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Filament-Induced Failure in Lithium-Reservoir-Free Solid-State Batteries
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  • Se Hwan Park
    Se Hwan Park
    Andlinger Center for Energy and the EnvironmentPrinceton University, Princeton, New Jersey 08540, United States
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    Orcidhttps://orcid.org/0000-0001-5579-0765
  • Abhinand Ayyaswamy
    Abhinand Ayyaswamy
    School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
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    Orcidhttps://orcid.org/0009-0007-3952-6287
  • Jonathan Gjerde
    Jonathan Gjerde
    Applied Physics Program, University of Michigan, Ann Arbor, Michigan 48109, United States
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  • W. Beck Andrews
    W. Beck Andrews
    Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States
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  • Bairav S. Vishnugopi
    Bairav S. Vishnugopi
    School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
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  • Michael Drakopoulos
    Michael Drakopoulos
    Brookhaven National Laboratory, National Synchrotron Light Source II, Upton, New York 11973, United States
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  • Nghia T. Vo
    Nghia T. Vo
    Brookhaven National Laboratory, National Synchrotron Light Source II, Upton, New York 11973, United States
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    Orcidhttps://orcid.org/0000-0002-3683-7377
  • Zhong Zhong
    Zhong Zhong
    Brookhaven National Laboratory, National Synchrotron Light Source II, Upton, New York 11973, United States
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  • Katsuyo Thornton
    Katsuyo Thornton
    Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States
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    Orcidhttps://orcid.org/0000-0002-1227-5293
  • Partha P. Mukherjee
    Partha P. Mukherjee
    School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
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  • Kelsey B. Hatzell*
    Kelsey B. Hatzell
    Andlinger Center for Energy and the EnvironmentPrinceton University, Princeton, New Jersey 08540, United States
    Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08540, United States
    Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08540, United States
    *E-mail: [email protected]
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    Orcidhttps://orcid.org/0000-0002-5222-7288
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ACS Energy Letters

Cite this: ACS Energy Lett. 2025, 10, 3, 1174–1182
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https://doi.org/10.1021/acsenergylett.5c00004
Published February 22, 2025

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Abstract

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Lithium-reservoir-free solid-state batteries can fail due to electrical shorting as a result of fracture and lithium metal filament formation. Mechanical stress at the solid electrolyte surface can induce fractures, which promote lithium filament growth. This stress arises from both electrochemical sources, due to lithium electrodeposition, and mechanical sources, such as external stack pressure. Solid electrolyte surface roughness and the applied stack pressure together affect stress development. This study combines electrochemical experiments, 3D synchrotron imaging, and mesoscale modeling to explore how stack pressure influences failure mechanisms in lithium free solid-state batteries. At low stack pressure, irregular lithium plating and the resulting high local current density drive failure. At higher stack pressure, uniform lithium plating is favored; however, notch-like features in the surface of the solid electrolyte experience high tensile stress, leading to fractures that cause premature short-circuiting.

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Pathways to increase a battery’s energy density include reducing or eliminating the volume or mass of components that do not store charge (e.g., current collectors and packaging), (1,2) cycling the active material in the cell to its fullest extent (by keeping the N/P ratio close to 1), (3−6) and pairing an energy-dense anode with a thick energy-dense cathode. (7) Lithium-reservoir-free (lithium-free) or anode-free solid-state battery architectures makes it possible to accomplish all of these goals. The cathode active material serves as the sole lithium source in a lithium-free architecture. (8) During charging, lithium ions deintercalate from a cathode and plate out as a metal electrode on a current collector at the anode. During discharge, the lithium metal electrode is stripped away. This architecture significantly reduces the anode’s volume, enabling higher energy densities. (9) Lithium-free solid-state batteries simplify manufacturing by eliminating the challenges of producing thin lithium metal. Currently, most studies use lithium metal with thicknesses around 100 μm because handling and manufacturing thinner lithium metal anodes (<25 μm) remain difficult. (8,10−12)

The morphology, texture, and density of the lithium metal formed during the first charge of a lithium-free solid-state battery can have a large impact on achievable current density, cycle lifetime, and degradation processes. (9,13,14) Achieving and sustaining uniform contact between the solid electrolyte and lithium metal anode throughout charge and discharge is challenging due to large volume changes. Strategies such as applying large external stack pressure, (10,15) and introducing seed alloys (16) or a high surface area interlayer (17) to facilitate fast diffusion have been pursued to improve contact between the anode and solid electrolyte during cycling. High stack pressure can promote uniform reaction and deposition, but it can also induce mechanical stress, potentially damaging the solid electrolyte. (18,19)

Lithium metal filament growth within solid electrolytes can lead to sudden cell failure. High local current densities caused by uneven electrodeposition create electrochemically generated stress hotspots, and external stack pressure can also generate stress concentrations at the surface and within the solid electrolyte surface. (20) The heterogeneity in electrochemical reactions and stress distribution is strongly influenced by the surface roughness of the solid electrolyte and stack pressure. (21,22) Mechanical stress on the solid electrolyte can lead to crack formation, allowing filaments to grow toward the counter electrode. (21,23) Filament initiation and propagation across a solid electrolyte is driven by a range of chemo-mechanical mechanisms. The current density, density of defects at the solid electrolyte interface, and capacity of electrodeposited lithium metal can all impact filament growth processes. (24−26) Depending on test conditions and solid electrolyte morphology, the dominant short circuit mechanism may vary. Given the simultaneous influence of these mechano-electrochemical factors, identifying the specific failure mechanism is essential to enhancing the stability of lithium-free solid-state batteries.

In this study, we examine lithium-filament-induced failure in lithium-free solid-state batteries under varying stack pressures, ranging from 2 to 20 MPa. Interfacial contact evolution and stress development at a current collector upon electrodeposition are investigated. Experimental and modeling results together reveal a transition in the dominant cause of filament growth ─ from high local current density to stack-pressure-induced fractures ─ as stack pressure increases. These findings provide critical insights into filament formation mechanisms, informing strategies to improve the stability and design of lithium-free solid-state batteries.

The electrochemical cells investigated in this work were fabricated by pelletizing LPSCl powders under a pressure of 300 MPa within a polyether ether ketone (PEEK) mold with an inner diameter of 6 mm, placing Li foil on one side of the pellet, and placing a stainless steel (SUS) current collector on the other side of the pellet (see Supporting Information for more details). The lithium metal was electrodeposited at commercially relevant current densities (1 mA cm–2) onto the stainless steel current collector at varying pressures (2–20 MPa, Figure S2). Figure 1 depicts results for cells fabricated with LPSCl with particle sizes around 5 μm. There is a sudden increase in voltage polarization upon lithium nucleation at the current collector and then a plateau in the voltage upon further deposition (e.g., plating capacity increases) (Figure 1a). The initial polarization decreases as the stack pressure increases. Higher stack pressure improves initial contact between the solid electrolyte and the current collector resulting in a more homogeneous lithium nucleation and subsequent deposition. Stack pressure can facilitate horizontal lithium creep which can increase the contact area between lithium electrodeposits and the solid electrolyte (Figure 1d–g). This increase in contact area can reduce the local current density and overpotential. (27)

Figure 1

Figure 1. (a) Voltage profiles of lithium plating onto the current collector under varying stack pressures, ranging from 2 to 20 MPa. (b) Maximum capacity before short circuit as a function of stack pressure. (c) 3D surface topography of LPSCl pellet. SEM images of lithium plated current collectors at a capacity of 0.5 mAh cm–2 under different stack pressures: (d) 2, (e) 5, (f) 10, and (g) 20 MPa. For clarity, lithium metal is shown in blue and the current collector in red.

