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Single-Ion Conducting Polymer Nanoparticles as Functional Fillers for Solid Electrolytes in Lithium Metal Batteries
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Applications of Polymer, Composite, and Coating Materials

Single-Ion Conducting Polymer Nanoparticles as Functional Fillers for Solid Electrolytes in Lithium Metal Batteries
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  • Luca Porcarelli*
    Luca Porcarelli
    POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain
    ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, 3125 Australia
    *E-mail: [email protected]
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    Orcidhttps://orcid.org/0000-0002-1624-382X
  • Preston Sutton
    Preston Sutton
    ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, 3125 Australia
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  • Vera Bocharova
    Vera Bocharova
    Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
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    Orcidhttps://orcid.org/0000-0003-4270-3866
  • Robert H. Aguirresarobe
    Robert H. Aguirresarobe
    POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain
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  • Haijin Zhu
    Haijin Zhu
    ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, 3125 Australia
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  • Nicolas Goujon
    Nicolas Goujon
    POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain
    ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, 3125 Australia
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    Orcidhttps://orcid.org/0000-0002-0555-2846
  • Jose R. Leiza
    Jose R. Leiza
    POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain
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  • Alexei Sokolov
    Alexei Sokolov
    Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
    Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States
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    Orcidhttps://orcid.org/0000-0002-8187-9445
  • Maria Forsyth*
    Maria Forsyth
    POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain
    ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, 3125 Australia
    Ikerbasque, Basque Foundation for Science, Maria Diaz de Haro 3, E−48011 Bilbao, Spain
    *E-mail: [email protected]
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    Orcidhttps://orcid.org/0000-0002-4273-8105
  • David Mecerreyes*
    David Mecerreyes
    POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain
    Ikerbasque, Basque Foundation for Science, Maria Diaz de Haro 3, E−48011 Bilbao, Spain
    *E-mail: [email protected]
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    Orcidhttps://orcid.org/0000-0002-0788-7156
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ACS Applied Materials & Interfaces

Cite this: ACS Appl. Mater. Interfaces 2021, 13, 45, 54354–54362
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https://doi.org/10.1021/acsami.1c15771
Published November 3, 2021

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Abstract

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Composite solid electrolytes including inorganic nanoparticles or nanofibers which improve the performance of polymer electrolytes due to their superior mechanical, ionic conductivity, or lithium transference number are actively being researched for applications in lithium metal batteries. However, inorganic nanoparticles present limitations such as tedious surface functionalization and agglomeration issues and poor homogeneity at high concentrations in polymer matrixes. In this work, we report on polymer nanoparticles with a lithium sulfonamide surface functionality (LiPNP) for application as electrolytes in lithium metal batteries. The particles are prepared by semibatch emulsion polymerization, an easily up-scalable technique. LiPNPs are used to prepare two different families of particle-reinforced solid electrolytes. When mixed with poly(ethylene oxide) and lithium bis(trifluoromethane)sulfonimide (LiTFSI/PEO), the particles invoke a significant stiffening effect (E′ > 106 Pa vs 105 Pa at 80 °C) while the membranes retain high ionic conductivity (σ = 6.6 × 10–4 S cm–1). Preliminary testing in LiFePO4 lithium metal cells showed promising performance of the PEO nanocomposite electrolytes. By mixing the particles with propylene carbonate without any additional salt, we obtain true single-ion conducting gel electrolytes, as the lithium sulfonamide surface functionalities are the only sources of lithium ions in the system. The gel electrolytes are mechanically robust (up to G′ = 106 Pa) and show ionic conductivity up to 10–4 S cm–1. Finally, the PC nanocomposite electrolytes were tested in symmetrical lithium cells. Our findings suggest that all-polymer nanoparticles could represent a new building block material for solid-state lithium metal battery applications.

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1. Introduction

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Solid-state lithium batteries (SSLBs) have the potential to extend the range of electric vehicles and enable large-scale storage for renewable energy. As the name implies, SSLBs have no liquid components, distinguishing them from traditional LIBs and resulting in safer and more energy-dense devices. The increased energy density of SSLBs is ascribed to a more compact design and the use of high capacity lithium metal electrodes, both of which hinge on the development of novel electrolyte materials. (1−3) Solid electrolytes that show fast lithium conduction, while avoiding the common drawbacks of liquid electrolytes such as flammability and leakage, have been extensively studied in recent years for this purpose. Among the different types of solid electrolytes, composite electrolytes that combine several materials such as polymer matrixes, inorganic nanoparticles, nanofibers, organic solvents, ionic liquids, and salts are an emerging class. (4) This is due to the limitations commonly typically shown by polymer (low ionic conductivity and lithium transference number) or inorganic solid electrolytes (low mechanical properties and interfacial stability).
An example of a composite system is obtained by mixing a conventional electrolyte matrix with nanosized fillers such as nanofibers or nanoparticles. Previous research on composite electrolytes of this type has focused on inorganic nanoparticles and polymeric nanofibers. (5) For example, inorganic nanoparticles have been used to immobilize or thicken liquid electrolytes, i.e., organic carbonates, glymes, or ionic liquids, while polymeric nanofibers such as cellulose nanofibers or electrospun PVDF nanofibers (6,7) have been used to mechanically reinforce electrolyte matrixes. (8,9) Inorganic nanoparticles have also been dispersed into polymer electrolytes, such as poly(ethylene oxide), with the aim to increase mechanical properties and ionic conductivity due to the nanostructuration effect. (10−12) However, inorganic nanoparticles suffer from agglomeration issues and poor homogeneity at high concentrations. Modifications of the inorganic nanoparticle surfaces with a polymeric shell or ionic functional groups were shown to improve nanoparticle dispersion and reduce particle agglomeration. Thus, functionalizing the nanoparticle surface with immobilized anions or polyanions has proven an effective strategy to prepare single-ion conducting electrolytes. (13−16) Despite these considerable research efforts, the synthesis of functionalized inorganic nanoparticles on a large scale presents some applicability issues such as specific surface chemistries for the grafting process and tedious purification procedures.
Surprisingly, much less attention has been paid to the use of functionalized polymeric nanoparticles despite polymers offering a wide range of easily up-scalable techniques. (17−21) For instance, emulsion polymerization, the more versatile polymerization technique to produce waterborne polymer dispersions, offers a straightforward and industrially feasible method to obtain polymer nanoparticles of a variety of compositions and with controllable and monodispersed sizes between 50 and 500 nm. (22,23) Recently, Kim et al. (24) reported the synthesis of ionic functional polymer nanoparticles by postfunctionalization strategies of polymer particles which, as indicated before, is the most straightforward option for mass production. Indeed, surface functionalization of the nanoparticles with ionic groups could be in principle carried out simply by including ionic monomers or polymerizable surfactants in the reaction formulation without the need for additional steps.
The first goal of this work is to investigate the synthesis of poly(methyl methacrylate)-functionalized polymer nanoparticles by a one-step and scalable emulsion polymerization process. The surface functionalization of the polymer nanoparticles will be attempted by including in the formulation the comonomer lithium 1-(3-(methacryloyloxy)propylsulfonyl)-1-(trifluoromethylsulfonyl)imide (LiMTFSI) which is a well-known monomer for obtaining lithium single-ion conducting polymer electrolytes. (25−27) The second goal of the work is to show the potential of these Li single-ion functional polymer nanoparticles in composite solid electrolytes for lithium batteries through two examples. In the first example, the particles were mixed with a typical solid polymer electrolyte based on lithium bis(trifluoromethanesufonyl)imide and poly(ethylene oxide). The polymer electrolyte showed high ionic conductivity and improved mechanical properties with respect to the nanoparticle-free polymer electrolyte. In the second example, the nanoparticles were combined with propylene carbonate (PC) to prepare single-ion composite gel electrolytes. The nanoparticle electrolytes showed promising ionic conductivity values and transference number close to unity. Finally, the two composite solid electrolytes were tested in symmetrical lithium cells and LiFePO4 lithium metal cells to investigate their potential in SSLBs.

2. Experimental Procedures

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Materials

Methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) were purchased from Sigma-Aldrich and vacuum distilled before use. Lithium 1-(3-(methacryloyloxy)propylsulfonyl)-1-(trifluoromethylsulfonyl)imide (LiMTFSI) was purchased from Specific Polymers and used as is. Ascorbic acid, tert-butyl hydroperoxide (70% solution in water, TBHP), and poly(ethylene oxide) (average MW 900 000 g/mol, PEO) were purchased from Sigma-Aldrich and used as is. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and battery grade propylene carbonate (PC) were purchased from Solvionic. Carbon-coated lithium iron phosphate (LiFePO4) was purchased from Aleees. Carbon black (C65) was purchased from Timcal.

Synthesis of Single-Ion Polymeric Particles by Polymerization in Disperse Media

A 250 mL three-neck flask equipped with a reflux condenser, N2 inlet, temperature probe, and three feeding inlets was first charged with 70 g of Milli-Q water, pre-heated to 80 °C, and purged with N2 for 20 min. Then the feeding of monomers and redox initiators was started at the same time. Feedings were maintained for 3 h under continuous N2 purging, and then the system was allowed to react for an additional 1 h. Table 1 contains the amounts used for the polymerization. After polymerization, the polymeric nanoparticle dispersion was filtered with an 80 μm nylon mesh to remove coagulated nanoparticles. The amount of coagulum was calculated based on the total solid content of the dispersion and was less than 1 wt %. The dispersions were dialyzed against Milli-Q water using Spectra-Por 4 membranes (MW cut-off 12000–14000 Da) to remove unattached ionic species.
Table 1. Formulation of the Dispersion Polymerization Reaction
IDinitial charge [g]feed 1 [g]feed 2 [g]feed 3 [g]size [nm]PDI
1water [70]LiMTFSI [2], ascorbic acid [0.228], water [10]MMA [9.196], EGDMA [0.184]TBHP [0.116], water [10]2000.079
2water [70]LiMTFSI [1], ascorbic acid [0.228], water [10]MMA [9.196], EGDMA [0.184]TBHP [0.116], water [10]1200.080
3water [70]LiMTFSI [0.5], ascorbic acid [0.228], water [10]MMA [9.196], EGDMA [0.184]TBHP [0.116], water [10]950.075

Titration of the LiMTFSI Surface Functionalities

A small volume of the dialyzed latexes were passed through a Dowex Marathon MSC cation exchange resin to exchange the lithium ions of the sulfonimide groups with titratable acidic protons. The concentration of acidic protons was measured using conductometric titration with a 5 mM NaOH aqueous solution. LiMTFSI incorporation was calculated as n/LIMTFSItheor, where n is number of moles of NaOH used in the titration until the end point and LIMTFSItheor is the theoretical number of moles of LIMTFSI in the formulation.

Preparation of the PEO/LiTFSI-Based Nanocomposite Electrolytes

A 5 wt % aqueous solution of poly(ethylene oxide) was mixed with a predetermined amount of LiTFSI (25% of PEO weight). Then the particle latex was mixed directly with the PEO/LiTFSI solution. The aqueous mixtures were casted onto silicon molds, and the water was removed by evaporation, producing self-standing composite polymer electrolyte films. The samples PEO/LiTFSI-based nanocomposite electrolytes were dried inside a Buchi high vacuum oven at 90 °C for 18 h before any further characterization.

Preparation of the PC-Based Gel Nanocomposite Electrolytes

Freeze-drying was used to remove water from the dialyzed nanoparticle dispersion. The obtained fine white powder was further dried under reduced pressure at 90 °C for 18 h and transferred into an argon-filled glovebox. Then the particles were mechanically mixed with dry propylene carbonate (20 to 60 wt % of LiPNPs in PC) to obtain the gel nanocomposite electrolytes.

Physical–Chemical Characterization

DMA experiments were performed on a PerkinElmer DMA 8000 in tension mode with a heating rate of 5 °C min–1, at 1 Hz frequency, at a strain of 25 μm, and in a N2 atmosphere. Small-amplitude oscillatory experiments were performed in a stress-controlled Anton Paar Physica MCR101 rheometer, and the experiments were carried out using 25 mm parallel plate geometry. All the experiments were conducted under linear viscoelastic conditions for the studied temperature range (strain = 0.5% and frequency 1 Hz). DSC experiments were performed on a Netzsch DSC 214 Polyma, using a heating rate of 5 °C min–1. Analysis was performed on second heating curves using Proteus software and AutoEvaluation. Broadband dielectric spectra in the frequency range of 10–1 to 106 Hz were measured using an Novocontrol Concept-80 system, which includes an Alpha-A impedance analyzer and a Quatro Cryosystem temperature control unit. The samples were placed between stainless steel parallel plates with a 20 mm diameter, and the separation between the electrodes was determined by the film thickness, approximately 0.2 mm. The samples were placed inside the cryostat in a dry nitrogen atmosphere. The samples were equilibrated for at least 15 min after each temperature step to achieve thermal stabilization within 0.2 K. Electrochemical impedance spectra were measured, applying a 10 mV perturbation in a frequency range of 10–1 to 106 Hz with an Autolab 302N potentiostat galvanostat, which includes a FRA32 M module and a Microcell HC temperature control unit. The samples were placed between gold-plated parallel plates with a 9 mm diameter, and the separation between the electrodes was determined by the film thickness, approximately 0.2 mm.

