON Interface Improved by Uniaxial Compression. ACS Appl. Energy Mater. 2019, 2 (4), 2913– 2920,  DOI: 10.1021/acsaem.9b00250
    Google Scholar
    46
    Insights into Sodium Ion Transfer at the Na/NASICON Interface Improved by Uniaxial Compression
    Uchida, Yasuhiro; Hasegawa, George; Shima, Kazunari; Inada, Miki; Enomoto, Naoya; Akamatsu, Hirofumi; Hayashi, Katsuro
    ACS Applied Energy Materials (2019), 2 (4), 2913-2920CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    A robust ceramic solid electrolyte with high ionic cond. is a key component for all-solid-state batteries (ASSBs). In terms of the demand for high-energy-d. storage, researchers have been tackling various challenges to use metal anodes, where a fundamental understanding on the metal/solid electrolyte interface is of particular importance. The Na+ superionic conductor, so-called NASICON, has high potential for application to ASSBs with a Na anode due to its high Na+ ion cond. at room temp., which has, however, faced a daunting issue of the significantly large interfacial resistance between Na and NASICON. In this work, we have successfully reduced the interfacial resistance as low as 14 Ω cm2 at room temp. by a simple mech. compression of a Na/NASICON assembly. We also demonstrate a fundamental study of the Na/NASICON interface in comparison with the Na/β''-alumina counterpart by means of the electrochem. impedance technique, which elucidates a stark difference between the activation energies for interfacial charge transfer: ∼0.6 eV for Na/NASICON and ∼0.3 eV for Na/β''-alumina. This result suggests the formation of a Na+-conductive interphase layer in pressing Na metal on the NASICON surface at room temp.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmsFegur0%253D&md5=bab5654226d744c8ea156b6f611f660a
  46. 46
    Patra, S.; Narayanasamy, J.; Chakravarty, S.; Murugan, R. Higher Critical Current Density in Lithium Garnets at Room Temperature by Incorporation of an Li4SiO4-Related Glassy Phase and Hot Isostatic Pressing. ACS Appl. Energy Mater. 2020, 3 (3), 2737– 2743,  DOI: 10.1021/acsaem.9b02400
    Google Scholar
    47
    Higher Critical Current Density in Lithium Garnets at Room Temperature by Incorporation of an Li4SiO4-Related Glassy Phase and Hot Isostatic Pressing
    Patra, Srabani; Narayanasamy, Janani; Chakravarty, Sujoy; Murugan, Ramaswamy
    ACS Applied Energy Materials (2020), 3 (3), 2737-2743CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    Inorg. solid electrolytes have achieved an important position in modern battery technol. A garnet-structured inorg. fast lithium-ion conductor is an exceptional solid electrolyte candidate due to its numerous advantages. However, on repeated cycling at high current densities, the growth of lithium dendrites through grain boundaries turns out to be a major impediment to the application of metallic lithium as an anode. This work shows the application of a hot isostatic pressing (HIP) treatment on an Li4SiO4 (LS)-added lithium garnet solid electrolyte, Li6.16Al0.28Zr2La3O12 (LLZA), resulting in a dense microstructure of the electrolyte along with LS-related glassy phase formation at the grain boundaries. This approach is substantiated to enhance the electrochem. performance of an Li|LLZA + LS(H)|Li sym. cell at room temp. by improving the interfacial contact, effectively suppressing lithium dendrite penetration, and attainment of a higher crit. c.d. (CCD) of 0.40 mA/cm2. The cycling performance achieved here represents a significant advancement toward demonstrating plating/stripping rates in lithium garnets with relevance to practical applications.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXjsV2ls70%253D&md5=0a4492dc4bc7b8c794d04b7c2cf3bd57
  47. 47
    Wu, J. F.; Pang, W. K.; Peterson, V. K.; Wei, L.; Guo, X. Garnet-Type Fast Li-Ion Conductors with High Ionic Conductivities for All-Solid-State Batteries. ACS Appl. Mater. Interfaces 2017, 9 (14), 12461– 12468,  DOI: 10.1021/acsami.7b00614
    Google Scholar
    48
    Garnet-Type Fast Li-Ion Conductors with High Ionic Conductivities for All-Solid-State Batteries
    Wu, Jian-Fang; Pang, Wei Kong; Peterson, Vanessa K.; Wei, Lu; Guo, Xin
    ACS Applied Materials & Interfaces (2017), 9 (14), 12461-12468CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    All-solid-state Li-ion batteries with metallic Li anodes and solid electrolytes could offer superior energy d. and safety over conventional Li-ion batteries. However, compared with org. liq. electrolytes, the low cond. of solid electrolytes and large electrolyte/electrode interfacial resistance impede their practical application. Garnet-type Li-ion conducting oxides are among the most promising electrolytes for all-solid-state Li-ion batteries. In this work, the large-radius Rb is doped at the La site of cubic Li6.10Ga0.30La3Zr2O12 to enhance the Li-ion cond. for the first time. The Li6.20Ga0.30La2.95Rb0.05Zr2O12 electrolyte exhibits a Li-ion cond. of 1.62 mS cm-1 at room temp., which is the highest cond. reported until now. All-solid-state Li-ion batteries are constructed from the electrolyte, metallic Li anode, and LiFePO4 active cathode. The addn. of Li(CF3SO2)2N electrolytic salt in the cathode effectively reduces the interfacial resistance, allowing for a high initial discharge capacity of 152 mAh/g and good cycling stability with 110 mAh/g retained after 20 cycles at a charge/discharge rate of 0.05 C at 60 °C.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXkvVyjsbo%253D&md5=5011c9a9292a84a6255d839ce9c53777
  48. 48
    Cheng, E. J.; Kimura, T.; Shoji, M.; Ueda, H.; Munakata, H.; Kanamura, K. Ceramic-Based Flexible Sheet Electrolyte for Li Batteries. ACS Appl. Mater. Interfaces 2020, 12 (9), 10382– 10388,  DOI: 10.1021/acsami.9b21251
    Google Scholar
    49
    Ceramic-Based Flexible Sheet Electrolyte for Li Batteries
    Cheng, Eric Jianfeng; Kimura, Takeshi; Shoji, Mao; Ueda, Hiroshi; Munakata, Hirokazu; Kanamura, Kiyoshi
    ACS Applied Materials & Interfaces (2020), 12 (9), 10382-10388CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    The increasing demand for high-energy-d. batteries stimulated the revival of research interest in Li-metal batteries. The garnet-type ceramic Li7La3Zr2O12 (LLZO) is one of the few solid-state fast-ion conductors that are stable against Li metal. However, the densification of LLZO powders usually requires high sintering temps. (e.g., 1200°C), which likely result in Li loss and various side reactions. From an engineering point of view, high-temp. sintering of thin LLZO electrolytes (brittle) at a large scale is difficult. Moreover, the high interfacial resistance between the solid LLZO electrolytes and electrodes is a notorious problem. Here, we report a practical synthesis of a flexible composite Al-doped LLZO (Al-LLZO) sheet electrolyte (75μm in thickness), which can be mass-produced at room temp. This ceramic-based flexible sheet electrolyte enables Li-metal batteries to operate at both 60 and 30°C, demonstrating its potential application for developing practical Li-metal batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXit1elur0%253D&md5=856f6d8150a056c14da23140b05dd7bc
  49. 49
    Huang, X.; Lu, Y.; Jin, J.; Gu, S.; Xiu, T.; Song, Z.; Badding, M. E.; Wen, Z. Method Using Water-Based Solvent to Prepare Li7La3Zr2O12 Solid Electrolytes. ACS Appl. Mater. Interfaces 2018, 10 (20), 17147– 17155,  DOI: 10.1021/acsami.8b01961
    Google Scholar
    50
    Method Using Water-Based Solvent to Prepare Li7La3Zr2O12 Solid Electrolytes
    Huang, Xiao; Lu, Yang; Jin, Jun; Gu, Sui; Xiu, Tongping; Song, Zhen; Badding, Michael E.; Wen, Zhaoyin
    ACS Applied Materials & Interfaces (2018), 10 (20), 17147-17155CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Li-garnet Li7La3Zr2O12 (LLZO) is a promising candidate of solid electrolytes for high-safety solid-state Li+ ion batteries. However, because of its high reactivity to water, the prepn. of LLZO powders and ceramics is not easy for large-scale amts. Herein, a method applying water-based solvent is proposed to demonstrate a possible soln. Ta-doped LLZO, i.e., Li6.4La3Zr1.4Ta0.6O12 (LLZTO), and its LLZTO/MgO composite ceramics are made by attrition milling, followed by a spray-drying process using water-based slurries. The impacts of parameters of the method on the structure and properties of green and sintered pellets are studied. A relative d. of ∼95%, a Li-ion cond. of ∼3.5 × 10-4 S/cm, and uniform grain size LLZTO/MgO garnet composite ceramics are obtained with an attrition-milled LLZTO/MgO slurry that contains 40 wt. % solids and 2 wt. % polyvinyl alc. binder. Li-sulfur batteries based on these ceramics are fabricated and work under 25° for 20 cycles with a Coulombic efficiency of 100%. This research demonstrates a promising mass prodn. method for the prepn. of Li-garnet ceramics.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXosVeks78%253D&md5=04d16f64552848b31c1866b8f8812478
  50. 50
    Yu, S.; Mertens, A.; Tempel, H.; Schierholz, R.; Kungl, H.; Eichel, R. A. Monolithic All-Phosphate Solid-State Lithium-Ion Battery with Improved Interfacial Compatibility. ACS Appl. Mater. Interfaces 2018, 10 (26), 22264– 22277,  DOI: 10.1021/acsami.8b05902
    Google Scholar
    51
    Monolithic All-Phosphate Solid-State Lithium-Ion Battery with Improved Interfacial Compatibility
    Yu, Shicheng; Mertens, Andreas; Tempel, Hermann; Schierholz, Roland; Kungl, Hans; Eichel, Ruediger-A.
    ACS Applied Materials & Interfaces (2018), 10 (26), 22264-22277CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    High interfacial resistance between solid electrolyte and electrode of ceramic all-solid-state batteries is a major reason for the reduced performance of these batteries. A solid-state battery using a monolithic all-phosphate concept based on screen printed thick LiTi2(PO4)3 anode and Li3V2(PO4)3 cathode composite layers on a densely sintered Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte has been realized with competitive cycling performance. The choice of materials was primarily based on the (electro-)chem. and mech. matching of the components instead of solely focusing on high-performance of individual components. Thus, the battery used a phosphate backbone in combination with tailored morphol. of the electrode materials to ensure good interfacial matching for a durable mech. stability. The operating voltage range of the active materials matches with the intrinsic electrochem. window of the electrolyte which resulted in high electrochem. stability. A highly competitive discharge capacity of 63.5 mAh/g at 0.39 C after 500 cycles, corresponding to 84% of the initial discharge capacity, was achieved. The anal. of interfacial charge transfer kinetics confirmed the structural and elec. properties of the electrodes and their interfaces with the electrolyte, as evidenced by the excellent cycling performance of the all-phosphate solid-state battery. These interfaces have been studied via impedance anal. with subsequent distribution of relaxation times anal. The prepd. solid-state battery could be processed and operated in air atm. owing to the low O sensitivity of the phosphate materials. The anal. of electrolyte/electrode interfaces after cycling demonstrates that the interfaces remained stable during cycling.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtFeis7zM&md5=d38d63d39154993761b8bce8a8725cb9
  51. 51
    Itaya, A.; Yamamoto, K.; Inada, R. Sintering Temperature Dependency on Sodium-Ion Conductivity for Na2Zn2TeO6 Solid Electrolyte. Int. J. Appl. Ceram Technol. 2021, 18 (6), 2085– 2090,  DOI: 10.1111/ijac.13847
    Google Scholar
    52
    Sintering temperature dependency on sodium-ion conductivity for Na2Zn2TeO6 solid electrolyte
    Itaya, Akihiro; Yamamoto, Kazuki; Inada, Ryoji
    International Journal of Applied Ceramic Technology (2021), 18 (6), 2085-2090CODEN: IJACCP; ISSN:1546-542X. (Wiley-Blackwell)
    We investigated the sintering temp. dependency on the properties of Na2Zn2TeO6 (NZTO) solid electrolyte synthesized via a conventional solid-state reaction method. Sintering temp. of calcined NZTO powder, which was obtained by the calcination of precursor at 850°C, was changed in the range from 650 to 850°C. X-ray diffraction anal. showed that P2-type layered NZTO phase was formed in all sintered samples without forming any secondary phases. The relative densities of sintered NZTO samples were approx. 83%-85% for the samples sintered at 700°C or higher. The all sintered samples showed sodium-ion cond. above 10-4 S cm-1 at room temp. and the highest cond. of 4.0 x 10-4 S cm-1 in the sample sintered at 750°C. The sintering temp. to obtain the highest room temp. cond. is 100°C lower than that used in previous works. Such low sintering temp. compared to other Na-based oxide solid electrolytes could be useful for co-sintering with electrode active materials for fabrication of all-solid-state sodium-ion battery.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhslCjtrnJ&md5=931ae75b3e19f831b40ac39c6a6b1bbf
  52. 52
    Yu, S.; Schmohl, S.; Liu, Z.; Hoffmeyer, M.; Schön, N.; Hausen, F.; Tempel, H.; Kungl, H.; Wiemhöfer, H. D.; Eichel, R. A. Insights into a Layered Hybrid Solid Electrolyte and Its Application in Long Lifespan High-Voltage All-Solid-State Lithium Batteries. J. Mater. Chem. A Mater. 2019, 7 (8), 3882– 3894,  DOI: 10.1039/C8TA11259B
    Google Scholar
    53
    Insights into a layered hybrid solid electrolyte and its application in long lifespan high-voltage all-solid-state lithium batteries
    Yu, Shicheng; Schmohl, Sebastian; Liu, Zigeng; Hoffmeyer, Marija; Schoen, Nino; Hausen, Florian; Tempel, Hermann; Kungl, Hans; Wiemhoefer, Hans-D.; Eichel, Ruediger-A.
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (8), 3882-3894CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    Direct integration of a metallic lithium anode with the ceramic Li1.3Al0.3Ti1.7(PO4)3 (LATP) electrolyte into an all-solid-state battery is highly challenging due to their chem. and electrochem. incompatibility. Herein, a layered hybrid solid electrolyte is designed by coating the ceramic LATP electrolyte with a protective polymer electrolyte, polyphosphazene/PVDF-HFP/LiBOB. This polymer electrolyte comprises highly Li+ conductive polyphosphazene and mech. stable PVDF-HFP as the polymer matrix, and the mobile lithium ions in the polymer layer are supplied by LiBOB. Equipped with both polymer and ceramic components, the hybrid electrolyte possesses favorable features, such as a flexible surface, high ionic cond., high chem. stability against lithium and wide electrochem. stability window (4.7 V), which all to help realize its application in all-solid-state lithium batteries. The prepd. all-solid-state battery with a metallic lithium anode and high-voltage Li3V2(PO4)3/CNT cathode shows high capacity and excellent cycling performance with negligible capacity loss over 500 cycles at 50 °C. Furthermore, the anal. of the hybrid solid electrolyte after long-term cycling demonstrates outstanding electrode/electrolyte interfacial stability. This study suggests that use of solid org.-inorg. hybrid electrolyte is a promising approach to circumvent the mech., chem. and electrochem. limitations at the interface of electrodes and ceramic electrolyte for all-solid-state batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtlWrsL8%253D&md5=a9714de5b1bb38a8ae4f40cf29d1d93d
  53. 53
    Zhang, Q.; Liang, F.; Qu, T.; Yao, Y.; Ma, W.; Yang, B.; Dai, Y. Effect on Ionic Conductivity of Na3+xZr2-xMxSi2PO12 (M = Y, La) by Doping Rare-Earth Elements. In IOP Conference Series: Materials Science and Engineering; Institute of Physics Publishing, 2018; Vol. 423.  DOI: 10.1088/1757-899X/423/1/012122 .
    Google Scholar
    There is no corresponding record for this reference.
  54. 54
    Kim, M.; Kim, G.; Lee, H. Tri-Doping of Sol–Gel Synthesized Garnet-Type Oxide Solid-State Electrolyte. Micromachines (Basel) 2021, 12 (2), 134,  DOI: 10.3390/mi12020134
    Google Scholar
    There is no corresponding record for this reference.
  55. 55
    Yang, J.; Wan, H. L.; Zhang, Z. H.; Liu, G. Z.; Xu, X. X.; Hu, Y. S.; Yao, X. Y. NASICON-Structured Na3.1Zr1.95Mg0.05Si2PO12 Solid Electrolyte for Solid-State Sodium Batteries. Rare Metals 2018, 37 (6), 480– 487,  DOI: 10.1007/s12598-018-1020-3
    Google Scholar
    56
    NASICON-structured Na3.1Zr1.95Mg0.05Si2PO12 solid electrolyte for solid-state sodium batteries
    Yang, Jing; Wan, Hong-Li; Zhang, Zhi-Hua; Liu, Gao-Zhan; Xu, Xiao-Xiong; Hu, Yong-Sheng; Yao, Xia-Yin
    Rare Metals (Beijing, China) (2018), 37 (6), 480-487CODEN: RARME8; ISSN:1001-0521. (Journal Publishing Center of University of Science and Technology Beijing)
    Using stable inorg. solid electrolyte to replace org. liq. electrolyte could significantly reduce potential safety risks of rechargeable batteries. Na-superionic conductor (NASICON)-structured solid electrolyte is one of the most promising sodium solid electrolytes and can be employed in solid-state sodium batteries. In this work, a NASICON-structured solid electrolyte Na3.1Zr1.95Mg0.05Si2PO12 was synthesized through a facile solid-state reaction, yielding high sodium-ionic cond. of 1.33 × 10-3 S·cm-1 at room temp. The results indicate that Mg2+ is a suitable and economical substitution ion to replace Zr4+, and this synthesis route can be scaled up for powder prepn. with low cost. In addn. to electrolyte material prepn., solid-state batteries with Na3.1Zr1.95Mg0.05Si2PO12 as electrolyte were assembled. A specific capacity of 57.9 mAh·g-1 is maintained after 100 cycles under a c.d. of 0.5C rate at room temp. The favorable cycling performance of the solid-state battery suggests that Na3.1Zr1.95Mg0.05Si2PO12 is an ideal electrolyte candidate for solid-state sodium batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXntVClsbo%253D&md5=ac3550de9af0bfbacc043bcfd78c67e2
  56. 56
    Afyon, S.; Kravchyk, K. v.; Wang, S.; van den Broek, J.; Hänsel, C.; Kovalenko, M. v.; Rupp, J. L. M. Building Better All-Solid-State Batteries with Li-Garnet Solid Electrolytes and Metalloid Anodes. J. Mater. Chem. A Mater. 2019, 7 (37), 21299– 21308,  DOI: 10.1039/C9TA04999A
    Google Scholar
    58
    Building better all-solid-state batteries with Li-garnet solid electrolytes and metalloid anodes
    Afyon, Semih; Kravchyk, Kostiantyn V.; Wang, Shutao; van den Broek, Jan; Hansel, Christian; Kovalenko, Maksym V.; Rupp, Jennifer L. M.
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (37), 21299-21308CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    All-solid-state batteries provide new opportunities to realize safe, non-flammable, and temp.-tolerant energy storage and display a huge potential to be the core of future energy storage devices, esp. in applications where energy d. is key to the technol. Garnet-type solid-state electrolytes based on cubic Li7La3Zr2O12 possess one of the highest Li+ conductivities, a wider electrochem. stability window compared to liq. electrolytes, and exceptional chem. and thermal stabilities among various solid electrolytes. Most of the first reports, however, employ lithium metal as the anode with unavoidable Li-dendrite formation through polycryst. Li-garnet electrolytes at current densities above 0.5 mA cm-2. Accordingly, alternative materials and processing strategies for anodes or interlayers are inherently needed for high currents and fast charging for Li-garnet-type battery integration. Here, we demonstrate, through the use of a composite anode based on antimony nanocrystals, that metalloids offer high and stable storage capacities of up to 330 mA h g-1 for Li-garnet all-solid-state batteries at reasonably high current densities (e.g. 240 mA g-1) at 95 °C. The results are also compared towards std. liq. type electrolytes and reveal high coulombic efficiencies and improved cycle stability for the solid-state cell design. Guidelines and aspects to process alternative materials and impact the interface design towards fast lithium charge transfer between the metalloid and the Li-garnet electrolyte are formulated. The architecture and scalable processing of metalloid-based batteries are obvious advantages of this work, opening a promising avenue to avoid Li-dendrite formation at high current loads in garnet-type all-solid-state rechargeable batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1yltbnF&md5=d45b2d12ad0eb478c3dcbd44fadc0678
  57. 57
    Dixit, M. B.; Verma, A.; Zaman, W.; Zhong, X.; Kenesei, P.; Park, J. S.; Almer, J.; Mukherjee, P. P.; Hatzell, K. B. Synchrotron Imaging of Pore Formation in Li Metal Solid-State Batteries Aided by Machine Learning. ACS Appl. Energy Mater. 2020, 3 (10), 9534– 9542,  DOI: 10.1021/acsaem.0c02053
    Google Scholar
    59
    Synchrotron Imaging of Pore Formation in Li Metal Solid-State Batteries Aided by Machine Learning
    Dixit, Marm B.; Verma, Ankit; Zaman, Wahid; Zhong, Xinlin; Kenesei, Peter; Park, Jun Sang; Almer, Jonathan; Mukherjee, Partha P.; Hatzell, Kelsey B.
    ACS Applied Energy Materials (2020), 3 (10), 9534-9542CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
    High-rate capable, reversible lithium metal anodes are necessary for next generation energy storage systems. In situ tomog. of Li|LLZO|Li cells is carried out to track morphol. transformations in Li metal electrodes. Machine learning enables tracking the lithium metal morphol. during galvanostatic cycling. Nonuniform lithium electrode kinetics are obsd. at both electrodes during cycling. Hot spots in lithium metal are correlated with microstructural anisotropy in LLZO. Mesoscale modeling reveals that regions with lower effective properties (transport and mech.) are nuclei for failure. Advanced visualization combined with electrochem. represents an important pathway toward resolving non-equil. effects that limit rate capabilities of solid-state batteries.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvVeru7nO&md5=9f0be51917aeebd9cb303e6881489a47
  58. 58
    Vishnugopi, B. S.; Dixit, M. B.; Hao, F.; Shyam, B.; Cook, J. B.; Hatzell, K. B.; Mukherjee, P. P. Mesoscale Interrogation Reveals Mechanistic Origins of Lithium Filaments along Grain Boundaries in Inorganic Solid Electrolytes. Adv. Energy Mater. 2022, 12 (3), 2102825,  DOI: 10.1002/aenm.202102825
    Google Scholar
    60
    Mesoscale Interrogation Reveals Mechanistic Origins of Lithium Filaments along Grain Boundaries in Inorganic Solid Electrolytes
    Vishnugopi, Bairav S.; Dixit, Marm B.; Hao, Feng; Shyam, Badri; Cook, John B.; Hatzell, Kelsey B.; Mukherjee, Partha P.
    Advanced Energy Materials (2022), 12 (3), 2102825CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
