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Low ionic conductivity, narrow electrochemical window and poor mechanical property are the core problems that polymer solid electrolyte is difficult for practical application. Choosing suitable polymer and regulating the ion transport path through inorganic fillers is an important method to solve the above problems. Herein, a polymeric matrix composite solid electrolyte(CSE) was achieved by combining electrospun Li7La3Zr2O12 (LLZO) fibers and highly viscoelastic polypropylene oxide(PPO). The PPO matrix provides the CSE with good mechanical property to 56.75 MPa. While the addition of fibrous LLZO improves the ion transport channels of the CSE, which boosts the ionic conductivity, electrochemical window and ion transport number up to 4.59 × 10− 4 S cm− 1 at room temperature, 5.4 V and 0.74, respectively, when the content of LLZO fiber is 7.5 wt% of PPO polymer. The prepared PPO-LLZO fibers electrolyte can be used in high-voltage solid-state lithium battery and shows good rate and cycle performances. This composite solid electrolyte film and its simplified preparation conditions is beneficial for practical applications in solid-state batteries. [ABSTRACT FROM AUTHOR]

The NASICON-type ceramic Li 1·5 Al 0.5 Ge 1.5 (PO4) 3 (LAGP) electrolyte has been proposed as the most competitive candidates of electrolyte materials toward solid-state Li metal batteries (LMBs) by reason of its high ionic conductivity, cyclic stability under extreme temperatures and wide voltage window. However, poor interface contact, high interfacial resistance and intractable mechanical properties greatly limit its practical applications. In this work, an inorganic-polymer "LAGP in PVDF" quasi-solid-state electrolyte (QSSE) is developed via solution casting method, in which pyr14TFSI ionic liquid (IL) and LiTFSI are combined as functional wetting interface. Benefiting from the coherent interaction of LAGP nanoparticles incorporated into the polymer matrix, and inherent protection of IL, the overall performance of the optimized QSSE include thermal stability, dense structure, flexibility and electrochemical properties. The XRD, SEM, XPS tests demonstrate that the IL using as a solid/electrolyte modified interlayer can enhance Li+ transport, interfacial infiltration and homogenize lithium deposition. The LiFePO 4 |PL-25LAGP|Li solid-state battery presents an excellent circulation performance under ambient temperature, which displayed an initial discharge specific capacity of 146.8 mAh g−1 at 0.5C and capacity retention of 96.25 % after 150 cycles. The flexibility PL-LAGP CSE shows superior safety and greater development potential for the "LAGP in PVDF" composite electrolyte in solid state LMBs. • The LAGP in PVDF" composite solid electrolyte is optimizing though component regulation. • The pyr14TFSI ionic liquid and LiTFSI are combined as functional wetting interface layer. • Unveiling the chemical reactions occurring in LAGP-PVDF QSSE and pyr14TFSI. [ABSTRACT FROM AUTHOR]

Polyethylene oxide (PEO)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is among the most promising candidates for developing solid polymer electrolytes (SPEs) for all‐solid‐state lithium‐metal batteries (ASSLMBs). However, practical applications of the PEO/LiTFSI system face challenges due to its relatively low ionic conductivity and low Li+ transference number. To address these issues, a method is proposed that incorporates multiple components, including zeolitic imidazolate frameworks (ZIF‐67) as fillers and ionic liquid electrolytes (ILEs) as plasticizers, into a PEO/LiTFSI matrix. By optimizing the fabrication process, ultra‐thin membranes of the integrated electrolyte PEO/LiTFSI‐ILE‐ZIF‐67 (PLiZ) with a thickness of 32 µm are developed, achieving high ionic conductivity (1.19 × 10−4 S cm−1 at 25 °C), broad electrochemical stability (5.66 V), and high lithium‐ion mobility (0.8). As a result, the fabricated ASSLMBs exhibited excellent cycle stability at both room temperature and 60 °C, delivering an initial specific discharge capacity of 166.4 mAh g−1 and an impressive capacity retention of 83.7% after 1000 cycles at 3C under 60 °C, corresponding to a low fading rate of 0.0163% per cycle. Additionally, the designed SPEs demonstrated high safety properties, as shown by the successful cutting and folding of a working LiFePO4/PLiZ/Li pouch cell. Therefore, this study presents a comprehensively improved method for developing high‐performance ASSLMBs. [ABSTRACT FROM AUTHOR]

[Display omitted] • A PVDF/CA/LATP CSE is developed via a facile solution-casting process. • PVDF/CA ratio and LATP fractions affect CSE's crystallinity and structural porosity. • The optimized CSE exhibits a high ionic conductivity of 4.9 × 10-4 S cm−1. • The optimized CSE possesses a wide electrochemical window up to 5.0 V vs. Li/Li+. • An LFP-based cell containing PVDF/CA/LATP CSE delivers over 160 mAh g−1 capacity. To enhance energy density and secure the safety of lithium-ion batteries, developing solid-state electrolytes is a promising strategy. In this study, a composite solid-state electrolyte (CSE) composed of poly(vinylidene difluoride) (PVDF)/cellulose acetate (CA) matrix, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, and Li 1.3 Al 0.3 Ti 1.7 (PO 4) 3 (LATP) fillers is developed via a facile solution-casting method. The PVDF/CA ratio, LiTFSI, and LATP fractions affect the crystallinity, structural porosity, and thermal and electrochemical stability of the PVDF/CA/LATP CSE. The optimized CSE (4P1C-40LT/20F) presents a high ionic conductivity of 4.9 × 10-4 S cm−1 and a wide electrochemical window up to 5.0 V vs. Li/Li+. A lithium iron phosphate-based cell containing the CSE delivers a high discharge capacity of over 160 mAh g−1 at 25 °C, outperforming its counterpart containing PVDF/CA polymer electrolyte. It also exhibits satisfactory cycling stability at 1C with approximately 90 % capacity retention at the 200th cycle. Additionally, its rate performance is promising, demonstrating a capacity retention of approximately 80 % under varied rates (2C/0.1C). The increased amorphous region, Li+ transportation pathways, and Li+ concentration of the 4P1C-40LT/20F CSE membrane facilitate Li+ migration within the CSE, thus improving the battery performance. [ABSTRACT FROM AUTHOR]

Despite their potential as next-generation energy storage devices, all-solid-state batteries (ASSBs) have not been widely developed because of the low ionic conductivity of solid electrolytes and the high interfacial impedance with electrodes. This study addressed these issues by enhancing the electrochemical properties through composition control. A composite solid electrolyte (CSE) was fabricated using Li6.5Ga0.2La2.95Rb0.05Zr2O12 (Ga–Rb-doped LLZO) and poly(ethylene oxide) (PEO) with various compositions. The results demonstrated high ionic conductivity and electrochemical stability when the weight ratio of Ga–Rb-doped LLZO to PEO was 6:4. These characteristics effectively mitigated Li dendrite formation and ensured excellent interfacial stability. Notably, LiFePO4/CSEs/Li full cells retained 92.3% of their initial capacity after 100 cycles at a 0.3 C rate. This study will promote the research and development of practical ASSBs incorporating LLZO solid electrolytes. [ABSTRACT FROM AUTHOR]

[Display omitted] Composite solid electrolytes (CSEs) composed of polymer matrix and inorganic fillers show considerable potential for applications in all-solid-state lithium (Li) metal batteries. However, challenges such as fillers agglomeration and low lithium ion transference number (t Li+) remain significant obstacles to the practical application of CSEs. Herein, a general strategy of graft polymerization on the fillers surface to modulate the interface compatibility with the polymer matrix is proposed, and CSEs are prepared to verify the feasibility. The microstructure and composition of the surface coating of the fillers are analyzed, with subsequent studies of the fillers distribution within the CSEs confirming the improved interface compatibility. The enhancement of interface compatibility facilitates uniform dispersion of fillers, thereby greatly improving the utilization of fillers. CSEs exhibits high ionic conductivity (0.163 mS·cm−1 at 30 °C) and t Li+ (0.77), which gives the battery excellent rate performance and cycle stability. Therefore, chemical grafting of polymer onto the fillers surface to enhance the interface compatibility with the polymer matrix represents a promising strategy for the practical application of solid-state batteries. [ABSTRACT FROM AUTHOR]