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Applying stack pressure during electrodeposition directly impacts the morphology, thickness, and distribution of the lithium metal at the solid electrolyte-stainless steel interface. Irregular contact between the current collector and the solid electrolyte causes current focusing, which leads to premature failure upon electrodeposition of low areal capacities at the stainless steel current collector. Increasing stack pressure from 2 to 10 MPa improves the maximum areal capacity, defined as the capacity before short circuit. Short circuits occur due to the growth via plating of a lithium metal filament through a crack in the solid electrolyte. (25) Short circuits occurred in the cells after plating capacities of 1.24, 2.56, and 4.56 mAh cm–2 under stack pressures of 2, 5, and 10 MPa, respectively (Figure 1a,b). The maximum capacity drops to 3.00 and 2.44 mAh cm–2 as the stack pressure increases to 15 and 20 MPa (Figure 1a,b). The solid electrolyte’s surface roughness directly influences both electrochemical and mechanical processes during lithium plating. It impacts the initial contact at the stainless steel/LPSCl interface and the pressure/stress distribution, shaping the mechano-electrochemical behavior of lithium. Using confocal microscopy, we measured the 3D surface topography of the solid electrolyte, revealing valleys and peaks with heights reaching up to 7 μm (Figure 1c).

The morphology of electrodeposited lithium (0.5 mAh cm–2) at the current collector is highly dependent on the stack pressure (Figure 1d–g). The lithium area coverage on the current collector surface (lithium plated area/total area ×100) increases from 44% to 97% (Figure 1d–f) as the stack pressure increases from 2 to 10 MPa. Little change in contact area is observed between 10 to 20 MPa (Figure 1f,g). Non-uniform lithium deposition disrupts the contact between the solid electrolyte and the stainless steel current collector. Lithium metal deposits form isolated islands that directly contact both the current collector and the solid electrolyte. However, areas of the stainless steel without lithium deposits fail to establish contact with the solid electrolyte. This uneven deposition reduces the overall contact area between the lithium metal and the solid electrolyte. Higher stack pressure drives lithium creep parallel to the interface, expanding the plating area and facilitating uniform lithium plating. This improvement in lithium plating uniformity is significant up to 10 MPa (see Figure 1d–f), but diminishes significantly beyond that threshold (see Figure 1f,g).

To understand the impact of stack pressure on the plating behavior, we developed a coupled electrochemical–mechanical modeling framework that captures the void evolution dynamics and interfacial complexities governed by heterogeneous reaction kinetics, interfacial stresses, and the spatial distribution of gap heights. (28) Based on the roughness profile of the LPSCl pellet (Figures 1c and S3), the stack pressure, and the current density, our model tracks the evolution of gaps between the lithium and LPSCl surfaces during plating. A detailed description of the governing equations and methods associated with the modeling framework is provided in Supporting Information (Section S4).

We examine the trends in potential evolution during plating, thereby assessing the combined mechanistic response through the rate of interfacial contact evolution. We utilize the experimentally measured roughness profile (Figure S3) as the initial condition to understand the void growth dynamics at various pressures (Figure 2a). Since the processes of lithium nucleation and growth on the bare current collector remain poorly understood, we begin simulating the void growth dynamics with 0.1 μm (i.e., ∼ 0.02 mAh cm–2) of plated lithium. Furthermore, the simulations are conducted up to the capacity at which the lithium/LPSCl interface becomes nearly conformal (∼100% contact) unless the experimentally measured maximum capacity has been reached. After nearly conformal contact is achieved, other competing mechanisms, such as lithium filament growth and solid electrolyte fracture, can significantly alter the potential behavior. We utilize our computational framework to predict the plating potential and contact evolution response under various operating stack pressures at a current density of 1 mA cm–2. Figure 2a shows an excellent agreement of our modeling results with experimental data, where an increase in pressure is reflected through a sharp gradient in potential near the start of plating. The modeling framework enables us to probe the rate of void reduction at the lithium/LPSCl interface driven by competing mechanisms resulting in its contact evolution profile (Figure 2b). This validation process evaluated through our modeling framework allows us to gain mechanistic insights via local plating currents thereby assessing the impact of failure modes (i.e., dendrite propagation, particle fracture) through changes in the potential response. We see a divergence in the potential response at 2 MPa after 1 mAh cm–2 (Figure 2a), likely due to the onset of lithium filaments penetrating through the solid electrolyte in the experiment, which is not modeled. The presence of Li dendrites inside the solid electrolyte could alter the electric potential distribution, hinting toward the observed variation in potential response at low pressures. In contrast, at a stack pressure of 5 MPa, we observe a 2-fold increase in the rate of contact ratio growth (i.e., ∼21.93% increase per mAh cm–2 from 0.1 to 0.9 mAh cm–2, compared with ∼10.8% at 2 MPa), attributed to the enhanced contributions of creep deformation and contact mechanics. Since gap reduction through contact mechanics is impacted by the thickness of the anode, creep deformation predominantly contributes to closure of gaps, especially at the start of plating in lithium-free solid-state batteries. Higher pressures result in smaller void gaps, enhancing the tendency for lithium self-diffusion to rapidly form contacting interfaces, as discussed in our previous work. (10)

Figure 2

Figure 2. Impact of stack pressure on the overall plating performance through the analysis of interfacial dynamics in lithium-free solid-state batteries. (a) Predicted and experimental potential evolution during plating experiments under various stack pressures ranging from 2 to 20 MPa. (b) Corresponding simulated interfacial contact evolution. Predicted contact maps at capacities of 0.1 and 0.9 mAh cm–2 with (c) 2 and (d) 5 MPa stack pressure at a current density of 1 mA cm–2. The dimensions of the contact maps are 60 × 60 μm, and the values below the contact maps indicate the percentage of contact area at their respective plated capacities (shown above the contact maps). (e) and (f) show the reaction heterogeneity at the lithium/solid electrolyte interface, as defined by eq 1, corresponding to (c) and (d), respectively. Regions of no color represent noncontact points that indicate zero current. A value of 0% current heterogeneity corresponds to points where the current density is equal to the mean current density (i.e., Iapp/contact area) and is indicated with dashed lines in these maps.

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Figure 2c,d demarcate the contact and noncontact regions at 0.1 and 0.9 mAh cm–2 capacities when operated at 2 and 5 MPa stack pressures, respectively. Figure 2e,f show the corresponding map of the reaction heterogeneity defined by

χ=i−imeanimean
(1)
where i is the local current density and imean is the mean current density given by imean = Iapp/contact area. For the stack pressure of 2 MPa, we examine the mechanistic origins of the faster onset of lithium dendritic growth and penetration into the solid electrolyte (Figure 2e), as compared to that of 5 MPa. At 0.1 mAh cm–2, certain regions exhibit severe reaction heterogeneity (i.e., 100% or 8.34 mA cm–2) leading to local plating hotspots with extensive lithium plating and increasing the likelihood of lithium filament penetration. Over the course of lithium plating process, lower pressure cases lead to slower growth of interfacial contact, resulting in minimal homogenization of reaction currents. The solid electrolyte roughness profile plays a key role in determining the extent of lithium plating heterogeneity, where taller ’peaks’ correspond to isolated islands of contact, while deeper ’valleys’ point to regions of delayed contact (Figure S3). The joint interplay of solid electrolyte interfacial roughness and the operating conditions govern the creation of localized point contact regions and their associated electric potential distribution, thereby connecting dendritic growth to failure. An increase in stack pressure to 5 MPa homogenizes lithium plating and current distribution, establishing higher connectivity between neighboring solid–solid point contacts, thus leading to lower current focusing (Figure 2d,f).