    Solid-state batteries (SSBs), utilizing a lithium metal anode, promise to deliver enhanced energy and power densities compared to conventional lithium-ion batteries. Penetration of lithium filaments through the solid-state electrolytes (SSEs) during electrodeposition poses major constraints on the safety and rate performance of SSBs. While microstructural attributes, esp. grain boundaries (GBs) within the SSEs are considered preferential metal propagation pathways, the underlying mechanisms are not fully understood yet. Here, a comprehensive insight is presented into the mechanistic interactions at the mesoscale including the electrochem.-mech. response of the GB-electrode junction and competing ion transport dynamics in the SSE. Depending on the GB transport characteristics, a highly non-uniform electrodeposition morphol. consisting of either cavities or protrusions at the GB-electrode interface is identified. Mech. stability anal. reveals localized strain ramps in the GB regions that can lead to brittle fracture of the SSE. For ionically less conductive GBs compared to the grains, a crack formation and void filling mechanism, triggered by the heterogeneous nature of electrochem.-mech. interactions is delineated at the GB-electrode junction. Concurrently, in situ X-ray tomog. of pristine and failed Li7La3Zr2O12 (LLZO) SSE samples confirm the presence of filamentous lithium penetration and validity of the proposed mesoscale failure mechanisms.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXislCjur7J&md5=9b10899811f52b85c48a0ee60028e65c
  59. 59
    Tenhaeff, W. E.; Rangasamy, E.; Wang, Y.; Sokolov, A. P.; Sakamoto, J.; Dudney, N. J.; Tenhaeff, W. E.; Rangasamy, E.; Wang, Y.; Sokolov, A. P.; Wolfenstine, J. Resolving the Grain Boundary and Lattice Impedance of Hot Pressed Li7La3Zr2O12 Garnet Electrolytes. ChemSusChem 2014, 1, 375– 378,  DOI: 10.1002/celc.201300022
    Google Scholar
    There is no corresponding record for this reference.
  60. 60
    Yu, S.; Siegel, D. J. Grain Boundary Softening: A Potential Mechanism for Lithium Metal Penetration through Stiff Solid Electrolytes. ACS Appl. Mater. Interfaces 2018, 10, 38151– 38158,  DOI: 10.1021/acsami.8b17223
    Google Scholar
    62
    Grain Boundary Softening: A Potential Mechanism for Lithium Metal Penetration through Stiff Solid Electrolytes
    Yu, Seungho; Siegel, Donald J.
    ACS Applied Materials & Interfaces (2018), 10 (44), 38151-38158CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Models based on linear elasticity suggest that a solid electrolyte with a high shear modulus will suppress dendrite formation in batteries that use metallic lithium as the neg. electrode. Nevertheless, recent expts. find that lithium can penetrate stiff solid electrolytes through microstructural features, such as grain boundaries. This failure mode emerges even in cases where the electrolyte has an av. shear modulus that is an order of magnitude larger than that of Li. Adopting the solid-electrolyte Li7La3Zr2O12 (LLZO) as a prototype, significant softening in elastic properties occurs in nanoscale regions near grain boundaries. Mol. dynamics simulations performed on tilt and twist boundaries reveal that the grain boundary shear modulus is up to 50% smaller than in bulk regions. Probably inhomogeneities in elastic properties arising from microstructural features provide a mechanism by which soft lithium can penetrate ostensibly stiff solid electrolytes.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvFSrtrvK&md5=a4bc1fab4aac1040157f1c12c4e0c44a
  61. 61
    Cheng, L.; Wu, C. H.; Jarry, A.; Chen, W.; Ye, Y.; Zhu, J.; Kostecki, R.; Persson, K.; Guo, J.; Salmeron, M.; Chen, G.; Doeff, M. Interrelationships among Grain Size, Surface Composition, Air Stability, and Interfacial Resistance of Al-Substituted Li7La3Zr2O12 Solid Electrolytes. ACS Appl. Mater. Interfaces 2015, 7 (32), 17649– 17655,  DOI: 10.1021/acsami.5b02528
    Google Scholar
    63
    Interrelationships among grain size, surface compn., air stability, and interfacial resistance of al-substituted Li7La3Zr2O12 solid electrolytes
    Cheng, Lei; Wu, Cheng Hao; Jarry, Angelique; Chen, Wei; Ye, Yifan; Zhu, Junfa; Kostecki, Robert; Persson, Kristin; Guo, Jinghua; Salmeron, Miquel; Chen, Guoying; Doeff, Marca
    ACS Applied Materials & Interfaces (2015), 7 (32), 17649-17655CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    The interfacial resistances of sym. lithium cells contg. Al-substituted Li7La3Zr2O12 (LLZO) solid electrolytes are sensitive to their microstructures and histories of exposure to air. Air exposure of LLZO samples with large grain sizes (∼150 μm) results in dramatically increased interfacial impedances in cells contg. them, compared to those with pristine large-grained samples. In contrast, a much smaller difference is seen between cells with small-grained (∼20 μm) pristine and air-exposed LLZO samples. A combination of soft X-ray absorption (sXAS) and Raman spectroscopy, with probing depths ranging from nanometer to micrometer scales, revealed that the small-grained LLZO pellets are more air-stable than large-grained ones, forming far less surface Li2CO3 under both short- and long-term exposure conditions. Surface sensitive XPS indicates that the better chem. stability of the small-grained LLZO is related to differences in the distribution of Al and Li at sample surfaces. D. functional theory calcns. show that LLZO can react via two different pathways to form Li2CO3. The first, more rapid, pathway involves a reaction with moisture in air to form LiOH, which subsequently absorbs CO2 to form Li2CO3. The second, slower, pathway involves direct reaction with CO2 and is favored when surface lithium contents are lower, as with the small-grained samples. These observations have important implications for the operation of solid-state lithium batteries contg. LLZO because the results suggest that the interfacial impedances of these devices is critically dependent upon specific characteristics of the solid electrolyte and how it is prepd.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXht1SgsbnE&md5=19b8095509b3758796891f19d9e07842
  62. 62
    Sharafi, A.; Haslam, C. G.; Kerns, R. D.; Wolfenstine, J.; Sakamoto, J. Controlling and Correlating the Effect of Grain Size with the Mechanical and Electrochemical Properties of Li7La3Zr2O12 Solid-State Electrolyte. J. Mater. Chem. A Mater. 2017, 5 (40), 21491– 21504,  DOI: 10.1039/C7TA06790A
    Google Scholar
    64
    Controlling and correlating the effect of grain size with the mechanical and electrochemical properties of Li7La3Zr2O12 solid-state electrolyte
    Sharafi, Asma; Haslam, Catherine G.; Kerns, Robert D.; Wolfenstine, Jeff; Sakamoto, Jeff
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2017), 5 (40), 21491-21504CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    Li7La3Zr2O12 (LLZO) solid-state electrolyte is garnering interest due to its potential to enable solid-state batteries (SSBs) using metallic Li anodes. However, Li metal propagates along LLZO grain boundaries at high Li plating current densities (above the crit. c.d., CCD). In the present study, we examd. whether microstructural aspects, such as grain size, could influence mech. and electrochem. properties thereby affecting the CCD. A unique densification technique (heating between 1100 and 1300 °C) was used to control grain size. Electron backscatter diffraction detd. that the grain size and the misorientation angle varied from 5 to 600 μm and 20 to 40°, resp. Vickers indentation was used to characterize the mech. properties and revealed that hardness decreased (9.9-6.8 GPa) with increasing grain size, but the fracture toughness was invariant (0.6 MPa m-1/2) at grain sizes ≥40 μm. DC and AC techniques were used to measure and correlate the CCD with grain size and showed that the CCD increased with increasing grain size achieving a max. of 0.6 mA cm-2. We believe the implications of this work could be far-reaching in that they represent a significant step towards understanding the mechanism(s) that control the stability of the Li-LLZO interface and a rational approach to increase the CCD in SSBs.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhs1Sksb%252FP&md5=eccb1f1d8cfb3d13b2237d27793aa772
  63. 63
    Shen, F.; Dixit, M.; Xiao, X.; Hatzell, K. The Effect of Pore Connectivity on Li Dendrite Propagation Within LLZO Electrolytes Observed with Synchrotron X-Ray Tomography. ACS Energy Lett. 2018, 3, 1056– 1061,  DOI: 10.1021/acsenergylett.8b00249
    Google Scholar
    65
    Effect of Pore Connectivity on Li Dendrite Propagation within LLZO Electrolytes Observed with Synchrotron X-ray Tomography
    Shen, Fengyu; Dixit, Marm B.; Xiao, Xianghui; Hatzell, Kelsey B.
    ACS Energy Letters (2018), 3 (4), 1056-1061CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
    Li7La3Zr2O12 (LLZO) is a garnet-type material that demonstrates promising characteristics for all-solid-state battery applications due to its high Li-ion cond. and its compatibility with Li metal. The primary limitation of LLZO is the propensity for short-circuiting at low current densities. Microstructure features such as grain boundaries, pore character, and d. all contribute to this shorting phenomenon. Toward the goal of understanding processing-structure relations for practical design of solid electrolytes, this study tracks structural transformations in solid electrolytes processed at 3 different temps. (1050, 1100, and 1150°) using synchrotron x-ray tomog. A subvolume of 300 μm3 captures the heterogeneity of the solid electrolyte microstructure while minimizing the computational intensity assocd. with 3D reconstructions. While the porosity decreases with increasing temp., the underlying connectivity of the pore region increases. Solid electrolytes with interconnected pores short circuit at lower crit. current densities than samples with less connected pores.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXmslyht7g%253D&md5=c0581bcf5ffa883e403c254e027e0006
  64. 64
    Cooper, C.; Sutorik, A. C.; Wright, J.; Luoto, E. A.; Gilde, G.; Wolfenstine, J. Mechanical Properties of Hot Isostatically Pressed Li0.35La0.55TiO3. In Advanced Engineering Materials; Wiley-VCH Verlag, 2014; Vol. 16, pp 755– 759.  DOI: 10.1002/adem.201400071 .
    Google Scholar
    There is no corresponding record for this reference.
  65. 65
    Dumon, A.; Huang, M.; Shen, Y.; Nan, C. W. High Li Ion Conductivity in Strontium Doped Li7La3Zr2O12 Garnet. Solid State Ion 2013, 243, 36– 41,  DOI: 10.1016/j.ssi.2013.04.016
    Google Scholar
    67
    High Li ion conductivity in strontium doped Li7La3Zr2O12 garnet
    Dumon, Alexandre; Huang, Mian; Shen, Yang; Nan, Ce-Wen
    Solid State Ionics (2013), 243 (), 36-41CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
    Strontium doped lithium ion garnets Li7La3Zr2O12 (LLZ) with 0.9 wt% to 8.4 wt% content of added Sr were synthesized via conventional solid-state reaction. X-ray diffraction patterns confirmed the cubic garnet structure of the sintered samples. A small amt. of strontium was substituted to lanthanum in LLZ lattice. Further anal. showed SrCO3 acted as a sintering aid for cubic LLZ ceramics and significantly increased the grain size of the sintered pellets. A cond. of 2.10 × 10-4 S/cm at 297 K was obtained for the undoped LLZ. The total ionic cond. reached a max. of about 5 × 10-4 S/cm at 297 K with an activation energy of about 0.31 eV for 1.7 wt% Sr added LLZ sintered for 20-24 h in alumina crucible.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXovFertbg%253D&md5=90a155c052ad055283f9eaec3e73e0b7
  66. 66
    Rettenwander, D.; Welzl, A.; Cheng, L.; Fleig, J.; Musso, M.; Suard, E.; Doeff, M. M.; Redhammer, G. J.; Amthauer, G. Synthesis, Crystal Chemistry, and Electrochemical Properties of Li7–2xLa3Zr2–xMoxO12 (x = 0.1–0.4): Stabilization of the Cubic Garnet Polymorph via Substitution of Zr4+ by Mo6+. Inorg. Chem. 2015, 54 (21), 10440– 10449,  DOI: 10.1021/acs.inorgchem.5b01895
    Google Scholar
    68
    Synthesis, Crystal Chemistry, and Electrochemical Properties of Li7-2xLa3Zr2-xMoxO12 (x = 0.1-0.4): Stabilization of the Cubic Garnet Polymorph via Substitution of Zr4+ by Mo6+
    Rettenwander, Daniel; Welzl, Andreas; Cheng, Lei; Fleig, Juergen; Musso, Maurizio; Suard, Emmanuelle; Doeff, Marca M.; Redhammer, Guenther J.; Amthauer, Georg
    Inorganic Chemistry (2015), 54 (21), 10440-10449CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
    Cubic Li7La3Zr2O12 (LLZO) garnets are exceptionally well suited to be used as solid electrolytes or protecting layers in "Beyond Li-ion Battery" concepts. Unfortunately, cubic LLZO is not stable at room temp. (RT) and has to be stabilized by supervalent dopants. In this study we demonstrate a new possibility to stabilize the cubic phase at RT via substitution of Zr4+ by Mo6+. A Mo6+ content of 0.25 per formula unit (pfu) stabilizes the cubic LLZO phase, and the soly. limit is about 0.3 Mo6+ pfu. Based on the results of neutron powder diffraction and Raman spectroscopy, Mo6+ is located at the octahedrally coordinated 16a site of the cubic garnet structure (space group Ia-3d). Since Mo6+ has a smaller ionic radius compared to Zr4+ the lattice parameter a0 decreases almost linearly as a function of the Mo6+ content. The highest bulk Li-ion cond. is found for the 0.25 pfu compn., with a typical RT value of 3.4 × 10-4 S cm-1. An addnl. significant resistive contribution originating from the sample interior (most probably from grain boundaries) could be identified in impedance spectra. The latter strongly depends on the prehistory and increases significantly after annealing at 700 °C in ambient air. Cyclic voltammetry expts. on cells contg. Mo6+-substituted LLZO indicate that the material is stable up to 6 V.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhs1ejsb7N&md5=0a142be1bed4f8e918d052dfd9fde069
  67. 67
    Inada, R.; Yasuda, S.; Hosokawa, H.; Saito, M.; Tojo, T.; Sakurai, Y. Formation and Stability of Interface between Garnet-Type Ta-Doped Li7La3Zr2O12 Solid Electrolyte and Lithium Metal Electrode. Batteries 2018, 4 (2), 26,  DOI: 10.3390/batteries4020026
    Google Scholar
    69
    Formation and stability of interface between garnet-type Ta-doped Li7La3Zr2O12 solid electrolyte and lithium metal electrode
    Inada, Ryoji; Yasuda, Satoshi; Hosokawa, Hiromasa; Saito, Masaya; Tojo, Tomohiro; Sakurai, Yoji
    Batteries (Basel, Switzerland) (2018), 4 (2), 26/1-26/12CODEN: BATTAT; ISSN:2313-0105. (MDPI AG)
    Garnet-type Li7-xLa3Zr2-xTaxO12 (LLZT) is considered a good candidate for the solid electrolyte in all-solid-state lithium batteries because of its reasonably high cond. around 10-3 S cm-1 at room temp. and stability against lithium (Li) metal with the lowest redox potential. In this study, we synthesized LLZT with a tantalum (Ta) content of 0.45 via a conventional solid-state reaction process and constructed a Li/LLZT/Li sym. cell by attaching Li metal foils on the polished top and bottom surfaces of an LLZT pellet. We investigated the influence of heating temps. and times on the interfacial charge-transfer resistance between LLZT and the Li metal electrode. In addn., the effect of the interface resistance on the stability for Li deposition and dissoln. was examd. using a galvanostatic cycling test. The lowest interfacial resistance of 25 Ω cm2 at room temp. was obtained by heating at 175°C (5°C lower than the m.p. of Li) for three to five hours. We confirmed that the c.d. at which the short circuit occurs in the Li/LLZT/Li cell via the propagation of Li dendrite into LLZT increases with decreasing interfacial charge transfer resistance.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvFCgsL8%253D&md5=ba149f06f5c745f38d7fc2149c3a16fd
  68. 68
    Nagao, K.; Nagata, Y.; Sakuda, A.; Hayashi, A.; Deguchi, M.; Hotehama, C.; Tsukasaki, H.; Mori, S.; Orikasa, Y.; Yamamoto, K.; Uchimoto, Y.; Tatsumisago, M. A Reversible Oxygen Redox Reaction in Bulk-Type All-Solid-State Batteries. Sci. Adv. 2020, 6, eaax7236,  DOI: 10.1126/sciadv.aax7236
    Google Scholar
    There is no corresponding record for this reference.
  69. 69
    Lee, Y. G.; Fujiki, S.; Jung, C.; Suzuki, N.; Yashiro, N.; Omoda, R.; Ko, D. S.; Shiratsuchi, T.; Sugimoto, T.; Ryu, S.; Ku, J. H.; Watanabe, T.; Park, Y.; Aihara, Y.; Im, D.; Han, I. T. High-Energy Long-Cycling All-Solid-State Lithium Metal Batteries Enabled by Silver–Carbon Composite Anodes. Nat. Energy 2020, 5 (4), 299– 308,  DOI: 10.1038/s41560-020-0575-z
    Google Scholar
    71
    High-energy long-cycling all-solid-state lithium metal batteries enabled by silver-carbon composite anodes
    Lee, Yong-Gun; Fujiki, Satoshi; Jung, Changhoon; Suzuki, Naoki; Yashiro, Nobuyoshi; Omoda, Ryo; Ko, Dong-Su; Shiratsuchi, Tomoyuki; Sugimoto, Toshinori; Ryu, Saebom; Ku, Jun Hwan; Watanabe, Taku; Park, Youngsin; Aihara, Yuichi; Im, Dongmin; Han, In Taek
    Nature Energy (2020), 5 (4), 299-308CODEN: NEANFD; ISSN:2058-7546. (Nature Research)
    An all-solid-state battery with a lithium metal anode is a strong candidate for surpassing conventional lithium-ion battery capabilities. However, undesirable Li dendrite growth and low Coulombic efficiency impede their practical application. Here we report that a high-performance all-solid-state lithium metal battery with a sulfide electrolyte is enabled by a Ag-C composite anode with no excess Li. We show that the thin Ag-C layer can effectively regulate Li deposition, which leads to a genuinely long electrochem. cyclability. In our full-cell demonstrations, we employed a high-Ni layered oxide cathode with a high specific capacity (>210 mAh g-1) and high areal capacity (>6.8 mAh cm-2) and an argyrodite-type sulfide electrolyte. A warm isostatic pressing technique was also introduced to improve the contact between the electrode and the electrolyte. A prototype pouch cell (0.6 Ah) thus prepd. exhibited a high energy d. (>900 Wh l-1), stable Coulombic efficiency over 99.8% and long cycle life (1,000 times).
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXls1Ciurg%253D&md5=872c8ac4fa1c77e763995431f3243d10
  70. 70
    Coeler, M.; van Laack, V.; Langer, F.; Potthoff, A.; Höhn, S.; Reuber, S.; Koscheck, K.; Wolter, M. Infiltrated and Isostatic Laminated Ncm and Lto Electrodes with Plastic Crystal Electrolyte Based on Succinonitrile for Lithium-Ion Solid State Batteries. Batteries 2021, 7 (1), 11,  DOI: 10.3390/batteries7010011
    Google Scholar
    72
    Infiltrated and isostatic laminated NCM and LTO electrodes with plastic crystal electrolyte based on succinonitrile for lithium-ion solid state batteries
    Coeler, Matthias; van Laack, Vanessa; Langer, Frederieke; Potthoff, Annegret; Hoehn, Soeren; Reuber, Sebastian; Koscheck, Katharina; Wolter, Mareike
    Batteries (Basel, Switzerland) (2021), 7 (1), 11CODEN: BATTAT; ISSN:2313-0105. (MDPI AG)
    We report a new process technique for electrode manufg. for all solid-state batteries. Porous electrodes are manufd. by a tape casting process and subsequently infiltrated by a plastic crystal polymer electrolyte (PCPE). With a following isostatic lamination process, the PCPE was further integrated deeply into the porous electrode layer, forming a composite electrode. The PCPE comprises the plastic crystal succinonitrile (SN), lithium conductive salt LiTFSI and polyacrylonitrile (PAN) and exhibits suitable thermal, rheol. (n = 0.6 Pa s @ 80°C 1 s-1) and electrochem. properties (σ > 10-4 S/cm @ 45°C). We detected a lowered porosity of infiltrated and laminated electrodes through Hg porosimetry, showing a redn. from 25.6% to 2.6% (NCM infiltrated to laminated) and 32.9% to 4.0% (LTO infiltrated to laminated). Infiltration of PCPE into the electrodes was further verified by FESEM images and EDS mapping of sulfur content of the conductive salt. Cycling tests of full cells with NCM and LTO electrodes with PCPE separator at 45°C showed up to 165 mAh/g at 0.03C over 20 cycles, which is about 97% of the total usable LTO capacity with a coulomb efficiency of between 98 and 99%. Cycling tests at 0.1C showed a capacity of ~ 128 mAh/g after 40 cycles. The C-rate of 0.2C showed a mean capacity of 127 mAh/g. In summary, we could manuf. full cells using a plastic crystal polymer electrolyte suitable for NCM and LTO active material, which is easily to be integrated into porous electrodes and which is being able to be used in future cell concepts like bipolar stacked cells.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXpt1emtbk%253D&md5=5d1bb1d29d7df843ba5943f686a8c172
  71. 71
    Kitajima, S.; Ryu, S.; Ku, J.; Kim, S.; Park, Y.; Im, D. Methodology for Enhancing the Ionic Conductivity of Superionic Halogen-Rich Argyrodites for All-Solid-State Lithium Batteries. Mater. Today Commun. 2021, 28, 102727,  DOI: 10.1016/j.mtcomm.2021.102727
    Google Scholar
    73
    Methodology for enhancing the ionic conductivity of superionic halogen-rich argyrodites for all-solid-state lithium batteries
    Kitajima, Shintaro; Ryu, Saebom; Ku, Junhwan; Kim, Soyeon; Park, Youngsin; Im, Dongmin
    Materials Today Communications (2021), 28 (), 102727CODEN: MTCAC7; ISSN:2352-4928. (Elsevier Ltd.)
    The development of high-performance all-solid-state lithium-ion batteries depends on the realization of solid-state electrolytes with high ionic cond. In this study, halogen-rich argyrodites with high ionic conductivities were fabricated, and their structural evolution was studied. In addn., the optimum heat treatment protocol for enhancing the ionic cond. of halogen-rich argyrodites (Li5.3PS4.3Cl1.7) was detd. by interpreting the reaction mechanism. Structural and thermal analyzes revealed that fast heating results in the formation of intermediates contg. PS4-3 units and Cl- ions, which remain in the material and decrease the ionic cond. (∼1.6 mS/cm at 25 °C). Surprisingly, slow heating, such as step heating, can promote the slow reaction that produces argyrodite from an intermediate, resulting in a high ionic cond. (∼5.0 mS/cm at 25 #176;C). Furthermore, we examd. the performance of all-solid-state batteries assembled with Li5.3PS4.3Cl1.7 as a solid-state electrolyte and found that the batteries employing Li5.3PS4.3Cl1.7 treated by a slow heating protocol performs better than the batteries employing Li5.3PS4.3Cl1.7 treated by a fast heating protocol, with an impressive specific capacity of 151.8 mAh/g at 1.0 C. Herein, we assert that further developing halogen-rich argyrodites as glass-ceramics may provide a long-sought soln. to realizing ASSBs capable of achieving a high rate.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvV2rtrrP&md5=d3a709bbe52df587811327280a5d9b39
  72. 72
    Federal Consortium for Advanced Batteries. Executive Summary, National Blueprint for Lithium Batteries, 2021–2030; U.S. Department of Energy, June 2021.
    Google Scholar
    There is no corresponding record for this reference.