Composite solid electrolytes (CSEs) integrate the fast ion conductivity of inorganic electrolytes and the excellent interfacial compatibility of polymer electrolytes. Typically, fluoropolymers and garnets are promising individuals to formulate cutting‐edge CSEs owing to their unique properties. However, the alkaline garnets can induce the dehydrofluorination of fluoropolymers, deteriorating their CSEs performance. Here, for the first time, NH4HCO3 is proposed as a sacrificial inhibitor to effectively prevent the garnet‐induced dehydrofluorination, using Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVH) as symbolic garnets and fluoropolymers, respectively. Various findings demonstrate that NH4HCO3 can buffer the alkalinity of LLZTO, thereby inhibiting the dehydrofluorination of PVH. In addition, NH4HCO3 can completely decompose to volatiles upon drying without compromising the properties of LLZTO and PVH. Additionally, a polymer‐in‐salt strategy is further introduced by adding high‐concentration LiTFSI salt to the above system, resulting in the PVH/LiTFSI/LLZTO (PLL) CSEs. Benefiting from the synergetic coupling of the sacrificial inhibitor and polymer‐in‐salt strategies, the PLL exhibits an exceptionally high ionic conductivity of 1.2 mS cm−1 at 25 °C and stable voltage of 5.09 V, outperforming other reported CSEs. Consequently, the PLL delivers impressive high‐rate cyclability in solid‐state lithium‐metal batteries with an outstanding capacity retention of 95.4% after 240 cycles at 1 C (25 °C). [ABSTRACT FROM AUTHOR]

Due to their higher safety, stability and energy density, all-solid-state batteries will be promising candidates for the next generation of lithium battery systems. The acquisition of high-performance solid-state electrolytes is pivotal in the actualization of all-solid-state batteries. By uniformly dispersing nanoscale Li1.3Al0.3Ti1.7(PO4)3 (LATP) powders into polyethylene oxide (PEO)-LiClO4 at varying mass ratios, a composite electrolyte membrane of approximately 50 μm thickness was prepared using the casting method. Subsequent characterization of these materials, accomplished through X-ray diffraction, scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic charge–discharge tests, unveiled intriguing findings. Although the beneficial effect of LATP on the conductivity of PEO is somewhat limited, it demonstrates a capability to reduce the interface impedance between polyethylene oxide and lithium metal, thereby enhancing interface stability. This research provides constructive insights and prompts for designing composite electrolytes for future all-solid-state batteries. [ABSTRACT FROM AUTHOR]

Highlights: This study introduces an innovative 3D-printed electrolyte with vertically aligned ion transport network, which contains well-dispersed nanoscale Ta-doped Li7La3Zr2O12 in a poly(ethylene glycol) diacrylate matrix. The 3DSE architecture enables efficient ion transport across the Li/electrolyte and electrolyte/cathode interfaces, which allows for increased active material mass loading and enhanced interfacial adhesion. The p-3DSE Li symmetric cell displays an impressive critical current density value of 1.92 mA cm−2 and stable operation for 2600 h at room temperature. Full cells using p-3DSE achieve notable areal capacities. Improving the long-term cycling stability and energy density of all-solid-state lithium (Li)-metal batteries (ASSLMBs) at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport. Solid electrolytes are generally studied as two-dimensional (2D) structures with planar interfaces, showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces. Herein, three-dimensional (3D) architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment. Multiple-type electrolyte films with vertical-aligned micro-pillar (p-3DSE) and spiral (s-3DSE) structures are rationally designed and developed, which can be employed for both Li metal anode and cathode in terms of accelerating the Li+ transport within electrodes and reinforcing the interfacial adhesion. The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm−2. The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm−2 (LFP) and 3.92 mAh cm−2 (NCM811). This unique design provides enhancements for both anode and cathode electrodes, thereby alleviating interfacial degradation induced by dendrite growth and contact loss. The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature. [ABSTRACT FROM AUTHOR]

Highlights: A scalable tape-casting method produces self-supported porous Li6.4La3Zr1.4Ta0.6O12. Combining the in-situ polymerization approach, a composite solid electrolyte with superior electrochemical properties is fabricated. Solid-state Li|CSE|LiNi0.8Co0.1Mn0.1O2 cells show remarkable cyclability and rate capability. LiF-and B-rich interphase layers mitigate interfacial reactions, enhancing solid-state battery performance. Composite solid electrolytes (CSEs) have emerged as promising candidates for safe and high-energy–density solid-state lithium metal batteries (SSLMBs). However, concurrently achieving exceptional ionic conductivity and interface compatibility between the electrolyte and electrode presents a significant challenge in the development of high-performance CSEs for SSLMBs. To overcome these challenges, we present a method involving the in-situ polymerization of a monomer within a self-supported porous Li6.4La3Zr1.4Ta0.6O12 (LLZT) to produce the CSE. The synergy of the continuous conductive LLZT network, well-organized polymer, and their interface can enhance the ionic conductivity of the CSE at room temperature. Furthermore, the in-situ polymerization process can also construct the integration and compatibility of the solid electrolyte–solid electrode interface. The synthesized CSE exhibited a high ionic conductivity of 1.117 mS cm−1, a significant lithium transference number of 0.627, and exhibited electrochemical stability up to 5.06 V vs. Li/Li+ at 30 °C. Moreover, the Li|CSE|LiNi0.8Co0.1Mn0.1O2 cell delivered a discharge capacity of 105.1 mAh g−1 after 400 cycles at 0.5 C and 30 °C, corresponding to a capacity retention of 61%. This methodology could be extended to a variety of ceramic, polymer electrolytes, or battery systems, thereby offering a viable strategy to improve the electrochemical properties of CSEs for high-energy–density SSLMBs. [ABSTRACT FROM AUTHOR]

The solid oxide electrolyte Li1.5Al0.5Ge1.5(PO4)3 (LAGP) with a NASICON structure has a high bulk ionic conductivity of 10−4 S cm−1 at room temperature and good stability in the air because of the strong P5+-O2− covalence bonding. However, the Ge4+ ions in LAGP are quickly reduced to Ge3+ on contact with the metallic lithium anode, and the LAGP ceramic has insufficient physical contact with the electrodes in all-solid-state batteries, which limits the large-scale application of the LAGP electrolyte in all-solid-state Li-metal batteries. Here, we prepared flexible PEO/LiTFSI/LAGP composite electrolytes, and the introduction of LAGP as a ceramic filler in polymer electrolytes increases the total ionic conductivity and the electrochemical stability of the composite electrolyte. Moreover, the flexible polymer shows good contact with the electrodes, resulting in a small interfacial resistance and stable cycling of all-solid-state Li-metal batteries. The influence of the external pressure and temperature on Li+ transfer across the Li/electrolyte interface is also investigated. [ABSTRACT FROM AUTHOR]

Composite solid electrolytes (CSEs), often incorporating succinonitrile (SCN), offer promi I confirm sing solutions for improving the performance of all-solid-state batteries. These electrolytes are typically made of ceramics such as Li7La3Zr2O12 (LLZO) and polymers such as poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). Garnet-applied polymer–ceramic electrolyte (g-PCE) is composed of PVDF-HFP, SCN, and LLZO. However, the interface between SCN and LLZO is reportedly unstable owing to the polymerization of SCN. This polymerization could cause two serious problems: (1) gelation during the mixing of LLZO and SCN and (2) degradation of ionic performance during charge and discharge. To prevent this catalytic reaction, polyacrylonitrile (PAN) can be added to the g-PCE (g-PPCE). PAN blocks the polymerization of SCN through a cyclization process involving La ions which occurs more rapidly than SCN polymerization. In this study, the enhanced chemical stability of the garnet-applied PAN-added polymer ceramic electrolyte (g-PPCE) was achieved by using an impregnation process which added SCN with 5 wt.% of PAN. The resulting CSE has an ionic conductivity of ~10-⁴ S/cm at room temperature. Coin-type cells assembled with LFP (LiFePO4) and LNCM (LiNi0.6Co0.2Mn0.2O2) cathodes with Li-metal anodes show specific discharge capacities of 150 and 167 mAh/g at 0.1 C, respectively, and stable cycle performance. Additionally, a pouch-type cell with a discharge capacity of 5 mAh also exhibits potential electrochemical performance. [ABSTRACT FROM AUTHOR]

The ceramic/polymer composite solid electrolyte prepared by a simple physical mixing method has the problem of packing agglomeration and uneven dispersion, resulting in excessive interface impedance, obvious polarization, and severe reduction in energy density of solid-state batteries eventually. Given this defect, a silane coupling agent (KH560) containing Si–O bonds with low rotational potential energy was introduced to modify the garnet-type solid electrolyte (Li6.4La3Zr1.4Ta0.6O12, LLZTO) and then a ceramic polymer composite particle (Si@LLZTO) was achieved, which could be distributed uniformly in a thermoplastic polyurethane (TPU) matrix. Besides, a reduction in the crystallinity of TPU was evoked by the great interfacial compatibility of the silane-modified inorganic fillers, thus the composite solid electrolyte (TPU-Si@LLZTO) exhibits higher ionic conductivity (2.9 × 10−4 S cm−1), a wider electrochemical window (5 V, vs. Li/Li+), and a higher ion transfer number (tLi+ = 0.40). Furthermore, TPU-Si@LLZTO electrolyte displayed long running stability over 1000 h, and excellent rate performance in all-solid-state batteries with the positive electrode of LiFePO4. In conclusion, functional silanes exhibited a positive effect in constructing a compatible solid–solid interface between inorganic fillers/polyurethane polymers and gave full play to the performance advantages of composite electrolytes. [ABSTRACT FROM AUTHOR]