Electrochemical lithium ion reduction contributes to mechanical stress. The stress induced by Li plating overpotential (σLi_plating) is described by (20)

σLi_plating=−FVmLi×η
(2)
Here, F is Faraday’s constant, VmLi is the molar volume of lithium metal, and η is the Li plating overpotential. Overpotential arises from various factors, including ohmic resistance, the interphase between lithium and the solid electrolyte, and contact resistance, making its accurate experimental measurement challenging. Additionally, spatial heterogeneity, such as current focusing, further complicates the process. According to the eq 2, a Li plating overpotential of 3 mV generates approximately 22 MPa of tensile stress. Under conditions of high local current density exceeding 8 times the applied global current density (observed in the 2 MPa case), this localized stress significantly increases. Such stress promotes the initiation of lithium filaments, leading to early cell failure at low stack pressure.

At a stack pressure of 10 MPa, interfacial contact rises sharply, reaching 94.3% at a capacity of 0.6 mAh cm–2 due to the prominence of creep deformation and lithium self-diffusion in quickly restoring conformal contact (Figure 2b). A larger interfacial contact at the start of plating allows for faster homogenization of reaction kinetics, thereby inducing uniform plating. At a capacity of 0.1 mAh cm–2, a stack pressure of 10 MPa provides 76.8% contact retention, resulting in fewer local reaction hotspots (χ < 20%), which is beneficial for interface stability during plating (Figure S4).

Our modeling framework captures a drastic variation in the creep material constant (see eq 2 in Supporting Information) as stack pressure increases from 2 to 20 MPa (see Table S1). We hypothesize that these changes in the creep material constant reflect an increased viscoplastic effect of metallic lithium, facilitating greater penetration into the solid electrolyte at such pressures and driving short circuit. (28,29) Higher interfacial pressures derived from such stack pressures can plastically deform lithium, causing it to flow into the solid electrolyte, thereby creating faster dendritic lithium growth within the solid electrolyte. Additionally, even at 20 MPa, during the early stage of Li plating (0.05 mAh cm–2) we fail to observe contact at the ’valleys’ of solid electrolyte roughness, indicating the impact of solid electrolyte roughness in reaction heterogeneity (Figure S5). (22) Thus, stack pressure plays a dual role in the plating performance of lithium-free solid-state batteries: low pressures lead to localized plating hotspots that promote lithium filament penetration, while excessively high pressures modulate the mechanical behavior of metallic lithium, causing it to flow into features of the rough solid electrolyte surface and induce fracture, as will be discussed later.

To provide insights into failure mechanisms and how stack pressure influences them, fracture and/or lithium filament-induced short-circuiting was investigated using X-ray computed tomography. As in the electrochemically characterized cells described above, solid electrolytes were assembled in lithium-free or anode-free configurations with a lithium metal counter electrode. Lithium metal was stripped from the counter electrode and plated onto the current collector at a current density of 1 mA cm–2 until failure was detected. To balance resolution and field of view, we selected a 4 mm field of view with a 1.3 μm voxel resolution to capture the lithium-penetration-induced crack in the solid electrolyte pellet. To ensure X-ray tomography captures the entire lithium plating area, we designed a custom cell architecture that confines lithium plating to the central 3 mm region of the current collector (Figures 3a and S6a). A 3 mm inner diameter O-ring restricts lithium plating to this region, while a 5 mm lithium–metal disk positioned beneath the current collector pushes it against the solid electrolyte pellet, maintaining nearly full contact despite the O-ring’s thickness. The lithium metal disk avoids direct contact with the solid electrolyte, remaining electrochemically inactive and serving solely as a conductive layer. The cells exhibit uniform pressure on the current collector in the test pressure range of 2–20 MPa as measured by pressure-sensitive films (Figure S7). Lithium plating tests with this custom cell reveal consistent trends in maximum capacity (Figure S6b,c). The maximum capacity increases from 1.54 to 5.23 mAh cm–2 as the stack pressure is increased from 2 to 10 MPa, but drops significantly to 1.52 mAh cm–2 at 20 MPa.

Figure 3

Figure 3. (a) Schematic illustration of the cell employed for X-ray tomography analysis. (b–e) Crack distribution within the pellet after short-circuiting with cracks shown in blue under varying stack pressures: (b) 2, (c) 5, (d) 10, and (e) 20 MPa. Images present top views of the failed pellets from the lithium counter electrode side.

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The pristine pellet before electrochemical reaction does not have any significant cracks (Figure S8). The attenuation contrast between the LPSCl solid electrolyte and dendritic lithium or cracks allows for clear segmentation (Figures S9 and S10). However, as reported previously, (30) the low density of lithium makes it difficult to distinguish lithium from empty spaces potentially present within cracks. In the top-view segmented images (Figure 3b–e), the blue regions represent a combined area of fractures and lithium metal. Based on the crack distribution across the pellet, it is highly likely that while some cracks are filled with lithium, other areas remain as dry cracks without lithium. Many cracks extend to the counter electrode side (Figures 3b–e and S10), and since a single lithium dendrite reaching the counter electrode can cause a short circuit, a significant portion of these cracks likely remains dry and lithium-free.

As stack pressure is increased from 2 to 10 MPa, the entire volume of cracking grows. Lithium filaments form continuously during the plating process, with each filament initiating at different plating capacities depending on factors such as the initial interfacial contact, the pellet’s surface morphology, and local inhomogeneities in lithium plating. Previous operando studies show that lithium filaments begin forming at varying times during plating, with new filaments initiating even after others have already started extending through the electrolyte pellet. (24,31) This continuous initiation of filaments and dendrites results in a higher amount of cracking as plating capacity increases. At lower stack pressures, the smaller lithium plating area creates a higher local current density, which causes lithium filaments to grow more quickly. As a result, filaments reach the counter electrode at lower capacities compared to those under higher stack pressures. (24,31)

At stack pressures between 5 and 10 MPa, cracks form within the lithium plating area (inside the 3 mm circle), especially near the edge of the 3 mm ring. The geometric effects of the current collector amplify local current density at the edges, driving crack formation near them. A finite-element model using COMSOL Multiphysics, detailed in Section S6 of the Supporting Information, predicts that the local current density at the edge of the current collector is approximately 6.4 times higher than in the central region (Figure S11). This preferential filament growth aligns with observations from a previous study using a lithium symmetric cell. (25) Between 2 and 10 MPa, variations in local current density within the lithium plating area (i.e., the lithium metal-current collector contact area) strongly drive filament growth and lead to cell failure. At 20 MPa, however, despite lithium electrodeposits nearly covering the entire current collector (Figure 1f,g), the pellet develops fewer cracks and achieves a lower maximum capacity. We hypothesize that increased stack pressure well beyond the level needed for conformal lithium contact generates mechanical stress at valley- or notch-like features on the solid electrolyte surface that contributes to cell failure. The next section analyzes the combined effects of surface roughness and stack pressure.