Cited By

Click to copy section linkSection link copied!

This article is cited by 2 publications.

  1. Marm Dixit, Nitin Muralidharan, Anuj Bisht, Charl J. Jafta, Christopher T. Nelson, Ruhul Amin, Rachid Essehli, Mahalingam Balasubramanian, Ilias Belharouak. Tailoring of the Anti-Perovskite Solid Electrolytes at the Grain-Scale. ACS Energy Letters 2023, 8 (5) , 2356-2364. https://doi.org/10.1021/acsenergylett.3c00265
  2. Karena W. Chapman, (Senior Editor, ACS Energy Letters)Yong-Sheng Hu, (Senior Editor, ACS Energy Letters)Kimberly A. See, (Topic Editor, ACS Energy Letters)Yang-Kook Sun (Senior Editor, ACS Energy Letters). Advances in Solid-State Batteries, a Virtual Issue, Part II. ACS Energy Letters 2023, 8 (2) , 1215-1217. https://doi.org/10.1021/acsenergylett.3c00085
Download PDF
Go to ACS Energy Letters
Get e-Alerts
Get e-Alerts

ACS Energy Letters

Cite this: ACS Energy Lett. 2022, 7, 11, 3936–3946
Click to copy citationCitation copied!
https://doi.org/10.1021/acsenergylett.2c01936
Published October 18, 2022

Copyright © 2022 The Authors. Published by American Chemical Society. This publication is licensed under

CC-BY-NC-ND 4.0 .

Article Views

12k

Altmetric

-

Citations

2
Learn about these metrics

Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.

  • Abstract

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 1

    Figure 1. (a) Current challenges in processing and integration of solid-state batteries. (b) Uneven density distribution by single uniaxial pressing in rigid die for cylinder. (c) Schematic diagram of a pressure vessel cavity into which the sample is inserted and subjected to isostatic pressure and temperature conditions, and temperature and pressure ranges for CIP (blue), WIP (green), and HIP (orange) techniques.

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 2

    Figure 2. ISP integration pathways into SSB manufacturing. (a) Possible packaging of SSB systems and the underlying tri-layer architectures. (b) ISP configurations of the components and assemblies envisioned for large-scale production.

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 3

    Figure 3. (a) Compilation of isostatic pressing parameters used in the SSB literature for densification and integration of solid electrolytes and cells, respectively. Largely CIP is the primary technique that is leveraged within the SSB community. Shaded markers indicate either HIP or WIP cycles. The color of the markers indicates the solid electrolyte material family (pink markers, LLZO; yellow markers, Na-based NASICONs; green markers, sulfides; gray marker, hybrid electrolyte). The data for this figure are collected from refs (33,34,36−56). (b) XRD patterns and optical images of LLZO before and after the HIP treatment. The scale bars represent 10 mm. Data adapted from ref (33). SEM images of anti-perovskite solid electrolytes processed under (c) uniaxial loading conditions, (d) CIP conditions, and (e) WIP conditions. The scale bars in all the SEM images are 10 μm. (f, g) Tomographic reconstruction slices and pore volume visualization of the anti-perovskites processed under CIP and WIP conditions along with the measured porosity. The sub-volume investigated for porosity evaluation and visualized here is 300 × 300 × 300 μm3.

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 4

    Figure 4. (a) Compilation of ionic conductivity data sets from literature that leveraged ISP processing methods for solid electrolyte densification. The marker colors represent different material families (garnet, Na-solid electrolytes, and Li-based NASICONs). The data are adapted from refs (33,38,39,41,43,51,53,55,65−67). (b) Discharge polarization curves and (c) capacity retention profiles from solid-state battery cells that were integrated into tri-layer configurations using ISP processes. The corresponding solid electrolyte system is indicated in the legend. The data for (b) and (c) are adapted from refs (37,43,44,50,56,68−71).

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 5

    Figure 5. (a) Overview of the protocol used for techno-economic analysis carried out here. (b) Typical features of a state-of-the-art CIP/WIP/HIP instrument commercially available today. Dimensions reflect the volume of the largest sample that can be accommodated within the instrument. Packing fraction represents the fraction of the available volume which will occupied by the material of interest. Cycles assumed are detailed in the Supporting Information. Cost per cycle and cost per volume are in U.S. dollars. (c) Projected volumes of solid electrolyte and cells that need to be processed to cater to the expected EV demands in the next 20 years. For details see the Supporting Information. Projected processing cost for (d) solid electrolyte processing and (e) cell integration considering different ISP protocols.

    High Resolution Image
    Download MS PowerPoint Slide

  • References

    This article references 72 other publications.