Solid electrolyte lithium batteries are the next generation of advanced energy devices. The incorporation of solid electrolytes can significantly improve the safety issue of lithium‐ion batteries. Organic‐inorganic composite solid electrolytes (CSE) are promising candidates for solid‐state batteries, but their application is mainly limited by low ionic conductivity. Many studies have shown that the architecture of ordered inorganic fillers in CSE can act as fast lithium‐ion transfer channels by auxiliary means, thus significantly improving the ionic conductivities. This review summarises the recent advances in CSE with different dimensional inorganic fillers. Various effective strategies for the construction of ordered structures in CSE are then presented. The review concludes with an outlook on the future development of CSE. This review aims to provide researchers with an in‐depth understanding of how to achieve ordered architectures in CSE for advanced solid state lithium batteries. [ABSTRACT FROM AUTHOR]

High ionic conductivity for solid electrolyte and stable electrode/electrolyte interface have always been the main requirements for solid-state lithium batteries. Herein, a high ionic conductive composite solid electrolyte (CSE) film was prepared by combining 1.3-dioxolanes (DOL) capable of in-situ polymerization with high ionic conductive Li 1.5 Al 0.5 Ge 1.5 (PO 4) 3 (LAGP)ceramic fillers. The CSE film also shows high interface compatibility and stability with lithium metal. The optimized poly-DOL (PDOL)-30% LAGP CSE exhibits a desirable dense and uniform structure, which endows the CSE with a high ion conductivity of 4.63 × 10−4 S cm−1, a high ion migration number up to 0.73 and a wide electrochemical stability window of 5.1 V. The assembled high-voltage NCM622/PDOL-30%LAGP CSE/Li solid-state cell exhibits good rate and cycle performances with a capacity of 125 mAh/g at 2 C and a capacity retention of 76% at 0.5C after 400 cycles with an average Coulomb efficiency of 99.7%. The PDOL-30%LAGP CSE also possesses a high inhibition ability of lithium dendrites owing to the dense and uniform structure and the stable electrolyte/lithium electrode interface including Li–Ge, LiF and CF 3 components. The Li/CSE/Li cell maintains a relatively stable voltage up to 650 h at a current density of 0.1 mA/cm2. This high ionic conductive composite solid electrolyte film shows a good application prospect in high-voltage solid-state lithium batteries. [Display omitted] • High ionic conductive PDOL/LAGP composite solid electrolyte film was achieved. • This composite solid electrolyte provides high ion transport capacity and high electrochmical window. • 3.The electrode/electrolyte interface stability was greatly improved by forming stable SEI composite film. [ABSTRACT FROM AUTHOR]

In order to enhance the electrochemical performance and mechanical properties of poly(ethylene oxide) (PEO)-based solid polymer electrolytes, composite solid electrolytes (CSE) composed of single-ion conducting polymer-modified SiO2, PEO and lithium salt were prepared and used in lithium-ion batteries in this work. The pyridyl disulfide terminated polymer (py-ss-PLiSSPSI) is synthesized through RAFT polymerization, then grafted onto SiO2 via thiol-disulfide exchange reaction between SiO2-SH and py-ss-PLiSSPSI. The chemical structure, surface morphology and elemental distribution of the as-prepared polymer and the PLiSSPSI-g-SiO2 nanoparticles have been investigated. Moreover, CSEs containing 2, 6, and 10 wt% PLiSSPSI-g-SiO2 nanoparticles (PLi-g-SiCSEs) are fabricated and characterized. The compatibility of the PLiSSPSI-g-SiO2 nanoparticles and the PEO can be effectively improved owing to the excellent dispersibility of the functionalized nanoparticles in the polymer matrix, which promotes the comprehensive performances of PLi-g-SiCSEs. The PLi-g-SiCSE-6 exhibits the highest ionic conductivity (0.22 mS·cm−1) at 60 °C, a large tLi+ of 0.77, a wider electrochemical window of 5.6 V and a rather good lithium plating/stripping performance at 60 °C, as well as superior mechanical properties. Hence, the CSEs containing single-ion conducting polymer modified nanoparticles are promising candidates for all-solid-state lithium-ion batteries. [ABSTRACT FROM AUTHOR]

Solid polymer electrolytes using poly(ethylene oxide) (PEO) as matrix are mostly applied due to the superior Li+ transfer ability of oxyethyl chain. However, the high crystallinity, low oxidation potential window, and insufficient mechanical strength hinder PEO deployment in solid‐state batteries. Here, a novel composite solid electrolyte combined PEO with a lithium‐doped high‐entropy oxide (Li0.25HEO) ceramic powder is presented, which exhibits excellent properties for solid‐state lithium metal battery applications. On one hand, the rich oxygen vacancies of Li0.25HEO surface are favorable to capturing anionic groups (e. g. TFSI−), reinforcing the Li+ dissociation. On the other hand, Li0.25HEO with abundant Lewis acid sites markedly promotes the PEO oxidation potential window. Additionally, the incorporation of Li0.25HEO ceramic powder can effectively inhibit the PEO crystallization and enhance the mechanic strength of the composite electrolyte as well. The assembled solid‐state lithium metal battery based on the composite solid electrolyte exhibits high rate capacity and durable cycle performance, showing potential development and application prospects. [ABSTRACT FROM AUTHOR]

To address the issue of lithium metal deposition, a Cs doped FA interlayer was constructed on the surface of CSE. The CSE with this interfacial layer exhibits enhanced ionic conductivity, high Li+ transference number, a wide electrochemical window, and excellent flame-retardant property. Furthermore, the Li||Li symmetric cell assembled using the CSE with this interfacial layer demonstrates stable electroplating/stripping tests over 2000h at 0.2 mA cm−2. In addition, the full cells with the Cs doped FA interlayer and LFP or NCM811 cathode exhibit remarkable electrochemical performance. [Display omitted] • DFT shows that Cs-doped FA contributes to the decomposition of LiTFSI to produce more freedom Li+. • The Cs doped FA interfacial layer can effectively inhibit lithium dendrite growth. • The symmetric Li||Li cell exhibits an exceptionally long life of more than 2000 h at 0.2 mA cm−2. • Solid-state lithium metal batteries with LiFePO 4 and NCM811 exhibit excellent cycling performance. Composite electrolytes have garnered considerable attention owing to ease of processing, flexibility, and cost-effectiveness. Nevertheless, their practical applicability has been hindered by the insufficient ionic conductivity and the formation of dendrites duo to solid–solid interfacial interactions. In this work, an interfacial layer with Cs-doped fluorapatite (Ca 5 (PO 4) 3 F, FA) as the filler was constructed to enhance the flame-retardant property of the composite electrolyte and inhibit dendrite growth during cycling process. The CSE with the Cs doped FA interfacial layer exhibits significant flame-retardant properties. Furthermore, the self-healing electrostatic shielding (SHES) mechanism of Cs+ effectively inhibits the growth of lithium dendrite and promotes uniform lithium deposition. The solid electrolyte integrated with the Cs doped FA interfacial layer exhibits a broad voltage window of 5.58 V vs. Li+/Li, high ionic conductivity of 5.43 × 10-4 S cm−1, and Li+ transference number of 0.716. Density functional theory (DFT) calculations reveal a competitive interaction between Cs+ and Li+ for TFSI- coordination, leading to reduced binding energy of LiTFSI and thus increasing the availability of free lithium ions, enhancing lithium ions mobility. Additionally, the symmetrical cell with the Cs doped FA interfacial layer demonstrates cyclic stability over 2000 h at 0.2 mA cm−2 due to the lower nucleation overpotential, demonstrating excellent lithium plating/stripping capabilities. The LFP||Li full cell shows a remarkable capacity retention of 99.54 % after 300 cycles at 0.5C, and 95.58 % with a higher Coulombic efficiency (CE) of 99 % after 600 cycles at 1C. In addition, the cell with this CSE and NCM811 cathode exhibits excellent capacity retention of 78 % after 150 cycles at 0.5C. This approach to designing interfacial layers offers new avenues for advancing solid-state lithium-metal batteries. [ABSTRACT FROM AUTHOR]

