A simple technique for transferring PEO: LiTFSI polymer electrolyte membranes in eutectic amorphous phase

<p indent="0mm">Since the commercialization of lithium-ion batteries in the 1990s, lithium-ion batteries have been successfully applied in portable electronics, electric vehicles, and grid energy storage. Although current organic liquid electrolytes have high ionic conductivities, they are inherently flammable, volatile, and prone to leakage. Moreover, severe side reactions and dendrite growth on the surface of the lithium anode during the charge-discharge process can cause safety hazards, which greatly impede their applications in lithium metal batteries. Solid electrolytes, including inorganic solid electrolytes and polymer electrolytes, are regarded as effective alternatives to organic liquid electrolytes for the construction of lithium metal batteries with high energy density and safety. Among them, solid polymer electrolytes offer excellent flexibility, processability, and interfacial compatibility over inorganic solid electrolytes, and they are extraordinarily promising for lithium metal batteries with high energy density and safety. Ideal solid polymer electrolytes should have following features: (1) High ionic conductivity (&gt; <sc>10 ^–4 S cm ^–1) </sc> at room temperature; (2) high lithium ion transference number (~1) to reduce the concentration polarization and improve the rate performance of batteries; (3) intimate contact at the electrode/electrolyte interfaces; (4) wide electrochemical window <sc>(&gt;4.5 V</sc> vs. Li/Li ⁺) to match high-voltage cathodes and improve the energy density of batteries; (5) good mechanical stability to resist processing, buffer electrode volume change and inhibit dendrite growth; (6) good thermal stability to withstand environmental changes. Generally, the ionic conductivity of pure solid polymer electrolytes at room temperature is low <sc>(~10 ^–6 S cm ^–1). </sc> Researchers have tried to improve the ionic conductivities by adjusting the lithium salt concentration, such as developing “polymer-in-salt” solid electrolytes. However, increasing the concentration of lithium salt leads to the deterioration of the mechanical strength. Strategies such as developing novel lithium salts, modifying polymer matrix, and incorporating inorganic fillers into solid polymer electrolytes are proposed to promote ionic conductivities of solid polymer electrolytes. In particular, composite polymer electrolytes, fabricated by dispersing a certain amount of inorganic fillers into solid polymer electrolytes, have improved ionic conductivities without sacrificing their mechanical performances. Poor interfacial property between electrodes and electrolytes is also a critical issue for solid polymer electrolytes. On one hand, poor and uneven solid/solid contacts at the electrode/electrolyte interfaces lead to high resistance and sluggish ionic transport kinetics. Furthermore, the volume change of the positive and negative electrodes in the charge/discharge process deteriorates the interfacial contacts, blocks the ion and electron transport through the interfaces, and greatly reduces the electrochemical reaction kinetics. On the other hand, the electrochemical windows of solid polymer electrolytes are usually narrow <sc>(＜4.5 V).</sc> During cycling, redox reactions are prone to occur at the electrode/electrolyte interfaces, causing battery failure. Solid polymer electrolytes have also poor thermal and mechanical stabilities. Therefore, design and synthesis of polymer-based solid electrolytes with excellent comprehensive performances and construction of fast and stable ion transport channels at the electrolyte/electrode interfaces are of great significance for the successful development of solid-state lithium metal batteries. This paper presents a brief review of the research progress in solid polymer electrolytes from two aspects: Improving the ionic conductivities of solid polymer electrolytes and enhancing the interfacial performance at electrolyte/electrode interfaces. First, targeted optimization strategies on ionic conductivities of solid polymer electrolytes, including constructing continuously aligned ionic transport paths and shortening the ionic transport distance, are summarized. Second, interface optimization strategies, including constructing wetting interfaces and synthesizing asymmetric electrolytes, are presented to reduce the interface resistance and improve the interfacial contact. Finally, perspectives on the development of solid polymer electrolytes and high-performance solid-state lithium metal batteries are discussed, and key research directions and advanced test methods are proposed. This review may provide a comprehensive understanding and further guidance for not only the material design of solid polymer electrolytes, but also the structural design of lithium metal batteries with favorable electrochemical and interfacial performances.