Pulsed Field-Gradient Nuclear Magnetic Resonance

PFG-NMR experiments were performed on a Bruker Avance III wide-bore NMR spectrometer equipped with a 5 mm Diff50 probe. The maximum strength of the gradient amplifier was 29.4 T/m. 19F and 7Li diffusion coefficients were measured with separate RF coils which were tuned to the target nuclei frequency. The diffusion time was 100 ms for both 1H and 19F, and the gradient pulse durations were 10 ms and 5 ms for 19F and 7Li, respectively. A sample amount of approximately 70 mg was first packed into a 4 mm ZrO2 magic-angle spinning (MAS) rotor, and the packed rotor was then inserted into a 5 mm glass tube for diffusion measurement. A pulsed-field gradient stimulated echo (PFG-STE) sequence was used to obtain the diffusion coefficient. (35) The sample temperature in the probe was calibrated in a temperature range of 0–70 °C, using the relative chemical shift separation between the OH and CH3 resonances of dry methanol. (36)

Coin Cell Assembly

A composition of 60 wt % of carbon-coated LiFePO4, 30 wt % of PEO-NP10, and 10 wt % of carbon black was used for cathode preparation. First, powders of active material and carbon black were gently mixed in a hand mortar and successively added to a 5 wt % aqueous solution of PEO-NP10. The suspension was homogenized using an Ultraturrax mixer for 1 h. The aqueous slurry was cast onto a carbon-coated aluminum current collector using a doctor-blade with a blade height of 300 μm. The electrodes where dried in an oven at 50 °C. A PEO-NP10 film was hot-pressed onto the electrodes (70 °C at 10 bar for 10 min), dried at 70 °C/high vacuum for 24 h, and transferred to the glovebox. The areal capacity of the LFP cathode was 0.6 mAh cm2. LiFePO4/PEO-NP10/lithium metal coin cells were assembled in the glovebox. The coin cells were cycled at 70 °C at a constant C/10 current regime between 2.5 and 3.8 V versus Li+/Li. Lithium symmetrical coin cells were assembled inside the glovebox by sandwiching a PC-NP20 or a PC-NP30 film in between two lithium metal disks.

3. Results and Discussion

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Synthesis of Lithium Sulfonamide Functional Poly(methyl methacrylate) Nanoparticles

As indicated previously, our goal here was to develop a one-pot synthetic method to obtain polymer nanoparticles which include lithium sulfonamide groups on their surface. These groups are the preferred option nowadays for the development of the so-called single-ion lithium conducting polymers due to the high charge delocalization of the sulfonamide anion which benefits lithium cation mobility. In our approach, single-ion nanoparticles were obtained in the form of a colloidal dispersion in water, commonly defined as latex, adapting a semibatch emulsion polymerization strategy reported in detail elsewhere. (19−21) Briefly, the reactor was initially charged with water, purged with a gentle flow of N2, and heated to 80 °C. Three streams were injected to the reactor: the first contained the main monomer (methyl methacrylate, MMA) and the cross-linker (ethylene glycol dimethacrylate, EGDMA); the second contained the functional comonomer (LiMTFSI) and the reductant of the redox pair used to generate radicals (ascorbic acid); the third stream was the oxidant (tert-butyl hydroperoxide, TBHP) of the redox pair. The solids content of the synthesized latex was 5 wt %. Notably, surfactants were not used in the emulsion polymerization process, and the stability of the latex was achieved by the incorporation of the functional monomers (LiMTFSI) to the surface of the polymer particles and the electrostatic repulsion of the negatively charged particles as schematically shown in Figure 1. Figure 1(a) shows a schematic representation of the polymeric nanoparticle synthesis. The prepared latexes were purified by dialysis to remove unreacted monomers. The ionic monomer LiMTFSI served multiple functions of (1) providing colloidal stability to the dispersion of polymeric particles, (2) providing the desired functionality into the surface of the polymer particles, and (3) control of the polymer particle size by adjusting its concentration in the reaction formulation. Interestingly, we were able to control the size of the polymer nanoparticles by changing the LiMTFSI concentration in the reaction formulation. Dynamic light scattering (DLS) revealed a correlation between the LiMTFSI concentration in the reaction formulation and the number-average size of the particles. The size increased from 95 to 200 nm when the LiMTFSI concentration in the reaction formulation decreased from 2 g to 0.5 g. All samples showed a narrow polydispersity index (PDI), as shown in Table 1.

Figure 1

Figure 1. (a) Schematic representation of the polymeric nanoparticle synthesis and structure. (b) FESEM image of the polymeric nanoparticles. (c) DSC trace of the polymeric nanoparticles between 0 °C and 145 °C, 2nd heating at 5 °C/min.

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Field emission scanning electron microscopy (FESEM) images confirmed the particle size as measured by DLS and showed uniform spherical morphology of the polymeric particles; see Figure 1(b). Among the different particles available, we selected the one with smaller size for further study (d = 95 nm, PDI = 0.075). The particles were characterized by a single glass transition temperature (Tg) at 122 °C, Figure 1(c). Besides the morphological characterization, a surface characterization of the particles was carried out to verify their functionality. By means of an acid–base titration method, we estimated that 80% mol of LiMTFSI monomer resides on the surface of the particles. Using this information, we calculated a surface density of five sulfonamide functional groups per nm2. The measured density value is higher than those achieved by Agrawal et al. via an inorganic nanoparticle functionalization process (1.3 chains per nm2), (28) thus demonstrating that our simple one-step method can replicate the result of a more complex synthesis of functionalized inorganic nanoparticles. Overall, the semibatch emulsion polymerization in the disperse media process described here leads to lithium sulfonamide functional poly(methyl methacrylate) nanoparticles of particle sizes between 90 and 200 nm. These latexes could be lyophilized to obtain polymer nanoparticles in the form of powders. In the next sections, the potential use of these functional nanoparticles in composite electrolytes for lithium batteries will be investigated.

Composite Solid All-Polymer Electrolytes Based on Poly(ethylene oxide) and Single-Ion Polymeric Nanoparticles

Solid electrolytes based on poly(ethylene oxide) (PEO) are considered reference materials for solid-state cells, and it is speculated that commercial solid-state batteries from Bolloré employ PEO-based electrolytes. (29) However, the ionic conductivity of PEO does not reach usable levels (10–4 S cm–1) until melting of the polymer semicrystalline regions (Tm ∼ 60 °C). At these high operating temperatures, PEO mechanical properties are lost and different strategies such as PEO cross-linking, blending, or the use of block copolymers have been proposed to circumvent this issue. On the other hand, the mechanical properties of PEO polymer electrolytes can be improved by preparing composites using nanosized reinforcement inorganic materials (SiO2 or TiO2 nanoparticles). (8,9) In this work, the single-ion polymeric nanoparticles were investigated here to the same end as reinforcement fillers improving the mechanical properties of PEO polymer electrolytes. For this purpose, we took as a reference electrolyte, a high molecular weight PEO (average MW 900 000 g/mol) with 25 wt % LiTFSI with respect to the PEO weight. The concentration of single-ion nanoparticles in the composites was varied between 10 and 50 wt % with respect to the total weight. The samples were named as follows: PEO-NP10, PEO-NP20, PEO-NP30, and PEO-NP50 (the number represents the weight percent of polymer particles in the composite). The composite electrolytes were prepared easily by mixing the particle latex directly with an aqueous solution of lithium bis(trifluoromethanesufonyl)imide and poly(ethylene oxide), Figure 2(a). Interestingly, the polymer latexes did not lose colloidal stability upon mixing with the polymer/lithium salt solution. The aqueous mixtures were cast onto silicon molds, and the water was removed by evaporation, producing self-standing composite polymer electrolyte films. This preparation process is very convenient and green because it does not require the use of solvents other than water.

Figure 2

Figure 2. Solid polymer electrolytes based on poly(ethylene oxide): LiTFSI (75:25 wt %) and single-ion nanoparticles (NPS) with loadings from 0 to 50 wt %. (a) Schematic representation of the composite electrolyte. (b) Photography of a composite electrolyte. (c) Plot of the storage modulus (E′) as a function of temperature. (d) Plot of DSC showing glass transitions and melting peaks, 2nd heating at 5 °C min–1. (e) Plot of ionic conductivity (σ) as a function of temperature. (f) Plot of specific capacity versus cycle number of a Li/PEO-NP10/LiFePO4 cell at 70 °C, electrode active loading 0.6 mAh cm2.

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Dynamic mechanical analysis (DMA) was used to determine the impact of the nanoparticle content on the modulus of the PEO-based composite electrolytes. Figure 2(b) shows the plot of the storage modulus between −60 °C and 90 °C, consisting of multiple characteristic plateaus. The low temperature plateau below −50 °C corresponds to the glassy state and is equal for all samples to approximately 2.0 × 109 Pa. This suggests that at low temperatures the stiffness of the samples is related to the PEO matrix and is independent of the nanoparticle concentration. As the samples are heated through the glass transition temperature of the PEO, between −50 °C and −40 °C, the stiffening effects of the nanoparticles that result from the PEO matrix–particle interactions become visible, seemingly reducing the storage modulus loss at the glass transition for higher particle concentrations. As the concentration increases, the softening associated with PEO transitioning to a rubbery state is effectively limited. At approximately 40 °C, all samples show a sharp loss in modulus corresponding to the PEO crystalline region melting, showing that the sample stiffness is related to both nanoparticle concentration and crystallized PEO. Above 70 °C, the nanoparticles alone still deliver a significant stiffening effect on the PEO matrix, increasing the storage modulus from the 106 Pa range to 107 Pa range. Figure 2(c) shows differential scanning calorimetry (DSC) curves of the PEO-based composite electrolytes. The graph shows that adding nanoparticles decreases the change in the heat flow at the glass transition around −45 °C, consistent with the DMA results. In addition, the melting peak of the PEO crystalline phase around 50 °C decreases as the concentration of nanoparticles increases. We note that while the transition signal and the melting peaks are weakening, the calculated values are relatively constant for all but the PEO-NP50 sample. The glass transition established from curve analysis is −42.0 ± 1.1 °C for PEO-NP0 through PEO-NP30, and −36.5 °C for PEO-NP50; see Table S1. Using a heat of fusion for 100% crystalline PEO of 196.6 J g–1, (30) the percent crystallinity of the PEO regions was found to be approximately 45% for all but the PEO-NP50 sample, where it was closer to 35%. While not totally conclusive, it does suggest that the high concentration of particles in the PEO-NP50 sample limits the crystallization of PEO matrix compared to the other samples.
Next, the conductivity was estimated from broadband dielectric spectroscopy (BDS) using the DC plateau from spectra in the conductivity representation. Figure 2(d) shows the plot of ionic conductivity between −10 °C and 80 °C, for PEO-NP10, PEO-NP20, and PEO-NP30. PEO-NP0 and PEO-NP50 were excluded due to low modulus and low conductivity, respectively. The electrolyte with the lowest polymeric nanoparticle loading, PEO-NP10, showed the highest ionic conductivity, 1.0 × 10–6 S cm–1 at 20 °C and 6.6 × 10–4 S cm–1 at 80 °C. Increasing the nanoparticle loading decreased the ionic conductivity for all samples. The lowest ionic conductivity values were measured for sample PEO-NP30, 9.0 × 10–8 S cm–1 at 20 °C, and 1.7 × 10–4 S cm–1 at 80 °C. The conductivity reduction with increased nanoparticle wt % is correlated with an overall stiffening of the samples, an increased tortuosity of the lithium ions path due to the presence of the particles, and overall decrease of mobile ion concentration. Finally, the electrochemical performance of the polymer nanoparticle composites was evaluated in LiFePO4 lithium metal cells where PEO-NP10 was used both as electrolyte material and binder for the positive electrode. The LFP loading in the cathode was 0.6 mAh cm2. Figure 2(f) shows long-term cycling performance at a constant current rate of C/10. After 100 cycles, the capacity retention was found to exceed 83% of the initial capacity, and the Coulombic efficiency approached 100%, demonstrating excellent cell performance of the composite electrolytes.

Composite Gel Electrolytes Based on Single-Ion Polymeric Nanoparticles and Propylene Carbonate

Gel polymer electrolytes are semisolid electrolytes which combine the mechanical and structural properties of polymers and the ionic conductivity of organic solvent or ionic liquid-based electrolytes. Gel polymer electrolytes can be prepared using a variety of materials as thickening agents such as polymer networks, supramolecular polymers, or block copolymers. Inorganic nanoparticles can be also used to obtain gel electrolyte. When gel electrolytes are combined with lithium single-ion conductors, a unique combination of high transference number and high ionic conductivity near room temperature can be achieved. (30) In this work, our dry polymer particles were directly mixed with propylene carbonate (PC) in ratios between 20 and 60 wt % to obtain composite gel electrolytes. The nanoparticle/PC mixtures were coded as PC-NP20, PC-NP30, PC-NP40, PC-NP50, and PC-NP60 where the number represents the wt % of polymeric nanoparticles. Figure 3(a,b) shows a schematic representation of the composite electrolyte together with a picture of sample PC-NP60. At 20 wt % nanoparticle loading, a viscous liquid was produced, and adding more than 30 wt % caused gelation of the liquid electrolyte, while increasing the particle concentration further effectively solidified the electrolyte. Figure 3(c) shows the evolution of the shear moduli for the different samples as a function of temperature. Our results show that the shear storage modulus (G′) increased with the polymer particle loading of the composite electrolyte. At room temperature, the G′ of NP-20 was around 10 Pa while the value of G′ for NP-60 approached 106 Pa, corresponding to a rubbery state. At higher temperatures, moduli of low loading samples (PC-NP20 and PC-NP30) decreased almost 3 orders of magnitude from initial values, while high loading samples decreased less than 1 order of magnitude over the same temperature range. Samples with the lowest particle loading showed shear loss modulus values (G′′) greater than G′ over the entire temperature range studied. PC-NP20 behaved as a free-flowing liquid throughout the experiment, suggesting that the particles are isolated in the PC matrix and cannot form percolating clusters to improve the mechanical properties of the composite. When increasing the particle loading to 30 wt %, the difference between G′′ and G′ decreases and NP-30 shows a crossing point just below room temperature. We hypothesize that the particles start to form percolating clusters at this stage, providing better mechanical properties to the electrolyte. For particle loadings equal to or higher than 40 wt %, G′ was higher than G′′, suggesting the formation of a mechanically robust network of polymeric particle clusters. With increasing temperature, the composite entered a free-flowing regime, as we observed a crossing point between G′ and G′′ slightly above 50 °C for NP-40. At this temperature, it is likely that the interparticle interactions of the suspected clusters are weakened, evidenced by the increased loss, disrupting their ability to stiffen the sample. Remarkably, PC-NP50 and PC-NP60 showed no crossing points between G′ and G′′ in the entire temperature range, suggesting that the polymeric particle network had percolated through the sample at these concentrations. The measured rheological properties are comparable with that of silica nanoparticle-reinforced PC electrolytes reported by Archer and co-workers. (28,31,32) In the more ridged samples (G′ > G′′), there is a weaker dependence between modulus and temperature, i.e., G′ only decreases 1 order of magnitude between 0 °C and 100 °C. However, in the free-flowing samples (G′′ > G′), the dependence between the modulus and the temperature is significant, up to 3 orders of magnitude for PC-NP20.