In pursuit of safer lithium-ion batteries, research is veering towards all-solid-state lithium batteries (ASSLBs) featuring solid electrolytes due to the safety concerns and low metal interfacial compatibility of liquid electrolytes. ASSLBs combined with composite solid electrolytes (CSEs) incorporating NASICON-type active fillers are especially appealing because of their inherent safety, ease of production, and high energy density. This study introduces a Li 1 · 5 Al 0.5 Ge 1.5 (PO 4) 3 (LAGP) framework created via tape casting and in situ thermal polymerization, achieving a CSE with notable ionic conductivity (0.791 mS cm−1), electrochemical stability up to 5.09 V, and a lithium-ion transference number of 0.72 at 30 °C. The Li|CSE|Li cell demonstrates low overpotential over 1000 h, and the Li|CSE|NCM811 coin cell delivers a discharge capacity of 180.9 mAh g−1, maintaining 84.6 % capacity after 200 cycles. Moreover, the Li|CSE|NCM811 pouch cell upholds a capacity of 116.41 mAh g−1 after 100 cycles, underscoring the 3D LAGP framework and in situ polymerization's role in enhancing ASSLB safety and functionality. The composite solid electrolyte, synthesized through a straightforward one-step in-situ polymerization process within a three-dimensional LAGP framework, exhibits excellent ionic conductivity and demonstrates superior electrochemical performance in all-solid-state lithium batteries. [Display omitted] • Composite Solid Electrolyte with 3D LAGP framework is synthesized. • The CSE showed the ionic conductivity of 7.91 × 10−4 S cm−1 at 30 °C. • The Li.|CSE|Li cell shows excellent stability over 1000 h with low over potential. • The Li.|CSE|NCM cell delivers excellent rate capability, and long cyclability. • The coin and pouch type cells show the applicability of the CSE. [ABSTRACT FROM AUTHOR]

MXene, without a doubt, has emerged as the fastest-growing family of materials in the past decade. Its potential in emerging solid-state batteries (SSBs) is particularly promising, as it offers new opportunities to create novel redox-active and ionically permeable phases. The diverse chemical compositions, exceptional electrochemical properties, and surface tunability of MXenes provide fertile ground for composite design, potentially leading to significant advancements in the next generation of SSBs. This review, specifically focusing on SSBs, explores the potential and promises of MXene-based materials in advanced energy storage systems while highlighting the current progress. Additionally, the review discusses the challenges that need to be addressed to fully exploit the potential of MXenes for integration into safe and high-energy density electrochemical storage technologies. [Display omitted] • Recent advances in using MXene in Solid State Batteries (SSBs) are presented. • The potential benefits of using and the role of MXene in SSBs are highlighted. • The scalability issues associated with MXene production are discussed. [ABSTRACT FROM AUTHOR]

Metal organic framework (MOF)-polymer composite solid electrolyte membrane with novel microstructure is expected to show attractive prospect for solid state lithium metal batteries. But the reported MOF were usually regarded as an entirety in composite solid electrolyte resulting in tradeoff between ionic conductivity and lithium dendrite inhibition ability. Herein, MOF-polymer composite membrane with vertically aligned channels and ultrathin MOF layer is proposed to decrease lithium ion transportation resistance obtained by simple phase inversion and in situ coordinated growth methods. The vertically aligned highways can decrease tortuous pathways and intensify ion conduction. The embedded ultrathin MOF layer on membrane surface leads to homogeneous plating/stripping of lithium. This novel structured MOF-polymer composite solid electrolyte exhibits improved ionic conductivity of 0.55 mS cm−1 at 22 ° C and lithium ion transference number of 0.87. Furthermore, the Li/Li symmetrical cell shows stable lithium plating/stripping performance for 1100 h at 0.1 mA cm−2 and 0.1 mA h cm−2. LiFePO 4 /MOF-polymer/Li coin battery demonstrates good rate capability and cycling performance with capacity retention of 82 % after 100 cycles at 0.2C and the pouch cell can light up the "DLUT" blue light lamp under folding and cutting states. This work encourages a new avenue to develop composite solid electrolytes with ion transportation highways and uniform distribution plane for solid lithium metal batteries. [Display omitted] • PVDF-HFP@ZIF-8 composite membrane is prepared through novel in situ coordinated growth method. • Composite solid electrolyte holds vertically aligned transfer highways to facilitate lithium ions conduction. • The ultrathin ZIF-8 layer embedded on membrane surface and ZIF-8 nanoparticles inlaid in highways anchor anions. • The composite solid electrolyte improves LiFePO 4 /Li battery performance. [ABSTRACT FROM AUTHOR]

Benefitting from the synergistic effect of the continuous 3D NZSP framework and PEO/PVDF-HFP asymmetric polymer electrolyte layer, the novel composite solid electrolyte for solid-state sodium metal batteries exhibits ultrahigh ion transference number and stability. [Display omitted] • A novel 3D-NZSP solid electrolyte was synthesized via using NaCl as the templatewe. • The 3D-15PNZSPP exhibits an outstanding transference number of 0.82 at temperature of 30 °C. • The Na/3D-15PNZSPP/Na symmetric cell can cycle for 700 h with a small overpotential. • The assembled Na 0.67 Li 0.24 Mn 0.76 O 2 /3D-15PNZSPP/Na batteries demonstrate remarkable cycling stability. The combination of a Na-ion conducting filler and polymer matrix in composite solid electrolyte (CSE) presents a promising and attractive strategy for improving the energy density and safety of the sodium-metal batteries. The agglomeration and precipitation of inorganic ceramic fillers in the polymer matrix present a major challenge leading to the decreased Na ion conductivity property and transference number, increased interfacial resistance, and worsened mechanical properties of CSEs. Herein, we introduce a novel composite solid electrolyte (denoted as 3D-15PNZSPP), comprising a three-dimensional interconnected porous Na 3 Zr 2 Si 2 PO 12 framework integrated with an asymmetric polymer electrolyte layer, which not only offers continuous conductive pathways and high mechanical strength for Na ions transfer, but also enhances the interfacial compatibility and expands the electrochemical stability window. The 3D-15PNZSPP CSE shows a high Na+ conductivity of 7.6 × 10−4 S cm−1 and an outstanding transference number of 0.82 at temperature of 30 °C. These characteristics enable the Na/3D-15PNZSPP/Na symmetric cell to cycle for over 700 h with a small overpotential. More importantly, the assembled all solid-state Na 0.67 Li 0.24 Mn 0.76 O 2 /3D-15PNZSPP/Na batteries demonstrate remarkable cycling stability and high rate capability, indicating a promising and facile strategy for designing ultra-safe and high-performance solid-state sodium metal batteries. [ABSTRACT FROM AUTHOR]

Solid-state lithium-metal batteries are one of the best candidates for next-generation energy storage devices. However, their applications are hindered by the low ionic conductivity at room temperature and the inadequate interfacial compatibility of solid-state electrolytes (SSEs). Hence, an organic/inorganic composite solid electrolyte (CSE) of Li 6.25 Ga 0.25 La 3 Zr 2 O 12 (LGLZO)/polyethylene oxide (PEO) films were constructed. It's found that the crystallinity of CSE is significantly reduced and the ionic conductivity is increased to 3.57 × 10−4 S cm−1 at room temperature, which is about 60 times higher than that of the pure PEO.And the interfacial impedance is 243.84 Ω cm2, electrochemical window of 5.1 V. The assembled Li symmetric battery has excellent cycling stability more than 1000 h at 0.15 mA cm−2. The Li/PEO-LiTFSI-60 wt% LGLZO/LiFePO 4 (LFP) all solid-state lithium batteries (ASSLBs) also delivers superior electrochemical performances. This work can provide a reference for the development and real-world implementation of ASSLBs at room temperature. [Display omitted] • The relationship between filler content and sample properties was investigated by modulating the amount of LGLZO. • The ionic conductivity of LGLZO/PEO electrolyte was increased to 3.57×10-4 S cm-1, which is 60 times that of PEO. The ionof LGLZO/PEO electrolyte was increased to 3.57×10−4 S cm−1, which is 60 times that of PEO. • The CCD of Li|PEO/LGLZO|Li reached 0.8 mA cm−2, and it could cycle for over 1000 hours at current density of 0.15 mA cm−2. • Li|PEO/LGLZO|LFP has discharge specific capacity of 135 mAh g-1 and capacity retention rate of 97.26% after 80 cycles. [ABSTRACT FROM AUTHOR]

The design and regulation of the ion transport channels in the polymer electrolyte is an important means to improve the lithium ion transport behavior of the electrolyte. In this work, we for the first time combined the high ionic conductive inorganic ceramic electrolyte Li 1.5 Al 0.5 Ge 1.5 (PO 4) 3 (LAGP) with flexible polypropylene oxide (PPO) polymer electrolyte to synthesize a high-filling LAGP/PPO composite solid electrolyte film and regulated the ion transport channels from 'Ceramics-in-Polymer' mode to 'Polymer-in-Ceramics' mode by optimizing the ratio of LAGP vs. PPO. The results reveal that when the LAGP content <40%, the electrolyte belongs to 'LAGP-in-PPO', and then changes to 'PPO-in-LAGP' when the LAGP content exceeds 40%. Compared with 'LAGP-in-PPO', the 'PPO-in-LAGP' shows better comprehensive properties, especially for the 75% LAGP-filled PPO electrolyte, the room-temperature ionic conductivity is as high as 3.46 × 10−4 Scm−1, the ion migration number and voltage stable window reach 0.83 and 4.78 V respectively. This high-filled composite electrolyte possesses high tensile stress of 40 MPa with a strain of 46% and withstands working environment up to 200 °C. The NCM622/Li solid-state battery composed of this electrolyte also presents good rate and cycle performances with a capacity retention of 80% after 230 cycles at 0.3C because of its high ion transport capability and good inhibition of lithium dendrites. This composite structural design is expected to develop high-performance solid-state electrolytes suitable for high-voltage solid-state lithium batteries. [ABSTRACT FROM AUTHOR]