Jeffamine® based polymers as highly conductive polymer electrolytes and cathode binder materials for battery application

Solid polymer electrolytes (SPEs) are regarded as promising candidates for next-generation solid-state lithium metal batteries (SSLMBs) due to their high flexibility and excellent processability, whereas their practical application remains a challenge to simultaneously achieve high ionic conductivity, superior inherent stability, and desirable interfacial compatibility with the Li metal anode. Here, we report a composite solid electrolyte (CSE) incorporating a three-dimensional zeolite network (3D Zeo) into a poly(ethylene oxide) (PEO) matrix containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt (3D Zeo/PEO). The interconnected 3D Zeo provides continuous Li+-conduction pathways and promotes the amorphization of the polymer and the dissociation of the Li salt via Lewis acid–base interactions. The resulting 3D Zeo/PEO CSE exhibits an ionic conductivity of 1.62 × 10−4 S cm−1 at room temperature and an electrochemical stability window up to 5.7 V vs. Li+/Li, significantly surpassing those of LiTFSI–PEO SPE (3.23 × 10−6 S cm−1, 4.9 V). Leveraging the regulatory effect of the 3D Zeo/PEO CSE on Li+ deposition and solid electrolyte interphase formation, the symmetric cell demonstrates stable cycling over 2300 h with an overpotential of 0.13 V, and the full cells also deliver superior high-rate capability and long-term stability with a capacity retention of 92% after 500 cycles at room temperature, far exceeding the performance of batteries using LiTFSI–PEO SPE and CSE with zeolite-based particle fillers. This work provides a promising approach for the design of CSEs to achieve high interfacial compatibility and uniform Li+ deposition for next-generation SSLMBs.

Copolymers comprising poly(ethylene glycol) acrylate soft unit and sulfobetaine methacrylate zwitterionic unit and its application in solid-state lithium metal battery at ambient temperature

Implementation of solid polymer electrolytes (SPEs) is believed to be one pathway forward in the development of lithium-metal batteries (LMBs) that are both safe and possesses high capacities. This combination is possible since the free-standing SPE maintains its mechanical integrity during electrochemical and thermal exposure while utilizing lithium metal as the negative electrode, thus accessing the extremely high theoretical capacity of lithium metal. The main drawback for SPEs are however the poor ionic conductivity compared to the liquid electrolytes used in lithium-ion batteries today.[1] The low ionic conductivity for SPEs stems from the conduction mechanism of the ions, which is a slower process in SPEs compared to in liquid electrolytes. In general, the conductivity in SPEs are confined to the amorphous regions, where segmental motion of the polymer chains facilitates the ion transport; while the crystalline regions restrict the movements of the polymer chains and impairs the ion transport.[2] The highly crystalline polyketone poly(1-oxoheptamethylene) (POHM) is a material that has shown interesting characteristics for implementation as a SPE in batteries. In earlier studies, the polyketone revealed an extensive improvement of the ionic conductivity upon increasing the salt concentration, although the crystallinity remained with a high melting point.[3] Herein this study, the effect of the crystallinity on the characteristics and the performance was investigated further. To understand its effect, a second less hydrogenated version of POHM was synthesized, POHM-75, which is fully amorphous at high salt concentrations. The characteristics of the polyketones were in addition also compared with the more well-studied SPEs, that is polyethylene oxide (PEO) and poly(trimethylene carbonate) (PTMC). Focus of the presentation is on the interplay between the ionic conductivity and mechanical stability for the polyketones, for which something different to the normally observed tradeoff between the two properties is observed. The electrochemical performance of the polyketones are furthermore evaluated when implemented as SPEs in LMBs at extreme temperature environments, a possible application area for mechanically stable SPEs.[1] D. Zhou, D. Shanmukaraj, A. Tkacheva, M. Armand, G. Wang, Chem 2019, 5, 2326-2352.[2] M. A. Ratner, P. Johansson, D. F. Shriver, MRS Bulletin 2011, 25, 31-37.[3] T. Eriksson, H. Gudla, Y. Manabe, T. Yoneda, D. Friesen, C. Zhang, Y. Inokuma, D. Brandell, J. Mindemark, Macromolecules 2022, 55, 10940-10949. Figure 1