Figure 3

Figure 3. Gel electrolytes based on propylene carbonate and single-ion nanoparticles. Nanoparticle loadings are between 20 and 60 wt %. (a) Schematic representation of the composite electrolyte. (b) Photography of a composite electrolyte. (c) Plot of shear (G′) and loss (G′′) modulus as a function of temperature. (d) Plot of ionic conductivity (σ) as a function of temperature. (e) Plot of shear modulus (G′) as a function of the ionic conductivity (σ). (f) Plot of self-diffusion coefficients for 7Li and 19F as a function of temperature.

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After investigating the rheological properties of the nanoparticle/PC composites, we investigated its electrochemical properties. It is worth remembering that the ionic conductivity of our gels can be only due to the free lithium cations, therefore essentially making these gels single-ion conductors, because the anion is attached to the particles. We used sample resistance obtained from electrochemical impedance spectroscopy (EIS) to calculate the ionic conductivity of the composites, Figure 3(d) shows the plot of ionic conductivity at different polymer nanoparticle loadings in the temperature range of 5 °C to 85 °C. The electrolyte with the lowest polymeric nanoparticle loading, PC-NP20, shows the highest ionic conductivity, 9.5 × 10–5 S cm–1 at 25 °C and 2.8 × 10–4 S cm–1 at 85 °C. Increasing the nanoparticle loading decreased the ionic conductivity for all samples. The lowest ionic conductivity values were measured for sample PC-NP60 (6.6 × 10–6 S cm–1 at 25 °C and 4.4 × 10–5 S cm–1 at 85 °C). Conductivities could be easily fit using the Arrhenius equation. The activation energy increases with nanoparticle loading and is between 16.1 kJ mol–1 for PC-NP20 and 29.9 kJ mol–1 for PC-NP60. Figure 3(e) shows a direct comparison of the shear modulus with the ionic conductivity. Lines are drawn as a guide to the eyes; the top left point of each line corresponds to 5 °C whereas the bottom right point corresponds to 85 °C. The plot shows that the moduli of the nanocomposites extend over 7 orders of magnitude (106 < G′ < 10–2 Pa). In contrast, ionic conductivity values extend over a smaller range of roughly 3 orders of magnitude (10–6 < σ < 10–4 S1– cm). In the region of solidlike behavior (G′ > G′′), the conductivity is much more sensitive to temperature than the modulus. This suggests that the nanoparticle network is relatively stable, and that the heat energy is activating more ions for conductivity rather than softening the sample by reducing the nanoparticle–nanoparticle or nanoparticle–PC interactions. This is compared with the liquidlike behavior (G′′ > G′), where the opposite is taking place. Samples PC-NP30 and PC-NP40 show a transition between the two regimes, but at different temperatures, suggesting that there is some critical nanoparticle concentration for each temperature where heat will activate ions faster than disrupt nanoparticle interactions.
Next, the pulsed field-gradient NMR (PFG NMR) method was used to measure the self-diffusion coefficients of the lithium ions (DLi) and the TFSI moieties attached to the polymeric particles (DF). Because the only fluorine atoms present in the systems are contained in the TFSI moieties, we could directly associate the DF to the self-diffusion of the anions (DMTFSI). We limited our investigation to three samples (PC-NP20, PC-NP30, and PC-NP40) because self-diffusion coefficients were too small to be measurable for higher NP concentrations. The 7Li NMR spectra showed a single signal, indicating the presence of a single coordination environment for the lithium ions in the samples. This evidence suggests that the lithium ions are dissociated from their highly delocalized MTFSI counter-ions and fully solvated by the propylene carbonate molecules. The temperature-dependent values of DLi and DMTFSI for the composite electrolytes are summarized in Table S2, and the Arrhenius plots are shown in Figure 3(f). Like the ionic conductivity values, the self-diffusion coefficients decreased with the particle loading for both DLi and DMTFSI. The electrolyte with the lowest polymeric nanoparticle loading, PC-NP20, showed the highest DLi of 9.75 × 10–11 m2 s–1 at 75 °C. Increasing the nanoparticle loading decreased the lithium self-diffusion for all samples. The lowest ionic diffusivity values were measured for sample NP-40, corresponding to 1.46 × 10–11 m2 s–1 at 75 °C. All samples showed DMTFSI values that are 3 to 4 orders of magnitude smaller than the DLi. DMTFSI for PC-NP20 was 2.24 × 10–13 m2 s–1 at 75 °C. When increasing the particle loading, the DMTFSI value at room temperature was too small to be measurable. Interestingly, the measured lithium self-diffusion coefficients were only slightly smaller than the values reported by Hayamizu et al. (33) for a 1 M LiTFSI in PC. However, the DMTFSI corresponding to our anionic nanoparticles were several orders of magnitude lower than the DTFSI values reported by the same authors for 1 M LiTFSI in PC. This is due to well established dynamics of anions in traditional dual ion solutions, where anions are usually faster than that of lithium ions that travel with a large solvation shell. However, the ionic mobility in our system is inverted, with Li being the more mobile of the two ions, proving that tethering the anions to a particle surface is an effective strategy for decreasing their motion.
To confirm this, we measured the lithium transference number of PC-NP20 using the Vincent and Bruce method. (34) The calculated value was t+ = 0.8 at 25 °C (Figure S1). This quick estimation of the lithium transference number suggests that our electrolyte does in fact behave very close to a single-ion conductor, bearing in mind that some small contribution may come from the migration of the anion-functionalized NPs. (15,16) Overall, this shows the validity of our goal to obtain single-ion gel polymer electrolytes simply by blending the lithium sulfonamide PMMA functional polymer nanoparticles with an organic solvent such as propylene carbonate. To demonstrate the suitability of these composite electrolytes for lithium metal batteries, coin cells were assembled and cycled galvanostatically at 50 °C. Figure 4 shows the performance of PC-NP30 and PC-NP40 in a symmetrical lithium cell cycled at 0.1 mA cm–2. The recorded overvoltage was 100 mV and 125 mV for NP30 and PC-NP40, respectively. The test was carried out over a period of 220 h and showed a relative stable overvoltage with no short-circuits. Although these initial results are encouraging, further optimization work is required to achieve lower overvoltages at higher current densities comparable to commercial grade electrodes for lithium batteries.

Figure 4

Figure 4. Gel electrolytes based on propylene carbonate and single-ion nanoparticles. Plot of the overpotential as a function of time for a symmetrical lithium cell cycled at 0.1 mA cm–2 at 50 °C with (a, b) PC-NP30 and (c, d) PC-NP40 electrolyte.

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4. Conclusions

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In this work, we reported the synthesis of lithium sulfonamide surface-functionalized polymer nanoparticles by a semibatch emulsion polymerization process that can be scaled-up easily. The lithium sulfonamide functionalization was introduced into cross-linked poly(methyl methacrylate) by including into the typical emulsion polymerization formulation just the LiMTFSI comonomer. Polymer nanoparticles of sizes ranging from 90 to 200 nm were obtained in gram scale with a surface functionalization of five functional groups per nm2 in the form of stable polymer latex or dry powder of nanoparticles after lyophilization. The polymer nanoparticles were used to prepare two different composite solid electrolytes for lithium batteries. In the first example, we used the particle as nanoreinforcement, or filler, to improve the mechanical properties of a reference electrolyte based on high molecular weight PEO and 25 wt % LiTFSI. The particles delivered a significant stiffening effect on the PEO matrix (E′ > 106 Pa at 80 °C) while the membranes retained high ionic conductivity values (σ = 6.6 × 10–4 S cm–1). In the second example, the particles were mixed directly with propylene carbonate without any additional salt. The obtained gel electrolytes were mechanically robust (up to G′ = 106 Pa) and exhibited a lithium transference number close to unity. This case shows that the polymer nanoparticle can be used as a functional filler to obtain single-ion lithium conducting composite solid electrolytes. Finally, the two families of particle-reinforced electrolytes were tested in of symmetrical lithium cells and LiFePO4 lithium metal cells, showing promising performance. Balancing mechanical properties and lithium-ion mobility of an electrolyte remains an elusive target that will require further research efforts; however, in this work we present a promising new building block material to address this technological challenge.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.1c15771.

  • DSC curve analysis, fitting results from Netzsch, self-diffusion coefficients table, and polarization and impedance spectra (PDF)

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Author Information

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  • Corresponding Authors
    • Luca Porcarelli - POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain;  ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, 3125 Australia;  Orcidhttps://orcid.org/0000-0002-1624-382X;  Email: [email protected]
    • Maria Forsyth - POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain;  ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, 3125 Australia;  Ikerbasque, Basque Foundation for Science, Maria Diaz de Haro 3, E−48011 Bilbao, Spain;  Orcidhttps://orcid.org/0000-0002-4273-8105;  Email: [email protected]
    • David Mecerreyes - POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain;  Ikerbasque, Basque Foundation for Science, Maria Diaz de Haro 3, E−48011 Bilbao, Spain;  Orcidhttps://orcid.org/0000-0002-0788-7156;  Email: [email protected]
  • Authors
    • Preston Sutton - ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, 3125 Australia
    • Vera Bocharova - Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States;  Orcidhttps://orcid.org/0000-0003-4270-3866
    • Robert H. Aguirresarobe - POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain
    • Haijin Zhu - ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, 3125 Australia
    • Nicolas Goujon - POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain;  ARC Centre of Excellence for Electromaterials Science and Institute for Frontier Materials, Deakin University, Melbourne, 3125 Australia;  Orcidhttps://orcid.org/0000-0002-0555-2846
    • Jose R. Leiza - POLYMAT University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018, Donostia−San Sebastian, Spain
    • Alexei Sokolov - Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States;  Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States;  Orcidhttps://orcid.org/0000-0002-8187-9445
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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L.P. has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska–Curie grant agreement no. 797295. P.S. has been funded by the SNSF (Swiss National Science Foundation) under project number P2FRP2_191846. J.R.L. and D.M. acknowledge the funding by the Basque Government (IT99-16). V.B. acknowledges support from the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory (ORNL), managed by UT-Battelle, LLC, for the U.S. Department of Energy under contract no. DE-AC05-00OR22725. A.S. acknowledges financial support for dielectric measurements and data discussions by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