Solid-state lithium batteries have attracted much attention due to their special properties of high safety and high energy density. Among them, the polymer electrolyte membrane with high ionic conductivity and a wide electrochemical window is a key part to achieve stable cycling of solid-state batteries. However, the low ionic conductivity and the high interfacial resistance limit its practical application. This work deals with the preparation of a composite solid electrolyte with high mechanical flexibility and non-flammability. Firstly, the crystallinity of the polymer is reduced, and the fluidity of Li+ between the polymer segments is improved by tertiary polymer polymerization. Then, lithium salt is added to form a solpolymer solution to provide Li+ and anion and then an inorganic solid electrolyte is added. As a result, the composite solid electrolyte has a Li+ conductivity (3.18 × 10−4 mS cm−1). The (LiNi0.5Mn1.5O4)LNMO/SPLL (PES-PVC-PVDF-LiBF4-LAZTP)/Li battery has a capacity retention rate of 98.4% after 100 cycles, which is much higher than that without inorganic oxides. This research provides an important reference for developing all-solid-state batteries in the greenhouse. [ABSTRACT FROM AUTHOR]

[Display omitted] All solid-state batteries (ASSBs) are regarded as promising energy storage batteries with high energy density and high safety. The polyethylene oxide (PEO)-based electrolyte with succinonitrile (SN) has attracted critical attention for its high ionic conductivity at room temperature. However, SN can react with Li metal to result in an unstable interface between electrolyte and electrode, which deteriorates the electrochemical performance. In this work, zeolitic imidazolate framework-67 (ZIF-67) is used as a filler to construct composite electrolytes and solve the aforementioned instability issue. The composite electrolyte shows nonflammability, high processability, and a competitive ionic conductivity of 2.78 * 10−5 S/cm at room temperature. Due to the regular dodecahedron structure and abundant Lewis acid sites, the composite electrolyte film exhibits a high Li-ion transference number of 0.654 and a wide electrochemical window of more than 5 V. Moreover, the ZIF-67 helps to construct a uniform and fast ion transport channel and can promote the generation of LiF to prevent SN from contacting Li anode, which contributes to the excellent stability of the Li symmetric batteries cycling for over 1000 h at a current density of 1 mA cm−2. And the assembled LiFePO 4 ||Li batteries based on the composite electrolyte display high discharge specific capacities of 158.6 and 70 mAh g−1 at 60 °C and room temperature, respectively. [ABSTRACT FROM AUTHOR]

An Li1.3Al0.3SnxTi1.7−x(PO4)3 (LATP-xSn) ceramic solid electrolyte was prepared by Sn doping via a solid phase method. The results showed that adding an Sn dopant with a larger ionic radius in a concentration of x = 0.35 enabled one to equivalently substitute Ti sites in the LATP crystal structure to the maximum extent. The uniform Sn doping could produce a stable LATP structure with small grain size and improved relative density. The lattice distortion induced by Sn doping also modified the transport channels of Li ions, which promoted the increase of ionic conductivity from 5.05 × 10−5 to 4.71 × 10−4 S/cm at room temperature. The SPE/LATP-0.35Sn/SPE composite solid electrolyte with a sandwich structure was prepared by coating, which had a high ionic conductivity of 5.9 × 10−5 S/cm at room temperature, a wide electrochemical window of 4.66 V vs. Li/Li+, and a good lithium-ion migration number of 0.38. The Li||Li symmetric battery test results revealed that the composite solid electrolyte could stably perform for 500 h at 60 °C under the current density of 0.2 mA/cm2, indicating its good interface stability with metallic lithium. Moreover, the analysis of the all-solid-state LiFePO4||SPE/LATP-0.35Sn/SPE||Li battery showed that the composite solid electrolyte had good cycling stability and rate performance. Under the conditions of 60 °C and 0.2 C, stable accumulation up to 200 cycles was achieved at a capacity retention ratio of 90.5% and a coulombic efficiency of about 100% after cycling test. [ABSTRACT FROM AUTHOR]

A composite solid electrolyte based on PEO‐NaTFSI (polyethylene oxide‐sodium bis(trifluoromethanesulfonyl)imide) and Na3Zr2Si2PO12 is fabricated for all‐solid‐state Na−S battery (ASSB). When the molar ratio of EO (ethylene oxide of PEO) to Na+ (sodium ion of NaTFSI) is 20 and the amount of Na3Zr2Si2PO12 is 30 wt%, a highest ionic conductivity of 3.14×10−4 S cm−1 and the sodium ion transference number of 0.66 are achieved at 60 °C. Harnessing the electrolyte's improved sodium ion transport abilities enables ASSB's assembled with a sulfur cathode and sodium metal anode to exhibit highly reversible current‐rates and capacity retention. At 0.2 C and 60 °C, the battery delivers a superior discharge capacity of 1110.0 mAh g−1 in the first cycle and maintains 666.8 mAh g−1 after 60 cycles with a stable Coulombic efficiency near 100 %. [ABSTRACT FROM AUTHOR]

A robust and fast healable composite solid-state electrolyte is developed by using functionalized LLZTO nanoparticles as the dynamic covalent crosslinking points, which exhibits long cycling stability and superior safety in lithium metal batteries even under abuse conditions. [Display omitted] • A novel strategy is proposed by utilizing LLZTO nanoparticles as crosslinking points to form dynamic imine bonds. • The abundant dynamic imine bonds endow the crosslinked network with rapid healing capabilities. • The stability of the battery is demonstrated by the long cycle life of symmetric cells and the abuse resistances of pouch cells. Flexible composite solid electrolytes (CSEs) show great potentials in high-energy all-solid-state lithium metal batteries owing to their easy fabrication, good electrochemical properties, and high safety. However, it remains challenging to achieve good interfacial compatibility between the inorganic fillers and polymer matrix, which affects the lithium-ion transport efficiency and electrochemical performances of CSEs. Herein, a dynamic crosslinked network with Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) nanoparticles as the cross-linking point is proposed for fabrication of a rapidly self-healing flexible CSE, which is signed as SHENE. The amino groups in the 3-aminopropyltriethoxysilane modified LLZTO behave as the bridge sites to react with the copolymer of 2-hydroxyethyl methacrylate- g -4-formylbenzoic acid and poly (ethylene glycol) methoxy acrylate to form imine bonds, which effectively connect the organic/inorganic interface. Compared to the traditional physical contact, the covalent imine bonds can not only enhance the interaction between the two phases, but also improve the dispersion of the ceramic LLZTO nanoparticles. Additionally, the dynamic reversibility of imine bonds allows for enhanced mechanical strength and self-repairing capabilities of SHENE. Therefore, a Li||Li symmetrical cell assembled with SHENE can stably cycle for 5000 h at 0.05 mA cm −2 and 25 °C. The corresponding Li/SHENE/LiFePO 4 full battery also exhibits good rate performance under various C-rates. Additionally, the Li/SHENE/LFP pouch cell exhibits superior safety under various abuse conditions. Therefore, this work provides new ideas for the uniform dispersion of ceramic nanoparticles in CSEs by the facile design of forming dynamic crosslinked networks. [ABSTRACT FROM AUTHOR]

The succinonitrile (SN) plastic crystal electrolyte with excellent comprehensive properties such as high room temperature (RT) ionic conductivity, wide electrochemical window and low cost, making it a promising candidate for RT solid-state lithium batteries (SSLBs). However, severe spontaneous chemical reactions between SN and active Li anode cause serious damage to the electrolyte/electrode interface, which still needs to be further improved. In this work, an in-situ polymerized SN-based composite solid-state electrolyte (CSE) is exploited to conquer the severe side-reactions between SN-based electrolyte and Li anode, the PALA0.5@-CSE (polyacrylonitrile (PAN): modified-Li l.3 Al 0.3 Ti l.7 (PO 4) 3 (LATP@) = 1:0.5, w/w) demonstrates an outstanding ionic conductivity (0.45 mS cm−1), high electrochemical stability (5.1 V) and improved Li+ transference number (0.67) at RT. The Li symmetric cells with PALA0.5@-CSE shows a high critical current density (CCD) of 1.2 mA cm−2, and the Li symmetric cells deliver excellent cycle stability over 500 h, demonstrating the superior ability of PALA0.5@-CSE to suppress the side-reactions between SN and Li anode and the rapid growth of Li dendrite. In Li||LiFePO 4 (LFP) full cell, the SSLBs provide excellent RT rate capability and stable cycling performance. Moreover, the PALA0.5@-CSE possesses high thermal stability and incombustibility, demonstrating its superior safety for the future utilization of SN-based SSLBs. The modification of LATP was effective at stabilizing the interface, the formed robust SEI film could alleviate the severe interfacial side reactions between SN and Li anode. [Display omitted] • High ionic conductivity (0.45 mS cm−1) and Li+ transference number (0.67) is achieved. • The robust SEI film effectively mitigates the uncontrollably parasitic side-reactions. • The PALA0.5@-CSE exhibits high thermal stability and nonflammable. • Solid-state SN-based lithium batteries show superior performances at room temperature. [ABSTRACT FROM AUTHOR]