To investigate how high stack pressure contributes to cell failure, we simulate the stress distribution within the electrolyte using the experimentally measured surface morphology shown in Figure 1c. We assume full contact between the electrolyte and lithium metal, which is reasonable for high stack pressures (10 MPa or greater) due to the low yield strength of lithium metal (0.57 to 1.26 MPa). (32) Experimental observations (Figure 1f,g) and interfacial contact modeling (Figure 2b) confirm nearly 100% contact at high stack pressure after plating 1 mAh cm–2 of lithium. We model the plated lithium in contact with the electrolyte as being under hydrostatic pressure equal to the applied stack pressure and implement this condition as a hydrostatic pressure boundary at the lithium/LPSCl interface. LPSCl is assumed to behave as a linear elastic solid; we consider the possibility of plasticity or creep of LPSCl, (33) but estimate that fracture will initiate before these effects become significant. This analysis and further details of the stress simulations are provided in the Supporting Information (Section S5).

The three-dimensional (3D) calculation was carried out on a selected area of experimental surface morphology data (Figure 4a), and two-dimensional (2D) plane-strain calculations were conducted on two different x–z slices of the same data (Figure 4b,c). The boundary conditions were set such that the electrolyte is allowed to expand freely in the in-plane direction, which is realistic due to the high elastic stiffness of LPSCl relative to the PEEK polymer that surrounds its sides in the experimental setup. The results are shown in Figure 4 (a: 3D, b, c: 2D), which demonstrate that tensile stress peaks at the tips of notch-like roughness features, with the highest tensile stress occurring at the tip of the tallest feature. Taller features exhibit higher tensile stress. The 2D simulations with larger features (∼7 μm) shows a maximum tensile stress of 45.1 MPa (Figure 4c), while the 2D simulation with smaller features (∼2 μm) exhibits a maximum of 16.8 MPa (Figure 4b). The stress distribution at the tip of the large feature in Figure 4c qualitatively resembles those around crack-like filaments observed via photoelasticity (see, e.g., ref (34)), although quantitatively the stresses will be highly sensitive to notch/crack geometry. (35) 2D plane-strain calculations yielded maximum tensile stresses about 50% higher than those of similar 3D cases (45.1 and 32.2 MPa, respectively). This was expected, as the 2D plane-strain calculations lack a relaxation mode that is available in 3D. (36)

Figure 4

Figure 4. Results from stress simulations with experimentally determined morphologies of the lithium/LPSCl interface under the stack pressure of 20 MPa. In all figures, LPSCl is on top of the lithium metal and full contact is assumed. (a) 3D surface plot of the LPSCl/lithium interface, with color indicating the largest principal stress, σ1, under stack pressure of 20 MPa. The variation in σ1 arises due to the roughness of under stack pressure at the LPSCl/lithium interface. (b, c) Plots of the tensile component of stress in the x direction for simulations with (b) smaller and (c) larger features in the interfacial morphology. The gray region at the bottom indicates bulk lithium, for which stress was not calculated.

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We considered an additional set of boundary conditions in which the electrolyte is fixed in the in-plane direction. The maximum tensile stress was found to be nearly an order of magnitude lower in the fixed boundary case, indicating that confinement may help to control detrimental stress concentration. Due to the linear nature of our model, the stress in the solid electrolyte is expected to change proportionally to the applied pressure. This is verified in Figure S12, which shows that the maximum tensile stress due to the stack pressure of 20 MPa is double that at 10 MPa. Thus, we can predict the peak tensile stress given the morphology of the lithium/LPSCl interface and a value of the peak tensile stress at one stack pressure. Additionally, we examined changing the amplitude of the roughness in the 2D simulations. For the surface morphology with small features (Figure 4b), peak tensile stress was observed in Figure S1a to increase linearly with roughness amplitude, while a sublinear relationship was found for the morphology with a larger feature (Figure 4c) in Figure S1b. A linear relationship between amplitude and stress is expected in the limit of a nearly flat surface. (36)

Stresses induced in the solid electrolyte due to the interaction between surface roughness and deformation of lithium due to stack pressure could significantly influence the initiation of lithium filaments. Recently, Ning et al. (25) reported a fracture strength of σfracture = 91.1 ± 14.5 MPa for LPSCl obtained via microcantilever beam experiments. Following Ning et al. (25) and other work that demonstrates a similarity between lithium filament growth through a solid electrolyte and classical fracture mechanics, (23,37) we can consider the initiation of filament growth as a fracture process that nucleates a crack at a location where the largest principal stress σ1 exceeds the fracture strength, σ1 > σfracture. The newly nucleated crack will continue to propagate as long as the criterion KI ≥ KIC is met, where KI is the mode I stress intensity factor at the crack tip and KIC is the fracture toughness, reported to be 0.69 ± 0.12 MPa m1/2 for LPSCl. (25) If the crack has not yet propagated completely through the solid electrolyte layer and the cell has not yet short circuited, plating of lithium along the crack path will increase pressure within the crack until propagation resumes. (20)

The local stress that induces crack nucleation includes contributions due to both the stack pressure σstack, as calculated in Figure 4, as well as the plating stress σLi_plating from eq 2. The maximum values of the largest principal stress σ1 in Figure 4, 45.1 MPa for 2D plane strain and 32.2 MPa for 3D, represent significant fractions (49.5% and 35.2%, respectively) of the σfracture. Thus, while stack pressure alone may not be sufficient to initiate a crack, along with the stress induced by lithium plating, it can initiate dendrite growth at 20 MPa stack pressure. As the stack pressure increases from 10 to 20 MPa, the stress at roughness features doubles, and this coincides with a significant reduction in maximum capacity (4.56 and 2.44 mAh cm–2 at 10 and 20 MPa respectively, Figure 1a,b). These observations strongly suggest that our model, in which tensile mechanical stresses arise from stack pressure at roughness features, can qualitatively explain the premature failure of the 20 MPa case relative to the 10 MPa case. The accelerated Li dendrite growth at higher stack pressure within empty cracks could contribute to premature short circuits. (25,38) However, the drastic drop in maximum capacity above 10 MPa (Figure 1a,b), where the value at 15 MPa (3.00 mAh cm–2) is much closer to 20 MPa (2.44 mAh cm–2) than to 10 MPa (4.56 mAh cm–2) supports that stack pressure-induced fracture is predominant mechanism of early short circuits at high stack pressure.

To examine the role of the surface morphology of the electrolyte, we now consider a pellet constructed with fine LPSCl powder, with particle diameters around 1 μm, which results in a smoother surface and smaller roughness features (less than 3 μm, Figure S13a). Similar to regular LPSCl (3–5 μm particle size, 7 μm maximum valley depth), the maximum capacity of fine LPSCl cells increases from 1.86 to 7.28 mAh cm–2 as stack pressure rises from 2 to 10 MPa (Figure S13b,c). The maximum capacity of fine LPSCl is ∼50% higher than regular LPSCl, which indicates that the smoother surface enables more even lithium electrodeposition, reducing local current density and thereby increasing the maximum capacity. In addition, unlike regular LPSCl, fine LPSCl cells exhibit only a minimal capacity decrease from 7.28 to 6.71 mAh cm–2 as stack pressure increases from 10 to 20 MPa (Figure S13b,c). This resilience at higher pressures may result from two factors. As indicated by the stress calculations described above, smoother surfaces reduce tensile stress by reducing the depth of notch-like features. Furthermore, fine LPSCl pellets have smaller grain size and lower porosity compared to larger LPSCl, (22) characteristics which have been found to enhance fracture toughness in ceramics. (39,40) The similar maximum capacity between 10 and 20 MPa suggests that the significant capacity decrease observed in regular LPSCl cells at 20 MPa (Figure 1a,b) is due to a stack pressure-induced fracture mechanism.