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    Srivastava, S.; Schaefer, J. L.; Yang, Z.; Tu, Z.; Archer, L. A. 25th Anniversary Article: Polymer-Particle Composites: Phase Stability and Applications in Electrochemical Energy Storage. Adv. Mater. 2014, 26, 201– 234,  DOI: 10.1002/adma.201303070
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    12
    25th Anniversary Article: Polymer-Particle Composites: Phase Stability and Applications in Electrochemical Energy Storage
    Srivastava, Samanvaya; Schaefer, Jennifer L.; Yang, Zichao; Tu, Zhengyuan; Archer, Lynden A.
    Advanced Materials (Weinheim, Germany) (2014), 26 (2), 201-234CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
    This review discusses progress in the last decade in understanding phase behavior, structure, and properties of nanoparticle-polymer composites. The review takes a decidedly polymers perspective and explores how phys. and chem. approaches may be employed to create hybrids with controlled distribution of particles. Applications are studied in two contexts of contemporary interest: battery electrolytes and electrodes. In the former, the role of dispersed and aggregated particles on ion-transport is considered. In the latter, the polymer is employed in such small quantities that it has been historically given titles such as binder and carbon precursor that underscore its perceived secondary role. Considering the myriad functions the binder plays in an electrode, it is surprising that highly filled composites have not received more attention. Opportunities in this and related areas are highlighted where recent advances in synthesis and polymer science are inspiring new approaches, and where newcomers to the field could make important contributions.
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  13. 13
    Villaluenga, I.; Inceoglu, S.; Jiang, X.; Chen, X. C.; Chintapalli, M.; Wang, D. R.; Devaux, D.; Balsara, N. P. Nanostructured Single-Ion-Conducting Hybrid Electrolytes Based on Salty Nanoparticles and Block Copolymers. Macromolecules 2017, 50, 1998– 2005,  DOI: 10.1021/acs.macromol.6b02522
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    13
    Nanostructured Single-Ion-Conducting Hybrid Electrolytes Based on Salty Nanoparticles and Block Copolymers
    Villaluenga, Irune; Inceoglu, Sebnem; Jiang, Xi; Chen, Xi Chelsea; Chintapalli, Mahati; Wang, Dunyang Rita; Devaux, Didier; Balsara, Nitash P.
    Macromolecules (Washington, DC, United States) (2017), 50 (5), 1998-2005CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
    We report on the synthesis and characterization of a series of microphase-sepd., single-ion-conducting block copolymer electrolytes. Salty nanoparticles comprising silsesquioxane cores with covalently bound polystyrenesulfonyllithium (trifluoromethylsulfonyl)imide (PSLiTFSI) chains were synthesized by nitroxide-mediated polymn. Hybrid electrolytes were obtained by mixing the salty nanoparticles into a microphase-sepd. polystyrene-b-poly(ethylene oxide) (SEO) block copolymer. Miscibility of PSLiTFSI and poly(ethylene oxide) (PEO) results in localization of the nanoparticles in the PEO-rich microphase. The morphol. of hybrid electrolytes was detd. by scanning TEM. We explore the relation between the morphol. and ionic cond. of the hybrid. The transference no. of the electrolyte with the highest ionic cond. was measured by dc polarization to confirm the single-ion-conducting character of the electrolyte. Discharge curves obtained from lithium metal-hybrid electrolyte-FePO4 batteries are compared to the data obtained from the batteries with a conventional block copolymer electrolyte.
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  14. 14
    Schaefer, J. L.; Yanga, D. A.; Archer, L. A. High Lithium Transference Number Electrolytes via Creation of 3-Dimensional, Charged, Nanoporous Networks from Dense Functionalized Nanoparticle Composites. Chem. Mater. 2013, 25, 834– 839,  DOI: 10.1021/cm303091j
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    14
    High lithium transference number electrolytes via creation of 3-dimensional, charged, nanoporous networks from dense functionalized nanoparticle composites
    Schaefer, Jennifer L.; Yanga, Dennis A.; Archer, Lynden A.
    Chemistry of Materials (2013), 25 (6), 834-839CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    High lithium transference no., tLi+, electrolytes are desired for use in both lithium-ion and lithium metal rechargeable battery technologies. Historically, low tLi+ electrolytes have hindered device performance by allowing ion concn. gradients within the cell, leading to high internal resistances that ultimately limit cell lifetime, charging rates, and energy d. Herein, we report on the synthesis and electrochem. features of electrolytes based on nanoparticle salts designed to provide high tLi+. . The salts are created by cofunctionalization of metal oxide nanoparticles with neutral org. ligands and tethered lithium salts. When dispersed in a conducting fluid such as tetraglyme, they spontaneously form a charged, nanoporous network of particles at moderate nanoparticle loadings. Modification of the tethered anion chem. from -SO3- to -SO3BF3- is shown to enhance ionic cond. of the electrolytes by facilitating ion pair dissocn. At a particle vol. fraction of 0.15, the electrolyte exists as a self-supported, nanoporous gel with an optimum ionic cond. of 10-4 S/cm at room temp. Galvanostatic polarization measurements on sym. lithium metal cells contg. the electrolyte show that the cell short circuit time, tSC, is inversely proportional to the square of the applied c.d. tSC ∼ J-2, consistent with previously predicted results for traditional polymer-in-salt electrolytes with low tLi+. . Our findings suggest that electrolytes with tLi+ ≈ 1 and good ion-pair dissocn. delay lithium dendrite nucleation and may lead to improved lithium plating in rechargeable batteries with metallic lithium anodes.
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  15. 15
    Zhang, H.; Li, C.; Piszcz, M.; Coya, E.; Rojo, T.; Rodriguez-Martinez, L. M.; Armand, M.; Zhou, Z. Single Lithium-Ion Conducting Solid Polymer Electrolytes: Advances and Perspectives. Chem. Soc. Rev. 2017, 46, 797– 815,  DOI: 10.1039/C6CS00491A
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    Single lithium-ion conducting solid polymer electrolytes: advances and perspectives
    Zhang, Heng; Li, Chunmei; Piszcz, Michal; Coya, Estibaliz; Rojo, Teofilo; Rodriguez-Martinez, Lide M.; Armand, Michel; Zhou, Zhibin
    Chemical Society Reviews (2017), 46 (3), 797-815CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    Electrochem. energy storage is one of the main societal challenges to humankind in this century. The performances of classical Li-ion batteries (LIBs) with non-aq. liq. electrolytes have made great advances in the past two decades, but the intrinsic instability of liq. electrolytes results in safety issues, and the energy d. of the state-of-the-art LIBs cannot satisfy the practical requirement. Therefore, rechargeable lithium metal batteries (LMBs) have been intensively investigated considering the high theor. capacity of lithium metal and its low neg. potential. However, the progress in the field of non-aq. liq. electrolytes for LMBs has been sluggish, with several seemingly insurmountable barriers, including dendritic Li growth and rapid capacity fading. Solid polymer electrolytes (SPEs) offer a perfect soln. to these safety concerns and to the enhancement of energy d. Traditional SPEs are dual-ion conductors, in which both cations and anions are mobile and will cause a concn. polarization thus leading to poor performances of both LIBs and LMBs. Single lithium-ion (Li-ion) conducting solid polymer electrolytes (SLIC-SPEs), which have anions covalently bonded to the polymer, inorg. backbone, or immobilized by anion acceptors, are generally accepted to have advantages over conventional dual-ion conducting SPEs for application in LMBs. A high Li-ion transference no. (LTN), the absence of the detrimental effect of anion polarization, and the low rate of Li dendrite growth are examples of benefits of SLIC-SPEs. To date, many types of SLIC-SPEs have been reported, including those based on org. polymers, org.-inorg. hybrid polymers and anion acceptors. In this review, a brief overview of synthetic strategies on how to realize SLIC-SPEs is given. The fundamental phys. and electrochem. properties of SLIC-SPEs prepd. by different methods are discussed in detail. In particular, special attention is paid to the SLIC-SPEs with high ionic cond. and high LTN. Finally, perspectives on the main challenges and focus on the future research are also presented.
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    Diederichsen, K. M.; McShane, E. J.; McCloskey, B. D. Promising Routes to a High Li+ Transference Number Electrolyte for Lithium Ion Batteries. ACS Energy Lett. 2017, 2, 2563– 2575,  DOI: 10.1021/acsenergylett.7b00792
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    16
    Promising Routes to a High Li+ Transference Number Electrolyte for Lithium Ion Batteries
    Diederichsen, Kyle M.; McShane, Eric J.; McCloskey, Bryan D.
    ACS Energy Letters (2017), 2 (11), 2563-2575CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
    A review. The continued search for routes to improve the power and energy d. of lithium ion batteries for elec. vehicles and consumer electronics has resulted in significant innovation in all cell components, particularly in electrode materials design. In this Review, we highlight an often less noted route to improving energy d.: increasing the Li+ transference no. of the electrolyte. Turning to Newman's original lithium ion battery models, we demonstrate that electrolytes with modestly higher Li+ transference nos. compared to traditional carbonate-based liq. electrolytes would allow higher power densities and enable faster charging (e.g., >2C), even if their cond. was substantially lower than that of conventional electrolytes. Most current research in high transference no. electrolytes (HTNEs) focuses on ceramic electrolytes, polymer electrolytes, and ionomer membranes filled with nonaq. solvents. We highlight a no. of the challenges limiting current HTNE systems and suggest addnl. work on promising new HTNE systems, such as "solvent-in-salt" electrolytes, perfluorinated solvent electrolytes, nonaq. polyelectrolyte solns., and solns. contg. anion-decorated nanoparticles.
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    Asua, J. M. Emulsion Polymerization: From Fundamental Mechanisms to Process Developments. J. Polym. Sci., Part A: Polym. Chem. 2004, 42, 1025– 1041,  DOI: 10.1002/pola.11096
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    Emulsion polymerization: From fundamental mechanisms to process developments
    Asua, Jose M.
    Journal of Polymer Science, Part A: Polymer Chemistry (2004), 42 (5), 1025-1041CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)
    A review. This highlight reviews the investigations carried out at The University of the Basque Country to develop a knowledge-based strategy to achieve these goals. First, the research in fundamental mechanisms is discussed. This includes studies in radical entry and exit, oil-sol. initiators, propagationrate consts. of acrylic monomers, processes involved in the formation of branched and crosslinked polymers, microstructure modification by postreaction operations, the formation of particle morphol., and reactive surfactants. The advanced math. models developed in the group are also reviewed. In the second part, the advances in process development (optimization, online monitoring and control, monomer removal, prodn. of high-solids, low-viscosity latexes, and process intensification) are presented.
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    Asua, J. M. Challenges for Industrialization of Miniemulsion Polymerization. Prog. Polym. Sci. 2014, 39, 1797– 1826,  DOI: 10.1016/j.progpolymsci.2014.02.009
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    Challenges for industrialization of miniemulsion polymerization
    Asua, Jose M.
    Progress in Polymer Science (2014), 39 (10), 1797-1826CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
    A review. Miniemulsion polymn. facilitates the synthesis of complex materials that cannot be produced otherwise. These materials have a broad range of potential applications including adhesives, coatings, anticounterfeiting, textile pigments, bio-based polymer dispersions, gene and drug delivery, anti-viral therapy, tissue engineering, catalyst supports, polymeric photoresists, energy storage and self-healing agents. However, 40 years after the pioneering work of Ugelstad, El-Aasser and Vanderhoff the promises have not been fulfilled and the presence of miniemulsion polymn. in com. products is scarce. This article reviews the advances in the field, discusses the reasons for this delay and analyzes the challenges that have to be overcome in order to fully use this process in com. practice.
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    Bilgin, S.; Tomovska, R.; Asua, J. M. Surfactant-Free High Solids Content Polymer Dispersions. Polymer 2017, 117, 64– 75,  DOI: 10.1016/j.polymer.2017.04.014
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    Surfactant-free high solids content polymer dispersions
    Bilgin, Sevilay; Tomovska, Radmila; Asua, Jose M.
    Polymer (2017), 117 (), 64-75CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)
    Surfactant-free high solids waterborne polymer dispersions were produced under industrial-like semicontinuous conditions by substituting traditional emulsifiers with stabilizing moieties in situ prodn. from a pH and temp. insensitive ionic monomer (sodium styrene sulfonate, NaSS). Copolymn. between NaSS and comonomers occurred through a mechanism that involves soln. polymn. in the aq. phase and compartmentalized polymn. in a shell created around the particles. This knowledge allowed the development of a polymn. strategy that led to high incorporation of NaSS (up to 83.5%). Solids contents over 60 wt% were achieved with modest concns. of NaSS (1.35 wt%) and a variety of monomers (acrylates, methacrylates, styrene) can be efficiently polymd. These latexes presented superior salt and freeze-thaw stability without compromising the water sensitivity of the films.
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    Bilgin, S.; Tomovska, R.; Asua, J. M. Effect of Ionic Monomer Concentration on Latex and Film Properties for Surfactant-Free High Solids Content Polymer Dispersions. Eur. Polym. J. 2017, 93, 480– 494,  DOI: 10.1016/j.eurpolymj.2017.06.029
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    Effect of ionic monomer concentration on latex and film properties for surfactant-free high solids content polymer dispersions
    Bilgin, Sevilay; Tomovska, Radmila; Asua, Jose M.
    European Polymer Journal (2017), 93 (), 480-494CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)
    Sodium styrene sulfonate (NaSS) was used to stabilize waterborne poly(Me methacrylate/butyl acrylate) dispersions obtained by surfactant-free seeded semicontinuous emulsion polymn. at 50 wt% solids content. The effect of NaSS concn. (0.175-3.6 wbm%) on the reaction kinetics, NaSS incorporation onto particles, colloidal stability and properties of emulsifier-free latexes and films was investigated. It was found that fraction of NaSS that was incorporated onto polymer particles increased with its concn. due to the increase of the ionic strength, which shifted the adsorption equil. of the NaSS contg. oligoradicals towards the polymer particles. Properties of the latexes (freeze-thaw and salt stability) improved with the concn. of NaSS and its incorporation. The lack of migration and formation of aggregates of the stabilizing moieties in the polymer films was demonstrated by water contact angle measurements and AFM images. This resulted in improved properties of the films (gloss, water uptake and mech. strength).
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    Bilgin, S.; Tomovska, R.; Asua, J. M. Fundamentals of Chemical Incorporation of Ionic Monomers onto Polymer Colloids: Paving the Way for Surfactant-Free Waterborne Dispersions. RSC Adv. 2016, 6, 63754– 63760,  DOI: 10.1039/C6RA07486C
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    Fundamentals of chemical incorporation of ionic monomers onto polymer colloids: paving the way for surfactant-free waterborne dispersions
    Bilgin, Sevilay; Tomovska, Radmila; Asua, Jose M.
    RSC Advances (2016), 6 (68), 63754-63760CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
    In this article, the fundamentals of the chem. incorporation of a pH and temp. insensitive ionic monomer (sodium styrene sulfonate, NaSS) onto polymer particles was investigated in an attempt to go beyond the current technol. for prodn. of a waterborne polymer dispersion, which is based on the use of surfactants to stabilize the dispersion. The success of this approach requires the chem. incorporation of NaSS onto the polymer particles and minimizing at the same time the amt. of water sol. polymer. It was found that the chem. incorporation of NaSS can be improved by increasing the concn. of the comonomer in the aq. phase, whereas the functionality of the comonomer did not play any significant role. Strategies to maximize incorporation of NaSS were proposed.
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    Lovell, P. A.; El-Aasser, M. S. Emulsion Polymerization and Emulsion Polymers; Wiley, 1997; pp 385– 436.
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    van Herk, A. M. Chemistry and Technology of Emulsion Polymerisation; Wiley, 2013; pp 214– 216.
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    Kim, B.; Kang, H.; Kim, K.; Wang, R.-Y.; Park, M. J. All-Solid-State Lithium-Organic Batteries Comprising Single-Ion Polymer Nanoparticle Electrolytes. ChemSusChem 2020, 13, 2271– 2279,  DOI: 10.1002/cssc.202000117
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    All-Solid-State Lithium-Organic Batteries Comprising Single-Ion Polymer Nanoparticle Electrolytes
    Kim, Boram; Kang, Haneol; Kim, Kyoungwook; Wang, Rui-Yang; Park, Moon Jeong
    ChemSusChem (2020), 13 (9), 2271-2279CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Advances in lithium battery technologies necessitate improved energy densities, long cycle lives, fast charging, safe operation, and environmentally friendly components. This study concerns lithium-org. batteries comprising bioinspired poly(4-vinyl catechol) (P4VC) cathode materials and single-ion conducting polymer nanoparticle electrolytes. The controlled synthesis of P4VC results in a two-step redox reaction with voltage plateaus at around 3.1 and 3.5 V, as well as a high initial specific capacity of 352 mAh g-1. The use of single-ion nanoparticle electrolytes enables high electrochem. stabilities up to 5.5 V, a high lithium transference no. of 0.99, high ionic conductivities, ranging from 0.2×10-3 to 10-3 S cm-1, and stable storage moduli of >10 MPa at 25-90°C. Lithium cells can deliver 165 mAh g-1 at 39.7 mA g-1 for 100 cycles and stable specific capacities of >100 mAh g-1 at a high c.d. of 794 mA g-1 for 500 cycles. As the first successful demonstration of solid-state single-ion polymer electrolytes in environmentally benign and cost-effective lithium-org. batteries, this work establishes a future research avenue for advancing lithium battery technologies.
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    Porcarelli, L.; Vlasov, P. S.; Ponkratov, D. O.; Lozinskaya, E. I.; Antonov, D. Y.; Nair, J. R.; Gerbaldi, C.; Mecerreyes, D.; Shaplov, A. S. Design of Ionic Liquid like Monomers towards Easy-Accessible Single-Ion Conducting Polymer Electrolytes. Eur. Polym. J. 2018, 107, 218– 228,  DOI: 10.1016/j.eurpolymj.2018.08.014
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    Design of ionic liquid like monomers towards easy-accessible single-ion conducting polymer electrolytes
    Porcarelli, Luca; Vlasov, Petr S.; Ponkratov, Denis O.; Lozinskaya, Elena I.; Antonov, Dmitrii Y.; Nair, Jijeesh R.; Gerbaldi, Claudio; Mecerreyes, David; Shaplov, Alexander S.
    European Polymer Journal (2018), 107 (), 218-228CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)
    The rational design of single-ion polymer electrolytes emerges as a primary strategy for enhancing the performance of Li ion batteries. With the aim to increase ionic cond., 4 novel ionic liq. monomers were designed and synthesized in high purity. Such monomers differ from the previously reported systems by (a) the presence of a long and flexible spacer between the methacrylate group and chem. bonded anion or (b) by a long perfluorinated side chain. The study of their free radical copolymn. with poly(ethylene glycol) Me ether methacrylate (PEGM) allowed to identify the impact of the copolymer compn. on thermal and ion conducting properties. The copolymer based on Li 3-4-(2-(methacryloyloxy)ethoxy)-4-oxobutanoyloxy propylsulfonyl-1-(trifluoromethylsulfonyl)imide showed the highest ionic cond. (1.9 × 10-6 and 2 × 10-5 S cm-1 at 25 and 70°, resp.) at [EO]/[Li] = 61 ratio, along with a wide electrochem. stability (4.2 V vs. Li+/Li) and high Li-ion transference no. (0.91). The prepd. copoly(ionic liq.)s (coPILs) were further applied for the assembly of Li/coPIL/LiFePO4 Li-metal cells, which were capable to reversibly operate at 70° delivering relatively high specific capacity (up to 115 mA h g-1) at medium C/15 current rate.
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    Porcarelli, L.; Aboudzadeh, M. A.; Rubatat, L.; Nair, J. R.; Shaplov, A. S.; Gerbaldi, C.; Mecerreyes, D. Single-Ion Triblock Copolymer Electrolytes Based on Poly (Ethylene Oxide) and Methacrylic Sulfonamide Blocks for Lithium Metal Batteries. J. Power Sources 2017, 364, 191– 199,  DOI: 10.1016/j.jpowsour.2017.08.023
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    Single-ion triblock copolymer electrolytes based on poly(ethylene oxide) and methacrylic sulfonamide blocks for lithium metal batteries
    Porcarelli, Luca; Aboudzadeh, M. Ali; Rubatat, Laurent; Nair, Jijeesh R.; Shaplov, Alexander S.; Gerbaldi, Claudio; Mecerreyes, David
    Journal of Power Sources (2017), 364 (), 191-199CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    Single-ion conducting polymer electrolytes represent the ideal soln. to reduce concn. polarization in lithium metal batteries (LMBs). This paper reports on the synthesis and characterization of single-ion ABA triblock copolymer electrolytes comprising PEO and poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) blocks, poly(LiMTFSI). Block copolymers are prepd. by reversible addn.-fragmentation chain transfer polymn., showing low glass transition temp. (-55 to 7°) and degree of crystallinity (51-0%). Comparatively high values of ionic cond. are obtained (up to ≈ 10-4 S cm-1 at 70°), combined with a lithium-ion transference no. close to unity (tLi+ ≈ 0.91) and a 4 V electrochem. stability window. In addn. to these promising features, solid polymer electrolytes are successfully tested in lithium metal cells at 70° providing long lifetime up to 300 cycles, and stable charge/discharge cycling at C/2 (≈100 mAh g-1).
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    Porcarelli, L.; Shaplov, A. S.; Bella, F.; Nair, J. R.; Mecerreyes, D.; Gerbaldi, C. Single-Ion Conducting Polymer Electrolytes for Lithium Metal Polymer Batteries That Operate at Ambient Temperature. ACS Energy Lett. 2016, 1, 678– 682,  DOI: 10.1021/acsenergylett.6b00216
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    Single-Ion Conducting Polymer Electrolytes for Lithium Metal Polymer Batteries that Operate at Ambient Temperature
    Porcarelli, Luca; Shaplov, Alexander S.; Bella, Federico; Nair, Jijeesh R.; Mecerreyes, David; Gerbaldi, Claudio
    ACS Energy Letters (2016), 1 (4), 678-682CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
    Safety issues rising from the use of conventional liq. electrolytes in lithium-based batteries are currently limiting their application to elec. vehicles and large-scale energy storage from renewable sources. Polymeric electrolytes represent a soln. to this problem due to their intrinsic safety. Ideally, polymer electrolytes should display both high lithium transference no. (t+Li) and ionic cond. Practically, strategies for increasing t+Li often result in low ionic cond. and vice versa. Herein, networked polymer electrolytes simultaneously displaying t+Li approaching unity and high ionic cond. (σ ≈ 10-4 S cm-1 at 25 °C) are presented. Lithium cells operating at room temp. demonstrate the promising prospect of these materials.
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    Agrawal, A.; Choudhury, S.; Archer, L. A. A Highly Conductive, Non-Flammable Polymer-Nanoparticle Hybrid Electrolyte. RSC Adv. 2015, 5, 20800– 20809,  DOI: 10.1039/C5RA01031D
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    A highly conductive, non-flammable polymer-nanoparticle hybrid electrolyte
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  • Abstract