[Display omitted] • Excellent-performance composite polymer electrolytes containing 10 wt% BN nanofillers with high dispersity were obtained. • The room-temperature ionic conductivity and the Li+ transference number of the composite electrolytes increase to 4 and 2 times those of the pristine electrolyte, respectively. • The high-content BN fillers can capture the anions, inhibit the polymer crystallization, and form fast-ion BN/polymer interfaces, thus improving the electrical properties. • The composite electrolyte-based metallic lithium batteries deliver greatly-enhanced rate performance and cycling stability at room temperature. Polyethylene oxide (PEO)-based solid-state electrolytes have great potential in the development of solid-state metallic lithium batteries. However, it is difficult to apply them in metallic lithium batteries at room temperature because of the poor ionic conductivity and the lithium dendrite-induced safety problem. Herein, high-performance composite polymer electrolytes (CPEs) are developed by filling high-content boron nitride (BN) nanosheets with well dispersity in the PEO-LiTFSI matrices. Theoretical calculations and experimental characterizations reveal that the BN nanofillers with a strong Lewis acid property can capture TFSI− to release more free Li+, reduce the polymer crystallinity, and facilitate the generation of rich BN/PEO-LiTFSI fast-ion interfaces. Thus, the ionic conductivity and the Li+ transference number of the CPEs at room temperature greatly increase to 4 and 2 times those of the pristine electrolyte, respectively. Hence, the Li/CPE/Li batteries can operate steadily at 0.05 mA/cm2 (0.05 mAh/cm2) and 30 °C for 1200 h. Furthermore, the LiFePO 4 /CPE/Li batteries show higher initial capacity of 132 mAh/g and capacity retention of 84 % after 90 cycles at 0.3C and 30 °C than the pristine electrolyte-based batteries (29 %). This study provides a feasible case to prepare excellent-performance CPE films containing high nanofiller content for room-temperature solid-state metallic lithium batteries. [ABSTRACT FROM AUTHOR]

[Display omitted] • Well-dispersed SiO 2 nanofluids boosting ion transport channels. • Continuous Li-ion diffusion pathways throughout 3D electrospun composite skeletons. • Stable and uniform Li-ions flux during the repeated plating/stripping processes. • Composite electrolytes enabling uniform Li deposition and high rate capability. Composite polymer electrolytes (CPEs) are considered as one of the most promising electrolytes for the next generation of solid-state lithium metal batteries (LMBs) because of their good flexibility, favorable interface contact, easy large-scale processing and improved safety. To address the severe agglomeration of inorganic nanofillers at the high-level loading, a new gel polymer electrolyte (GPE) was fabricated by electrospun membranes adopting polyacrylonitrile (PAN) as the host matrix and solvent-free SiO 2 nanofluids (NFs) as nanofillers, presenting low crystallinity, high electrolyte uptake, superior flexibility, and large porosity. The as-prepared PAN/SiO 2 GPEs containing 20 % SiO 2 NFs show the optimum mechanical and thermal properties, the maximum ionic conductivity (3.44 x 10−4 S cm−1) and Li+ transfer number (0.73), and the widest electrochemical stable window (4.99 V). Benefiting from multiple advantages, the percolated 3D Li+ transport networks are well-established to suppress the electrode polarization and Li dendrite growth. Further, the abundant ester groups on the SiO 2 NFs shell and Lewis acid-based sites on SiO 2 cores are favored to dissociate lithium salts and produce more free Li+. Accordingly, the assembled solid-state LiFePO 4 /Li cell exhibits superior cycling stability (132.7 mAh/g after 500 cycles at 3C with a retention of 90.8 %) and rate capability (80.4 mAh/g at 25C) at ambient temperature. This work provides a facile strategy to fabricate GPEs by incorporating solvent-free NFs containing inorganic cores for LMBs with high-rate capability, good cycling stability, and high safety. [ABSTRACT FROM AUTHOR]

Transition metal carbides (NiNbCeC) over mesoporous silica (SBA-15) can be filled into the Polyethylene Oxide (PEO)-LiTFSI. [Display omitted] • NiNbCeC in SBA-15 boosts PEO conductivity in composite solid electrolytes. • TMC fillers lower PEO crystallinity, enhancing ionic conductivity. • Investigated Ce impact on TMC interaction in solid electrolyte matrix. • Novel solid electrolyte in Li-S battery shows impressive room temp cycling. • In-depth analysis of failure modes in solid-state Li-S batteries conducted. Solid polymer electrolytes (SPEs) were investigated for several decades due to their good compatibility with electrodes. However, meeting the essential requirements for solid polymer electrolytes, including enhanced ionic conductivity, superior solubility with conductive lithium salts, and robust interface stability when in contact with a Li anode, remains a formidable challenge. In our work, we found that transition metal carbides (NiNbCeC) over mesoporous silica (SBA-15) can be filled into the Polyethylene Oxide (PEO) matrix to form composite solid electrolytes which can greatly improve the ionic conductivity of PEO. We investigate a series of transition metal carbides with varying mass ratios of Cerium (5%, 10%, and 20%) to fabricate All-Solid-State Li-S batteries (ASSLi-S). Our results demonstrate that different mass ratios of Cerium play a pivotal role in enhancing the ionic conductivity of the composite solid electrolytes, reducing impedance levels from 9150 O (20% Ce) to 4000 O (5% Ce) to 1730 O (10% Ce). At room temperature, the high initial specific capacity at 1C and reversible specific capacity after 100 cycles are 525 and 363 mAh/g, 605 and 403 mAh/g, 246.3 mAh/g and 63.28 mAh/g for 5% Ce, 10%, and 20%, respectively. Furthermore, long-term cycling tests of ASSLi-S cells at 0.5C reveal promising performance, with the cell containing 10% Ce solid electrolytes delivering an initial specific capacity of 1165.7 mAh/g and maintaining 335 mAh/g after 200 cycles. This represents a significant breakthrough, demonstrating that PEO-based solid electrolytes can achieve impressive electrochemical results at room temperature. SEM characterization was employed to assess the volume change in the solid electrolyte layer and elemental distribution of solid electrolyte materials through cross-sectional analysis. This analysis revealed that the failure modes of solid-state Li-S cells can also be attributed to the migration of sulfur elements from the cathode to the solid electrolyte layer during the cycling process. XRD was utilized to study the crystallinity of composite solid electrolytes. This study represents a significant stride in the progress of high-performance solid polymer electrolytes for All-Solid-State Li-S batteries, shedding light on the failure modes of such batteries. It underscores the potential of composites based on transition metal carbides in addressing crucial challenges for their practical implementation in Solid-State Lithium-Sulfur Batteries. [ABSTRACT FROM AUTHOR]

Alumina powders have been widely used in lithium-ion batteries such as separator coating, electrode surface modification and electrolyte fillers. Rod-like alumina with its special aspect ratio is expected to open up a new application direction. In this work, alumina nanorods were prepared by a facile hydrothermal method. The aspect ratio and morphology of alumina nanorods were optimized by adjusting the hydrothermal temperature, hydrothermal synthesis time, volume ratio, directing agent, and sintering temperature. γ-Al 2 O 3 nanorods with a diameter of 200–300 nm and a mean length of 5 μm and α-Al 2 O 3 with a diameter of 100–200 nm and mean length of 5 μm were obtained by calcining the alumina precursor (AACH) at 800 °C and 1200 °C, respectively. The prepared alumina nanorods were added into polymer solid electrolyte, which promoted the dissociation of the lithium salt and stabilized the propylene polycarbonate (PPC) polymer, resulting in an improved potential window (4.5 V) and ionic conductivity (3.7 × 10−4 S/cm) of the PPC-based polymer solid electrolyte (SE). An NCM622/SE/Li solid-state battery showed enhanced electrochemical performance at ambient temperature with an initial discharge capacity of 188.5 mAh/g and a retention capacity of 158.1 mAh/g after 200 cycles at a current density of 0.5 C. These alumina nanorods have potential to be widely used in high-performance solid electrolytes. [ABSTRACT FROM AUTHOR]