Solid polymer electrolytes (SPEs) possess improved thermal and mechanical stability as safe energy storage devices. However, their low ion mobilities and poor electrochemical stabilities still hinder the wide industrial application of SPEs. Herein, we introduce an SPE design that provides an enormous number of electrochemically stable pathways and space for lithium-ion transport, blending polymer (polydopamine) hollow nanospheres with an inactive inorganic template into a poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) based SPE. Hollow silica acts as a template for polydopamine processing a large contact area with the polymer electrolyte, and the interface between the polymer electrolyte and hollow composite fillers provides amounts of ion transport channels. In addition, theoretical calculations reveal a strong adsorption between polydopamine and TFSI-, which suppresses the TFSI- motion and meanwhile facilitates the selective Li+ transport. The hollow polydopamine can serve as a versatile platform for anion trapping and has large compatible and stable depression for a well-defined ion transfer interface layer, forming a three-in-one nanocomposite for the enhancement of ionic conductivity with no sacrifice of the mechanical properties. Experimental data confirmed the high mobility of ions within the composite electrolyte with an ionic conductivity of 0.189 mS cm-1 in comparison to the SPE without additives (0.105 mS cm-1) at 60 °C. The mobility of the Li+ increases after adding the polymer-coated inorganic additives, associated with a noticeable enlargement of the electrochemical window. Furthermore, an all-solid-state Li/LiFePO4 battery with a hollow polydopamine nanoparticle-polymer composite electrolyte shows long life, high reversible capacity (134.9 mAh g-1), and high capacity retention (97.2%) after 205 cycles at 0.2 C.

Electrolyte plays a pivotal role in Li-ion battery (LIB). Generally, it has been considered as a liquid phase material that allows for reasonable dissolution ability of inorganic salt and ion transportability across the electrodes. Since conventional liquid electrolytes faced limitations to improve battery performance, the solid-state electrolyte has raised rapidly to replace the liquid electrolyte. Solid polymer electrolyte (SPE) is one of the most promising solid-state electrolytes, it has attracted attention due to its strength as an electrolyte such as high accessibility, tolerance against volume change of electrodes, and reasonable chemical/thermal stability. Especially poly(ethylene oxide) (PEO) or PEO-based electrolytes have been widely developed, because of their outstanding Li salt dissolution ability. PEO forms a unique helical complex structure with Li salt, the complex is highly stable. It allows PEO to dissolve Li salt much easier than other polyethers, such as poly(propylene oxide) or poly(oxymethylene). However, the high stability of the complex could disturb fast ionic conduction in electrolyte medium, it is the reason why PEO electrolyte has poor ionic conductivity at ambient temperature (10-7 to 10-6S/cm at room temperature). Crown ethers, the macrocycles composed of ethylene oxide, also attract attention for SPEs. Even though the monomer is the same (ethylene oxide) for both PEO and Crown ethers, the properties of each complex are different. Crown ether electrolyte shows higher ionic conductivity than PEO electrolyte at ambient temperature, it is assumed that the crown ether electrolyte is an amorphous phase while PEO electrolyte has high crystallinity below the melting point (60~80%). Crown ether is also promising for Li metal batteries. Crown ether is the hosting material that has a preorganized acceptor structure (also well-known as macrocyclic effect), therefore it can adjust kinetics of reduction on the surface of Li metal anode. Even though promising abilities of crown ether electrolytes have been reported, their ion conduction mechanisms are yet understood well. Therefore, it is worth studying about complex structure and ion conduction mechanism of crown ether electrolyte for a better understanding of SPE, and further, it can be a milestone to design new SPEs. To understand the complex structure and ion conduction mechanism in crown ether electrolytes, we performed both experimental and theoretical analysis. We synthesized the complexes of different sizes of crown ethers (12-crown-4, 15-crown-5, and 18-crown-6) and Li salts (LiTFSI, LiClO4, LiBF4, and LiI). The complexes are characterized by Fourier transformed infrared (FTIR), X-ray diffraction (XRD), nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), and AC impedance analysis. DFT calculation and molecular dynamics for each complex were performed to obtain an atomistic description of the complexes.