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    Figure 1

    Figure 1. (a) Schematic representation of the polymeric nanoparticle synthesis and structure. (b) FESEM image of the polymeric nanoparticles. (c) DSC trace of the polymeric nanoparticles between 0 °C and 145 °C, 2nd heating at 5 °C/min.

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    Figure 2

    Figure 2. Solid polymer electrolytes based on poly(ethylene oxide): LiTFSI (75:25 wt %) and single-ion nanoparticles (NPS) with loadings from 0 to 50 wt %. (a) Schematic representation of the composite electrolyte. (b) Photography of a composite electrolyte. (c) Plot of the storage modulus (E′) as a function of temperature. (d) Plot of DSC showing glass transitions and melting peaks, 2nd heating at 5 °C min–1. (e) Plot of ionic conductivity (σ) as a function of temperature. (f) Plot of specific capacity versus cycle number of a Li/PEO-NP10/LiFePO4 cell at 70 °C, electrode active loading 0.6 mAh cm2.

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    Figure 3

    Figure 3. Gel electrolytes based on propylene carbonate and single-ion nanoparticles. Nanoparticle loadings are between 20 and 60 wt %. (a) Schematic representation of the composite electrolyte. (b) Photography of a composite electrolyte. (c) Plot of shear (G′) and loss (G′′) modulus as a function of temperature. (d) Plot of ionic conductivity (σ) as a function of temperature. (e) Plot of shear modulus (G′) as a function of the ionic conductivity (σ). (f) Plot of self-diffusion coefficients for 7Li and 19F as a function of temperature.

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    Figure 4

    Figure 4. Gel electrolytes based on propylene carbonate and single-ion nanoparticles. Plot of the overpotential as a function of time for a symmetrical lithium cell cycled at 0.1 mA cm–2 at 50 °C with (a, b) PC-NP30 and (c, d) PC-NP40 electrolyte.