Summary: Polymer solid electrolyte with high ionic conductivity at room‐temperature is most likely to be widely used in solid‐state lithium batteries. In this work, the novel surface lithiated TiO2 nanorods were firstly used as ionic conductor in polymer solid electrolyte. The surface lithiated TiO2 nanorods‐filled polypropylene carbonate polymer composite solid electrolyte (CSE) has an uniform composite structure with a thickness of about 60 μm. The ionic conductivity at room‐temperature is 1.21 × 10−4 S cm−1 and the electrochemical stability window is up to 4.6 V (vs Li+/Li). The assembled NCM622/CSE/Li solid‐state battery shows a stable cycle performance with a retention capacity of 120 mAh g−1 after 200 cycles at the current density of 0.3 C and a high coulomb efficiency of 99%. Compared with TiO2 particles, this novel surface lithiated TiO2 nanorods can provide more continuous ion transport channels and more Lewis acid‐base reactive sites, provide a novel way to enhance the lithium ion transport in polymer solid electrolyte. [ABSTRACT FROM AUTHOR]

Thin solid‐state electrolytes with nonflammability, high ionic conductivity, low interfacial resistance, and good processability are urgently required for next‐generation safe, high energy density lithium metal batteries. Here, a 3D Li6.75La3Zr1.75Ta0.25O12 (LLZTO) self‐supporting framework interconnected by polytetrafluoroethylene (PTFE) binder is prepared through a simple grinding method without any solvent. Subsequently, a garnet‐based composite electrolyte is achieved through filling the flexible 3D LLZTO framework with a succinonitrile solid electrolyte. Due to the high content of garnet ceramic (80.4 wt%) and high heat‐resistance of the PTFE binder, such a composite electrolyte film with nonflammability and high processability exhibits a wide electrochemical window of 4.8 V versus Li/Li+ and high ionic transference number of 0.53. The continuous Li+ transfer channels between interconnected LLZTO particles and succinonitrile, and the soft electrolyte/electrode interface jointly contribute to a high ambient‐temperature ionic conductivity of 1.2 × 10−4 S cm−1 and excellent long‐term stability of the Li symmetric battery (stable at a current density of 0.1 mA cm−2 for over 500 h). Furthermore, as‐prepared LiFePO4|Li and LiNi0.5Mn0.3Co0.2O2|Li batteries based on the thin composite electrolyte exhibit high discharge specific capacities of 153 and 158 mAh g−1 respectively, and desirable cyclic stabilities at room temperature. [ABSTRACT FROM AUTHOR]

Summary: Solid‐state batteries (SSBs) with room temperature (RT) performances had been one of the most promising technologies for energy storage. To achieve a chemical stable and high ionic conductive solid electrolyte, herein, a titania (TiO2) (B) nanorods‐filled poly(propylene carbonate) (PPC)‐based organic/inorganic composite solid electrolyte (CSE) was prepared for the first time. It was found that by using TiO2(B) nanorods, the ionic conductivity of the CSE membrane could be improved to 1.52 × 10−4 S/cm, the electrochemical stable window was more than 4.6 V, and the tensile strength reaches 27 MPa with a strain less than 6%. The CSE was applied for SSB and showed excellent room temperature electrochemical performances. At 25°C, the LiFePO4/CSE/Li SSB with 3%TiO2‐filled CSE had the first cycle specific discharge capacity of 162 mAh/g with a capacity retention of 93% after 100 cycles at 0.3C. While the NCM622/CSE/Li SSB with 3%TiO2‐filled CSE had the first specific discharge capacity of 165 mAh/g with a capacity retention of 88% after 100 cycles at 0.3C. The enhancement effect of TiO2(B) nanorods could be ascribed that the rod‐like fillers provide more continuous Li‐ion transport path compared with nano particles, and the surface porosity and composition of TiO2(B) nanorods could also improve the interfacial contact and Lewis acid‐base reaction sites between polymer and fillers. The TiO2(B) nanorods‐filled CSE with high chemical stability, potential window, and ionic conductivity was promising to meet the requirements of SSBs. [ABSTRACT FROM AUTHOR]

Low ionic conductivity at room temperature and poor interfacial compatibility are the main obstacles to restrain the practical application of polymer solid electrolytes. In this work, lanthanum zirconate (LZO) fibers were prepared by electrospinning method and used for the first time as fillers in sandwich polypropylene carbonate (PPC)-based solid electrolyte. Meanwhile, a graphite coating was applied on one surface of the composite solid electrolyte (CSE) membrane. The results show that the LZO fibers significantly increases the room-temperature electrochemical performance of the CSE, and the graphite coating enhances the interfacial compatibility between electrolyte and lithium anode. Furthermore, an ultra-thin PPC-LZO CSE with a total thickness of 22 μm was prepared and used in NCM622/CSE/Li solid-state cell, which shows an initial discharge capacity of 165.6 mAh/g at the current density of 0.5C and a remaining capacity of 113.0 mAh/g after 250 cycles at room temperature. Rise to 1C, the cell shows an initial discharge capacity of 154.2 mAh/g with a remaining capacity of 95.6 mAh/g after 250 cycles. This ultra-thin CSE is expected to be widely applied in high energy-density solid-state battery with excellent room-temperature electrochemical performances. [ABSTRACT FROM AUTHOR]

• SbF 3 is employed as an additive in PEO-LLZTO composite solid electrolyte (SbF 3 @CSE). • A composite interfacial layer is in-situ built by contacting SbF 3 @CSE with Li metal. • The interfacial layer regulates the deposition behavior of Li at anodic interface. • Remarkable current density and long-cycle performance are achieved in ASSLBs. The PEO-LLZTO composite solid electrolyte (CSE) is considered as one of the most promising solid-state electrolytes (SSEs). However, there is still a serious problem caused by dendrite penetration due to the uneven deposition of Li on the interface. Construction of Li alloy-rich artificial interfacial layers is proved to be an ideal solution to hinder Li dendrite growth. However, traditional coating methods often result in thick and uneven interfacial layer, causing unsatisfied Li plating behavior. In this work, commercial SbF 3 is firstly used as a solid-state electrolyte additive to in-situ construct an ultrathin and uniform Li-Sb alloy-rich artificial interfacial layer, which optimized the Li deposition behavior. The Li//Li symmetric cell with SbF 3 @CSE solid electrolyte exhibits a high working current density of 1.5 mA·cm−2 and an extended cycle life about 980 h at 0.2 mA·cm−2. Moreover, the LiFePO 4 //Li cell shows a greatly improved cycle stability and Coulombic efficiency compared with Blank CSE, in which the LiFePO 4 /SbF 3 @CSE/ Li delivers a stable cycle performance at 1C for nearly 200 cycles (91.3% capacity retention), and it also exhibits superior rate capability of about 140 mAh·g−1 at 1C. These results demonstrate the modified electrolyte holds large potential for all-solid-state lithium metal battery applications. [ABSTRACT FROM AUTHOR]

The composite combined Li 7 La 3 Zr 2 O 12 (LLZO) and PEO is viewed as a promising solid-state electrolyte for lithium-ion batteries due to its chemical stability, wide electrochemical window, mechanical flexibility and easy fabrication procedure. However, the primary challenges of low ionic conductivity and poor interfacial compatibility remain unresolved. Herein, a co-modified composite solid-state electrolyte based on the porous Al-doped LLZO (Al-LLZO) garnet scaffold cooperated with Ca-coordinated Dynasylan IMEO (Triethoxy-3-(2-imidazolin-1-yl) propylsilane, named DI) and PEO (denoted as CSE-DI-Ca) is reported. Benefiting from the fast lithium ion conduction in porous Al-LLZO network and interfacial strengthening modification between ceramics and polymer, CSE-DI-Ca exhibits a high ionic conductivity of 6.38✕10−4 S cm−1 at room temperature. The unique ceramic structure of CSE-DI-Ca also leads to an enlarged electrochemical window of 6 V vs. Li+/Li, good thermal stability under 360 °C, and an improved mechanical strength of 8.91 MPa to block lithium dendrites. Furthermore, as an evidence of the compatibility with high-voltage battery, the LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)|CSE-DI-Ca|Li coin cell delivers an initial discharge capacity of 130.2 mAh g−1 at 0.1 C at room temperature and maintains a capacity of 127.3 mAh g−1 after 120 cycles. All these superior properties indicate that the as-prepared composite holds great promise as an effective solid-state electrolyte to be used in next-generation lithium-ion batteries. The composite electrolyte with a special structure is designed, in which the porous Al-LLZO scaffold prepared by polycarbonate templates shows continuous Li-ion pathways in the PEO matrix. This composite electrolyte exhibits a high ionic conductivity of 6.38✕10−4 S cm−1 at room temperature, an enlarged electrochemical window of 6 V vs. Li+/Li, good thermal stability under 360 °C, and an improved mechanical strength of 8.91 MPa to block lithium dendrites. The solid-state lithium ion batteries of the NCM622|CSE-DI-Ca|Li delivers an initial discharge capacity of 130.2 mAh g−1 at 0.1 C at room temperature and maintains a capacity of 127.3 mAh g−1 after 120 cycles. [Display omitted] • Porous Al-LLZO scaffold is prepared by polycarbonate templates. • CSE with porous Al-LLZO shows higher ionic conductivity than that with non-porous Al-LLZO. • Optimized CSE-DI-Ca shows excellent flexibility, high ionic conductivity and electrochemical stability. • CSE-DI-Ca can effectively prevent lithium dendrites piercing during a long cycle of battery. • LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)|CSE-DI-Ca|Li coin cell delivers an initial discharge capacity of 130.2 mAh g−1 and maintains a capacity of 127.3 mAh g−1 after 120 cycles. [ABSTRACT FROM AUTHOR]