Graphitic carbon nitride assisted PVDF-HFP based solid electrolyte to realize high performance solid-state lithium metal batteries

Solid-state sodium ion batteries are frequently referred to as the most promising technology for next-generation energy storage applications. However, developing a suitable solid electrolyte with high ionic conductivity, excellent electrolyte–electrode interfaces, and a wide electrochemical stability window, remains a major challenge. Although solid-polymer electrolytes have attracted great interest due to their low cost, low density and very good processability, they generally have significantly lower ionic conductivity and poor mechanical strength. Here, we report on the development of a low-cost composite solid polymer electrolyte comprised of poly(ethylene oxide), poly(vinylpyrrolidone) and sodium hexafluorophosphate, mixed with indium arsenide nanowires. We show that the addition of 1.0% by weight of indium arsenide nanowires increases the sodium ion conductivity in the polymer to 1.50 × 10−4 Scm−1 at 40 °C. In order to explain this remarkable characteristic, we propose a new transport model in which sodium ions hop between close-spaced defect sites present on the surface of the nanowires, forming an effective complex conductive percolation network. Our work represents a significant advance in the development of novel solid polymer electrolytes with embedded engineered ultrafast 1D percolation networks for near-future generations of low-cost, high-performance batteries with excellent energy storage capabilities.

Lithium-metal batteries (LMBs) with high energy densities are highly desirable for energy storage, but generally suffer from dendrite growth and side reactions in liquid electrolytes; thus the need for solid electrolytes with high mechanical strength, ionic conductivity, and compatible interface arises. Herein, a thiol-branched solid polymer electrolyte (SPE) is introduced featuring high Li+ conductivity (2.26 × 10-4 S cm-1 at room temperature) and good mechanical strength (9.4 MPa)/toughness (≈500%), thus unblocking the tradeoff between ionic conductivity and mechanical robustness in polymer electrolytes. The SPE (denoted as M-S-PEGDA) is fabricated by covalently cross-linking metal-organic frameworks (MOFs), tetrakis (3-mercaptopropionic acid) pentaerythritol (PETMP), and poly(ethylene glycol) diacrylate (PEGDA) via multiple CSC bonds. The SPE also exhibits a high electrochemical window (>5.4 V), low interfacial impedance (<550 Ω), and impressive Li+ transference number (tLi+ = 0.44). As a result, Li||Li symmetrical cells with the thiol-branched SPE displayed a high stability in a >1300 h cycling test. Moreover, a Li|M-S-PEGDA|LiFePO4 full cell demonstrates discharge capacity of 143.7 mAh g-1 and maintains 85.6% after 500 cycles at 0.5 C, displaying one of the most outstanding performances for SPEs to date.