    1. 1
      Janek, J.; Zeier, W. G. A Solid Future for Battery Development. Nat. Energy 2016, 1, 16141,  DOI: 10.1038/nenergy.2016.141
      There is no corresponding record for this reference.
    2. 2
      Manthiram, A.; Yu, X.; Wang, S. Lithium Battery Chemistries Enabled by Solid-State Electrolytes. Nat. Rev. Mater. 2017, 2 (4), 103,  DOI: 10.1038/natrevmats.2016.103
      There is no corresponding record for this reference.
    3. 3
      Dixit, M. B.; Park, J.-S.; Kenesei, P.; Almer, J.; Hatzell, K. B. Status and Prospect of in Situ and Operando Characterization of Solid-State Batteries. Energy Environ. Sci. 2021, 14, 4672– 4711,  DOI: 10.1039/D1EE00638J
      3
      Status and prospect of in situ and operando characterization of solid-state batteries
      Dixit, Marm B.; Park, Jun-Sang; Kenesei, Peter; Almer, Jonathan; Hatzell, Kelsey B.
      Energy & Environmental Science (2021), 14 (9), 4672-4711CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      Electrification of the transportation sector relies on radical re-imagining of energy storage technologies to provide affordable, high energy d., durable and safe systems. Next generation energy storage systems will need to leverage high energy d. anodes and high voltage cathodes to achieve the required performance metrics (longer vehicle range, long life, prodn. costs, safety). Solid-state batteries (SSBs) are promising materials technol. for achieving these metrics by enabling these electrode systems due to the underlying material properties of the solid electrolyte (viz. mech. strength, electrochem. stability, ionic cond.). Electro-chemo-mech. degrdn. in SSBs detrimentally impact the Coulombic efficiencies, capacity retention, durability and safety in SSBs restricting their practical implementation. Solid|solid interfaces in SSBs are hot-spots of dynamics that contribute to the degrdn. of SSBs. Characterizing and understanding the processes at the solid|solid interfaces in SSBs is crucial towards designing of resilient, durable, high energy d. SSBs. This work provides a comprehensive and crit. summary of the SSB characterization with a focus on in situ and operando studies. Addnl., perspectives on exptl. design, emerging characterization techniques and data anal. methods are provided. This work provides a thorough anal. of current status of SSB characterization as well as highlights important avenues for future work.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhs1CktrbO&md5=c8833cfa1785cbc3da687472752a1787
    4. 4
      Dixit, M.; Parejiya, A.; Essehli, R.; Muralidharan, N.; Haq, S. U.; Amin, R.; Belharouak, I. SolidPAC Is an Interactive Battery-on-Demand Energy Density Estimator for Solid-State Batteries. Cell Rep. Phys. Sci. 2022, 3 (2), 100756,  DOI: 10.1016/j.xcrp.2022.100756
      4
      SolidPAC is an interactive battery-on-demand energy density estimator for solid-state batteries
      Dixit, Marm; Parejiya, Anand; Essehli, Rachid; Muralidharan, Nitin; Haq, Shomaz Ul; Amin, Ruhul; Belharouak, Ilias
      Cell Reports Physical Science (2022), 3 (2), 100756CODEN: CRPSF5; ISSN:2666-3864. (Elsevier Inc.)
      Solid-state batteries hold the promise to be highly impactful next-generation technologies for high-energy and -power-d. rechargeable battery applications. It is crucial to identify the metrics that an emerging battery technol. should fulfil to achieve parity with conventional Li-ion batteries, primarily in terms of energy d. However, limited approaches exist today to assess and extrapolate the impact of battery designs and choices of cell components on the cell-level energy d. of a solid-state battery. Herein, we introduce the solid-state battery performance analyzer and calculator (SolidPAC), an interactive exptl. toolkit to enable the design of a solid-state battery for user-specified application requirements. The toolkit is flexible enough to assist the battery community in quantifying the impact of materials chem. and fractions, electrode thicknesses and loadings, and electron flows on cell energy d. and costs and in utilizing inverse engineering concepts to correlate the cell energy d. output to materials and cell design inputs.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38Xht1WjsrjL&md5=2488debf203c396065f2e4137d4c6519
    5. 5
      Randau, S.; Weber, D. A.; Kötz, O.; Koerver, R.; Braun, P.; Weber, A.; Ivers-Tiffée, E.; Adermann, T.; Kulisch, J.; Zeier, W. G.; Richter, F. H.; Janek, J. Benchmarking the Performance of All-Solid-State Lithium Batteries. Nat. Energy 2020, 5 (3), 259– 270,  DOI: 10.1038/s41560-020-0565-1
      5
      Benchmarking the performance of all-solid-state lithium batteries
      Randau, Simon; Weber, Dominik A.; Koetz, Olaf; Koerver, Raimund; Braun, Philipp; Weber, Andre; Ivers-Tiffee, Ellen; Adermann, Torben; Kulisch, Joern; Zeier, Wolfgang G.; Richter, Felix H.; Janek, Juergen
      Nature Energy (2020), 5 (3), 259-270CODEN: NEANFD; ISSN:2058-7546. (Nature Research)
      Increasing the specific energy, energy d., specific power, energy efficiency and energy retention of electrochem. storage devices are major incentives for the development of all-solid-state batteries. However, a general evaluation of all-solid-state battery performance is often difficult to derive from published reports, mostly due to the interdependence of performance measures, but also due to the lack of a basic ref. system. Here, we present all-solid-state batteries reduced to the bare min. of compds., contg. only a lithium metal anode, β-Li3PS4 solid electrolyte and Li(Ni0.6Co0.2Mn0.2)O2 cathode active material. We use this minimalistic system to benchmark the performance of all-solid-state batteries. In a Ragone-type graph, we compare literature data for thiophosphate-, oxide-, phosphate- and polymer-based all-solid-state batteries with our minimalistic cell. Using fundamental equations for key performance parameters, we identify research targets towards high energy, high power and practical all-solid-state batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXls1Ciurs%253D&md5=9c8e4a5f98bf58f87d9971ffbf1a5955
    6. 6
      Hatzell, K. B.; Chen, X. C.; Cobb, C.; Dasgupta, N. P.; Dixit, M. B.; Marbella, L. E.; McDowell, M. T.; Mukherjee, P.; Verma, A.; Viswanathan, V.; Westover, A.; Zeier, W. G. Challenges in Lithium Metal Anodes for Solid State Batteries. ACS Energy Lett. 2020, 5, 922– 934,  DOI: 10.1021/acsenergylett.9b02668
      6
      Challenges in Lithium Metal Anodes for Solid-State Batteries
      Hatzell, Kelsey B.; Chen, Xi Chelsea; Cobb, Corie L.; Dasgupta, Neil P.; Dixit, Marm B.; Marbella, Lauren E.; McDowell, Matthew T.; Mukherjee, Partha P.; Verma, Ankit; Viswanathan, Venkatasubramanian; Westover, Andrew S.; Zeier, Wolfgang G.
      ACS Energy Letters (2020), 5 (3), 922-934CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
      A review. In this Perspective, we highlight recent progress and challenges related to the integration of lithium metal anodes in solid-state batteries. While prior reports have suggested that solid electrolytes may be impermeable to lithium metal, this hypothesis has been disproven under a variety of electrolyte compns. and cycling conditions. Herein, we describe the mechanistic origins and importance of lithium filament growth and interphase formation in inorg. and org. solid electrolytes. Multimodal techniques that combine real and reciprocal space imaging and modeling will be necessary to fully understand nonequil. dynamics at these buried interfaces. Currently, most studies on lithium electrode kinetics at solid electrolyte interfaces are completed in sym. Li-Li configurations. To fully understand the challenges and opportunities afforded by Li-metal anodes, full-cell expts. are necessary. Finally, the impacts of operating conditions on solid-state batteries are largely unknown with respect to pressure, geometry, and break-in protocols. Given the rapid growth of this community and the diverse portfolio of solid electrolytes, we highlight the need for detailed reporting of exptl. conditions and standardization of protocols across the community.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXjtlWrsLo%253D&md5=118bf765db2b34bb743ca396b89b8a6c
    7. 7
      Schnell, J.; Knörzer, H.; Imbsweiler, A. J.; Reinhart, G. Solid versus Liquid─A Bottom-Up Calculation Model to Analyze the Manufacturing Cost of Future High-Energy Batteries. Energy Technology 2020, 8 (3), 1901237,  DOI: 10.1002/ente.201901237
      7
      Solid versus Liquid-A Bottom-Up Calculation Model to Analyze the Manufacturing Cost of Future High-Energy Batteries
      Schnell, Joscha; Knoerzer, Heiko; Imbsweiler, Anna Julia; Reinhart, Gunther
      Energy Technology (Weinheim, Germany) (2020), 8 (3), 1901237CODEN: ETNEFN; ISSN:2194-4296. (Wiley-VCH Verlag GmbH & Co. KGaA)
      All-solid-state batteries (ASSB) are promising candidates for future energy storage. However, only a little is known about the manufg. costs for industrial prodn. Herein, a detailed bottom-up calcn. is performed to est. the required investment and to facilitate comparison with conventional lithium-ion batteries (LIB). Results indicate that sulfide-based ASSBs can indeed be competitive if the material compatibility issues can be solved and prodn. is successfully scaled. In contrast, oxide-based ASSBs will probably not be able to compete if cost is the decisive factor. A sensitivity anal. with Monte Carlo simulation reveals that the inert gas atm. required for sulfide-based ASSBs contributes little to the overall cell costs, whereas the sintering step for oxide-based ASSBs is highly crit. The calcn. also indicates that inhouse manufg. of the lithium anode will be cheaper than purchasing the lithium foil externally if the cell producer has sufficient processing know-how. Finally, the aerosol deposition method is investigated, revealing that a deposition rate far above 1000 mm3 min-1 would be required to make the technol. economically feasible in ASSB prodn. The results of this study will help researchers and industry prioritize development efforts and push the scale-up of future high-energy batteries with improved performance.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXksVGlu7g%253D&md5=87a671fcc6929f61b16f3b000693fbc6
    8. 8
      Hatzell, K. B.; Zheng, Y. Prospects on Large-Scale Manufacturing of Solid State Batteries. MRS Energy Sustainability 2021, 8 (1), 33– 39,  DOI: 10.1557/s43581-021-00004-w
      There is no corresponding record for this reference.
    9. 9
      Schnell, J.; Günther, T.; Knoche, T.; Vieider, C.; Köhler, L.; Just, A.; Keller, M.; Passerini, S.; Reinhart, G. All-Solid-State Lithium-Ion and Lithium Metal Batteries – Paving the Way to Large-Scale Production. J. Power Sources 2018, 382, 160– 175,  DOI: 10.1016/j.jpowsour.2018.02.062
      9
      All-solid-state lithium-ion and lithium metal batteries - paving the way to large-scale production
      Schnell, Joscha; Guenther, Till; Knoche, Thomas; Vieider, Christoph; Koehler, Larissa; Just, Alexander; Keller, Marlou; Passerini, Stefano; Reinhart, Gunther
      Journal of Power Sources (2018), 382 (), 160-175CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Challenges and requirements for the large-scale prodn. of all-solid-state lithium-ion and lithium metal batteries are herein evaluated via workshops with experts from renowned research institutes, material suppliers, and automotive manufacturers. Aiming to bridge the gap between materials research and industrial mass prodn., possible solns. for the prodn. chains of sulfide and oxide based all-solid-state batteries from electrode fabrication to cell assembly and quality control are presented. Based on these findings, a detailed comparison of the prodn. processes for a sulfide based all-solid-state battery with conventional lithium-ion cell prodn. is given, showing that processes for composite electrode fabrication can be adapted with some effort, while the fabrication of the solid electrolyte separator layer and the integration of a lithium metal anode will require completely new processes. This work identifies the major steps towards mass prodn. of all-solid-state batteries, giving insight into promising manufg. technologies and helping stakeholders, such as machine engineering, cell producers, and original equipment manufacturers, to plan the next steps towards safer batteries with increased storage capacity.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXjtlaqtbc%253D&md5=970ae25e087dd33eb2c03871e6bbaee8
    10. 10
      Dixit, M.; Muralidharan, N.; Parejiya, A.; Amin, R.; Essehli, R.; Belharouak, I. Current Status and Prospects of Solid-State Batteries as the Future of Energy Storage: Management and Applications of Energy Storage Devices. Intech Open 2021, 39– 61,  DOI: 10.5772/intechopen.98701
      There is no corresponding record for this reference.
    11. 11
      Albertus, P.; Anandan, V.; Ban, C.; Balsara, N.; Belharouak, I.; Buettner-Garrett, J.; Chen, Z.; Daniel, C.; Doeff, M.; Dudney, N. J.; Dunn, B.; Harris, S. J.; Herle, S.; Herbert, E.; Kalnaus, S.; Libera, J. A.; Lu, D.; Martin, S.; McCloskey, B. D.; McDowell, M. T.; Meng, Y. S.; Nanda, J.; Sakamoto, J.; Self, E. C.; Tepavcevic, S.; Wachsman, E.; Wang, C.; Westover, A. S.; Xiao, J.; Yersak, T. Challenges for and Pathways toward Li-Metal-Based All-Solid-State Batteries. ACS Energy Lett. 2021, 6 (4), 1399– 1404,  DOI: 10.1021/acsenergylett.1c00445
      11
      Challenges for and Pathways toward Li-Metal-Based All-Solid-State Batteries
      Albertus, Paul; Anandan, Venkataramani; Ban, Chunmei; Balsara, Nitash; Belharouak, Ilias; Buettner-Garrett, Josh; Chen, Zonghai; Daniel, Claus; Doeff, Marca; Dudney, Nancy J.; Dunn, Bruce; Harris, Stephen J.; Herle, Subramanya; Herbert, Eric; Kalnaus, Sergiy; Libera, Joesph A.; Lu, Dongping; Martin, Steve; McCloskey, Bryan D.; McDowell, Matthew T.; Meng, Y. Shirley; Nanda, Jagjit; Sakamoto, Jeff; Self, Ethan C.; Tepavcevic, Sanja; Wachsman, Eric; Wang, Chunsheng; Westover, Andrew S.; Xiao, Jie; Yersak, Thomas
      ACS Energy Letters (2021), 6 (4), 1399-1404CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
      A review. Solid-state batteries hold great promise for high-energy batteries for elec. vehicles and other applications. While the potential is great, success is contingent on solving crit. challenges in materials science, processing science, and fabrication of practical full cells. This focus article has outlined several key challenges in the hope that they will encourage and inspire solns. and the eventual realization of high-energy solid-state batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXmvVCmsLY%253D&md5=8de2940c82b1d2767d98def586dae92e
    12. 12
      Zheng, F.; Kotobuki, M.; Song, S.; Lai, M. O.; Lu, L. Review on Solid Electrolytes for All-Solid-State Lithium-Ion Batteries. J. Power Sources 2018, 389 (April), 198– 213,  DOI: 10.1016/j.jpowsour.2018.04.022
      12
      Review on solid electrolytes for all-solid-state lithium-ion batteries
      Zheng, Feng; Kotobuki, Masashi; Song, Shufeng; Lai, Man On; Lu, Li
      Journal of Power Sources (2018), 389 (), 198-213CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      All-solid-state (ASS) lithium-ion battery has attracted great attention due to its high safety and increased energy d. One of key components in the ASS battery (ASSB) is solid electrolyte that dets. performance of the ASSB. Many types of solid electrolytes have been investigated in great detail in the past years, including NASICON-type, garnet-type, perovskite-type, LISICON-type, LiPON-type, Li3N-type, sulfide-type, argyrodite-type, anti-perovskite-type and many more. This paper aims to provide comprehensive reviews on some typical types of key solid electrolytes and some ASSBs, and on gaps that should be resolved.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXnsFWjsLY%253D&md5=3cb31a091d2fff8bfc994dc6853179e2
    13. 13
      Quartarone, E.; Mustarelli, P. Electrolytes for Solid-State Lithium Rechargeable Batteries: Recent Advances and Perspectives. Chem. Soc. Rev. 2011, 40 (5), 2525,  DOI: 10.1039/c0cs00081g
      13
      Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives
      Quartarone, Eliana; Mustarelli, Piercarlo
      Chemical Society Reviews (2011), 40 (5), 2525-2540CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      This crit. review presents an overview of the various classes of Li+ conductors for use as electrolytes in lithium polymer batteries and all-solid state microbatteries. Initially, we recall the main models for ion transport and the structure-transport relationships at the basis of the obsd. cond. behaviors. Emphasis is then placed on the physico-chem. and functional parameters relevant for optimal electrolytes prepn., as well as on the techniques of choice for their evaluation. Finally, the state of the art of polymer and ceramic electrolytes is reported, and the most interesting strategies for the future developments are described (121 refs.).
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXkvVWjtLY%253D&md5=9492a31219e7b6c1e4b6221805b5c600
    14. 14
      Thangadurai, V.; Narayanan, S.; Pinzaru, D. Garnet-Type Solid-State Fast Li Ion Conductors for Li Batteries: Critical Review. Chem. Soc. Rev. 2014, 43 (13), 4714– 4727,  DOI: 10.1039/c4cs00020j
      14
      Garnet-type solid-state fast Li ion conductors for Li batteries: critical review
      Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana
      Chemical Society Reviews (2014), 43 (13), 4714-4727CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. Batteries are electrochem. devices that store elec. energy in the form of chem. energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and elec. vehicles. Conventional LiBs use an org. polymer electrolyte, which exhibits several safety issues including leakage, poor chem. stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power d. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compds. are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion cond. of ∼10-6 at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion cond. of 10-3 S cm-1 at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chem. stable at higher temps. and voltages compared to polymer electrolytes. Here, we discuss the chem. compn.-structure-ionic cond. relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXpsVKisrg%253D&md5=cf00b77444023feaa2fc3faed1423c1e
    15. 15
      Alexander, G. v.; Indu, M. S.; Murugan, R. Review on the Critical Issues for the Realization of All-Solid-State Lithium Metal Batteries with Garnet Electrolyte: Interfacial Chemistry, Dendrite Growth, and Critical Current Densities Ionics; Springer Science and Business Media Deutschland GmbH, 2021; pp 4105– 4126.  DOI: 10.1007/s11581-021-04190-y o
      There is no corresponding record for this reference.
    16. 16
      Singh, N.; Horwath, J. P.; Bonnick, P.; Suto, K.; Stach, E. A.; Matsunaga, T.; Muldoon, J.; Arthur, T. S. The Role of Lithium Iodide Addition to Lithium Thiophosphate: Implications beyond Conductivity. Chem. Mater. 2020, 32, 7150– 7158,  DOI: 10.1021/acs.chemmater.9b05286
      16
      Role of Lithium Iodide Addition to Lithium Thiophosphate: Implications beyond Conductivity
      Singh, Nikhilendra; Horwath, James P.; Bonnick, Patrick; Suto, Koji; Stach, Eric A.; Matsunaga, Tomoya; Muldoon, John; Arthur, Timothy S.
      Chemistry of Materials (2020), 32 (17), 7150-7158CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      Because of their high cond. and potential to utilize lithium metal, lithium thiophosphate electrolytes have attracted significant attention to realize solid-state batteries for vehicle applications. However, lithium metal still presents many challenges in potentially maximizing the battery energy d. One important requirement is to limit the amt. of lithium metal during cell construction or to operate the cell under limited lithium conditions. Here, the interface between lithium thiophosphate and lithium iodide-doped lithium thiophosphate with lithium metal is investigated. Lithium iodide plays a protective role at the interface and enables improved lithium cycling. Operando transmission electron microscopy anal. reveals delamination and dead lithium at the interface as major challenges for solid-state batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFWgtrvL&md5=d9ae5b14873cc515acba79e1d4250740
    17. 17
      Dixit, M. B.; Singh, N.; Horwath, J. P.; Shevchenko, P. D.; Jones, M.; Stach, E. A.; Arthur, T. S.; Hatzell, K. B. In Situ Investigation of Chemomechanical Effects in Thiophosphate Solid Electrolytes. Matter 2020, 3 (6), 2138– 2159,  DOI: 10.1016/j.matt.2020.09.018
      There is no corresponding record for this reference.
    18. 18