This study identifies dominant failure mechanisms caused by lithium filament penetration in lithium-free solid-state batteries for various values of stack pressure. The combined effects of stack pressure and surface roughness create heterogeneity in lithium plating and stress at the solid electrolyte surface. Lithium plating kinetics and stress modeling reveal the primary causes of short-circuiting. At low stack pressures, uneven lithium electrodeposition generates localized high current densities, which accelerate dendritic growth. X-ray computed tomography confirms that filaments grow faster at regions with higher local current density. As stack pressure increases from 2 to 10 MPa, the lithium plating area expands, resulting in a gradual rise in maximum capacity. At a high stack pressure of 20 MPa, although lithium electrodeposits nearly cover the entire current collector, the applied stack pressure generates high tensile stress at the tips of notch-like features on the solid electrolyte surface. The sharp drop in maximum capacity and the high tensile stress at 20 MPa indicate that the combined stresses from electrochemical lithium electrodeposition (σLi plating) and mechanical stack pressure (σstack) exceed the critical crack propagation stress. This stress causes fractures in the solid electrolyte, leading to premature short circuits. A solid electrolyte with a smoother surface and higher mechanical strength effectively mitigates external stack pressure-induced premature short circuits. Developing solid electrolytes with these characteristics is crucial for preventing failure in lithium-free solid-state batteries.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.5c00004.

  • Method; Schematic illustration of the test setup; Solid electrolyte surface roughness; Additional modeling results of contact maps and reaction heterogeneity; Electrochemical lithium plating results using cell employed for X-ray tomography analysis; Pressure distribution analysis results; Additional X-ray tomography results; Current density simulation results; Additional stress modeling results; Electrochemical lithium plating results using fine LPSCl pellet (PDF)

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Author Information

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  • Corresponding Author
    • Kelsey B. Hatzell - Andlinger Center for Energy and the EnvironmentPrinceton University, Princeton, New Jersey 08540, United States;  Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08540, United States;  Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08540, United States;  Orcidhttps://orcid.org/0000-0002-5222-7288;  Email: [email protected]
  • Authors
    • Se Hwan Park - Andlinger Center for Energy and the EnvironmentPrinceton University, Princeton, New Jersey 08540, United States;  Orcidhttps://orcid.org/0000-0001-5579-0765
    • Abhinand Ayyaswamy - School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States;  Orcidhttps://orcid.org/0009-0007-3952-6287
    • Jonathan Gjerde - Applied Physics Program, University of Michigan, Ann Arbor, Michigan 48109, United States
    • W. Beck Andrews - Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States
    • Bairav S. Vishnugopi - School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
    • Michael Drakopoulos - Brookhaven National Laboratory, National Synchrotron Light Source II, Upton, New York 11973, United States
    • Nghia T. Vo - Brookhaven National Laboratory, National Synchrotron Light Source II, Upton, New York 11973, United States;  Orcidhttps://orcid.org/0000-0002-3683-7377
    • Zhong Zhong - Brookhaven National Laboratory, National Synchrotron Light Source II, Upton, New York 11973, United States
    • Katsuyo Thornton - Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States;  Orcidhttps://orcid.org/0000-0002-1227-5293
    • Partha P. Mukherjee - School of Mechanical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was funded by the DOE Basic Energy Science Energy Frontier Research Center (MUSIC) under DE-SC0023438. This research used resources 27-ID (HEX) of the National Synchrotron Light Source II, a U.S. Department of Energy Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract No. DE-SC0023462. The computational resources for large-scale simulations reported in this work were provided by Anvil at the RCAC through Allocation No. TG-DMR110007 from the Advanced Cyberinfrastructure Coordination Ecosystem: Services and Support (ACCESS (41)) program, which is supported by National Science Foundation Grant Nos. 2138259, 2138286, 2138307, 2137603, and 2138296. The authors acknowledge the use of the Imaging and Analysis Center (IAC) operated by the Princeton Materials Institute at Princeton University, which is supported in part by the Princeton Center for Complex Materials (PCCM), a National Science Foundation (NSF) Materials Research Science and Engineering Center (MRSEC; DMR-2011750).

References

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  • Abstract

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    Figure 1

    Figure 1. (a) Voltage profiles of lithium plating onto the current collector under varying stack pressures, ranging from 2 to 20 MPa. (b) Maximum capacity before short circuit as a function of stack pressure. (c) 3D surface topography of LPSCl pellet. SEM images of lithium plated current collectors at a capacity of 0.5 mAh cm–2 under different stack pressures: (d) 2, (e) 5, (f) 10, and (g) 20 MPa. For clarity, lithium metal is shown in blue and the current collector in red.

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    Figure 2

    Figure 2. Impact of stack pressure on the overall plating performance through the analysis of interfacial dynamics in lithium-free solid-state batteries. (a) Predicted and experimental potential evolution during plating experiments under various stack pressures ranging from 2 to 20 MPa. (b) Corresponding simulated interfacial contact evolution. Predicted contact maps at capacities of 0.1 and 0.9 mAh cm–2 with (c) 2 and (d) 5 MPa stack pressure at a current density of 1 mA cm–2. The dimensions of the contact maps are 60 × 60 μm, and the values below the contact maps indicate the percentage of contact area at their respective plated capacities (shown above the contact maps). (e) and (f) show the reaction heterogeneity at the lithium/solid electrolyte interface, as defined by eq 1, corresponding to (c) and (d), respectively. Regions of no color represent noncontact points that indicate zero current. A value of 0% current heterogeneity corresponds to points where the current density is equal to the mean current density (i.e., Iapp/contact area) and is indicated with dashed lines in these maps.

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    Figure 3

    Figure 3. (a) Schematic illustration of the cell employed for X-ray tomography analysis. (b–e) Crack distribution within the pellet after short-circuiting with cracks shown in blue under varying stack pressures: (b) 2, (c) 5, (d) 10, and (e) 20 MPa. Images present top views of the failed pellets from the lithium counter electrode side.

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    Figure 4

    Figure 4. Results from stress simulations with experimentally determined morphologies of the lithium/LPSCl interface under the stack pressure of 20 MPa. In all figures, LPSCl is on top of the lithium metal and full contact is assumed. (a) 3D surface plot of the LPSCl/lithium interface, with color indicating the largest principal stress, σ1, under stack pressure of 20 MPa. The variation in σ1 arises due to the roughness of under stack pressure at the LPSCl/lithium interface. (b, c) Plots of the tensile component of stress in the x direction for simulations with (b) smaller and (c) larger features in the interfacial morphology. The gray region at the bottom indicates bulk lithium, for which stress was not calculated.