All-solid-state lithium batteries (ASSBs) are considered like the next generation of electrochemical energy storage devices because of their safety and their high energy density up to 400Wh/kg. The all-solid-state battery is composed of a positive electrode (e.g., NMC (Li(Ni1∕3Mn1∕3Co1∕3)O2)), a negative one (Li), and a solid electrolyte, which is the critical component, composed of inorganic compound and/or solid polymer electrolyte (SPE) [1]. On the one hand, SPE have the advantage of an easy shaping with the technique already used in the manufacture of batteries and their flexibility allows obtaining a good interface with the electrode materials [2]. On the other hand, inorganic compounds generally have high ionic conductivity (10-3S/cm), they are stable electrochemically vs Li/Li+ and their transport number is close to 1 to promote the diffusion/migration of Li+ ions only. In order to combine the advantages of both types of materials, hybrid materials have been designed [3].First, a new adaptable polymer matrix based on PEO derivatives has been developed. A solvent-free synthesis has been designed from liquid and commercial precursors Poly(ethylene glycol) methyl methacrylate (PEGM) and Poly(ethylene glycol) dimethacrylate (PEGDM). These latter were copolymerized with Lithium 3-[(trifluoromethane)sulfonamidosulfonyl] propyl methacrylate (MTFSLi). The anion TFSI- is thus grafted to the PEO network, allowing exclusively the diffusion of the Li+ ion. This polymer matrix can be thus classified as single-ion conductor. In addition, the proportions between PEGM and PEGDM, acting as crosslinker, can be easily tuned. The PEGDM proportion controls the cross-linking density which modifies not only the glass transition temperature (Tg), but also the storage modulus (E’) and the free volume, and consequently the ionic conductivity of the polymer matrix which is the main property required for SPE. Finally, a ratio of PEGM:PEGDM (80:20) allows obtaining homogeneous SPE, self-standing and soft at room temperature, amorphous with a Tg of -41°C. The EO/Li ratio was then modulated in single-ion networks with the MTFSLi proportion, and an optimum in ionic conductivity of 2.10-7 S/cm @25°C has been measured for EO/Li ratio of about 20. The transport number measured by the Bruce and Vincent method [4] was t+=1,0 for the single ion conductor, demonstrating the effective grafting of the counter anion. This value has been validated by measuring the diffusion coefficients of 7Li and 19F in NMR. To our knowledge, this is the first time a real unity transport number is reported in the literature for a polymer electrolyte. Moreover, the electrochemical stability of this single ion system extends from 0 to 6V vs Li+/Li. These experiments suggest the interest of using the single-ion polymer in the formulation of composite positive electrode with high potential cathode materials, due to its stability in potential. Li metal is considered the ultimate anode for Li-batteries. The long-term electrochemical stability has been evaluated in symmetric Li/polymer electrolyte/Li cell. The cell is cycled at a constant current density of 0.2 mA/cm2. After 200 h of cycling the voltage reaches solely 2V. Accordingly, the grafting of the anion to the network limits an overpotential in the cell, allowing a more stable system over time.Second, the garnet Li6.4La3Zr2Al0.2O12 (LLZO) of the oxide family was associated to the previous polymer matrix. This garnet presents a high conductivity (10-4 S/cm @ 25°C), a good chemical stability not only against lithium metal but also against air and humidity, which is not the case of sulphides homologues. A 3D-fibrous network obtained by the electrospinning method was carried out with a solution containing the inorganic precursors, a polymer and an appropriate solvent [5]. Then this membrane is calcined at 850°C to obtain the 3D fibrous network of LLZO. The resulting self-standing porous inorganic material (~80% of porosity) exhibits a conductivity of the order of 10-6 S/cm @25°C. It was then impregnated with the polymer matrix precursors by capillarity and following by a polymerization. A self-standing membrane as thin as 80 µm containing 9%vol of LLZO was obtained. The conductivity of this hybrid membrane is comparable to that of the polymer (10-7S/cm @ 25°C). The resulting hybrid is mainly polymeric where the ionic conduction was realized by the polymeric matrix and the inorganic acts as a mechanical reinforcement. Preliminary results on high content of LLZO hybrid will also be presented, where a synergy of the both components is observed.[1] Janek. Nature Energy. 2016. Vol 1(9)p.16141. [2] Yue. Energy Storage Materials. 2016. Vol 5p.139-164. [3] Zheng. Chem Soc Rev. 2020. Vol 49p.8790-8839. [4] Bruce. Solid State Ion. 1988. Vol 28–30p.918–922. [5] A. La Monaca. Electrochemistry Communications. 2019. Vol 104p.106483. Figure 1