      Homann, G.; Meister, P.; Stolz, L.; Brinkmann, J. P.; Kulisch, J.; Adermann, T.; Winter, M.; Kasnatscheew, J. High-Voltage All-Solid-State Lithium Battery with Sulfide-Based Electrolyte: Challenges for the Construction of a Bipolar Multicell Stack and How to Overcome Them. ACS Appl. Energy Mater. 2020, 3 (4), 3162– 3168,  DOI: 10.1021/acsaem.0c00041
      18
      High-Voltage All-Solid-State Lithium Battery with Sulfide-Based Electrolyte: Challenges for the Construction of a Bipolar Multicell Stack and How to Overcome Them
      Homann, Gerrit; Meister, Paul; Stolz, Lukas; Brinkmann, Jan Paul; Kulisch, Joern; Adermann, Torben; Winter, Martin; Kasnatscheew, Johannes
      ACS Applied Energy Materials (2020), 3 (4), 3162-3168CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      Solid electrolytes can be the key for the desired goal of increased safety and specific energies of batteries. On a cell and battery pack level, the all-solid nature and the absence of liq. electrolyte leakage are considered to enable safe and effective performance realization of the rechargeable Li metal electrode and bipolar cell stacking, resp. Well performing Li metal cells with high-energy/voltage pos. electrodes such as LiNi0.6Mn0.2Co0.2O2 (NMC622) can already be cycled when using a blend of the sulfidic solid electrolyte such as β-Li3PS4 (LPS) and Li salt in poly(ethylene)oxide (PEO). However, operation of a bipolar stack using these cell materials utilizing the common Al/Cu clad as bipolar plate results in an immediate short circuit, because of an ionic intercell connection via molten LiTFSI/PEO. Oversizing the area of the bipolar plates can prevent such a short circuit and indeed enables a partial charge of the stack, but after a certain time, the next cell failure is obsd., consisting of severe, sulfur caused, corrosion of copper which was used as metal substrate for the lithium anode. The exchange of the sulfide incompatible Cu collector by (also area-oversized) stainless steel can finally enable a failure-free performance of the bipolar cell stack, which performs similar to a single cell with regard to cycling stability.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXkvFyjsL4%253D&md5=ccb4220513f6ae0b37b7b418992be0c5
    19. 19
      Lau, J.; DeBlock, R. H.; Butts, D. M.; Ashby, D. S.; Choi, C. S.; Dunn, B. S. Sulfide Solid Electrolytes for Lithium Battery Applications. Adv. Energy Mater. 2018, 8 (27), 1800933,  DOI: 10.1002/aenm.201800933
      There is no corresponding record for this reference.
    20. 20
      Dixit, M. B.; Zaman, W.; Bootwala, Y.; Zheng, Y.; Hatzell, M. C.; Hatzell, K. B. Scalable Manufacturing of Hybrid Solid Electrolytes with Interface Control. ACS Appl. Mater. Interfaces 2019, 11 (48), 45087– 45097,  DOI: 10.1021/acsami.9b15463
      20
      Scalable Manufacturing of Hybrid Solid Electrolytes with Interface Control
      Dixit, Marm B.; Zaman, Wahid; Bootwala, Yousuf; Zheng, Yanjie; Hatzell, Marta C.; Hatzell, Kelsey B.
      ACS Applied Materials & Interfaces (2019), 11 (48), 45087-45097CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Hybrid solid electrolytes are promising alternatives for high energy d., metallic Li batteries. Scalable manufg. of multi-material electrolytes with tailored transport pathways can provide an avenue toward controlling Li stripping and deposition mechanisms in all solid state devices. A novel roll-to-roll compatible coextrusion device is demonstrated to study meso-structural control during manufg. Solid electrolytes with 25 wt.\% and 75wt.\% PEO-LLZO compns. were studied. The coextrusion head is demonstrated to effectively process multi-material films with strict compositional gradients in a single-pass. Av. manufg. variability of 5.75 ± 1.2μm is obsd. in the thickness across all the electrolytes manufd. Coextruded membrane with 1 mm stripes shows the highest room temp. cond. of 8.8 × 10-6 S cm-1 compared to the cond. of single material films (25%:1.2 × 10-6 S cm-1 , 75%:1.8 × 10-6 S cm-1 ). Distribution of relaxation times and effective mean field theory calcns. suggest that the interface generated between the two materials possess high ion-conducting properties. Computational simulations were used to further substantiate the influence of macro-scale interfaces on ion transport.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitFSqt7nL&md5=52b792eef365abb2a907505d9f5bc0f3
    21. 21
      Keller, M.; Varzi, A.; Passerini, S. Hybrid Electrolytes for Lithium Metal Batteries. J. Power Sources 2018, 392 (April), 206– 225,  DOI: 10.1016/j.jpowsour.2018.04.099
      21
      Hybrid electrolytes for lithium metal batteries
      Keller, Marlou; Varzi, Alberto; Passerini, Stefano
      Journal of Power Sources (2018), 392 (), 206-225CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      This perspective article discusses the most recent developments in the field of hybrid electrolytes, here referred to electrolytes composed of two, well-defined ion-conducting phases, for high energy d. lithium metal batteries. The two phases can be both solid, as e.g., two inorg. conductors or one inorg. and one polymer conductor, or, differently, one liq. and one inorg. conductor. In this latter case, they are referred as quasi-solid hybrid electrolytes. Techniques for the appropriate characterization of hybrid electrolytes are discussed emphasizing the importance of ionic conduction and interfacial properties. On this view, multilayer systems are also discussed in more detail. Investigations on Lewis acid-base interactions, activation energies for lithium-ion transfer between the phases, and the formation of an interphase between the components are reviewed and analyzed. The application of different hybrid electrolytes in lithium metal cells with various cathode compns. is also discussed. Fabrication methods for the feasibility of large-scale applications are briefly analyzed and different cell designs and configurations, which are most suitable for the integration of hybrid electrolytes, are detd. Finally, the specific energy of cells contg. different hybrid electrolytes is estd. to predict possible enhancement in energy with respect to the current lithium-ion battery technol.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXovFGltr4%253D&md5=cfd041bbb8d101d20355a231a7a018b8
    22. 22
      Mahmud, L. S.; Muchtar, A.; Somalu, M. R. Challenges in Fabricating Planar Solid Oxide Fuel Cells: A Review. Renewable Sustainable Energy Rev. 2017, 72, 105– 116,  DOI: 10.1016/j.rser.2017.01.019
      23
      Challenges in fabricating planar solid oxide fuel cells: A review
      Mahmud, L. S.; Muchtar, A.; Somalu, M. R.
      Renewable & Sustainable Energy Reviews (2017), 72 (), 105-116CODEN: RSERFH; ISSN:1364-0321. (Elsevier Ltd.)
      A review. Most technologies for fabricating solid oxide fuel cells (SOFCs) are adopted from ceramic-fabrication methods. Selecting an appropriate method of prepg. SOFC components is a main concern for many researchers because the method can strongly affect SOFC properties and performance. The method must be reproducible and highly controllable to improve SOFC performance and durability. SOFC fabrication methods have been customized to achieve high power outputs at low operation temps. and thus broaden the choice of material and reduce fabrication cost. This article provides an overview of planar SOFC fabrication methods. Planar SOFC fabrication methods such as uniaxial pressing, tape casting, screen printing, dip coating, and slurry spin coating are discussed because these methods are cost effective. This article also discusses the tech. parameters that can influence the processes of these methods and SOFC performance. The methods of prepg. the materials of SOFC components are discussed because these methods directly affect the fabrication process.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtlClsLw%253D&md5=068a1e72ebab99e053ccbdcdcbf8cf93
    23. 23
      Robertson, I. M.; Schaffer, G. B. Review of Densification of Titanium Based Powder Systems in Press and Sinter Processing. Powder Metallurgy 2010, 53 (2), 146– 162,  DOI: 10.1179/174329009X434293
      24
      Review of densification of titanium based powder systems in press and sinter processing
      Robertson, I. M.; Schaffer, G. B.
      Powder Metallurgy (2010), 53 (2), 146-162CODEN: PWMTAU; ISSN:0032-5899. (Maney Publishing)
      A review. The development of novel extractive metallurgy techniques for titanium offers the prospect of lower cost Ti powder and therefore wider application of Ti. This review is largely confined to coverage of the low cost press and sinter methods of powder metallurgy, consisting of cold pressing of mixed elemental powders followed by sintering without the application of external pressure. Cold die compaction, sintering behavior and densification are reviewed in detail. Some information on powders and cold isostatic pressing is included. Microstructure, mech. properties and applications are considered in less detail. The review deals mostly with the sintering of alloys, but there is some ref. to synthesis of intermetallic compds., such as the shape memory alloy NiTi and Ti aluminides for high temp. applications. Densification is discussed in terms of the four fundamental processing variables: compaction pressure, particle size, sintering temp., and sintering time. Other factors such as alloy compn., the form of alloying addn., type and impurity content of powders and heating rate are also considered.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXpt1ymt7w%253D&md5=68e1b11b17189b8f073b3654e7cb260a
    24. 24
      Hotza, D.; di Luccio, M.; Wilhelm, M.; Iwamoto, Y.; Bernard, S.; Diniz da Costa, J. C. Silicon Carbide Filters and Porous Membranes: A Review of Processing, Properties, Performance and Application. J. Membr. Sci. 2020, 610, 118193,  DOI: 10.1016/j.memsci.2020.118193
      25
      Silicon carbide filters and porous membranes: A review of processing, properties, performance and application
      Hotza, Dachamir; Di Luccio, Marco; Wilhelm, Michaela; Iwamoto, Yuji; Bernard, Samuel; Diniz da Costa, Joao C.
      Journal of Membrane Science (2020), 610 (), 118193CODEN: JMESDO; ISSN:0376-7388. (Elsevier B.V.)
      A review. Silicon carbide (SiC) filters and porous membranes is a growing industry with deployment for gas and liq. sepn. processes. In view of its importance, the research efforts into the development of SiC filters and membranes are of growing interest around the world. Therefore, this review paper is focused on the latest advancements in SiC and SiC composites used for the prepn. of substrates and thin films in filters and membranes. There is a multitude of methods used to prep. filters and membranes of different shapes (tubular, honeycomb, flat sheets and multi-channel), which are influenced by precursor mixt. and sintering conditions. In turn, these processing conditions affect porosity and pore size, which affects the transport and sepn. properties of SiC filters and membranes. SiC particles size and distribution allow for the precise control of pore size in membranes, leading to high gas sepn. factors. In addn., SiC has strong thermal stability properties that are very desirable for high temp. gas cleaning. Together with gas and liq. transport and sepn. properties, this review also addresses the potential applications in gas and liq. sepn. processes, coupled with thermal/chem. stability properties. Future challenges are highlighted towards further research efforts.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtVSjtrzM&md5=a429eff4a67a86f85a4e5f565e7340ad
    25. 25
      Song, J. -H; Evans, J. R. G. A Die Pressing Test for the Estimation of Agglomerate Strength. J. Am. Ceram. Soc. 1994, 77 (3), 806– 814,  DOI: 10.1111/j.1151-2916.1994.tb05369.x
      26
      A die pressing test for the estimation of agglomerate strength
      Song, Jin Hua; Evans, Julian R. G.
      Journal of the American Ceramic Society (1994), 77 (3), 806-14CODEN: JACTAW; ISSN:0002-7820.
      A die pressing test was developed for quick and inexpensive estn. of the agglomerate strength of ceramic powders. The crit. nominal pressure (pc) at which contact areas between agglomerates start to increase rapidly was found from the relationship between change in sample height and applied pressure in uniaxial single-ended die pressing. A quant. microscopic method was used for measuring the area fraction (ψ) of agglomerates which transmits the force through the assembly. A die pressing agglomerate strength, σd, is defined as σd = 0.7 pc/ψ. This strength was compared with the agglomerate tensile strength obtained from single agglomerate diametral compression tests and found to be 50% higher than the latter because of multipoint loading. A suggested guideline is that the mean agglomerate tensile strength is approx. 52% of pc detd. in a die pressing test for spherical agglomerates. In addn. to agglomerate tensile strength, the mean agglomerate size, the interior macropore structure of agglomerates, as well as the packing efficiencies between and inside agglomerates can be estd. by the procedure.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXit1CrsbY%253D&md5=41da21d1d1a5ef3b002579256d51adf8
    26. 26
      Mahesh, M. L. V.; Bhanu Prasad, V. v.; James, A. R. A Comparison of Different Powder Compaction Processes Adopted for Synthesis of Lead-Free Piezoelectric Ceramics. Eur. Phys. J. B 2016, 89 (4), 108,  DOI: 10.1140/epjb/e2016-60390-6
      There is no corresponding record for this reference.
    27. 27
      Attia, U. M. Cold-Isostatic Pressing of Metal Powders: A Review of the Technology and Recent Developments. Crit. Rev. Solid State Mater. Sci. 2021, 46 (6), 587– 610,  DOI: 10.1080/10408436.2021.1886043
      28
      Cold-isostatic pressing of metal powders: a review of the technology and recent developments
      Attia, Usama M.
      Critical Reviews in Solid State and Materials Sciences (2021), 46 (6), 587-610CODEN: CCRSDA; ISSN:1040-8436. (Taylor & Francis, Inc.)
      Cold-isostatic pressing (CIP) is a powder-based, near-net-shape technol. for the prodn. of metal and ceramic components. CIP has been commonly used for processing ceramics, but not as widely used for metals. Recent developments in process capability and powder metallurgy, however, have allowed CIP to be increasingly used in the manuf. of high-performance metal parts. Advantages such as solid-state processing, uniform microstructure, shape complexity, low tooling cost and process scalability have made CIP a viable processing route for metals. In addn., the potential to produce near-net-shape parts with minimal material waste has made the process more widely acceptable in niche applications, such as aerospace and automotive. This review assesses the state of the technol. in terms of capabilities and limitations, materials, tool design and fabrication, process modeling, post processing and assessment. The review also highlights challenges and research gaps in using CIP for producing metal parts, with a focus on potential areas of improvement and recent developments that address these challenges.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXkvFCrt7o%253D&md5=4c5b3769a19df40a45302e13f8b9bfee
    28. 28
      Bocanegra-Bernal, M. H. Hot Isostatic Pressing (HIP) Technology and Its Applications to Metals and Ceramics. J. Mater. Sci. 2004, 39 (21), 6399– 6420,  DOI: 10.1023/B:JMSC.0000044878.11441.90
      29
      Hot Isostatic Pressing (HIP) technology and its applications to metals and ceramics
      Bocanegra-Bernal, M. H.
      Journal of Materials Science (2004), 39 (21), 6399-6420CODEN: JMTSAS; ISSN:0022-2461. (Kluwer Academic Publishers)
      This review examines some of the components of this increasingly exploited technol. as well as the application of which will surely increase as a result of const. development in equipment design and extensive research in the field of ceramic and metal materials in general for the prodn. of fully dense and reliable parts. Newly developed high temp. HIP equipment can offer potential improvements to material properties relative to more conventional techniques as a possible soln. to the manuf. of ceramic and metal components for airframe and structural components where crit. and highly stressed applications are required. By the use the near net shape techniques, exotic materials can be used more cost effectively than machining from solid. Designers and manufacturers alike can make better products by introducing HIP to their prodn. route.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXosVyjtb4%253D&md5=5c89e8c43afa2e2308d4175cfca8e08f
    29. 29
      Radomir, I.; Geamăn, V.; Stoicănescu, M. Densification Mechanisms Made During Creep Techniques Applied to the Hot Isostatic Pressing. Procedia Soc. Behav Sci. 2012, 62, 779– 782,  DOI: 10.1016/j.sbspro.2012.09.131
      There is no corresponding record for this reference.
    30. 30
      Swinkels, F. B.; Wilkinson, D. S.; Arzt, E.; Ashby, M. F. Mechanisms of Hot-Isostatic Pressing. Acta Metall. 1983, 31 (11), 1829– 1840,  DOI: 10.1016/0001-6160(83)90129-3
      31
      Mechanisms of hot-isostatic pressing
      Swinkels, F. B.; Wilkinson, D. S.; Arzt, E.; Ashby, M. F.
      Acta Metallurgica (1983), 31 (11), 1829-40CODEN: AMETAR; ISSN:0001-6160.
      The hot-isostatic pressing of Pb, Sn, and polymethylmethacrylate [9011-14-7] powders was studied by using a rig enabling continuous measurement of d. The dominant mechanisms of densification were plastic yielding and power-low creep. Large discrepancies were found between the data and previous models for these mechanisms. Improved models, while still approx., include new phys. ideas and give a better description of the expts.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaL2cXhtFSkug%253D%253D&md5=d1546fc6027e74e70dcf6af283005643
    31. 31
      du Plessis, A.; Macdonald, E. Hot Isostatic Pressing in Metal Additive Manufacturing: X-Ray Tomography Reveals Details of Pore Closure. Addit. Manuf. 2020, 34, 101191,  DOI: 10.1016/J.ADDMA.2020.101191
      32
      Hot isostatic pressing in metal additive manufacturing: X-ray tomography reveals details of pore closure
      du Plessis, A.; Macdonald, E.
      Additive Manufacturing (2020), 34 (), 101191CODEN: AMDAD2; ISSN:2214-7810. (Elsevier B.V.)
      Hot isostatic pressing (HIP) of additively manufd. metals is a widely adopted and effective method to improve the d. and microstructure homogeneity within geometrically-complex metal structures fabricated with laser powder bed fusion (LPBF). The role of pores in the fatigue performance of additively manufd. metal parts is increasingly being recognized as a crit. factor and HIP post-processing is now heralded as a method to eliminate pores, esp. for high-criticality applications such as in the aerospace industry. In this work, X-ray tomog. was employed to provide insights into pore closure efficiency by HIP for an intentional and artificially-induced cavity as well as for a range of typical process-induced pores (lack of fusion, keyhole, contour pores, etc.) in coupon samples of Ti6Al4V. Subsequent heat treatments (annealing after HIP) in some cases resulted in internal pore reopening for previously closed internal pores as well as a new "blistering" effect obsd. for some near-surface pores, which the authors believe is reported for the first time. Implications of these results for quality control and HIP processing of LPBF parts are discussed. Finally, the utility of using HIP to consolidate intentionally-unmelted powder in order to improve prodn. rates of powder bed fusion has great potential and is preliminarily demonstrated.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFajsrbF&md5=ce3119b912d5e24e3d9e30b317de804f
    32. 32
      Loh, N. L.; Sia, K. Y. An Overview of Hot Isostatic Pressing. J. Mater. Process Technol. 1992, 30 (1), 45– 65,  DOI: 10.1016/0924-0136(92)90038-T
      There is no corresponding record for this reference.
    33. 33
      Sugata, S.; Saito, N.; Watanabe, A.; Watanabe, K.; Kim, J. D.; Kitagawa, K.; Suzuki, Y.; Honma, I. Quasi-Solid-State Lithium Batteries Using Bulk-Size Transparent Li7La3Zr2O12 Electrolytes. Solid State Ion 2018, 319, 285– 290,  DOI: 10.1016/j.ssi.2018.02.029
      There is no corresponding record for this reference.
    34. 34
      Huang, X.; Lu, Y.; Guo, H.; Song, Z.; Xiu, T.; Badding, M. E.; Wen, Z. None-Mother-Powder Method to Prepare Dense Li-Garnet Solid Electrolytes with High Critical Current Density. ACS Appl. Energy Mater. 2018, 1 (10), 5355– 5365,  DOI: 10.1021/acsaem.8b00976
      35
      None-Mother-Powder Method to Prepare Dense Li-Garnet Solid Electrolytes with High Critical Current Density
      Huang, Xiao; Lu, Yang; Guo, Haojie; Song, Zhen; Xiu, Tongping; Badding, Michael E.; Wen, Zhaoyin