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      Wang, Xiaoen; Kerr, Robert; Chen, Fangfang; Goujon, Nicolas; Pringle, Jennifer M.; Mecerreyes, David; Forsyth, Maria; Howlett, Patrick C.
      Advanced Materials (Weinheim, Germany) (2020), 32 (18), 1905219CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. With increasing demands for safe, high capacity energy storage to support personal electronics, newer devices such as unmanned aerial vehicles, as well as the commercialization of elec. vehicles, current energy storage technologies are facing increased challenges. Although alternative batteries have been intensively investigated, lithium (Li) batteries are still recognized as the preferred energy storage soln. for the consumer electronics markets and next generation automobiles. However, the commercialized Li batteries still have disadvantages, such as low capacities, potential safety issues, and unfavorable cycling life. Therefore, the design and development of electromaterials toward high-energy-d., long-life-span Li batteries with improved safety is a focus for researchers in the field of energy materials. Herein, recent advances in the development of novel org. electrolytes are summarized toward solid-state Li batteries with higher energy d. and improved safety. On the basis of new insights into ionic conduction and design principles of org.-based solid-state electrolytes, specific strategies toward developing these electrolytes for Li metal anodes, high-energy-d. cathode materials (e.g., high voltage materials), as well as the optimization of cathode formulations are outlined. Finally, prospects for next generation solid-state electrolytes are also proposed.
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    5. 5
      Zhou, D.; Shanmukaraj, D.; Tkacheva, A.; Armand, M.; Wang, G. Polymer Electrolytes for Lithium-Based Batteries: Advances and Prospects. Chem. 2019, 5, 2326– 2352,  DOI: 10.1016/j.chempr.2019.05.009
      5
      Polymer Electrolytes for Lithium-Based Batteries: Advances and Prospects
      Zhou, Dong; Shanmukaraj, Devaraj; Tkacheva, Anastasia; Armand, Michel; Wang, Guoxiu
      Chem (2019), 5 (9), 2326-2352CODEN: CHEMVE; ISSN:2451-9294. (Cell Press)
      A review. Polymer electrolytes have attracted great interest for next-generation lithium (Li)-based batteries in terms of high energy d. and safety. In this review, we summarize the ion-transport mechanisms, fundamental properties, and prepn. techniques of various classes of polymer electrolytes, such as solvent-free polymer electrolytes (SPEs), gel polymer electrolytes (GPEs), and composite polymer electrolytes (CPEs). We also introduce the recent advances of non-aq. Li-based battery systems, in which their performances can be intrinsically enhanced by polymer electrolytes. Those include high-voltage Li-ion batteries, flexible Li-ion batteries, Li-metal batteries, lithium-sulfur (Li-S) batteries, lithium-oxygen (Li-O2) batteries, and smart Li-ion batteries. Esp., the advantages of polymer electrolytes beyond safety improvement are highlighted. Finally, the remaining challenges and future perspectives are outlined to provide strategies to develop novel polymer electrolytes for high-performance Li-based batteries.
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    6. 6
      Aldalur, I.; Wang, X.; Santiago, A.; Goujon, N.; Echeverría, M.; Martínez-Ibáñez, M.; Piszcz, M.; Howlett, P. C.; Forsyth, M.; Armand, M.; Zhang, H. Nanofiber-Reinforced Polymer Electrolytes toward Room Temperature Solid-State Lithium Batteries. J. Power Sources 2020, 448, 227424,  DOI: 10.1016/j.jpowsour.2019.227424
      6
      Nanofiber-reinforced polymer electrolytes toward room temperature solid-state lithium batteries
      Aldalur, Itziar; Wang, Xiaoen; Santiago, Alexander; Goujon, Nicolas; Echeverria, Maria; Martinez-Ibanez, Maria; Piszcz, Michal; Howlett, Patrick C.; Forsyth, Maria; Armand, Michel; Zhang, Heng
      Journal of Power Sources (2020), 448 (), 227424CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Safe and efficient utilization of electrochem. energy is of prime importance for e-mobility and sustainable development of the current society. Solid state batteries (SSBs) have emerged as one of the most promising solns. to address aforementioned challenges due to the replacement of conventional liq. electrolytes with inherently safer solid electrolytes. Polymer electrolyte (PE)-based SSBs have better processability and flexibility than inorg. electrolyte-based ones; however, the room temp. (RT) operation of the PE-based SSBs remains as one of the most crit. issues. Herein, a nanofiber-reinforced polymer electrolyte (NRPE) comprising of poly(vinylidene fluoride) fibers along with a high mol. wt. though flowable polymer matrix is proposed as an innovative electrolyte for SSBs. These NRPEs are self-standing, highly conductive, and stable against Li metal (Li°) electrode, endowing the Li° || LiFePO4 cells with good performances at operational temps. down to RT. The outstanding physicochem. and electrochem. properties of NRPEs make them as appealing candidates for attaining high-performance SSBs.
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    7. 7
      Zhou, Y.; Wang, X.; Zhu, H.; Armand, M.; Forsyth, M.; Greene, G. W.; Pringle, J. M.; Howlett, P. C. N-Ethyl-N-Methylpyrrolidinium Bis(Fluorosulfonyl)Imide-Electrospun Polyvinylidene Fluoride Composite Electrolytes: Characterization and Lithium Cell Studies. Phys. Chem. Chem. Phys. 2017, 19, 2225– 2234,  DOI: 10.1039/C6CP07415D
      7
      N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide-electrospun polyvinylidene fluoride composite electrolytes: characterization and lithium cell studies
      Zhou, Yundong; Wang, Xiaoen; Zhu, Haijin; Armand, Michel; Forsyth, Maria; Greene, George W.; Pringle, Jennifer M.; Howlett, Patrick C.
      Physical Chemistry Chemical Physics (2017), 19 (3), 2225-2234CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      Using the org. ionic plastic crystal N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ([C2mpyr][FSI]) with electrospun nanofibers, LiFSI doped [C2mpyr][FSI]-PVdF composites were developed as solid state, self-standing electrolyte membranes. Different Li salt concn. were studied, with 10 mol% LiFSI found to be optimal amongst those assessed. Composites with different wt. ratios of plastic crystal and polymer were prepd. and 10 wt.% polymer gave the highest cond. The effects of PVdF incorporation on the morphol., thermal, and structural properties of the org. ionic plastic crystal were studied. Ion mobilities were also studied using solid-state NMR techniques. The electrolytes were then assembled into Li sym. cells and cycled galvanostatically at 0.13 mA/cm2 at both ambient temp. and at 50°, for >500 cycles.
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    8. 8
      Qin, H.; Fu, K.; Zhang, Y.; Ye, Y.; Song, M.; Kuang, Y.; Jang, S.-H.; Jiang, F.; Cui, L. Flexible Nanocellulose Enhanced Li+ Conducting Membrane for Solid Polymer Electrolyte. Energy Storage Mater. 2020, 28, 293– 299,  DOI: 10.1016/j.ensm.2020.03.019
      There is no corresponding record for this reference.
    9. 9
      Meesorn, W.; Shirole, A.; Vanhecke, D.; de Espinosa, L. M.; Weder, C. A Simple and Versatile Strategy To Improve the Mechanical Properties of Polymer Nanocomposites with Cellulose Nanocrystals. Macromolecules 2017, 50, 2364– 2374,  DOI: 10.1021/acs.macromol.6b02629
      9
      A Simple and Versatile Strategy To Improve the Mechanical Properties of Polymer Nanocomposites with Cellulose Nanocrystals
      Meesorn, Worarin; Shirole, Anuja; Vanhecke, Dimitri; de Espinosa, Lucas Montero; Weder, Christoph
      Macromolecules (Washington, DC, United States) (2017), 50 (6), 2364-2374CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
      Cellulose nanocrystals (CNCs) are widely studied as reinforcing fillers for polymers. In many cases the mech. properties of polymer/CNC nanocomposites do not match the theor. predictions, arguably on account of CNC aggregation. This problem can be mitigated through the addn. of a small amt. of a judiciously selected polymeric dispersant that also serves as a binder among the CNCs. We show that the addn. of 1-5% wt./wt. poly(vinyl alc.) (PVA) has a very significant impact on the mech. properties of poly(ethylene oxide-co-epichlorohydrin)/CNC nanocomposites. Remarkable improvements of the stiffness and strength were obsd. at a PVA content as low as 1% wt./wt., and the extent of reinforcement increased up to a PVA content of 5% wt./wt., where Young's modulus, storage modulus, and strength increased by up to 5-fold vis a´ vis the PVA-free nanocomposites. Similar effects were obsd. for CNC nanocomposites made with polyurethane or poly(Me acrylate) matrixes, demonstrating that the approach is broadly exploitable. Laser scanning microscopy based resonance energy transfer expts. that involved nanocomposites made with CNCs and PVA that had been labeled with rhodamine and fluorescein, resp., confirmed that the enhanced mech. properties of the three-component nanocomposites are indeed related to an improved dispersion of the CNCs.
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    10. 10
      Fan, L.; Wei, S.; Li, S.; Li, Q.; Lu, Y. Recent Progress of the Solid-State Electrolytes for High-Energy Metal-Based Batteries. Adv. Energy Mater. 2018, 8, 1702657,  DOI: 10.1002/aenm.201702657
      There is no corresponding record for this reference.
    11. 11
      Che, H.; Chen, S.; Xie, Y.; Wang, H.; Amine, K.; Liao, X.-Z.; Ma, Z.-F. Electrolyte Design Strategies and Research Progress for Room-Temperature Sodium-Ion Batteries. Energy Environ. Sci. 2017, 10, 1075– 1101,  DOI: 10.1039/C7EE00524E
      11
      Electrolyte design strategies and research progress for room-temperature sodium-ion batteries
      Che, Haiying; Chen, Suli; Xie, Yingying; Wang, Hong; Amine, Khalil; Liao, Xiao-Zhen; Ma, Zi-Feng
      Energy & Environmental Science (2017), 10 (5), 1075-1101CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      A review. Electrolyte design or functional development is very effective at promoting the performance of sodium-ion batteries, which are attractive for electrochem. energy storage devices due to abundant sodium resources and low cost. This review discusses recent advances on electrolytes for sodium-ion batteries and comprehensive electrolyte design strategies for various materials systems as well as functional applications. The discussion is divided into three electrolyte types: liq., solid state, and gel state. Liq. electrolytes are further divided into different solvent types, including org. carbonate ester, ether, ionic liq., and water. Solid-state electrolytes also contain two types: solid polymer and glass-ceramic composite. The challenges and prospects of electrolytes for sodium-ion batteries are discussed as well.
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    12. 12
      Srivastava, S.; Schaefer, J. L.; Yang, Z.; Tu, Z.; Archer, L. A. 25th Anniversary Article: Polymer-Particle Composites: Phase Stability and Applications in Electrochemical Energy Storage. Adv. Mater. 2014, 26, 201– 234,  DOI: 10.1002/adma.201303070
      12
      25th Anniversary Article: Polymer-Particle Composites: Phase Stability and Applications in Electrochemical Energy Storage
      Srivastava, Samanvaya; Schaefer, Jennifer L.; Yang, Zichao; Tu, Zhengyuan; Archer, Lynden A.
      Advanced Materials (Weinheim, Germany) (2014), 26 (2), 201-234CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)
      This review discusses progress in the last decade in understanding phase behavior, structure, and properties of nanoparticle-polymer composites. The review takes a decidedly polymers perspective and explores how phys. and chem. approaches may be employed to create hybrids with controlled distribution of particles. Applications are studied in two contexts of contemporary interest: battery electrolytes and electrodes. In the former, the role of dispersed and aggregated particles on ion-transport is considered. In the latter, the polymer is employed in such small quantities that it has been historically given titles such as binder and carbon precursor that underscore its perceived secondary role. Considering the myriad functions the binder plays in an electrode, it is surprising that highly filled composites have not received more attention. Opportunities in this and related areas are highlighted where recent advances in synthesis and polymer science are inspiring new approaches, and where newcomers to the field could make important contributions.
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    13. 13
      Villaluenga, I.; Inceoglu, S.; Jiang, X.; Chen, X. C.; Chintapalli, M.; Wang, D. R.; Devaux, D.; Balsara, N. P. Nanostructured Single-Ion-Conducting Hybrid Electrolytes Based on Salty Nanoparticles and Block Copolymers. Macromolecules 2017, 50, 1998– 2005,  DOI: 10.1021/acs.macromol.6b02522
      13
      Nanostructured Single-Ion-Conducting Hybrid Electrolytes Based on Salty Nanoparticles and Block Copolymers
      Villaluenga, Irune; Inceoglu, Sebnem; Jiang, Xi; Chen, Xi Chelsea; Chintapalli, Mahati; Wang, Dunyang Rita; Devaux, Didier; Balsara, Nitash P.
      Macromolecules (Washington, DC, United States) (2017), 50 (5), 1998-2005CODEN: MAMOBX; ISSN:0024-9297. (American Chemical Society)
      We report on the synthesis and characterization of a series of microphase-sepd., single-ion-conducting block copolymer electrolytes. Salty nanoparticles comprising silsesquioxane cores with covalently bound polystyrenesulfonyllithium (trifluoromethylsulfonyl)imide (PSLiTFSI) chains were synthesized by nitroxide-mediated polymn. Hybrid electrolytes were obtained by mixing the salty nanoparticles into a microphase-sepd. polystyrene-b-poly(ethylene oxide) (SEO) block copolymer. Miscibility of PSLiTFSI and poly(ethylene oxide) (PEO) results in localization of the nanoparticles in the PEO-rich microphase. The morphol. of hybrid electrolytes was detd. by scanning TEM. We explore the relation between the morphol. and ionic cond. of the hybrid. The transference no. of the electrolyte with the highest ionic cond. was measured by dc polarization to confirm the single-ion-conducting character of the electrolyte. Discharge curves obtained from lithium metal-hybrid electrolyte-FePO4 batteries are compared to the data obtained from the batteries with a conventional block copolymer electrolyte.
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    14. 14
      Schaefer, J. L.; Yanga, D. A.; Archer, L. A. High Lithium Transference Number Electrolytes via Creation of 3-Dimensional, Charged, Nanoporous Networks from Dense Functionalized Nanoparticle Composites. Chem. Mater. 2013, 25, 834– 839,  DOI: 10.1021/cm303091j
      14
      High lithium transference number electrolytes via creation of 3-dimensional, charged, nanoporous networks from dense functionalized nanoparticle composites
      Schaefer, Jennifer L.; Yanga, Dennis A.; Archer, Lynden A.