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      There is no corresponding record for this reference.
    14. 14
      Kazyak, E.; Wang, M. J.; Lee, K.; Yadavalli, S.; Sanchez, A. J.; Thouless, M.; Sakamoto, J.; Dasgupta, N. P. Understanding the electro-chemo-mechanics of Li plating in anode-free solid-state batteries with operando 3D microscopy. Matter 2022, 5, 3912– 3934,  DOI: 10.1016/j.matt.2022.07.020
      14
      Understanding the electro-chemo-mechanics of Li plating in anode-free solid-state batteries with operando 3D microscopy
      Kazyak, Eric; Wang, Michael J.; Lee, Kiwoong; Yadavalli, Srinivas; Sanchez, Adrian J.; Thouless, M. D.; Sakamoto, Jeff; Dasgupta, Neil P.
      Matter (2022), 5 (11), 3912-3934CODEN: MATTCG; ISSN:2590-2385. (Elsevier Inc.)
      Anode-free solid-state batteries can enable high energy densities and the ability to manuf. high-quality interfaces. However, during in situ anode formation, dynamic mech. stresses influence the initial Li metal plating morphol. This work utilizes operando 3D video microscopy to characterize electrode morphol. during in situ anode formation on garnet Li7La3Zr2O12 (LLZO) solid electrolytes. The coupled morphol. evolution and electrochem. signatures are identified and are attributed to changes in stress at the interface. We demonstrate the influence of stress on both thermodn. and kinetic behaviors at the interface. A mechanistic framework provides insight into the importance of tuning the interfacial toughness, current collector properties, stack pressure, and cell geometry to optimize performance and control plating uniformity. Informed by these insights, the areal Li coverage after 2 mAh/cm2 of plating is increased from 50% to 95%. The understanding from this study informs future optimization of in situ anode formation in solid-state systems.
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    15. 15
      Kasemchainan, J.; Zekoll, S.; Spencer Jolly, D.; Ning, Z.; Hartley, G. O.; Marrow, J.; Bruce, P. G. Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells. Nature materials 2019, 18, 1105– 1111,  DOI: 10.1038/s41563-019-0438-9
      15
      Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells
      Kasemchainan, Jitti; Zekoll, Stefanie; Spencer Jolly, Dominic; Ning, Ziyang; Hartley, Gareth O.; Marrow, James; Bruce, Peter G.
      Nature Materials (2019), 18 (10), 1105-1111CODEN: NMAACR; ISSN:1476-1122. (Nature Research)
      A crit. c.d. on stripping is identified that results in dendrite formation on plating and cell failure. When the stripping c.d. removes Li from the interface faster than it can be replenished, voids form in the Li at the interface and accumulate on cycling, increasing the local c.d. at the interface and ultimately leading to dendrite formation on plating, short circuit and cell death. This occurs even when the overall c.d. is considerably below the threshold for dendrite formation on plating. For the Li/Li6PS5Cl/Li cell, this is 0.2 and 1.0 mA cm-2 at 3 and 7 MPa pressure, resp., compared with a crit. current for plating of 2.0 mA cm-2 at both 3 and 7 MPa. The pressure dependence on stripping indicates that creep rather than Li diffusion is the dominant mechanism transporting Li to the interface. The crit. stripping current is a major factor limiting the power d. of Li anode solid-state cells. Considerable pressure may be required to achieve even modest power densities in solid-state cells.
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    16. 16
      Sandoval, S. E.; Lewis, J. A.; Vishnugopi, B. S.; Nelson, D. L.; Schneider, M. M.; Cortes, F. J. Q.; Matthews, C. M.; Watt, J.; Tian, M.; Shevchenko, P. Structural and electrochemical evolution of alloy interfacial layers in anode-free solid-state batteries. Joule 2023, 7, 2054– 2073,  DOI: 10.1016/j.joule.2023.07.022
      There is no corresponding record for this reference.
    17. 17
      Park, S. H.; Jun, D.; Lee, G. H.; Lee, S. G.; Jung, J. E.; Bae, K. Y.; Son, S.; Lee, Y. J. Designing 3D Anode Based on Pore-Size-Dependent Li Deposition Behavior for Reversible Li-Free All-Solid-State Batteries. Advanced Science 2022, 9, 2203130,  DOI: 10.1002/advs.202203130
      There is no corresponding record for this reference.
    18. 18
      Wang, M. J.; Choudhury, R.; Sakamoto, J. Characterizing the Li-solid-electrolyte interface dynamics as a function of stack pressure and current density. Joule 2019, 3, 2165– 2178,  DOI: 10.1016/j.joule.2019.06.017
      18
      Characterizing the Li-Solid-Electrolyte Interface Dynamics as a Function of Stack Pressure and Current Density
      Wang, Michael J.; Choudhury, Rishav; Sakamoto, Jeff
      Joule (2019), 3 (9), 2165-2178CODEN: JOULBR; ISSN:2542-4351. (Cell Press)
      The replacement of conventional liq. electrolytes with solid electrolytes has the potential to safely enable energy-dense Li-metal anodes. Because of the challenges surrounding solid-solid interfaces, it is crucial to better understand the Li-metal-solid-electrolyte interface. This work utilizes stack pressure to correlate mechanics with the electrochem. behavior of Li-electrolyte cells during galvanostatic cycling. Sym. cells are constructed using Li7La3Zr2O12 and tested using AC and DC techniques under dynamic stack pressure conditions. It is demonstrated that significant polarization occurs during galvanostatic cycling at a current-dependent "crit. stack pressure.". Using ref. electrodes, this effect is isolated to the Li stripping electrode. This suggests that at low pressures, the Li stripping rate exceeds the rate at which mech. deformation replenishes the interface, inducing the formation of voids and ultimately increasing resistance. This anal. not only motivates the need for further understanding of the Li-metal-solid-electrolyte interface but also provides guidelines for the future design of all-solid-state batteries.
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    19. 19
      Zhao, L.; Wang, Q. J.; Zhang, X.; Hatzell, K. B.; Zaman, W.; Martin, T. V.; Wang, Z. Laplace-Fourier transform solution to the electrochemical kinetics of a symmetric lithium cell affected by interface conformity. J. Power Sources 2022, 531, 231305,  DOI: 10.1016/j.jpowsour.2022.231305
      19
      Laplace-Fourier transform solution to the electrochemical kinetics of a symmetric lithium cell affected by interface conformity
      Zhao, Le; Wang, Q. Jane; Zhang, Xin; Hatzell, Kelsey B.; Zaman, Wahid; Martin, Tobias V.; Wang, Zhanjiang
      Journal of Power Sources (2022), 531 (), 231305CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Lithium (Li)-metal batteries using solid-state electrolytes (SSEs) have attracted extensive attention owing to their high energy d. However, the interface issues arising from the Li stripping/plating cycles pose a major challenge for the applications of these batteries. This paper reports a three-dimensional (3D) time-dependent electrokinetic model, built based on the Nernst-Planck equation with electroneutrality assumption, to quantify the effects of interface conformity, external pressure, electrolyte Young's modulus, and ionic cond. on the electrochem. behaviors of sym. solid-state lithium cells. The evolution of interface morphol. is related to the surface roughness, elastoplastic deformation, creep, and plating of the Li metal. The Laplace-Fourier domain soln. is anal. derived, and the numerical soln. is solved by implementing Talbot's Laplace transform method and the continuous convolution-Fourier transform (CC-FT) algorithm. A no. of cases are analyzed, and the results reveal that a non-conformal interface with imperfect contact can induce uneven field distributions and that the nonuniformity increases with contact loss, and that the impact of external pressure on the redn. in ionic cond. of SSE is similar to its effect on the potential drop. The results also suggest that the external pressure of 12.5 MPa can lead to relatively uniform deposition in a ceramic electrolyte system, while only 2 MPa is required in a polymer electrolyte system. In addn., A pressure of at least 2 MPa is needed to maintain the high ionic cond. level for polymer composite SSEs of 14-16% vol. LLZO particles.