      ACS Applied Energy Materials (2018), 1 (10), 5355-5365CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      Cubic Li-garnet Li7La3Zr2O12 (c-LLZO) is a promising Li+ ion conductor for applications as a ceramic solid electrolyte in next generation high safety Li batteries. The sintering temp. of c-LLZO is usually >1100°, where Li-loss is severe, esp. in conventional air ambient sintering method. Covering the green body with mother powder is often adopted for compensating the Li-loss. The mother powder having the same compn. as the green body cannot be repeatedly use, which raises the cost of the c-LLZO ceramics. A self-compensating Li-loss method without mother powder is proposed and studied to prep. high-quality c-LLZO ceramics. In this method, excess Li is added to c-LLZO green pellets to self-compensate Li-loss at high temp. The impact of different amts. of excess Li and crucible material, such as Pt, MgO, Al2O3, and ZrO2 was studied. With optimized such sintering method, Ta doped LLZO pellets with 10% excess Li can be well sintered inside low-cost MgO crucible without mother powder at 1250° for only 40 min and lab. scale prodn. is demonstrated. The ceramics have relative densities of ∼96%, conductivities of ∼6.47 × 10-4 S cm-1 and crit. c.d. of 1.15 mA cm-2 at 25°, which is fundamental for further researches on solid-state batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhs1Klt7bP&md5=e21cdaf524951aabd5a40620060e462d
    35. 35
      Zahiri, B.; Patra, A.; Kiggins, C.; Yong, A. X. B.; Ertekin, E.; Cook, J. B.; Braun, P. V. Revealing the Role of the Cathode-Electrolyte Interface on Solid-State Batteries. Nat. Mater. 2021, 20, 1392– 1400,  DOI: 10.1038/s41563-021-01016-0
      36
      Revealing the role of the cathode-electrolyte interface on solid-state batteries
      Zahiri, Beniamin; Patra, Arghya; Kiggins, Chadd; Yong, Adrian Xiao Bin; Ertekin, Elif; Cook, John B.; Braun, Paul V.
      Nature Materials (2021), 20 (10), 1392-1400CODEN: NMAACR; ISSN:1476-1122. (Nature Portfolio)
      Interfaces have crucial, but still poorly understood, roles in the performance of secondary solid-state batteries. Here, using crystallog. oriented and highly faceted thick cathodes, we directly assess the impact of cathode crystallog. and morphol. on the long-term performance of solid-state batteries. The controlled interface crystallog., area and microstructure of these cathodes enables an understanding of interface instabilities unknown (hidden) in conventional thin-film and composite solid-state electrodes. A generic and direct correlation between cell performance and interface stability is revealed for a variety of both lithium- and sodium-based cathodes and solid electrolytes. Our findings highlight that minimizing interfacial area, rather than its expansion as is the case in conventional composite cathodes, is key to both understanding the nature of interface instabilities and improving cell performance. Our findings also point to the use of dense and thick cathodes as a way of increasing the energy d. and stability of solid-state batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhtFCms7bF&md5=a1ec4bc8b65aea7d9804fc9f8c6b121e
    36. 36
      Hou, M.; Qu, T.; Zhang, Q.; Yaochun, Y.; Dai, Y.; Liang, F.; Okuma, G.; Hayashi, K. Investigation of the Stability of NASICON-Type Solid Electrolyte in Neutral-Alkaline Aqueous Solutions. Corros. Sci. 2020, 177, 109012,  DOI: 10.1016/j.corsci.2020.109012
      37
      Investigation of the stability of NASICON-type solid electrolyte in neutral-alkaline aqueous solutions
      Hou, Minjie; Qu, Tao; Zhang, Qingkai; Yao, Yaochun; Dai, Yongnian; Liang, Feng; Okuma, Gaku; Hayashi, Katsuro
      Corrosion Science (2020), 177 (), 109012CODEN: CRRSAA; ISSN:0010-938X. (Elsevier Ltd.)
      The effects of aq. solns. with different pH values on the ionic cond. of Na3Zr2Si2PO12 (NASICON) are studied at room temp. The ionic cond. of NASCION reduced severely in the soln. with pH value of 7. The AC impedance method was used to study the changes of the bulk, grain boundary, and cracking surface resistances of the sample under different conditions. The electrolyte morphol., cell parameters, Na+ site occupancy fraction, and microscopic strain change were obtained by SEM and XRD data refinement. According to above anal., the degrdn. processes of hydration, grain refinement, and surface cracking were obsd. gradually, the corresponding corrosion mechanism of NASICON in aq. solns. was explained.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXitVCltrrF&md5=ad00ecee37705201fbdac25a10cd0bdb
    37. 37
      van den Broek, J.; Rupp, J. L. M.; Afyon, S. Boosting the Electrochemical Performance of Li-Garnet Based All-Solid-State Batteries with Li4Ti5O12 Electrode: Routes to Cheap and Large Scale Ceramic Processing. J. Electroceram. 2017, 38 (2–4), 182– 188,  DOI: 10.1007/s10832-017-0079-9
      38
      Boosting the electrochemical performance of Li-garnet based all-solid-state batteries with Li4Ti5O12 electrode: Routes to cheap and large scale ceramic processing
      van den Broek, Jan; Rupp, Jennifer L. M.; Afyon, Semih
      Journal of Electroceramics (2017), 38 (2-4), 182-188CODEN: JOELFJ; ISSN:1385-3449. (Springer)
      All-solid-state batteries based on fast Li+ conducting solid electrolytes such as Li7La3Zr2O12 (LLZO) give perspective on safe, non-inflammable, and temp. tolerant energy storage. Despite the promise, ceramic processing of whole battery assemblies reaching close to theor. capacities and finding optimal strategies to process large-scale and low cost battery cells remains a challenge. Here, we tackle these issues and report on a solid-state battery cell composed of Li4Ti5O12 / c-Li6.25Al0.25La3Zr2O12 / metallic Li delivering capacities around 70-75 Ah/kg with reversible cycling at a rate of 8 A/kg (for 2.5-1.0 V, 95°C). A key aspect towards the increase in capacity and Li+ transfer at the solid electrolyte-electrode interface is found to be the intimate embedding of grains and their connectivity, which can be implemented by the isostatic pressing of cells during their prepn. We suggest that simple adaptation of ceramic processing, such as the applied pressure during processing, strongly alters the electrochem. performance by assuring good grain contacts at the electrolyte-electrode interface. Among the garnet-type all-solid-state ceramic battery assemblies in the field, considerably improved capacities and cycling properties are demonstrated for Li4Ti5O12 / c-Li6.25Al0.25La3Zr2O12 / metallic Li pressed cells, giving new perspectives on cheap ceramic processing and up-scalable garnet-based all-solid-state batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXlvFWrtro%253D&md5=6ac34f6d5945a246ac846f75122cdfeb
    38. 38
      Lu, J.; Li, Y. Conductivity and Stability of Li3/8Sr7/16–3x/2LaxZr1/4Ta3/4O3 Superionic Solid Electrolytes. Electrochim. Acta 2018, 282, 409– 415,  DOI: 10.1016/j.electacta.2018.06.085
      39
      Conductivity and stability of Li3/8Sr7/16-3x/2LaxZr1/4Ta3/4O3 superionic solid electrolytes
      Lu, Jiayao; Li, Ying
      Electrochimica Acta (2018), 282 (), 409-415CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)
      Oxide solid electrolytes Li3/8Sr7/16-3x/2LaxZr1/4Ta3/4O3 (LSLZT, x = 0, 0.025, 0.05) with different A-site vacancy were synthesized using conventional solid-state reaction procedure at 1300°. Approx. single-phase perovskite-type was obtained which was analyzed by x-ray diffraction. Also, scanning electron microscope, a.c. impedance spectroscopy and potentiostatic polarization measurement methods were adopted to study the microstructure, Li+ conductivities and electronic conductivities of the samples, resp. Among these samples, the optimal compn. of Li3/8Sr7/16-3x/2LaxZr1/4Ta3/4O3 (x = 0.025) was selected with bulk cond. of 1.26 × 10-3 S cm-1, total cond. of 3.30 × 10-4 S cm-1, electronic cond. of 6.60 × 10-9 S cm-1 at 30° and activation energy of 0.28 eV. Also, the cyclic voltammogram anal. indicated the stability of this solid electrolyte at voltages >1.3 V against metallic Li. The solid electrolyte as a separator in LiFePO4/Li half-cell showed good cycle performance that comprises 98.7% of original values at 0.2 C charge-discharge rates after 50 cycles.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtFCmurjK&md5=d8b5578abc149913e8add5fb48ff67fa
    39. 39
      Reinacher, J.; Berendts, S.; Janek, J. Preparation and Electrical Properties of Garnet-Type Li6BaLa2Ta2O12 Lithium Solid Electrolyte Thin Films Prepared by Pulsed Laser Deposition. Solid State Ion 2014, 258, 1– 7,  DOI: 10.1016/j.ssi.2014.01.046
      There is no corresponding record for this reference.
    40. 40
      Shin, R. H.; Son, S. I.; Han, Y. S.; Kim, Y. do; Kim, H. T.; Ryu, S. S.; Pan, W. Sintering Behavior of Garnet-Type Li7La3Zr2O12-Li3BO3 Composite Solid Electrolytes for All-Solid-State Lithium Batteries. Solid State Ion 2017, 301, 10– 14,  DOI: 10.1016/j.ssi.2017.01.005
      There is no corresponding record for this reference.
    41. 41
      Huang, L.; Wen, Z.; Wu, M.; Wu, X.; Liu, Y.; Wang, X. Electrochemical Properties of Li1.4Al0.4Ti1.6(PO4)3 Synthesized by a Co-Precipitation Method. J. Power Sources 2011, 196 (16), 6943– 6946,  DOI: 10.1016/j.jpowsour.2010.11.140
      42
      Electrochemical properties of Li1.4Al0.4Ti1.6(PO4)3 synthesized by a co-precipitation method
      Huang, Lezhi; Wen, Zhaoyin; Wu, Meifen; Wu, Xiangwei; Liu, Yu; Wang, Xiuyan
      Journal of Power Sources (2011), 196 (16), 6943-6946CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Sub-micron Li1.4Al0.4Ti1.6(PO4)3 (LATP) ceramic powder is synthesized by a co-pptn. method which can be applied for mass prodn. A pure Nasicon phase is confirmed by XRD and the primary particle size of the product is 200-500 nm. The sinterability of LATP is studied and the relative d. of 97% reached at a sintering temp. ≥900° for 6 h. The bulk Li ionic cond. of the sintered pellet is 2.19 × 10-3 S cm-1, and a total cond. of 1.83 × 10-4 S cm-1 is obtained.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXmvFyku7s%253D&md5=eefd37f74c45bc8190979804d04e704d
    42. 42
      He, M.; Cui, Z.; Han, F.; Guo, X. Construction of Conductive and Flexible Composite Cathodes for Room-Temperature Solid-State Lithium Batteries. J. Alloys Compd. 2018, 762, 157– 162,  DOI: 10.1016/j.jallcom.2018.05.255
      43
      Construction of conductive and flexible composite cathodes for room-temperature solid-state lithium batteries
      He, Minghui; Cui, Zhonghui; Han, Feng; Guo, Xiangxin
      Journal of Alloys and Compounds (2018), 762 (), 157-162CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
      Interfacial issues arising from the poor interface contact and poor interface stability between the stiff solid-state electrolytes (SSEs) and the electrodes have restricted the development of successful solid-state batteries (SSBs). Herein, we demonstrate that constructing flexible composite cathodes by introducing conductive frameworks consisting of succinonitrile and lithium salt significantly improves the contact performance and interface stability between garnet solid electrolyte and LiFePO4 cathode, enabling the resulted SSBs cycling steadily with high capacity even at room temp. The introduction of such flexible frameworks not only enables close contact between the cathode and the stiff SSE, but also bridges every electrode and electrolyte particles together forming interconnected three-dimensional ionic conductive paths, reducing the total resistance to one-half of the batteries without such frameworks. On the other hand, the network is flexible enough to accommodate the vol. change of LiFeO4 during cycling. These advantages endow that the SSBs of Li/SSE/LiFePO4 with the flexible composite cathodes demonstrate an initial discharge capacity of 149.8 mAh g-1 and the Coulombic efficiency of 99% after 100 cycles at 0.05 C under room temp. This method demonstrated here to integrate electrodes and stiff electrolytes by introducing flexible components will provides inspirations for people to construct high-performance room-temp. SSBs.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtVamtrbK&md5=46574b48a6e09888ba4aa4b7a8d6afdd
    43. 43
      Shen, L.; Yang, J.; Liu, G.; Avdeev, M.; Yao, X. High Ionic Conductivity and Dendrite-Resistant NASICON Solid Electrolyte for All-Solid-State Sodium Batteries. Mater. Today Energy 2021, 20, 100691,  DOI: 10.1016/j.mtener.2021.100691
      44
      High ionic conductivity and dendrite-resistant NASICON solid electrolyte for all-solid-state sodium batteries
      Shen, L.; Yang, J.; Liu, G.; Avdeev, M.; Yao, X.
      Materials Today Energy (2021), 20 (), 100691CODEN: MTEACH; ISSN:2468-6069. (Elsevier Ltd.)
      The low ionic cond. and poor dendrites suppression capability of Na3Zr2Si2PO12 solid electrolyte limit the practical application of all-solid-state sodium batteries. Herein, the optimized Na3.4Mg0.1Zr1.9Si2.2P0.8O12 electrolyte is obtained by simultaneously substituting the Zr4+ with Mg2+ and P5+ with Si4+ through solid-state reaction. The Na3.4Mg0.1Zr1.9Si2.2P0.8O12 electrolyte has superior room temp. ionic cond. of 3.6 x 10-3 S cm-1, which is 17 times higher than that of pristine Na3Zr2Si2PO122. No short circuit of the Na/Na3.4Mg0.1Zr1.9Si2.2P0.8O12/Na sym. battery is obsd. up to 2.0 mA cm-2, and the sym. battery displays stable sodium plating/stripping cycles for over 2000 h at 0.1 mA cm-2 and 300 h at 1.0 mA cm-2. The resultant Na3.4Mg0.1Zr1.9Si2.2P0.8O12 electrolyte is further employed in two all-solid-state sodium batteries. The Na3V2(PO4)3/Na3.4Mg0.1Zr1.9Si2.2P0.8O12/Na all-solid-state sodium battery maintains a discharge capacity of 93.3 mAh g-1 at 0.1C after 50 cycles, and the FeS2/Na3.4Mg0.1Zr1.9Si2.2P0.8O12/Na all-solid-state sodium battery delivers a discharge capacity of 173.1 mAh g-1 at 0.1C after 20 cycles, which are significantly enhanced compared with those based on pristine Na3Zr2Si2PO12 . This strategy provides an efficient method to prep. optimized NASICON solid electrolytes with high ionic cond. and excellent dendrites suppression capability and promotes the practical application of all-solid-state sodium batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXntFOltLg%253D&md5=69b4a1683b0593fd6ff0eddc739f005f
    44. 44
      Yang, J.; Huang, Z.; Zhang, P.; Liu, G.; Xu, X.; Yao, X. Titanium Dioxide Doping toward High-Lithium-Ion-Conducting Li1.5Al0.5Ge1.5(PO4)3 Glass-Ceramics for All-Solid-State Lithium Batteries. ACS Appl. Energy Mater. 2019, 2 (10), 7299– 7305,  DOI: 10.1021/acsaem.9b01268
      45
      Titanium Dioxide Doping toward High-Lithium-Ion-Conducting Li1.5Al0.5Ge1.5(PO4)3 Glass-Ceramics for All-Solid-State Lithium Batteries
      Yang, Jing; Huang, Zhen; Zhang, Peng; Liu, Gaozhan; Xu, Xiaoxiong; Yao, Xiayin
      ACS Applied Energy Materials (2019), 2 (10), 7299-7305CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      Developing solid electrolytes with high Li-ion cond. is crucial to realize high-performance all-solid-state Li batteries. The substitution of ions with larger ionic radius can enlarge the Li+ migration tunnels and therefore enhance the Li-ion cond. Ti4+ is employed to partially replace Ge4+ in Li2O-Al2O3-GeO2-P2O5 glass-ceramics electrolyte to improve its cond. The highest total Li-ion cond. of 1.07 × 10-3 S cm-1 at room temp. is obtained from Li1.5Al0.5Ge1.5(PO4)3-7.5% TiO2 sample sintered at 900° for 6 h. The bulk and grain boundary conductivities are 1.67 × 10-3 S cm-1 and 2.99 × 10-3 S cm-1, resp., which are superior than that of the pristine Li1.5Al0.5Ge1.5(PO4)3 counterpart. Both bulk and grain boundary conductivities of the sample have been significantly improved, which could be attributed to the increase of bottleneck sizes of the Li+ migration tunnels and the decrease of grain boundary area. All-solid-state Li batteries employing LiFePO4 as cathode and solid electrolyte as separator and ionic conductor are assembled. A reversible capacity of 132.3 mA-h g-1 is delivered after 200 cycles under a c.d. of 0.1 C with a capacity retention ratio of 91.1%, showing the solid electrolyte is ideal for all-solid-state Li-battery applications.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhslKgtbbF&md5=3975d93228925f489174f1af99bb6a44
    45. 45
      Uchida, Y.; Hasegawa, G.; Shima, K.; Inada, M.; Enomoto, N.; Akamatsu, H.; Hayashi, K. Insights into Sodium Ion Transfer at the Na/NASICON Interface Improved by Uniaxial Compression. ACS Appl. Energy Mater. 2019, 2 (4), 2913– 2920,  DOI: 10.1021/acsaem.9b00250
      46
      Insights into Sodium Ion Transfer at the Na/NASICON Interface Improved by Uniaxial Compression
      Uchida, Yasuhiro; Hasegawa, George; Shima, Kazunari; Inada, Miki; Enomoto, Naoya; Akamatsu, Hirofumi; Hayashi, Katsuro
      ACS Applied Energy Materials (2019), 2 (4), 2913-2920CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      A robust ceramic solid electrolyte with high ionic cond. is a key component for all-solid-state batteries (ASSBs). In terms of the demand for high-energy-d. storage, researchers have been tackling various challenges to use metal anodes, where a fundamental understanding on the metal/solid electrolyte interface is of particular importance. The Na+ superionic conductor, so-called NASICON, has high potential for application to ASSBs with a Na anode due to its high Na+ ion cond. at room temp., which has, however, faced a daunting issue of the significantly large interfacial resistance between Na and NASICON. In this work, we have successfully reduced the interfacial resistance as low as 14 Ω cm2 at room temp. by a simple mech. compression of a Na/NASICON assembly. We also demonstrate a fundamental study of the Na/NASICON interface in comparison with the Na/β''-alumina counterpart by means of the electrochem. impedance technique, which elucidates a stark difference between the activation energies for interfacial charge transfer: ∼0.6 eV for Na/NASICON and ∼0.3 eV for Na/β''-alumina. This result suggests the formation of a Na+-conductive interphase layer in pressing Na metal on the NASICON surface at room temp.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXmsFegur0%253D&md5=bab5654226d744c8ea156b6f611f660a
    46. 46
      Patra, S.; Narayanasamy, J.; Chakravarty, S.; Murugan, R. Higher Critical Current Density in Lithium Garnets at Room Temperature by Incorporation of an Li4SiO4-Related Glassy Phase and Hot Isostatic Pressing. ACS Appl. Energy Mater. 2020, 3 (3), 2737– 2743,  DOI: 10.1021/acsaem.9b02400
      47
      Higher Critical Current Density in Lithium Garnets at Room Temperature by Incorporation of an Li4SiO4-Related Glassy Phase and Hot Isostatic Pressing
      Patra, Srabani; Narayanasamy, Janani; Chakravarty, Sujoy; Murugan, Ramaswamy
      ACS Applied Energy Materials (2020), 3 (3), 2737-2743CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      Inorg. solid electrolytes have achieved an important position in modern battery technol. A garnet-structured inorg. fast lithium-ion conductor is an exceptional solid electrolyte candidate due to its numerous advantages. However, on repeated cycling at high current densities, the growth of lithium dendrites through grain boundaries turns out to be a major impediment to the application of metallic lithium as an anode. This work shows the application of a hot isostatic pressing (HIP) treatment on an Li4SiO4 (LS)-added lithium garnet solid electrolyte, Li6.16Al0.28Zr2La3O12 (LLZA), resulting in a dense microstructure of the electrolyte along with LS-related glassy phase formation at the grain boundaries. This approach is substantiated to enhance the electrochem. performance of an Li|LLZA + LS(H)|Li sym. cell at room temp. by improving the interfacial contact, effectively suppressing lithium dendrite penetration, and attainment of a higher crit. c.d. (CCD) of 0.40 mA/cm2. The cycling performance achieved here represents a significant advancement toward demonstrating plating/stripping rates in lithium garnets with relevance to practical applications.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXjsV2ls70%253D&md5=0a4492dc4bc7b8c794d04b7c2cf3bd57
    47. 47
      Wu, J. F.; Pang, W. K.; Peterson, V. K.; Wei, L.; Guo, X. Garnet-Type Fast Li-Ion Conductors with High Ionic Conductivities for All-Solid-State Batteries. ACS Appl. Mater. Interfaces 2017, 9 (14), 12461– 12468,  DOI: 10.1021/acsami.7b00614
      48
      Garnet-Type Fast Li-Ion Conductors with High Ionic Conductivities for All-Solid-State Batteries
      Wu, Jian-Fang; Pang, Wei Kong; Peterson, Vanessa K.; Wei, Lu; Guo, Xin