      Chemistry of Materials (2013), 25 (6), 834-839CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      High lithium transference no., tLi+, electrolytes are desired for use in both lithium-ion and lithium metal rechargeable battery technologies. Historically, low tLi+ electrolytes have hindered device performance by allowing ion concn. gradients within the cell, leading to high internal resistances that ultimately limit cell lifetime, charging rates, and energy d. Herein, we report on the synthesis and electrochem. features of electrolytes based on nanoparticle salts designed to provide high tLi+. . The salts are created by cofunctionalization of metal oxide nanoparticles with neutral org. ligands and tethered lithium salts. When dispersed in a conducting fluid such as tetraglyme, they spontaneously form a charged, nanoporous network of particles at moderate nanoparticle loadings. Modification of the tethered anion chem. from -SO3- to -SO3BF3- is shown to enhance ionic cond. of the electrolytes by facilitating ion pair dissocn. At a particle vol. fraction of 0.15, the electrolyte exists as a self-supported, nanoporous gel with an optimum ionic cond. of 10-4 S/cm at room temp. Galvanostatic polarization measurements on sym. lithium metal cells contg. the electrolyte show that the cell short circuit time, tSC, is inversely proportional to the square of the applied c.d. tSC ∼ J-2, consistent with previously predicted results for traditional polymer-in-salt electrolytes with low tLi+. . Our findings suggest that electrolytes with tLi+ ≈ 1 and good ion-pair dissocn. delay lithium dendrite nucleation and may lead to improved lithium plating in rechargeable batteries with metallic lithium anodes.
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    15. 15
      Zhang, H.; Li, C.; Piszcz, M.; Coya, E.; Rojo, T.; Rodriguez-Martinez, L. M.; Armand, M.; Zhou, Z. Single Lithium-Ion Conducting Solid Polymer Electrolytes: Advances and Perspectives. Chem. Soc. Rev. 2017, 46, 797– 815,  DOI: 10.1039/C6CS00491A
      15
      Single lithium-ion conducting solid polymer electrolytes: advances and perspectives
      Zhang, Heng; Li, Chunmei; Piszcz, Michal; Coya, Estibaliz; Rojo, Teofilo; Rodriguez-Martinez, Lide M.; Armand, Michel; Zhou, Zhibin
      Chemical Society Reviews (2017), 46 (3), 797-815CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      Electrochem. energy storage is one of the main societal challenges to humankind in this century. The performances of classical Li-ion batteries (LIBs) with non-aq. liq. electrolytes have made great advances in the past two decades, but the intrinsic instability of liq. electrolytes results in safety issues, and the energy d. of the state-of-the-art LIBs cannot satisfy the practical requirement. Therefore, rechargeable lithium metal batteries (LMBs) have been intensively investigated considering the high theor. capacity of lithium metal and its low neg. potential. However, the progress in the field of non-aq. liq. electrolytes for LMBs has been sluggish, with several seemingly insurmountable barriers, including dendritic Li growth and rapid capacity fading. Solid polymer electrolytes (SPEs) offer a perfect soln. to these safety concerns and to the enhancement of energy d. Traditional SPEs are dual-ion conductors, in which both cations and anions are mobile and will cause a concn. polarization thus leading to poor performances of both LIBs and LMBs. Single lithium-ion (Li-ion) conducting solid polymer electrolytes (SLIC-SPEs), which have anions covalently bonded to the polymer, inorg. backbone, or immobilized by anion acceptors, are generally accepted to have advantages over conventional dual-ion conducting SPEs for application in LMBs. A high Li-ion transference no. (LTN), the absence of the detrimental effect of anion polarization, and the low rate of Li dendrite growth are examples of benefits of SLIC-SPEs. To date, many types of SLIC-SPEs have been reported, including those based on org. polymers, org.-inorg. hybrid polymers and anion acceptors. In this review, a brief overview of synthetic strategies on how to realize SLIC-SPEs is given. The fundamental phys. and electrochem. properties of SLIC-SPEs prepd. by different methods are discussed in detail. In particular, special attention is paid to the SLIC-SPEs with high ionic cond. and high LTN. Finally, perspectives on the main challenges and focus on the future research are also presented.
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    16. 16
      Diederichsen, K. M.; McShane, E. J.; McCloskey, B. D. Promising Routes to a High Li+ Transference Number Electrolyte for Lithium Ion Batteries. ACS Energy Lett. 2017, 2, 2563– 2575,  DOI: 10.1021/acsenergylett.7b00792
      16
      Promising Routes to a High Li+ Transference Number Electrolyte for Lithium Ion Batteries
      Diederichsen, Kyle M.; McShane, Eric J.; McCloskey, Bryan D.
      ACS Energy Letters (2017), 2 (11), 2563-2575CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
      A review. The continued search for routes to improve the power and energy d. of lithium ion batteries for elec. vehicles and consumer electronics has resulted in significant innovation in all cell components, particularly in electrode materials design. In this Review, we highlight an often less noted route to improving energy d.: increasing the Li+ transference no. of the electrolyte. Turning to Newman's original lithium ion battery models, we demonstrate that electrolytes with modestly higher Li+ transference nos. compared to traditional carbonate-based liq. electrolytes would allow higher power densities and enable faster charging (e.g., >2C), even if their cond. was substantially lower than that of conventional electrolytes. Most current research in high transference no. electrolytes (HTNEs) focuses on ceramic electrolytes, polymer electrolytes, and ionomer membranes filled with nonaq. solvents. We highlight a no. of the challenges limiting current HTNE systems and suggest addnl. work on promising new HTNE systems, such as "solvent-in-salt" electrolytes, perfluorinated solvent electrolytes, nonaq. polyelectrolyte solns., and solns. contg. anion-decorated nanoparticles.
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    17. 17
      Asua, J. M. Emulsion Polymerization: From Fundamental Mechanisms to Process Developments. J. Polym. Sci., Part A: Polym. Chem. 2004, 42, 1025– 1041,  DOI: 10.1002/pola.11096
      17
      Emulsion polymerization: From fundamental mechanisms to process developments
      Asua, Jose M.
      Journal of Polymer Science, Part A: Polymer Chemistry (2004), 42 (5), 1025-1041CODEN: JPACEC; ISSN:0887-624X. (John Wiley & Sons, Inc.)
      A review. This highlight reviews the investigations carried out at The University of the Basque Country to develop a knowledge-based strategy to achieve these goals. First, the research in fundamental mechanisms is discussed. This includes studies in radical entry and exit, oil-sol. initiators, propagationrate consts. of acrylic monomers, processes involved in the formation of branched and crosslinked polymers, microstructure modification by postreaction operations, the formation of particle morphol., and reactive surfactants. The advanced math. models developed in the group are also reviewed. In the second part, the advances in process development (optimization, online monitoring and control, monomer removal, prodn. of high-solids, low-viscosity latexes, and process intensification) are presented.
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    18. 18
      Asua, J. M. Challenges for Industrialization of Miniemulsion Polymerization. Prog. Polym. Sci. 2014, 39, 1797– 1826,  DOI: 10.1016/j.progpolymsci.2014.02.009
      18
      Challenges for industrialization of miniemulsion polymerization
      Asua, Jose M.
      Progress in Polymer Science (2014), 39 (10), 1797-1826CODEN: PRPSB8; ISSN:0079-6700. (Elsevier Ltd.)
      A review. Miniemulsion polymn. facilitates the synthesis of complex materials that cannot be produced otherwise. These materials have a broad range of potential applications including adhesives, coatings, anticounterfeiting, textile pigments, bio-based polymer dispersions, gene and drug delivery, anti-viral therapy, tissue engineering, catalyst supports, polymeric photoresists, energy storage and self-healing agents. However, 40 years after the pioneering work of Ugelstad, El-Aasser and Vanderhoff the promises have not been fulfilled and the presence of miniemulsion polymn. in com. products is scarce. This article reviews the advances in the field, discusses the reasons for this delay and analyzes the challenges that have to be overcome in order to fully use this process in com. practice.
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    19. 19
      Bilgin, S.; Tomovska, R.; Asua, J. M. Surfactant-Free High Solids Content Polymer Dispersions. Polymer 2017, 117, 64– 75,  DOI: 10.1016/j.polymer.2017.04.014
      19
      Surfactant-free high solids content polymer dispersions
      Bilgin, Sevilay; Tomovska, Radmila; Asua, Jose M.
      Polymer (2017), 117 (), 64-75CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)
      Surfactant-free high solids waterborne polymer dispersions were produced under industrial-like semicontinuous conditions by substituting traditional emulsifiers with stabilizing moieties in situ prodn. from a pH and temp. insensitive ionic monomer (sodium styrene sulfonate, NaSS). Copolymn. between NaSS and comonomers occurred through a mechanism that involves soln. polymn. in the aq. phase and compartmentalized polymn. in a shell created around the particles. This knowledge allowed the development of a polymn. strategy that led to high incorporation of NaSS (up to 83.5%). Solids contents over 60 wt% were achieved with modest concns. of NaSS (1.35 wt%) and a variety of monomers (acrylates, methacrylates, styrene) can be efficiently polymd. These latexes presented superior salt and freeze-thaw stability without compromising the water sensitivity of the films.
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    20. 20
      Bilgin, S.; Tomovska, R.; Asua, J. M. Effect of Ionic Monomer Concentration on Latex and Film Properties for Surfactant-Free High Solids Content Polymer Dispersions. Eur. Polym. J. 2017, 93, 480– 494,  DOI: 10.1016/j.eurpolymj.2017.06.029
      20
      Effect of ionic monomer concentration on latex and film properties for surfactant-free high solids content polymer dispersions
      Bilgin, Sevilay; Tomovska, Radmila; Asua, Jose M.
      European Polymer Journal (2017), 93 (), 480-494CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)
      Sodium styrene sulfonate (NaSS) was used to stabilize waterborne poly(Me methacrylate/butyl acrylate) dispersions obtained by surfactant-free seeded semicontinuous emulsion polymn. at 50 wt% solids content. The effect of NaSS concn. (0.175-3.6 wbm%) on the reaction kinetics, NaSS incorporation onto particles, colloidal stability and properties of emulsifier-free latexes and films was investigated. It was found that fraction of NaSS that was incorporated onto polymer particles increased with its concn. due to the increase of the ionic strength, which shifted the adsorption equil. of the NaSS contg. oligoradicals towards the polymer particles. Properties of the latexes (freeze-thaw and salt stability) improved with the concn. of NaSS and its incorporation. The lack of migration and formation of aggregates of the stabilizing moieties in the polymer films was demonstrated by water contact angle measurements and AFM images. This resulted in improved properties of the films (gloss, water uptake and mech. strength).
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    21. 21
      Bilgin, S.; Tomovska, R.; Asua, J. M. Fundamentals of Chemical Incorporation of Ionic Monomers onto Polymer Colloids: Paving the Way for Surfactant-Free Waterborne Dispersions. RSC Adv. 2016, 6, 63754– 63760,  DOI: 10.1039/C6RA07486C
      21
      Fundamentals of chemical incorporation of ionic monomers onto polymer colloids: paving the way for surfactant-free waterborne dispersions
      Bilgin, Sevilay; Tomovska, Radmila; Asua, Jose M.
      RSC Advances (2016), 6 (68), 63754-63760CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      In this article, the fundamentals of the chem. incorporation of a pH and temp. insensitive ionic monomer (sodium styrene sulfonate, NaSS) onto polymer particles was investigated in an attempt to go beyond the current technol. for prodn. of a waterborne polymer dispersion, which is based on the use of surfactants to stabilize the dispersion. The success of this approach requires the chem. incorporation of NaSS onto the polymer particles and minimizing at the same time the amt. of water sol. polymer. It was found that the chem. incorporation of NaSS can be improved by increasing the concn. of the comonomer in the aq. phase, whereas the functionality of the comonomer did not play any significant role. Strategies to maximize incorporation of NaSS were proposed.
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    22. 22
      Lovell, P. A.; El-Aasser, M. S. Emulsion Polymerization and Emulsion Polymers; Wiley, 1997; pp 385– 436.
      There is no corresponding record for this reference.
    23. 23
      van Herk, A. M. Chemistry and Technology of Emulsion Polymerisation; Wiley, 2013; pp 214– 216.
      There is no corresponding record for this reference.
    24. 24
      Kim, B.; Kang, H.; Kim, K.; Wang, R.-Y.; Park, M. J. All-Solid-State Lithium-Organic Batteries Comprising Single-Ion Polymer Nanoparticle Electrolytes. ChemSusChem 2020, 13, 2271– 2279,  DOI: 10.1002/cssc.202000117
      24
      All-Solid-State Lithium-Organic Batteries Comprising Single-Ion Polymer Nanoparticle Electrolytes
      Kim, Boram; Kang, Haneol; Kim, Kyoungwook; Wang, Rui-Yang; Park, Moon Jeong
      ChemSusChem (2020), 13 (9), 2271-2279CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Advances in lithium battery technologies necessitate improved energy densities, long cycle lives, fast charging, safe operation, and environmentally friendly components. This study concerns lithium-org. batteries comprising bioinspired poly(4-vinyl catechol) (P4VC) cathode materials and single-ion conducting polymer nanoparticle electrolytes. The controlled synthesis of P4VC results in a two-step redox reaction with voltage plateaus at around 3.1 and 3.5 V, as well as a high initial specific capacity of 352 mAh g-1. The use of single-ion nanoparticle electrolytes enables high electrochem. stabilities up to 5.5 V, a high lithium transference no. of 0.99, high ionic conductivities, ranging from 0.2×10-3 to 10-3 S cm-1, and stable storage moduli of >10 MPa at 25-90°C. Lithium cells can deliver 165 mAh g-1 at 39.7 mA g-1 for 100 cycles and stable specific capacities of >100 mAh g-1 at a high c.d. of 794 mA g-1 for 500 cycles. As the first successful demonstration of solid-state single-ion polymer electrolytes in environmentally benign and cost-effective lithium-org. batteries, this work establishes a future research avenue for advancing lithium battery technologies.
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    25. 25
      Porcarelli, L.; Vlasov, P. S.; Ponkratov, D. O.; Lozinskaya, E. I.; Antonov, D. Y.; Nair, J. R.; Gerbaldi, C.; Mecerreyes, D.; Shaplov, A. S. Design of Ionic Liquid like Monomers towards Easy-Accessible Single-Ion Conducting Polymer Electrolytes. Eur. Polym. J. 2018, 107, 218– 228,  DOI: 10.1016/j.eurpolymj.2018.08.014
      25
      Design of ionic liquid like monomers towards easy-accessible single-ion conducting polymer electrolytes
      Porcarelli, Luca; Vlasov, Petr S.; Ponkratov, Denis O.; Lozinskaya, Elena I.; Antonov, Dmitrii Y.; Nair, Jijeesh R.; Gerbaldi, Claudio; Mecerreyes, David; Shaplov, Alexander S.
      European Polymer Journal (2018), 107 (), 218-228CODEN: EUPJAG; ISSN:0014-3057. (Elsevier Ltd.)