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    20. 20
      Porz, L.; Swamy, T.; Sheldon, B. W.; Rettenwander, D.; Frömling, T.; Thaman, H. L.; Berendts, S.; Uecker, R.; Carter, W. C.; Chiang, Y.-M. Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv. Energy Mater. 2017, 7, 1701003,  DOI: 10.1002/aenm.201701003
      There is no corresponding record for this reference.
    21. 21
      Singh, D. K.; Henss, A.; Mogwitz, B.; Gautam, A.; Horn, J.; Krauskopf, T.; Burkhardt, S.; Sann, J.; Richter, F. H.; Janek, J. Li6PS5Cl microstructure and influence on dendrite growth in solid-state batteries with lithium metal anode. Cell reports physical science 2022, 3, 101043,  DOI: 10.1016/j.xcrp.2022.101043
      There is no corresponding record for this reference.
    22. 22
      Lin, L.; Ayyaswamy, A.; Zheng, Y.; Fan, A.; Vishnugopi, B. S.; Mukherjee, P. P.; Hatzell, K. B. Nonintuitive Role of Solid Electrolyte Porosity on Failure. ACS Energy Letters 2024, 9, 2387– 2393,  DOI: 10.1021/acsenergylett.4c00744
      There is no corresponding record for this reference.
    23. 23
      Fincher, C. D.; Athanasiou, C. E.; Gilgenbach, C.; Wang, M.; Sheldon, B. W.; Carter, W. C.; Chiang, Y.-M. Controlling dendrite propagation in solid-state batteries with engineered stress. Joule 2022, 6, 2794– 2809,  DOI: 10.1016/j.joule.2022.10.011
      23
      Controlling dendrite propagation in solid-state batteries with engineered stress
      Fincher, Cole D.; Athanasiou, Christos E.; Gilgenbach, Colin; Wang, Michael; Sheldon, Brian W.; Carter, W. Craig; Chiang, Yet-Ming
      Joule (2022), 6 (12), 2794-2809CODEN: JOULBR; ISSN:2542-4351. (Cell Press)
      Metal-dendrite penetration is a mode of electrolyte failure that threatens the viability of metal-anode-based solid-state batteries. Whether dendrites are driven by mech. failure or electrochem. degrdn. of solid electrolytes remains an open question. If internal mech. forces drive failure, superimposing a compressive load that counters internal stress may mitigate dendrite penetration. Here, we investigate this hypothesis by dynamically applying mech. loads to growing dendrites in Li6.6La3Zr1.6Ta0.4O12 solid electrolytes. Operando microscopy reveals marked deflection in the dendrite growth trajectory at the onset of compressive loading. For sufficient loading, this deflection averts cell failure. Using fracture mechanics, we quantify the impact of stack pressure and in-plane stresses on dendrite trajectory, chart the residual stresses required to prevent short-circuit failure, and propose design approaches to achieve such stresses. For the materials studied here, we show that dendrite propagation is dictated by electrolyte fracture, with electronic leakage playing a negligible role.
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    24. 24
      Reisecker, V.; Flatscher, F.; Porz, L.; Fincher, C.; Todt, J.; Hanghofer, I.; Hennige, V.; Linares-Moreau, M.; Falcaro, P.; Ganschow, S. Effect of pulse-current-based protocols on the lithium dendrite formation and evolution in all-solid-state batteries. Nat. Commun. 2023, 14, 2432,  DOI: 10.1038/s41467-023-37476-y
      There is no corresponding record for this reference.
    25. 25
      Ning, Z.; Li, G.; Melvin, D. L.; Chen, Y.; Bu, J.; Spencer-Jolly, D.; Liu, J.; Hu, B.; Gao, X.; Perera, J. Dendrite initiation and propagation in lithium metal solid-state batteries. Nature 2023, 618, 287– 293,  DOI: 10.1038/s41586-023-05970-4
      25
      Dendrite initiation and propagation in lithium metal solid-state batteries
      Ning, Ziyang; Li, Guanchen; Melvin, Dominic L. R.; Chen, Yang; Bu, Junfu; Spencer-Jolly, Dominic; Liu, Junliang; Hu, Bingkun; Gao, Xiangwen; Perera, Johann; Gong, Chen; Pu, Shengda D.; Zhang, Shengming; Liu, Boyang; Hartley, Gareth O.; Bodey, Andrew J.; Todd, Richard I.; Grant, Patrick S.; Armstrong, David E. J.; Marrow, T. James; Monroe, Charles W.; Bruce, Peter G.
      Nature (London, United Kingdom) (2023), 618 (7964), 287-293CODEN: NATUAS; ISSN:1476-4687. (Nature Portfolio)
      All-solid-state batteries with a Li anode and ceramic electrolyte have the potential to deliver a step change in performance compared with today's Li-ion batteries1,2. However, Li dendrites (filaments) form on charging at practical rates and penetrate the ceramic electrolyte, leading to short circuit and cell failure3,4. Previous models of dendrite penetration have generally focused on a single process for dendrite initiation and propagation, with Li driving the crack at its tip5-9. Here we show that initiation and propagation are sep. processes. Initiation arises from Li deposition into subsurface pores, by means of microcracks that connect the pores to the surface. Once filled, further charging builds pressure in the pores owing to the slow extrusion of Li (viscoplastic flow) back to the surface, leading to cracking. By contrast, dendrite propagation occurs by wedge opening, with Li driving the dry crack from the rear, not the tip. Whereas initiation is detd. by the local (microscopic) fracture strength at the grain boundaries, the pore size, pore population d. and c.d., propagation depends on the (macroscopic) fracture toughness of the ceramic, the length of the Li dendrite (filament) that partially occupies the dry crack, c.d., stack pressure and the charge capacity accessed during each cycle. Lower stack pressures suppress propagation, markedly extending the no. of cycles before short circuit in cells in which dendrites have initiated.
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    26. 26
      Choudhury, R.; Wang, M.; Sakamoto, J. The effects of electric field distribution on the interface stability in solid electrolytes. J. Electrochem. Soc. 2020, 167, 140501,  DOI: 10.1149/1945-7111/abc034
      There is no corresponding record for this reference.
    27. 27
      Zhang, X.; Wang, Q. J.; Harrison, K. L.; Roberts, S. A.; Harris, S. J. Pressure-driven interface evolution in solid-state lithium metal batteries. Cell Reports Physical Science 2020, 1, 100012,  DOI: 10.1016/j.xcrp.2019.100012
      There is no corresponding record for this reference.
    28. 28
      Vishnugopi, B. S.; Naik, K. G.; Kawakami, H.; Ikeda, N.; Mizuno, Y.; Iwamura, R.; Kotaka, T.; Aotani, K.; Tabuchi, Y.; Mukherjee, P. P. Asymmetric Contact Loss Dynamics during Plating and Stripping in Solid-State Batteries. Adv. Energy Mater. 2023, 13, 2203671,  DOI: 10.1002/aenm.202203671
      There is no corresponding record for this reference.
    29. 29