Solid polymer electrolytes offer a promising pathway toward safe, high-energy solid-state lithium metal batteries. However, their practical deployment remains limited by insufficient ionic conductivity, narrow oxidative stability windows, and poor interfacial compatibility with metal anodes. In particular, conventional polymer systems such as PEO typically operate below ∼3.8 V and cannot sustain high-voltage cathode chemistry. In this work, a solid polymer electrolyte based on a proprietary carbonate–fluorinated methacrylate copolymer PIRION-F (denoted as PCFMA) is developed and systematically evaluated. Comprehensive FTIR, X-ray diffraction, differential scanning calorimetry, TGA, and scanning electron microscopy analyses confirm the amorphous nature of the polymer, its robust thermal stability, and the dense microstructure of the solid electrolyte membrane. The PCFMA exhibits outstanding LiTFSI solubility, high ionic conductivity (0.1 mS cm–1 at room temperature and 1.2 mS cm–1 at 70 °C), and a wide oxidative stability window up to ∼4.8 V vs Li+/Li, enabling operation with high-voltage cathodes. Li symmetric cells display ultrastable cycling for over 4500 h with low polarization. All-solid-state Li//NCM622 and high-voltage Ni-rich cells further show reversible charge/discharge behavior and strong capacity retention during extended cycling at room temperature. To contextualize broader manufacturability, an independent multilayer pouch-cell prototype fabricated by a technology startup collaborator delivers a cell-level energy density of 523 Wh kg–1. Collectively, these results demonstrate the strong potential of PCFMA-based solid electrolytes for next-generation high-voltage solid-state lithium metal batteries.

Practical implementations of solid polymer electrolytes (SPEs) in solid‐state lithium‐metal batteries (SSLMBs) are inhibited by the limited lithium‐ion (Li+) transport and poor‐quality interface between SPEs and both electrodes. SPEs exhibit lower ionic conductivity than other electrolytes and are oxidized and decomposed by oxide‐based cathode materials in high‐voltage windows. SSLMBs are also long‐term destabilized by parasitic side reactions at the electrode–electrolyte interfaces and Li dendrite formations. This study proposes a selectively designed Janus‐structured polymer electrolyte (JPE), which is more physically and chemically compatible with the electrodes than other SPEs. The proposed JPE includes a cathode‐facing composite polymer electrolyte (C‐CPE) containing succinonitrile and Li7La3Zr2O12, and an anode‐facing composite polymer electrolyte (A‐CPE) incorporating fluoroethylene carbonate (FEC). The C‐CPE layer provides additional Li+ paths and increases the antioxidant properties, improving the high‐voltage tolerance of the SSLMB, while the A‐CPE layer alleviates side reactions with the Li metal anode and improves the stability against protruding dendrites. Full cells of Li|JPE|Ni0.8Co0.15Al0.05O2 and Li|JPE|LiCoO2 remain stable over 1600 cycles at 1 C, demonstrating the potential of the JPE structures for SSLMBs. Moreover, symmetric Li||Li cells assembled with the JPE cycle over 2500 h at 0.1 mA cm−2 and 1000 h at 0.5 mA cm−2.