      The rational design of single-ion polymer electrolytes emerges as a primary strategy for enhancing the performance of Li ion batteries. With the aim to increase ionic cond., 4 novel ionic liq. monomers were designed and synthesized in high purity. Such monomers differ from the previously reported systems by (a) the presence of a long and flexible spacer between the methacrylate group and chem. bonded anion or (b) by a long perfluorinated side chain. The study of their free radical copolymn. with poly(ethylene glycol) Me ether methacrylate (PEGM) allowed to identify the impact of the copolymer compn. on thermal and ion conducting properties. The copolymer based on Li 3-4-(2-(methacryloyloxy)ethoxy)-4-oxobutanoyloxy propylsulfonyl-1-(trifluoromethylsulfonyl)imide showed the highest ionic cond. (1.9 × 10-6 and 2 × 10-5 S cm-1 at 25 and 70°, resp.) at [EO]/[Li] = 61 ratio, along with a wide electrochem. stability (4.2 V vs. Li+/Li) and high Li-ion transference no. (0.91). The prepd. copoly(ionic liq.)s (coPILs) were further applied for the assembly of Li/coPIL/LiFePO4 Li-metal cells, which were capable to reversibly operate at 70° delivering relatively high specific capacity (up to 115 mA h g-1) at medium C/15 current rate.
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    26. 26
      Porcarelli, L.; Aboudzadeh, M. A.; Rubatat, L.; Nair, J. R.; Shaplov, A. S.; Gerbaldi, C.; Mecerreyes, D. Single-Ion Triblock Copolymer Electrolytes Based on Poly (Ethylene Oxide) and Methacrylic Sulfonamide Blocks for Lithium Metal Batteries. J. Power Sources 2017, 364, 191– 199,  DOI: 10.1016/j.jpowsour.2017.08.023
      26
      Single-ion triblock copolymer electrolytes based on poly(ethylene oxide) and methacrylic sulfonamide blocks for lithium metal batteries
      Porcarelli, Luca; Aboudzadeh, M. Ali; Rubatat, Laurent; Nair, Jijeesh R.; Shaplov, Alexander S.; Gerbaldi, Claudio; Mecerreyes, David
      Journal of Power Sources (2017), 364 (), 191-199CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Single-ion conducting polymer electrolytes represent the ideal soln. to reduce concn. polarization in lithium metal batteries (LMBs). This paper reports on the synthesis and characterization of single-ion ABA triblock copolymer electrolytes comprising PEO and poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) blocks, poly(LiMTFSI). Block copolymers are prepd. by reversible addn.-fragmentation chain transfer polymn., showing low glass transition temp. (-55 to 7°) and degree of crystallinity (51-0%). Comparatively high values of ionic cond. are obtained (up to ≈ 10-4 S cm-1 at 70°), combined with a lithium-ion transference no. close to unity (tLi+ ≈ 0.91) and a 4 V electrochem. stability window. In addn. to these promising features, solid polymer electrolytes are successfully tested in lithium metal cells at 70° providing long lifetime up to 300 cycles, and stable charge/discharge cycling at C/2 (≈100 mAh g-1).
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    27. 27
      Porcarelli, L.; Shaplov, A. S.; Bella, F.; Nair, J. R.; Mecerreyes, D.; Gerbaldi, C. Single-Ion Conducting Polymer Electrolytes for Lithium Metal Polymer Batteries That Operate at Ambient Temperature. ACS Energy Lett. 2016, 1, 678– 682,  DOI: 10.1021/acsenergylett.6b00216
      27
      Single-Ion Conducting Polymer Electrolytes for Lithium Metal Polymer Batteries that Operate at Ambient Temperature
      Porcarelli, Luca; Shaplov, Alexander S.; Bella, Federico; Nair, Jijeesh R.; Mecerreyes, David; Gerbaldi, Claudio
      ACS Energy Letters (2016), 1 (4), 678-682CODEN: AELCCP; ISSN:2380-8195. (American Chemical Society)
      Safety issues rising from the use of conventional liq. electrolytes in lithium-based batteries are currently limiting their application to elec. vehicles and large-scale energy storage from renewable sources. Polymeric electrolytes represent a soln. to this problem due to their intrinsic safety. Ideally, polymer electrolytes should display both high lithium transference no. (t+Li) and ionic cond. Practically, strategies for increasing t+Li often result in low ionic cond. and vice versa. Herein, networked polymer electrolytes simultaneously displaying t+Li approaching unity and high ionic cond. (σ ≈ 10-4 S cm-1 at 25 °C) are presented. Lithium cells operating at room temp. demonstrate the promising prospect of these materials.
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    28. 28
      Agrawal, A.; Choudhury, S.; Archer, L. A. A Highly Conductive, Non-Flammable Polymer-Nanoparticle Hybrid Electrolyte. RSC Adv. 2015, 5, 20800– 20809,  DOI: 10.1039/C5RA01031D
      28
      A highly conductive, non-flammable polymer-nanoparticle hybrid electrolyte
      Agrawal, Akanksha; Choudhury, Snehashis; Archer, Lynden A.
      RSC Advances (2015), 5 (27), 20800-20809CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      We report on the phys. properties of lithium-ion conducting nanoparticle-polymer hybrid electrolytes created by dispersing bidisperse mixts. of polyethylene glycol (PEG)-functionalized silica nanoparticles in an aprotic liq. host. At high particle contents, we find that the ionic cond. is a non-monotonic function of the fraction of larger particles xL in the mixts., and that for the nearly sym. case xL ≈ 0.5 (i.e. equal vol. fraction of small and large particles), the room temp. ionic cond. is nearly ten-times larger than in similar nanoparticle hybrid electrolytes comprised of the pure small (xL ≈ 0) or large (xL ≈ 1) particle components. Complementary trends are seen in the activation energy for ion migration and effective tortuosity of the electrolytes, which both exhibit min. near xL ≈ 0.5. Characterization of the electrolytes by dynamic rheol. reveals that the max. cond. coincides with a distinct transition in soft glassy properties from a jammed to partially jammed and back to jammed state, as the fraction of large particles is increased from 0 to 1. This finding implies that the cond. enhancement arises from purely entropic loss of correlation between nanoparticle centers arising from particle size dispersity. As a consequence of these physics, it is now possible to create hybrid electrolytes with MPa elastic moduli and mS cm-1 ionic cond. levels at room temp. using common aprotic liq. media as the electrolyte solvent. Remarkably, we also find that even in highly flammable liq. media, the bidisperse nanoparticle hybrid electrolytes can be formulated to exhibit low or no flammability without compromising their favorable room temp. ionic cond. and mech. properties.
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    29. 29
      Blue Solutions. https://www.blue-solutions.com/app/assets-bluesolutions/uploads/2021/04/0414_bsol_2102265_brochure_16_pages_gb.pdf (accessed Oct 10, 2021).
      There is no corresponding record for this reference.
    30. 30
      Qiu, W.; Wunderlich, B. Reversible Melting of High Molar Mass Poly(Oxyethylene). Thermochim. Acta 2006, 448, 136– 146,  DOI: 10.1016/j.tca.2006.07.005
      30
      Reversible melting of high molar mass poly(oxyethylene)
      Qiu, Wulin; Wunderlich, Bernhard
      Thermochimica Acta (2006), 448 (2), 136-146CODEN: THACAS; ISSN:0040-6031. (Elsevier B.V.)
      The heat capacity, Cp, of poly(oxyethylene), POE, with a molar mass of 900,000 Da, was analyzed by temp.-modulated differential scanning calorimetry, TMDSC. The high molar mass POE crystals are in a folded-chain macroconformation and show some locally reversible melting, starting already at about 250 K. At 335 K the thermodn. heat capacity reaches the level of the melt. The end of melting of a high-crystallinity sample was analyzed quasi-isothermally with varying modulation amplitudes from 0.2 to 3.0 K to study the reversible crystallinity. A new internal calibration method was developed which allows to quant. assess small fractions of reversibly melting crystals in the presence of the reversible heat capacity and large amts. of irreversible melting. The specific reversibility decreases to small values in the vicinity of the end of melting, but does not seem to go to zero. The reversible melting is close to sym. with a small fraction crystg. slower than melting, i.e., under the chosen condition some of the melting and crystn. remains reversing. The collected data behave as one expects for a crystn. governed by mol. nucleation and not as one would expect from the formation of an intermediate mesophase on crystn. The method developed allows a study of the active surface of melting and crystn. of flexible macromols.
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    31. 31
      Deng, K.; Zeng, Q.; Wang, D.; Liu, Z.; Qiu, Z.; Zhang, Y.; Xiao, M.; Meng, Y. Single-ion conducting gel polymer electrolytes: design, preparation and application. J. Mater. Chem. A 2020, 8, 1557– 1577,  DOI: 10.1039/C9TA11178F
      31
      Single-ion conducting gel polymer electrolytes: design, preparation and application
      Deng, Kuirong; Zeng, Qingguang; Wang, Da; Liu, Zheng; Qiu, Zhenping; Zhang, Yangfan; Xiao, Min; Meng, Yuezhong
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2020), 8 (4), 1557-1577CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      A review. Electrolytes as pivotal components of lithium-ion batteries (LIBs) and lithium metal batteries (LMBs) affect the capacity, cycle stability, safety and operating conditions of the batteries. An ideal electrolyte should possess high ionic cond., enhanced safety, unity lithium ion transference no. (LITN) and good electrochem. stability. Single-ion conducting solid polymer electrolytes (SIC-SPEs) have garnered considerable attention due to their unique unity LITNs. In SIC-SPEs, immobilization of anions gives rise to unity LITNs, the absences of anionic concn. polarization, low internal impedances, higher discharge voltages and suppressions of lithium dendrite growth. Single-ion conducting gel polymer electrolytes (SIC-GPEs) can be fabricated by adding plasticizers to SIC-SPEs to enhance the ionic conductivities. Meanwhile, the original feature of unity LITNs (∼0.98) remains. Therefore, SIC-GPEs have been widely applied in LFP cells, LTO cells, LMO cells and Li/S cells, which showed excellent cycle stabilities, good rate capabilities and high capacities at ambient temp. Good compatibility with lithium metal anodes and suppression of lithium dendrites that benefited from immobilization of anions are also inherited for SIC-GPEs. The current status of SIC-GPEs in terms of designs, prepn. methods, electrochem. performances and applications is described in this review. The development directions and future prospects of SIC-GPEs are also discussed.
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    32. 32
      Schaefer, J. L.; Moganty, S. S.; Archer, L. A. Nanoscale Organic Hybrid Electrolytes. Adv. Mater. 2010, 22, 3677– 3680,  DOI: 10.1002/adma.201000898
      There is no corresponding record for this reference.
    33. 33
      Hayamizu, K.; Aihara, Y.; Arai, S.; Price, W. S. Self-Diffusion Coefficients of Lithium, Anion, Polymer, and Solvent in Polymer Gel Electrolytes Measured Using 7Li, 19F, and 1H Pulsed-Gradient Spin-Echo NMR. Electrochim. Acta 2000, 45, 1313– 1319,  DOI: 10.1016/S0013-4686(99)00338-2
      33
      Self-diffusion coefficients of lithium, anion, polymer, and solvent in polymer gel electrolytes measured using 7Li, 19F, and 1H pulsed-gradient spin-echo NMR
      Hayamizu, Kikuko; Aihara, Yuichi; Arai, Shigemasa; Price, William S.
      Electrochimica Acta (2000), 45 (8-9), 1313-1319CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Science Ltd.)
      Four series of soln. and corresponding polymer gel electrolyte systems were studied. The systems were composed of a solvent (γ-butyrolactone (GBL) or propylene carbonate (PC)), 3 different concns. of a lithium salt (LiBF4 or lithium bis(trifluoromethanesulfonyl)-imide (LiTFSI)), and poly(ethylene glycol diacrylate) of mol. wt. 4000 (PEO), which was cross-linked to form the polymer gels. The self-diffusion coeffs. of the lithium, the anions, the solvents, and the polymer were obtained independently using 7Li, 19F, and 1H pulsed-gradient spin-echo NMR measurements. From the individual diffusion coeffs. of each component of the GBL-LiBF4, GBL-LiTFSI, PC-LiBF4, and PC-LiTFSI solns. and the corresponding polymer gel electrolytes, the solvation and the solvent-dependent behavior of the lithium and the anions are clearly shown. Esp. in the gels, the lithium binding with the PEO matrix were found to be quite different depending on whether the solvent was PC or GBL.
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    34. 34
      Evans, J.; Vincent, C. A.; Bruce, P. G. Electrochemical Measurement of Transference Numbers in Polymer Electrolytes. Polymer 1987, 28, 2324– 2328,  DOI: 10.1016/0032-3861(87)90394-6
      34
      Electrochemical measurement of transference numbers in polymer electrolytes
      Evans, James; Vincent, Colin A.; Bruce, Peter G.
      Polymer (1987), 28 (13), 2324-8CODEN: POLMAG; ISSN:0032-3861.
      Electrochem. methods for the detn. of transference nos. in polymer electrolytes were considered and a new technique which overcomes some of the problems assocd. with other methods in current use is described. Results are given of measurements of the transference nos. of Li and trifluoromethanesulfonate ions in poly(ethylene oxide) at 90°. A mean value of 0.46 ± 0.02 is reported for Li.
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    35. 35
      Tanner, J. E.; Stejskal, E. O. Restricted Self-Diffusion of Protons in Colloidal Systems by the Pulsed-Gradient, Spin-Echo Method. J. Chem. Phys. 1968, 49, 1768– 1777,  DOI: 10.1063/1.1670306
      35
      Restricted self-diffusion of protons in colloidal systems by the pulsed-gradient, spin-echo method
      Tanner, J. E.; Stejskal, E. O.
      Journal of Chemical Physics (1968), 49 (4), 1768-77CODEN: JCPSA6; ISSN:0021-9606.
      The pulsed-gradient, spinecho technique has been used to study self-diffusion of protons in several colloidal systems in order to exam. the usefulness of that technique in detg. the extent to which the free movement of mols. in these systems is restricted by the colloidal structures present. The pulsed-gradient expt. is preferred to the steady-gradient expt. because it affords better definition and control over the time during which diffusion is observed. Diffusion times between 1 sec. and 10-3 sec. have been used. One artificial system of thin liq. layers, three different kinds of plant cells, and one emulsion have been studied. Clear indications of restricted diffusion are found in all the systems. When fitted to theoretical expressions derived for such behavior, the data yielded a description of each system, as seen by the diffusing mols., adequately in agreement with the known structure and properties. Criteria for recognizing and analyzing restricted diffusion are discussed. Necessary conditions for the successful study of restricted diffusion are also discussed.
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    36. 36
      Van Geet, A. L. Calibration of Methanol Nuclear Magnetic Resonance Thermometer at Low Temperature. Anal. Chem. 1970, 42, 679– 680,  DOI: 10.1021/ac60288a022
      36
      Calibration of methanol nuclear magnetic resonance thermometer at low temperature
      Van Geet, Anthony L.
      Analytical Chemistry (1970), 42 (6), 679-80CODEN: ANCHAM; ISSN:0003-2700.
      The data obtained by measuring the PMR chem. shift between the Me and OH group on MeOH at 175-330°K can be fitted by a quadratic equation with 0.8°K root mean sq. error. Also, over 50°K temp. intervals, the data can be fitted to straight lines. The straight-line approxns. agree with the quadratic equation within 0.7°K.
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  • Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.1c15771.

    • DSC curve analysis, fitting results from Netzsch, self-diffusion coefficients table, and polarization and impedance spectra (PDF)


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