      ACS Applied Materials & Interfaces (2017), 9 (14), 12461-12468CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      All-solid-state Li-ion batteries with metallic Li anodes and solid electrolytes could offer superior energy d. and safety over conventional Li-ion batteries. However, compared with org. liq. electrolytes, the low cond. of solid electrolytes and large electrolyte/electrode interfacial resistance impede their practical application. Garnet-type Li-ion conducting oxides are among the most promising electrolytes for all-solid-state Li-ion batteries. In this work, the large-radius Rb is doped at the La site of cubic Li6.10Ga0.30La3Zr2O12 to enhance the Li-ion cond. for the first time. The Li6.20Ga0.30La2.95Rb0.05Zr2O12 electrolyte exhibits a Li-ion cond. of 1.62 mS cm-1 at room temp., which is the highest cond. reported until now. All-solid-state Li-ion batteries are constructed from the electrolyte, metallic Li anode, and LiFePO4 active cathode. The addn. of Li(CF3SO2)2N electrolytic salt in the cathode effectively reduces the interfacial resistance, allowing for a high initial discharge capacity of 152 mAh/g and good cycling stability with 110 mAh/g retained after 20 cycles at a charge/discharge rate of 0.05 C at 60 °C.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXkvVyjsbo%253D&md5=5011c9a9292a84a6255d839ce9c53777
    48. 48
      Cheng, E. J.; Kimura, T.; Shoji, M.; Ueda, H.; Munakata, H.; Kanamura, K. Ceramic-Based Flexible Sheet Electrolyte for Li Batteries. ACS Appl. Mater. Interfaces 2020, 12 (9), 10382– 10388,  DOI: 10.1021/acsami.9b21251
      49
      Ceramic-Based Flexible Sheet Electrolyte for Li Batteries
      Cheng, Eric Jianfeng; Kimura, Takeshi; Shoji, Mao; Ueda, Hiroshi; Munakata, Hirokazu; Kanamura, Kiyoshi
      ACS Applied Materials & Interfaces (2020), 12 (9), 10382-10388CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      The increasing demand for high-energy-d. batteries stimulated the revival of research interest in Li-metal batteries. The garnet-type ceramic Li7La3Zr2O12 (LLZO) is one of the few solid-state fast-ion conductors that are stable against Li metal. However, the densification of LLZO powders usually requires high sintering temps. (e.g., 1200°C), which likely result in Li loss and various side reactions. From an engineering point of view, high-temp. sintering of thin LLZO electrolytes (brittle) at a large scale is difficult. Moreover, the high interfacial resistance between the solid LLZO electrolytes and electrodes is a notorious problem. Here, we report a practical synthesis of a flexible composite Al-doped LLZO (Al-LLZO) sheet electrolyte (75μm in thickness), which can be mass-produced at room temp. This ceramic-based flexible sheet electrolyte enables Li-metal batteries to operate at both 60 and 30°C, demonstrating its potential application for developing practical Li-metal batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXit1elur0%253D&md5=856f6d8150a056c14da23140b05dd7bc
    49. 49
      Huang, X.; Lu, Y.; Jin, J.; Gu, S.; Xiu, T.; Song, Z.; Badding, M. E.; Wen, Z. Method Using Water-Based Solvent to Prepare Li7La3Zr2O12 Solid Electrolytes. ACS Appl. Mater. Interfaces 2018, 10 (20), 17147– 17155,  DOI: 10.1021/acsami.8b01961
      50
      Method Using Water-Based Solvent to Prepare Li7La3Zr2O12 Solid Electrolytes
      Huang, Xiao; Lu, Yang; Jin, Jun; Gu, Sui; Xiu, Tongping; Song, Zhen; Badding, Michael E.; Wen, Zhaoyin
      ACS Applied Materials & Interfaces (2018), 10 (20), 17147-17155CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Li-garnet Li7La3Zr2O12 (LLZO) is a promising candidate of solid electrolytes for high-safety solid-state Li+ ion batteries. However, because of its high reactivity to water, the prepn. of LLZO powders and ceramics is not easy for large-scale amts. Herein, a method applying water-based solvent is proposed to demonstrate a possible soln. Ta-doped LLZO, i.e., Li6.4La3Zr1.4Ta0.6O12 (LLZTO), and its LLZTO/MgO composite ceramics are made by attrition milling, followed by a spray-drying process using water-based slurries. The impacts of parameters of the method on the structure and properties of green and sintered pellets are studied. A relative d. of ∼95%, a Li-ion cond. of ∼3.5 × 10-4 S/cm, and uniform grain size LLZTO/MgO garnet composite ceramics are obtained with an attrition-milled LLZTO/MgO slurry that contains 40 wt. % solids and 2 wt. % polyvinyl alc. binder. Li-sulfur batteries based on these ceramics are fabricated and work under 25° for 20 cycles with a Coulombic efficiency of 100%. This research demonstrates a promising mass prodn. method for the prepn. of Li-garnet ceramics.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXosVeks78%253D&md5=04d16f64552848b31c1866b8f8812478
    50. 50
      Yu, S.; Mertens, A.; Tempel, H.; Schierholz, R.; Kungl, H.; Eichel, R. A. Monolithic All-Phosphate Solid-State Lithium-Ion Battery with Improved Interfacial Compatibility. ACS Appl. Mater. Interfaces 2018, 10 (26), 22264– 22277,  DOI: 10.1021/acsami.8b05902
      51
      Monolithic All-Phosphate Solid-State Lithium-Ion Battery with Improved Interfacial Compatibility
      Yu, Shicheng; Mertens, Andreas; Tempel, Hermann; Schierholz, Roland; Kungl, Hans; Eichel, Ruediger-A.
      ACS Applied Materials & Interfaces (2018), 10 (26), 22264-22277CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      High interfacial resistance between solid electrolyte and electrode of ceramic all-solid-state batteries is a major reason for the reduced performance of these batteries. A solid-state battery using a monolithic all-phosphate concept based on screen printed thick LiTi2(PO4)3 anode and Li3V2(PO4)3 cathode composite layers on a densely sintered Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte has been realized with competitive cycling performance. The choice of materials was primarily based on the (electro-)chem. and mech. matching of the components instead of solely focusing on high-performance of individual components. Thus, the battery used a phosphate backbone in combination with tailored morphol. of the electrode materials to ensure good interfacial matching for a durable mech. stability. The operating voltage range of the active materials matches with the intrinsic electrochem. window of the electrolyte which resulted in high electrochem. stability. A highly competitive discharge capacity of 63.5 mAh/g at 0.39 C after 500 cycles, corresponding to 84% of the initial discharge capacity, was achieved. The anal. of interfacial charge transfer kinetics confirmed the structural and elec. properties of the electrodes and their interfaces with the electrolyte, as evidenced by the excellent cycling performance of the all-phosphate solid-state battery. These interfaces have been studied via impedance anal. with subsequent distribution of relaxation times anal. The prepd. solid-state battery could be processed and operated in air atm. owing to the low O sensitivity of the phosphate materials. The anal. of electrolyte/electrode interfaces after cycling demonstrates that the interfaces remained stable during cycling.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhtFeis7zM&md5=d38d63d39154993761b8bce8a8725cb9
    51. 51
      Itaya, A.; Yamamoto, K.; Inada, R. Sintering Temperature Dependency on Sodium-Ion Conductivity for Na2Zn2TeO6 Solid Electrolyte. Int. J. Appl. Ceram Technol. 2021, 18 (6), 2085– 2090,  DOI: 10.1111/ijac.13847
      52
      Sintering temperature dependency on sodium-ion conductivity for Na2Zn2TeO6 solid electrolyte
      Itaya, Akihiro; Yamamoto, Kazuki; Inada, Ryoji
      International Journal of Applied Ceramic Technology (2021), 18 (6), 2085-2090CODEN: IJACCP; ISSN:1546-542X. (Wiley-Blackwell)
      We investigated the sintering temp. dependency on the properties of Na2Zn2TeO6 (NZTO) solid electrolyte synthesized via a conventional solid-state reaction method. Sintering temp. of calcined NZTO powder, which was obtained by the calcination of precursor at 850°C, was changed in the range from 650 to 850°C. X-ray diffraction anal. showed that P2-type layered NZTO phase was formed in all sintered samples without forming any secondary phases. The relative densities of sintered NZTO samples were approx. 83%-85% for the samples sintered at 700°C or higher. The all sintered samples showed sodium-ion cond. above 10-4 S cm-1 at room temp. and the highest cond. of 4.0 x 10-4 S cm-1 in the sample sintered at 750°C. The sintering temp. to obtain the highest room temp. cond. is 100°C lower than that used in previous works. Such low sintering temp. compared to other Na-based oxide solid electrolytes could be useful for co-sintering with electrode active materials for fabrication of all-solid-state sodium-ion battery.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhslCjtrnJ&md5=931ae75b3e19f831b40ac39c6a6b1bbf
    52. 52
      Yu, S.; Schmohl, S.; Liu, Z.; Hoffmeyer, M.; Schön, N.; Hausen, F.; Tempel, H.; Kungl, H.; Wiemhöfer, H. D.; Eichel, R. A. Insights into a Layered Hybrid Solid Electrolyte and Its Application in Long Lifespan High-Voltage All-Solid-State Lithium Batteries. J. Mater. Chem. A Mater. 2019, 7 (8), 3882– 3894,  DOI: 10.1039/C8TA11259B
      53
      Insights into a layered hybrid solid electrolyte and its application in long lifespan high-voltage all-solid-state lithium batteries
      Yu, Shicheng; Schmohl, Sebastian; Liu, Zigeng; Hoffmeyer, Marija; Schoen, Nino; Hausen, Florian; Tempel, Hermann; Kungl, Hans; Wiemhoefer, Hans-D.; Eichel, Ruediger-A.
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (8), 3882-3894CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      Direct integration of a metallic lithium anode with the ceramic Li1.3Al0.3Ti1.7(PO4)3 (LATP) electrolyte into an all-solid-state battery is highly challenging due to their chem. and electrochem. incompatibility. Herein, a layered hybrid solid electrolyte is designed by coating the ceramic LATP electrolyte with a protective polymer electrolyte, polyphosphazene/PVDF-HFP/LiBOB. This polymer electrolyte comprises highly Li+ conductive polyphosphazene and mech. stable PVDF-HFP as the polymer matrix, and the mobile lithium ions in the polymer layer are supplied by LiBOB. Equipped with both polymer and ceramic components, the hybrid electrolyte possesses favorable features, such as a flexible surface, high ionic cond., high chem. stability against lithium and wide electrochem. stability window (4.7 V), which all to help realize its application in all-solid-state lithium batteries. The prepd. all-solid-state battery with a metallic lithium anode and high-voltage Li3V2(PO4)3/CNT cathode shows high capacity and excellent cycling performance with negligible capacity loss over 500 cycles at 50 °C. Furthermore, the anal. of the hybrid solid electrolyte after long-term cycling demonstrates outstanding electrode/electrolyte interfacial stability. This study suggests that use of solid org.-inorg. hybrid electrolyte is a promising approach to circumvent the mech., chem. and electrochem. limitations at the interface of electrodes and ceramic electrolyte for all-solid-state batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtlWrsL8%253D&md5=a9714de5b1bb38a8ae4f40cf29d1d93d
    53. 53
      Zhang, Q.; Liang, F.; Qu, T.; Yao, Y.; Ma, W.; Yang, B.; Dai, Y. Effect on Ionic Conductivity of Na3+xZr2-xMxSi2PO12 (M = Y, La) by Doping Rare-Earth Elements. In IOP Conference Series: Materials Science and Engineering; Institute of Physics Publishing, 2018; Vol. 423.  DOI: 10.1088/1757-899X/423/1/012122 .
      There is no corresponding record for this reference.
    54. 54
      Kim, M.; Kim, G.; Lee, H. Tri-Doping of Sol–Gel Synthesized Garnet-Type Oxide Solid-State Electrolyte. Micromachines (Basel) 2021, 12 (2), 134,  DOI: 10.3390/mi12020134
      There is no corresponding record for this reference.
    55. 55
      Yang, J.; Wan, H. L.; Zhang, Z. H.; Liu, G. Z.; Xu, X. X.; Hu, Y. S.; Yao, X. Y. NASICON-Structured Na3.1Zr1.95Mg0.05Si2PO12 Solid Electrolyte for Solid-State Sodium Batteries. Rare Metals 2018, 37 (6), 480– 487,  DOI: 10.1007/s12598-018-1020-3
      56
      NASICON-structured Na3.1Zr1.95Mg0.05Si2PO12 solid electrolyte for solid-state sodium batteries
      Yang, Jing; Wan, Hong-Li; Zhang, Zhi-Hua; Liu, Gao-Zhan; Xu, Xiao-Xiong; Hu, Yong-Sheng; Yao, Xia-Yin
      Rare Metals (Beijing, China) (2018), 37 (6), 480-487CODEN: RARME8; ISSN:1001-0521. (Journal Publishing Center of University of Science and Technology Beijing)
      Using stable inorg. solid electrolyte to replace org. liq. electrolyte could significantly reduce potential safety risks of rechargeable batteries. Na-superionic conductor (NASICON)-structured solid electrolyte is one of the most promising sodium solid electrolytes and can be employed in solid-state sodium batteries. In this work, a NASICON-structured solid electrolyte Na3.1Zr1.95Mg0.05Si2PO12 was synthesized through a facile solid-state reaction, yielding high sodium-ionic cond. of 1.33 × 10-3 S·cm-1 at room temp. The results indicate that Mg2+ is a suitable and economical substitution ion to replace Zr4+, and this synthesis route can be scaled up for powder prepn. with low cost. In addn. to electrolyte material prepn., solid-state batteries with Na3.1Zr1.95Mg0.05Si2PO12 as electrolyte were assembled. A specific capacity of 57.9 mAh·g-1 is maintained after 100 cycles under a c.d. of 0.5C rate at room temp. The favorable cycling performance of the solid-state battery suggests that Na3.1Zr1.95Mg0.05Si2PO12 is an ideal electrolyte candidate for solid-state sodium batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXntVClsbo%253D&md5=ac3550de9af0bfbacc043bcfd78c67e2
    56. 56
      Afyon, S.; Kravchyk, K. v.; Wang, S.; van den Broek, J.; Hänsel, C.; Kovalenko, M. v.; Rupp, J. L. M. Building Better All-Solid-State Batteries with Li-Garnet Solid Electrolytes and Metalloid Anodes. J. Mater. Chem. A Mater. 2019, 7 (37), 21299– 21308,  DOI: 10.1039/C9TA04999A
      58
      Building better all-solid-state batteries with Li-garnet solid electrolytes and metalloid anodes
      Afyon, Semih; Kravchyk, Kostiantyn V.; Wang, Shutao; van den Broek, Jan; Hansel, Christian; Kovalenko, Maksym V.; Rupp, Jennifer L. M.
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2019), 7 (37), 21299-21308CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      All-solid-state batteries provide new opportunities to realize safe, non-flammable, and temp.-tolerant energy storage and display a huge potential to be the core of future energy storage devices, esp. in applications where energy d. is key to the technol. Garnet-type solid-state electrolytes based on cubic Li7La3Zr2O12 possess one of the highest Li+ conductivities, a wider electrochem. stability window compared to liq. electrolytes, and exceptional chem. and thermal stabilities among various solid electrolytes. Most of the first reports, however, employ lithium metal as the anode with unavoidable Li-dendrite formation through polycryst. Li-garnet electrolytes at current densities above 0.5 mA cm-2. Accordingly, alternative materials and processing strategies for anodes or interlayers are inherently needed for high currents and fast charging for Li-garnet-type battery integration. Here, we demonstrate, through the use of a composite anode based on antimony nanocrystals, that metalloids offer high and stable storage capacities of up to 330 mA h g-1 for Li-garnet all-solid-state batteries at reasonably high current densities (e.g. 240 mA g-1) at 95 °C. The results are also compared towards std. liq. type electrolytes and reveal high coulombic efficiencies and improved cycle stability for the solid-state cell design. Guidelines and aspects to process alternative materials and impact the interface design towards fast lithium charge transfer between the metalloid and the Li-garnet electrolyte are formulated. The architecture and scalable processing of metalloid-based batteries are obvious advantages of this work, opening a promising avenue to avoid Li-dendrite formation at high current loads in garnet-type all-solid-state rechargeable batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1yltbnF&md5=d45b2d12ad0eb478c3dcbd44fadc0678
    57. 57
      Dixit, M. B.; Verma, A.; Zaman, W.; Zhong, X.; Kenesei, P.; Park, J. S.; Almer, J.; Mukherjee, P. P.; Hatzell, K. B. Synchrotron Imaging of Pore Formation in Li Metal Solid-State Batteries Aided by Machine Learning. ACS Appl. Energy Mater. 2020, 3 (10), 9534– 9542,  DOI: 10.1021/acsaem.0c02053
      59
      Synchrotron Imaging of Pore Formation in Li Metal Solid-State Batteries Aided by Machine Learning
      Dixit, Marm B.; Verma, Ankit; Zaman, Wahid; Zhong, Xinlin; Kenesei, Peter; Park, Jun Sang; Almer, Jonathan; Mukherjee, Partha P.; Hatzell, Kelsey B.
      ACS Applied Energy Materials (2020), 3 (10), 9534-9542CODEN: AAEMCQ; ISSN:2574-0962. (American Chemical Society)
      High-rate capable, reversible lithium metal anodes are necessary for next generation energy storage systems. In situ tomog. of Li|LLZO|Li cells is carried out to track morphol. transformations in Li metal electrodes. Machine learning enables tracking the lithium metal morphol. during galvanostatic cycling. Nonuniform lithium electrode kinetics are obsd. at both electrodes during cycling. Hot spots in lithium metal are correlated with microstructural anisotropy in LLZO. Mesoscale modeling reveals that regions with lower effective properties (transport and mech.) are nuclei for failure. Advanced visualization combined with electrochem. represents an important pathway toward resolving non-equil. effects that limit rate capabilities of solid-state batteries.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhvVeru7nO&md5=9f0be51917aeebd9cb303e6881489a47
    58. 58
      Vishnugopi, B. S.; Dixit, M. B.; Hao, F.; Shyam, B.; Cook, J. B.; Hatzell, K. B.; Mukherjee, P. P. Mesoscale Interrogation Reveals Mechanistic Origins of Lithium Filaments along Grain Boundaries in Inorganic Solid Electrolytes. Adv. Energy Mater. 2022, 12 (3), 2102825,  DOI: 10.1002/aenm.202102825
      60
      Mesoscale Interrogation Reveals Mechanistic Origins of Lithium Filaments along Grain Boundaries in Inorganic Solid Electrolytes
      Vishnugopi, Bairav S.; Dixit, Marm B.; Hao, Feng; Shyam, Badri; Cook, John B.; Hatzell, Kelsey B.; Mukherjee, Partha P.
      Advanced Energy Materials (2022), 12 (3), 2102825CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)
      Solid-state batteries (SSBs), utilizing a lithium metal anode, promise to deliver enhanced energy and power densities compared to conventional lithium-ion batteries. Penetration of lithium filaments through the solid-state electrolytes (SSEs) during electrodeposition poses major constraints on the safety and rate performance of SSBs. While microstructural attributes, esp. grain boundaries (GBs) within the SSEs are considered preferential metal propagation pathways, the underlying mechanisms are not fully understood yet. Here, a comprehensive insight is presented into the mechanistic interactions at the mesoscale including the electrochem.-mech. response of the GB-electrode junction and competing ion transport dynamics in the SSE. Depending on the GB transport characteristics, a highly non-uniform electrodeposition morphol. consisting of either cavities or protrusions at the GB-electrode interface is identified. Mech. stability anal. reveals localized strain ramps in the GB regions that can lead to brittle fracture of the SSE. For ionically less conductive GBs compared to the grains, a crack formation and void filling mechanism, triggered by the heterogeneous nature of electrochem.-mech. interactions is delineated at the GB-electrode junction. Concurrently, in situ X-ray tomog. of pristine and failed Li7La3Zr2O12 (LLZO) SSE samples confirm the presence of filamentous lithium penetration and validity of the proposed mesoscale failure mechanisms.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXislCjur7J&md5=9b10899811f52b85c48a0ee60028e65c
    59. 59
      Tenhaeff, W. E.; Rangasamy, E.; Wang, Y.; Sokolov, A. P.; Sakamoto, J.; Dudney, N. J.; Tenhaeff, W. E.; Rangasamy, E.; Wang, Y.; Sokolov, A. P.; Wolfenstine, J. Resolving the Grain Boundary and Lattice Impedance of Hot Pressed Li7La3Zr2O12 Garnet Electrolytes. ChemSusChem 2014, 1, 375– 378,  DOI: 10.1002/celc.201300022
      There is no corresponding record for this reference.
    60. 60
      Yu, S.; Siegel, D. J. Grain Boundary Softening: A Potential Mechanism for Lithium Metal Penetration through Stiff Solid Electrolytes. ACS Appl. Mater. Interfaces 2018, 10, 38151– 38158,  DOI: 10.1021/acsami.8b17223
      62
      Grain Boundary Softening: A Potential Mechanism for Lithium Metal Penetration through Stiff Solid Electrolytes
      Yu, Seungho; Siegel, Donald J.