      Cao, D.; Zhang, K.; Li, W.; Zhang, Y.; Ji, T.; Zhao, X.; Cakmak, E.; Zhu, J.; Cao, Y.; Zhu, H. Nondestructively Visualizing and Understanding the Mechano-Electro-chemical Origins of “Soft Short” and “Creeping” in All-Solid-State Batteries. Adv. Funct. Mater. 2023, 33, 2307998,  DOI: 10.1002/adfm.202307998
      There is no corresponding record for this reference.
    30. 30
      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, 2138– 2159,  DOI: 10.1016/j.matt.2020.09.018
      There is no corresponding record for this reference.
    31. 31
      Kazyak, E.; Garcia-Mendez, R.; LePage, W. S.; Sharafi, A.; Davis, A. L.; Sanchez, A. J.; Chen, K.-H.; Haslam, C.; Sakamoto, J.; Dasgupta, N. P. Li penetration in ceramic solid electrolytes: operando microscopy analysis of morphology, propagation, and reversibility. Matter 2020, 2, 1025– 1048,  DOI: 10.1016/j.matt.2020.02.008
      There is no corresponding record for this reference.
    32. 32
      Fincher, C. D.; Ojeda, D.; Zhang, Y.; Pharr, G. M.; Pharr, M. Mechanical properties of metallic lithium: from nano to bulk scales. Acta Mater. 2020, 186, 215– 222,  DOI: 10.1016/j.actamat.2019.12.036
      32
      Mechanical properties of metallic lithium: from nano to bulk scales
      Fincher, Cole D.; Ojeda, Daniela; Zhang, Yuwei; Pharr, George M.; Pharr, Matt
      Acta Materialia (2020), 186 (), 215-222CODEN: ACMAFD; ISSN:1359-6454. (Elsevier Ltd.)
      Despite renewed interest in lithium metal anodes, unstable electrodeposition of Li during operation has obstructed progress in practical battery applications. While deformation mechanics likely play a key role in Li's mech. stability as an anode material, reports of Li's mech. properties vary widely, perhaps due to variations in testing procedures. Through bulk tensile testing and nanoindentation, we provide a comprehensive assessment of the strain-rate and length-scale dependent mech. properties of Li in its most commonly used form: high purity com. foil. We find that bulk Li exhibits a yield strength between 0.57 and 1.26 MPa for strain rates from 5E-4 s-1 to 5E-1 s-1. For indentation tests with target ̇P/P = 0.05 s-1, the hardness decreases precipitously from nearly 43 MPa to 7.5 MPa as the indentation depth increases from 250 nm to 10μm. The plastic properties measured from bulk and nanoindentation testing exhibit strong strain-rate dependencies, with stress exponents of n = 6.55 and 6.9, resp. We implement finite element anal. to relate the indentation depth to length scales of relevance in battery applications. Overall, the results presented herein may provide important guidance in designing Li anode architectures and charging conditions to mitigate unstable growth of Li during electrochem. cycling.
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    33. 33
      Papakyriakou, M.; Lu, M.; Liu, Y.; Liu, Z.; Chen, H.; McDowell, M. T.; Xia, S. Mechanical behavior of inorganic lithium-conducting solid electrolytes. J. Power Sources 2021, 516, 230672,  DOI: 10.1016/j.jpowsour.2021.230672
      33
      Mechanical behavior of inorganic lithium-conducting solid electrolytes
      Papakyriakou, Marc; Lu, Mu; Liu, Yuhgene; Liu, Zhantao; Chen, Hailong; McDowell, Matthew T.; Xia, Shuman
      Journal of Power Sources (2021), 516 (), 230672CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      All-solid-state batteries using lithium-conducting solid electrolytes (SEs) require not only favorable electrochem. properties but also optimal mech. properties. SEs need to exhibit high enough stiffness to resist lithium dendrite growth while also being compliant and ductile enough to accommodate volumetric expansions of the electrodes. Thus, understanding the chemo-mech. behavior of SE materials is essential for their effective development and deployment. In this work, the temp.-dependent deformation behavior of a range of inorg. sulfide (LSPS, LPSCl) and oxide (LAGP, LLZTO) SEs has been systematically investigated for the first time. Quasi-static, viscoelastic, and viscoplastic nanoindentation experimentation was conducted on these materials over a range of temps. (from -40 to 300°C). The elastic modulus and hardness properties of the sulfide vs. oxide material categories largely grouped together, with the cold pressed and subsequently sintered LLZTO oxide showing favorably low hardness and high tendency to creep. While all the oxide and sulfide materials exhibited minimal viscoelastic damping, consistent viscoplastic creep behavior was obsd. and quant. analyzed. The temp. dependence of the creep stress exponent was key for identifying the dominant creep mechanism in the material systems.
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    34. 34
      Athanasiou, C. E.; Fincher, C. D.; Gilgenbach, C.; Gao, H.; Carter, W. C.; Chiang, Y.-M.; Sheldon, B. W. Operando measurements of dendrite-induced stresses in ceramic electrolytes using photoelasticity. Matter 2024, 7, 95– 106,  DOI: 10.1016/j.matt.2023.10.014
      There is no corresponding record for this reference.
    35. 35
      Savruk, M. P.; Kazberuk, A. Stress Concentration at Notches; Springer International Publishing: Cham, 2017. DOI:  DOI: 10.1007/978-3-319-44555-7 .
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      Gao, H. Stress concentration at slightly undulating surfaces. Journal of the Mechanics and Physics of Solids 1991, 39, 443– 458,  DOI: 10.1016/0022-5096(91)90035-M
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      McConohy, G.; Xu, X.; Cui, T.; Barks, E.; Wang, S.; Kaeli, E.; Melamed, C.; Gu, X. W.; Chueh, W. C. Mechanical regulation of lithium intrusion probability in garnet solid electrolytes. Nature Energy 2023, 8, 241– 250,  DOI: 10.1038/s41560-022-01186-4
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      Park, S. H.; Naik, K. G.; Vishnugopi, B. S.; Mukherjee, P. P.; Hatzell, K. B. Lithium Kinetics in Ag-C Porous Interlayer in Reservoir-Free Solid-State Batteries. Adv. Energy Mater. 2024, 2405129,  DOI: 10.1002/aenm.202405129
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    39. 39
      Mussler, B.; Swain, M. V.; Claussen, N. Dependence of fracture toughness of alumina on grain size and test technique. J. Am. Ceram. Soc. 1982, 65, 566– 572,  DOI: 10.1111/j.1151-2916.1982.tb10783.x
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      Jelitto, H.; Schneider, G. A. Fracture toughness of porous materials-Experimental methods and data. Data in brief 2019, 23, 103709,  DOI: 10.1016/j.dib.2019.103709
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      Boerner, T. J.; Deems, S.; Furlani, T. R.; Knuth, S. L.; Towns, J. ACCESS: Advancing Innovation: NSF’s Advanced Cyberinfrastructure Coordination Ecosystem: Services and Support. Practice and Experience in Advanced Research Computing 2023: Computing for the Common Good-PEARC23, Portland, OR, July 23–27, 2023, ACM, 2023; pp 173– 176.
      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.5c00004.

    • Method; Schematic illustration of the test setup; Solid electrolyte surface roughness; Additional modeling results of contact maps and reaction heterogeneity; Electrochemical lithium plating results using cell employed for X-ray tomography analysis; Pressure distribution analysis results; Additional X-ray tomography results; Current density simulation results; Additional stress modeling results; Electrochemical lithium plating results using fine LPSCl pellet (PDF)


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