Lithium metal has generated significant interest as an anode material because of its high theoretical capacity (3860 mAh/g). However, issues such as dendrite growth and lithium loss during cycling make this material incompatible with current liquid electrolytes. Solid polymer electrolytes (SPE) have been proposed as a potential replacement as they are non-flammable, able to resist dendrite growth, have decent ionic conductivity and good interfacial contact with lithium metal.One aspect that is often overlooked is the fact that passivation layers, initially reported by Naudin et Al (1), often form on the lithium metal surface and are hence intrinsic to the chemical composition of the lithium surface (2, 3). According to Otto et Al (4), residual quantities of atmospheric gases are often present in lithium metal storage environments, thus electrode surface modification is inevitable. This passivation layer is expected to impact the reactivity of the lithium metal anode (LMA) towards SPE. Moreover, such phenomenon was originally described by Peled et Al as the solid electrolyte interface (SEI) (5). Lithium metal reactivity towards PEO, suspected by Galluzo et Al (6), was recently reported by Liu et Al (7), under optimized conditions (ultra-thin neat materials), but the impact of this phenomenon in a realistic LMA environment has not been extensively investigated.In this study, the impact of gas exposure on a LMA was investigated by exposing freshly cut lithium rods to O2, CO2 and N2. The resultant passivation layers were characterized via XPS. The effect of passivation layer formation on LMA reactivity towards SPE was measured by exposing samples with pre-characterized passivation layers to common SPE materials. The resultant interface was characterized using Raman spectroscopy. SPE-passivation layer reactivity was correlated to ageing properties by EIS and kinetic charge transfer characteristics in galvanostatic linear polarization at the LMA-SPE interface, in a symmetric Li – SPE – Li stack.This study revealed that the chemical composition of the lithium metal passivation layer affects its reactivity towards SPE as well as the electrochemical performance of a Li-SPE-Li symmetric cell. A thorough characterization of the lithium metal passivation layer is essential for the understanding of some of the fundamental factors affecting all solid-state lithium metal battery performance and is therefore consubstantial with the development of modified LMA. C. Naudin et al., Characterization of the lithium surface by infrared and Raman spectroscopies. Journal of Power Sources 124, 518-525 (2003).S.-K. Otto et al., In-Depth Characterization of Lithium-Metal Surfaces with XPS and ToF-SIMS: Toward Better Understanding of the Passivation Layer. Chemistry of Materials 33, 859-867 (2021).P. R. G. Zhuang, F. Kong, F. McLarnon The reaction of clean Li surfaces with small molecules in ultrahigh vacuum: II. Journal of The Electrochemical Society, 159-164 (1998).S.-K. Otto et al., Storage of Lithium Metal: The Role of the Native Passivation Layer for the Anode Interface Resistance in Solid State Batteries. ACS Applied Energy Materials 4, 12798-12807 (2021).E. Peled, Film forming reaction at the lithium/electrolyte interface. Journal of Power Sources 9, 253-266 (1983).M. D. Galluzzo et al., Dissolution of Lithium Metal in Poly(ethylene oxide). ACS Energy Letters 4, 903-907 (2019).P. Liu et al., Increasing Ionic Conductivity of Poly(ethylene oxide) by Reaction with Metallic Li. Advanced Energy and Sustainability Research 3, 2100142 (2022).

Solid polymer electrolytes (SPEs) offer a promising route toward safe and high-performance electrochemical energy storage, yet a fundamental challenge in SPEs involves improving ionic conductivity while maintaining selective cation transport. The hurdle exists because ion transport is typically coupled closely to polymer segmental dynamics. Herein, a glassy single-ion-conducting polymer, poly-[lithium sulfonyl-(trifluoromethane sulfonyl)-imide methacrylate] (PLiMTFSI), in which the anions were tethered to the polymer, was blended with a flexible polymer, poly-(oligo-oxyethylene methyl ether methacrylate) (POEM), and a series of small-molecule lithium salts, in which the anions were untethered [lithium bis-(trifluoromethanesulfonyl)-imide (LiTFSI), lithium bis-(fluorosulfonyl)-imide (LiFSI), lithium trifluoromethanesulfonate (LiTf), or lithium perchlorate (LiClO4)]. The impact of salt anion volume and tethered-to-untethered anion ratio on the ion conduction behavior and thermal properties of blend electrolytes was investigated. In some cases, conductivity could be enhanced through this ternary blend approach. For example, a POEM-based polymer blend containing a bulky salt anion (TFSI-) and an equimolar mixture of PLiMTFSI and LiTFSI exhibited a Li+ conductivity (4.8 × 10-4 S/cm) an order of magnitude higher than that of a comparable POEM/LiTFSI system (6.3 × 10-5 S/cm) at 100 °C. This enhancement was attributed to a more than 9-fold increase in lithium transference number (0.66 in the ternary blend vs 0.07 in POEM/LiTFSI). Overall, this study highlights the potential for tuning anion composition and mobility to achieve relatively high ionic conductivities and maintain selective cation transport in SPEs, offering a pathway to enable batteries that tolerate elevated temperatures.