      ACS Applied Materials & Interfaces (2018), 10 (44), 38151-38158CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Models based on linear elasticity suggest that a solid electrolyte with a high shear modulus will suppress dendrite formation in batteries that use metallic lithium as the neg. electrode. Nevertheless, recent expts. find that lithium can penetrate stiff solid electrolytes through microstructural features, such as grain boundaries. This failure mode emerges even in cases where the electrolyte has an av. shear modulus that is an order of magnitude larger than that of Li. Adopting the solid-electrolyte Li7La3Zr2O12 (LLZO) as a prototype, significant softening in elastic properties occurs in nanoscale regions near grain boundaries. Mol. dynamics simulations performed on tilt and twist boundaries reveal that the grain boundary shear modulus is up to 50% smaller than in bulk regions. Probably inhomogeneities in elastic properties arising from microstructural features provide a mechanism by which soft lithium can penetrate ostensibly stiff solid electrolytes.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvFSrtrvK&md5=a4bc1fab4aac1040157f1c12c4e0c44a
    61. 61
      Cheng, L.; Wu, C. H.; Jarry, A.; Chen, W.; Ye, Y.; Zhu, J.; Kostecki, R.; Persson, K.; Guo, J.; Salmeron, M.; Chen, G.; Doeff, M. Interrelationships among Grain Size, Surface Composition, Air Stability, and Interfacial Resistance of Al-Substituted Li7La3Zr2O12 Solid Electrolytes. ACS Appl. Mater. Interfaces 2015, 7 (32), 17649– 17655,  DOI: 10.1021/acsami.5b02528
      63
      Interrelationships among grain size, surface compn., air stability, and interfacial resistance of al-substituted Li7La3Zr2O12 solid electrolytes
      Cheng, Lei; Wu, Cheng Hao; Jarry, Angelique; Chen, Wei; Ye, Yifan; Zhu, Junfa; Kostecki, Robert; Persson, Kristin; Guo, Jinghua; Salmeron, Miquel; Chen, Guoying; Doeff, Marca
      ACS Applied Materials & Interfaces (2015), 7 (32), 17649-17655CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      The interfacial resistances of sym. lithium cells contg. Al-substituted Li7La3Zr2O12 (LLZO) solid electrolytes are sensitive to their microstructures and histories of exposure to air. Air exposure of LLZO samples with large grain sizes (∼150 μm) results in dramatically increased interfacial impedances in cells contg. them, compared to those with pristine large-grained samples. In contrast, a much smaller difference is seen between cells with small-grained (∼20 μm) pristine and air-exposed LLZO samples. A combination of soft X-ray absorption (sXAS) and Raman spectroscopy, with probing depths ranging from nanometer to micrometer scales, revealed that the small-grained LLZO pellets are more air-stable than large-grained ones, forming far less surface Li2CO3 under both short- and long-term exposure conditions. Surface sensitive XPS indicates that the better chem. stability of the small-grained LLZO is related to differences in the distribution of Al and Li at sample surfaces. D. functional theory calcns. show that LLZO can react via two different pathways to form Li2CO3. The first, more rapid, pathway involves a reaction with moisture in air to form LiOH, which subsequently absorbs CO2 to form Li2CO3. The second, slower, pathway involves direct reaction with CO2 and is favored when surface lithium contents are lower, as with the small-grained samples. These observations have important implications for the operation of solid-state lithium batteries contg. LLZO because the results suggest that the interfacial impedances of these devices is critically dependent upon specific characteristics of the solid electrolyte and how it is prepd.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXht1SgsbnE&md5=19b8095509b3758796891f19d9e07842
    62. 62
      Sharafi, A.; Haslam, C. G.; Kerns, R. D.; Wolfenstine, J.; Sakamoto, J. Controlling and Correlating the Effect of Grain Size with the Mechanical and Electrochemical Properties of Li7La3Zr2O12 Solid-State Electrolyte. J. Mater. Chem. A Mater. 2017, 5 (40), 21491– 21504,  DOI: 10.1039/C7TA06790A
      64
      Controlling and correlating the effect of grain size with the mechanical and electrochemical properties of Li7La3Zr2O12 solid-state electrolyte
      Sharafi, Asma; Haslam, Catherine G.; Kerns, Robert D.; Wolfenstine, Jeff; Sakamoto, Jeff
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2017), 5 (40), 21491-21504CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      Li7La3Zr2O12 (LLZO) solid-state electrolyte is garnering interest due to its potential to enable solid-state batteries (SSBs) using metallic Li anodes. However, Li metal propagates along LLZO grain boundaries at high Li plating current densities (above the crit. c.d., CCD). In the present study, we examd. whether microstructural aspects, such as grain size, could influence mech. and electrochem. properties thereby affecting the CCD. A unique densification technique (heating between 1100 and 1300 °C) was used to control grain size. Electron backscatter diffraction detd. that the grain size and the misorientation angle varied from 5 to 600 μm and 20 to 40°, resp. Vickers indentation was used to characterize the mech. properties and revealed that hardness decreased (9.9-6.8 GPa) with increasing grain size, but the fracture toughness was invariant (0.6 MPa m-1/2) at grain sizes ≥40 μm. DC and AC techniques were used to measure and correlate the CCD with grain size and showed that the CCD increased with increasing grain size achieving a max. of 0.6 mA cm-2. We believe the implications of this work could be far-reaching in that they represent a significant step towards understanding the mechanism(s) that control the stability of the Li-LLZO interface and a rational approach to increase the CCD in SSBs.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhs1Sksb%252FP&md5=eccb1f1d8cfb3d13b2237d27793aa772
    63. 63
      Shen, F.; Dixit, M.; Xiao, X.; Hatzell, K. The Effect of Pore Connectivity on Li Dendrite Propagation Within LLZO Electrolytes Observed with Synchrotron X-Ray Tomography. ACS Energy Lett. 2018, 3, 1056– 1061,  DOI: 10.1021/acsenergylett.8b00249
      65
      Effect of Pore Connectivity on Li Dendrite Propagation within LLZO Electrolytes Observed with Synchrotron X-ray Tomography
      Shen, Fengyu; Dixit, Marm B.; Xiao, Xianghui; Hatzell, Kelsey B.
      ACS Energy Letters (2018), 3 (4), 1056-1061CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
      Li7La3Zr2O12 (LLZO) is a garnet-type material that demonstrates promising characteristics for all-solid-state battery applications due to its high Li-ion cond. and its compatibility with Li metal. The primary limitation of LLZO is the propensity for short-circuiting at low current densities. Microstructure features such as grain boundaries, pore character, and d. all contribute to this shorting phenomenon. Toward the goal of understanding processing-structure relations for practical design of solid electrolytes, this study tracks structural transformations in solid electrolytes processed at 3 different temps. (1050, 1100, and 1150°) using synchrotron x-ray tomog. A subvolume of 300 μm3 captures the heterogeneity of the solid electrolyte microstructure while minimizing the computational intensity assocd. with 3D reconstructions. While the porosity decreases with increasing temp., the underlying connectivity of the pore region increases. Solid electrolytes with interconnected pores short circuit at lower crit. current densities than samples with less connected pores.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXmslyht7g%253D&md5=c0581bcf5ffa883e403c254e027e0006
    64. 64
      Cooper, C.; Sutorik, A. C.; Wright, J.; Luoto, E. A.; Gilde, G.; Wolfenstine, J. Mechanical Properties of Hot Isostatically Pressed Li0.35La0.55TiO3. In Advanced Engineering Materials; Wiley-VCH Verlag, 2014; Vol. 16, pp 755– 759.  DOI: 10.1002/adem.201400071 .
      There is no corresponding record for this reference.
    65. 65
      Dumon, A.; Huang, M.; Shen, Y.; Nan, C. W. High Li Ion Conductivity in Strontium Doped Li7La3Zr2O12 Garnet. Solid State Ion 2013, 243, 36– 41,  DOI: 10.1016/j.ssi.2013.04.016
      67
      High Li ion conductivity in strontium doped Li7La3Zr2O12 garnet
      Dumon, Alexandre; Huang, Mian; Shen, Yang; Nan, Ce-Wen
      Solid State Ionics (2013), 243 (), 36-41CODEN: SSIOD3; ISSN:0167-2738. (Elsevier B.V.)
      Strontium doped lithium ion garnets Li7La3Zr2O12 (LLZ) with 0.9 wt% to 8.4 wt% content of added Sr were synthesized via conventional solid-state reaction. X-ray diffraction patterns confirmed the cubic garnet structure of the sintered samples. A small amt. of strontium was substituted to lanthanum in LLZ lattice. Further anal. showed SrCO3 acted as a sintering aid for cubic LLZ ceramics and significantly increased the grain size of the sintered pellets. A cond. of 2.10 × 10-4 S/cm at 297 K was obtained for the undoped LLZ. The total ionic cond. reached a max. of about 5 × 10-4 S/cm at 297 K with an activation energy of about 0.31 eV for 1.7 wt% Sr added LLZ sintered for 20-24 h in alumina crucible.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXovFertbg%253D&md5=90a155c052ad055283f9eaec3e73e0b7
    66. 66
      Rettenwander, D.; Welzl, A.; Cheng, L.; Fleig, J.; Musso, M.; Suard, E.; Doeff, M. M.; Redhammer, G. J.; Amthauer, G. Synthesis, Crystal Chemistry, and Electrochemical Properties of Li7–2xLa3Zr2–xMoxO12 (x = 0.1–0.4): Stabilization of the Cubic Garnet Polymorph via Substitution of Zr4+ by Mo6+. Inorg. Chem. 2015, 54 (21), 10440– 10449,  DOI: 10.1021/acs.inorgchem.5b01895
      68
      Synthesis, Crystal Chemistry, and Electrochemical Properties of Li7-2xLa3Zr2-xMoxO12 (x = 0.1-0.4): Stabilization of the Cubic Garnet Polymorph via Substitution of Zr4+ by Mo6+
      Rettenwander, Daniel; Welzl, Andreas; Cheng, Lei; Fleig, Juergen; Musso, Maurizio; Suard, Emmanuelle; Doeff, Marca M.; Redhammer, Guenther J.; Amthauer, Georg
      Inorganic Chemistry (2015), 54 (21), 10440-10449CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
      Cubic Li7La3Zr2O12 (LLZO) garnets are exceptionally well suited to be used as solid electrolytes or protecting layers in "Beyond Li-ion Battery" concepts. Unfortunately, cubic LLZO is not stable at room temp. (RT) and has to be stabilized by supervalent dopants. In this study we demonstrate a new possibility to stabilize the cubic phase at RT via substitution of Zr4+ by Mo6+. A Mo6+ content of 0.25 per formula unit (pfu) stabilizes the cubic LLZO phase, and the soly. limit is about 0.3 Mo6+ pfu. Based on the results of neutron powder diffraction and Raman spectroscopy, Mo6+ is located at the octahedrally coordinated 16a site of the cubic garnet structure (space group Ia-3d). Since Mo6+ has a smaller ionic radius compared to Zr4+ the lattice parameter a0 decreases almost linearly as a function of the Mo6+ content. The highest bulk Li-ion cond. is found for the 0.25 pfu compn., with a typical RT value of 3.4 × 10-4 S cm-1. An addnl. significant resistive contribution originating from the sample interior (most probably from grain boundaries) could be identified in impedance spectra. The latter strongly depends on the prehistory and increases significantly after annealing at 700 °C in ambient air. Cyclic voltammetry expts. on cells contg. Mo6+-substituted LLZO indicate that the material is stable up to 6 V.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhs1ejsb7N&md5=0a142be1bed4f8e918d052dfd9fde069
    67. 67
      Inada, R.; Yasuda, S.; Hosokawa, H.; Saito, M.; Tojo, T.; Sakurai, Y. Formation and Stability of Interface between Garnet-Type Ta-Doped Li7La3Zr2O12 Solid Electrolyte and Lithium Metal Electrode. Batteries 2018, 4 (2), 26,  DOI: 10.3390/batteries4020026
      69
      Formation and stability of interface between garnet-type Ta-doped Li7La3Zr2O12 solid electrolyte and lithium metal electrode
      Inada, Ryoji; Yasuda, Satoshi; Hosokawa, Hiromasa; Saito, Masaya; Tojo, Tomohiro; Sakurai, Yoji
      Batteries (Basel, Switzerland) (2018), 4 (2), 26/1-26/12CODEN: BATTAT; ISSN:2313-0105. (MDPI AG)
      Garnet-type Li7-xLa3Zr2-xTaxO12 (LLZT) is considered a good candidate for the solid electrolyte in all-solid-state lithium batteries because of its reasonably high cond. around 10-3 S cm-1 at room temp. and stability against lithium (Li) metal with the lowest redox potential. In this study, we synthesized LLZT with a tantalum (Ta) content of 0.45 via a conventional solid-state reaction process and constructed a Li/LLZT/Li sym. cell by attaching Li metal foils on the polished top and bottom surfaces of an LLZT pellet. We investigated the influence of heating temps. and times on the interfacial charge-transfer resistance between LLZT and the Li metal electrode. In addn., the effect of the interface resistance on the stability for Li deposition and dissoln. was examd. using a galvanostatic cycling test. The lowest interfacial resistance of 25 Ω cm2 at room temp. was obtained by heating at 175°C (5°C lower than the m.p. of Li) for three to five hours. We confirmed that the c.d. at which the short circuit occurs in the Li/LLZT/Li cell via the propagation of Li dendrite into LLZT increases with decreasing interfacial charge transfer resistance.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvFCgsL8%253D&md5=ba149f06f5c745f38d7fc2149c3a16fd
    68. 68
      Nagao, K.; Nagata, Y.; Sakuda, A.; Hayashi, A.; Deguchi, M.; Hotehama, C.; Tsukasaki, H.; Mori, S.; Orikasa, Y.; Yamamoto, K.; Uchimoto, Y.; Tatsumisago, M. A Reversible Oxygen Redox Reaction in Bulk-Type All-Solid-State Batteries. Sci. Adv. 2020, 6, eaax7236,  DOI: 10.1126/sciadv.aax7236
      There is no corresponding record for this reference.
    69. 69
      Lee, Y. G.; Fujiki, S.; Jung, C.; Suzuki, N.; Yashiro, N.; Omoda, R.; Ko, D. S.; Shiratsuchi, T.; Sugimoto, T.; Ryu, S.; Ku, J. H.; Watanabe, T.; Park, Y.; Aihara, Y.; Im, D.; Han, I. T. High-Energy Long-Cycling All-Solid-State Lithium Metal Batteries Enabled by Silver–Carbon Composite Anodes. Nat. Energy 2020, 5 (4), 299– 308,  DOI: 10.1038/s41560-020-0575-z
      71
      High-energy long-cycling all-solid-state lithium metal batteries enabled by silver-carbon composite anodes
      Lee, Yong-Gun; Fujiki, Satoshi; Jung, Changhoon; Suzuki, Naoki; Yashiro, Nobuyoshi; Omoda, Ryo; Ko, Dong-Su; Shiratsuchi, Tomoyuki; Sugimoto, Toshinori; Ryu, Saebom; Ku, Jun Hwan; Watanabe, Taku; Park, Youngsin; Aihara, Yuichi; Im, Dongmin; Han, In Taek
      Nature Energy (2020), 5 (4), 299-308CODEN: NEANFD; ISSN:2058-7546. (Nature Research)
      An all-solid-state battery with a lithium metal anode is a strong candidate for surpassing conventional lithium-ion battery capabilities. However, undesirable Li dendrite growth and low Coulombic efficiency impede their practical application. Here we report that a high-performance all-solid-state lithium metal battery with a sulfide electrolyte is enabled by a Ag-C composite anode with no excess Li. We show that the thin Ag-C layer can effectively regulate Li deposition, which leads to a genuinely long electrochem. cyclability. In our full-cell demonstrations, we employed a high-Ni layered oxide cathode with a high specific capacity (>210 mAh g-1) and high areal capacity (>6.8 mAh cm-2) and an argyrodite-type sulfide electrolyte. A warm isostatic pressing technique was also introduced to improve the contact between the electrode and the electrolyte. A prototype pouch cell (0.6 Ah) thus prepd. exhibited a high energy d. (>900 Wh l-1), stable Coulombic efficiency over 99.8% and long cycle life (1,000 times).
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXls1Ciurg%253D&md5=872c8ac4fa1c77e763995431f3243d10
    70. 70
      Coeler, M.; van Laack, V.; Langer, F.; Potthoff, A.; Höhn, S.; Reuber, S.; Koscheck, K.; Wolter, M. Infiltrated and Isostatic Laminated Ncm and Lto Electrodes with Plastic Crystal Electrolyte Based on Succinonitrile for Lithium-Ion Solid State Batteries. Batteries 2021, 7 (1), 11,  DOI: 10.3390/batteries7010011
      72
      Infiltrated and isostatic laminated NCM and LTO electrodes with plastic crystal electrolyte based on succinonitrile for lithium-ion solid state batteries
      Coeler, Matthias; van Laack, Vanessa; Langer, Frederieke; Potthoff, Annegret; Hoehn, Soeren; Reuber, Sebastian; Koscheck, Katharina; Wolter, Mareike
      Batteries (Basel, Switzerland) (2021), 7 (1), 11CODEN: BATTAT; ISSN:2313-0105. (MDPI AG)
      We report a new process technique for electrode manufg. for all solid-state batteries. Porous electrodes are manufd. by a tape casting process and subsequently infiltrated by a plastic crystal polymer electrolyte (PCPE). With a following isostatic lamination process, the PCPE was further integrated deeply into the porous electrode layer, forming a composite electrode. The PCPE comprises the plastic crystal succinonitrile (SN), lithium conductive salt LiTFSI and polyacrylonitrile (PAN) and exhibits suitable thermal, rheol. (n = 0.6 Pa s @ 80°C 1 s-1) and electrochem. properties (σ > 10-4 S/cm @ 45°C). We detected a lowered porosity of infiltrated and laminated electrodes through Hg porosimetry, showing a redn. from 25.6% to 2.6% (NCM infiltrated to laminated) and 32.9% to 4.0% (LTO infiltrated to laminated). Infiltration of PCPE into the electrodes was further verified by FESEM images and EDS mapping of sulfur content of the conductive salt. Cycling tests of full cells with NCM and LTO electrodes with PCPE separator at 45°C showed up to 165 mAh/g at 0.03C over 20 cycles, which is about 97% of the total usable LTO capacity with a coulomb efficiency of between 98 and 99%. Cycling tests at 0.1C showed a capacity of ~ 128 mAh/g after 40 cycles. The C-rate of 0.2C showed a mean capacity of 127 mAh/g. In summary, we could manuf. full cells using a plastic crystal polymer electrolyte suitable for NCM and LTO active material, which is easily to be integrated into porous electrodes and which is being able to be used in future cell concepts like bipolar stacked cells.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXpt1emtbk%253D&md5=5d1bb1d29d7df843ba5943f686a8c172
    71. 71
      Kitajima, S.; Ryu, S.; Ku, J.; Kim, S.; Park, Y.; Im, D. Methodology for Enhancing the Ionic Conductivity of Superionic Halogen-Rich Argyrodites for All-Solid-State Lithium Batteries. Mater. Today Commun. 2021, 28, 102727,  DOI: 10.1016/j.mtcomm.2021.102727
      73
      Methodology for enhancing the ionic conductivity of superionic halogen-rich argyrodites for all-solid-state lithium batteries
      Kitajima, Shintaro; Ryu, Saebom; Ku, Junhwan; Kim, Soyeon; Park, Youngsin; Im, Dongmin
      Materials Today Communications (2021), 28 (), 102727CODEN: MTCAC7; ISSN:2352-4928. (Elsevier Ltd.)
      The development of high-performance all-solid-state lithium-ion batteries depends on the realization of solid-state electrolytes with high ionic cond. In this study, halogen-rich argyrodites with high ionic conductivities were fabricated, and their structural evolution was studied. In addn., the optimum heat treatment protocol for enhancing the ionic cond. of halogen-rich argyrodites (Li5.3PS4.3Cl1.7) was detd. by interpreting the reaction mechanism. Structural and thermal analyzes revealed that fast heating results in the formation of intermediates contg. PS4-3 units and Cl- ions, which remain in the material and decrease the ionic cond. (∼1.6 mS/cm at 25 °C). Surprisingly, slow heating, such as step heating, can promote the slow reaction that produces argyrodite from an intermediate, resulting in a high ionic cond. (∼5.0 mS/cm at 25 #176;C). Furthermore, we examd. the performance of all-solid-state batteries assembled with Li5.3PS4.3Cl1.7 as a solid-state electrolyte and found that the batteries employing Li5.3PS4.3Cl1.7 treated by a slow heating protocol performs better than the batteries employing Li5.3PS4.3Cl1.7 treated by a fast heating protocol, with an impressive specific capacity of 151.8 mAh/g at 1.0 C. Herein, we assert that further developing halogen-rich argyrodites as glass-ceramics may provide a long-sought soln. to realizing ASSBs capable of achieving a high rate.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhvV2rtrrP&md5=d3a709bbe52df587811327280a5d9b39
    72. 72
      Federal Consortium for Advanced Batteries. Executive Summary, National Blueprint for Lithium Batteries, 2021–2030; U.S. Department of Energy, June 2021.
      There is no corresponding record for this reference.

  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.2c01936.

    • Anti-perovskite solid electrolyte preparation and characterization details, including Figures S1–S5 (PDF)

    • Excel sheet summarizing the referenced experimental data from literature (XLSX)

    • Excel sheet that includes the techno-economic model for ISP (XLSX)


    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.