Summary: High ionic conductivity at room temperature (RT) and good ion transport capability at electrode/electrolyte interface are fundamental requirements for high‐rate solid‐state lithium batteries (SSBs). In this work, we designed a poly (propylene carbonate) (PPC)‐based organic/inorganic composite solid electrolyte (CSE) membrane with high filling of tantalum‐doped lithium lanthanum zirconium oxide (LLZTO) and functionalized layers for enhancing the RT rate performance of SSB. The synergistic effect of LLZTO and interfacial functionalized layers endows the NCM622/CSE/Li battery with high‐rate and cycling performances at RT. The SSB with 20% LLZTO‐filled solid electrolyte shows the initial capacities of 162.0, 148.5 and 130.1 mAh g−1 at 1C, 2C, and 3C respectively, with retention capacities of 115.6, 104, and 100.6 mAh g−1 after 150 cycles. This strategy for an organic/inorganic CSE is of great practical significance for the development of high‐rate SSBs. [ABSTRACT FROM AUTHOR]

• Two IL@MOF solid electrolytes with high ionic conductivity and thermal stability were prepared. • The host-gust interactions between the MOF and IL molecules were probed by comparative investigation. • Halide ions in the pores of host framework affecting the conductivity of IL@MOF were investigated. A three-dimensional NbO-type MOF with the formula Cu 2 (EBTC)(H 2 O) 2 ·[G] (compound 1) (EBTC4− = 1,1′-ethynebenzene-3,3′,5,5′-tetracarboxylate; G = guest molecules) was synthesized using a solvothermal method. The guest-free framework (2) was obtained by heating methanol-exchanged 1 at 130 °C under vacuum. The [Cu 2 (EBTC)(H 2 O) 2 ·(1.5[BMIM]Cl)] ∞ (3) and [Cu 2 (EBTC)(H 2 O) 2 ·(2.1[EMIM]Br)] ∞ (4), belong to IL@MOF, were prepared by the guest-exchange approach using 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) and 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) reside in the pores of 2 , respectively. The 3 and 4 show weak intermolecular interactions between the – C C – in the organic linkers and guest molecules and thermally stable up to 230 °C at least. The ionic conductivity value of 3 is about one order of magnitude higher than that of 4 at the same temperature. This study suggested the possibility of promising application of useful MOF as composited solid electrolytes via clathrates of ionic liquid for electrochemical devices. [ABSTRACT FROM AUTHOR]

Abstract Compared to currently used liquid-electrolyte lithium batteries, all-solid-state lithium batteries are safer and possess longer cycle life and have less requirements on packaging and state-of-charge monitoring circuits. Among various types of solid electrolytes, composite solid electrolytes, which are composed of active or passive inorganic fillers and polymer matrices, have been considered as promising electrolyte candidates for all-solid-state lithium batteries. Incorporation of inorganic fillers into the polymer matrices has been demonstrated as an effective method to achieve high ionic conductivity and excellent interfacial contact with the electrodes. In this review article, we first summarize the historical development of composite solid electrolytes. Contribution of both inert inorganic fillers and active Li-ion conductors to the ionic conductivity, electrochemical stability, and mechanical properties of the composite solid electrolytes are elaborated. Possible mechanisms of conductivity enhancement by inorganic fillers are broadly discussed. Examples of different composite solid electrolyte design concepts, such as inorganic nanoparticle/polymer, inorganic nanofiber/polymer, and other inorganic/polymer composite solid electrolytes, are introduced and their advantages and disadvantages are discussed. Inorganic filler/polymer composite solid electrolytes studied for use in various Li battery systems including Li-ion, Li-sulfur, and Li-metal batteries are evaluated. Promising designs of composite solid electrolytes and cathode materials used in all-solid-state Li batteries are also introduced. Finally, future perspectives on current requirements of composite solid electrolyte technologies are highlighted. [ABSTRACT FROM AUTHOR]

Abstract Conductivity of composite solid electrolytes CsNO 2 –A (A = MgO, Al 2 O 3 , SiO 2) were systematically investigated. It was found that in all cases heterogeneous doping leads to the increase in the conductivity. Composite solid electrolyte based on CsNO 2 with additives of nanocrystalline γ-alumina has the highest ionic conductivities exceeding 3.6 ∙ 10−2 S/cm at 629 K. Composites with MgO have lower conductivity and contain nitrate groups formed during synthesis. In general, composites containing basic oxides exhibit stronger conductivity enhancement on heterogeneous doping. Composites containing additives of SiO 2 have lower conductivity despite of high specific surface area that is probably caused by its acidic nature. The results of the conductivity studies are in a qualitative agreement with the 133Cs NMR data: the character of the variation of the NMR spectra is similar for CsNO 2 – A (A = Al 2 O 3 , MgO) composites and differ from those for CsNO 2 – SiO 2 composite. Highlights • Conductivity and 133Cs NMR spectra of composite solid electrolytes CsNO 2 -A (A=MgO, Al 2 O 3 , SiO 2) were systematically investigated. • Composite solid electrolyte CsNO 2 -Al 2 O 3 has the highest ionic conductivities exceeding 3.6•10-2 S/cm at 356 °C. • Composites containing basic oxides exhibit stronger conductivity enhancement on heterogeneous doping. [ABSTRACT FROM AUTHOR]

Abstract Conductivity of composite solid electrolytes (1 − x) CsNO 2 –xA (A =MgO, Al 2 O 3 , SnO 2) was systematically investigated. It was found that in all cases heterogeneous doping leads to the increase in the conductivity. Conductivity goes through a maximum as a function of the oxide concentration that is explained by additional contribution of the interface regions. However, in contrast to known composites, at small concentration of oxides the character of the Arrhenius dependences is similar to that of pure cesium nitrite, where intrinsic and extrinsic conductivity regions are observed. At high concentration of the heterogeneous dopant the character of Arrhenius dependences changes and no change in slope of the Arrhenius dependences is observed. According to thermal analysis data, at high concentration of oxide amorphous interface-stabilized phase of CsNO 2 forms on the oxide interface. Composite solid electrolytes based on CsNO 2 with additives of nanocrystalline γ-alumina and SnO 2 have a high ionic conductivities exceeding 10−2 S/cm at 356 °C. Composites containing additives of MgO have lower conductivity despite of high specific surface area. Highlights • A comparative study of ionic conductivity in a series of composites CsNO 2 – A (A= MgO, Al 2 O 3 ,SnO 2) was carried out. • High ionic conductivity is caused by contribution of interface-stabilized amorphous phase. • High ionic conductivity of order of 10-2 S/cm at 350 C was observed. [ABSTRACT FROM AUTHOR]

In this study, a Li 6.5 Ga 0.2 La 2.95 Rb 0.05 Zr 2 O 12 garnet-type solid electrolyte with high ion conductivity was prepared. The particle size was reduced to the nano size through a ball milling process, and the effect of the change in particle size on the all-solid-state batterie was investigated. As all-solid-state batteries have better stability than liquid electrolytes and serve as separators to help increase energy density, much research has been conducted recently. However, their conductivity is much lower than that of the liquid electrolyte. Therefore, an experiment was conducted on the difference in particle size to improve the ionic conductivity and energy density. Reducing the average particle size of the LLZO samples from approximately 10 to 0.6 μm using a ball milling process increased the ionic conductivity of the pellet from 1.27 × 10–3 to 1.58 × 10–3 S cm-1 at 25 °C. The ionic conductivity of the sheet decreased from 2.96 × 10–4 to 2.60 × 10–4 S cm-1 at 70 °C, but lithium transference number increased from 0.56 to 0.64. Therefore, the structural and electrochemical properties of the LLZO-bare and LLZO-ball-milled were investigated using powder X-ray diffraction analysis, field-emission scanning electron microscopy, electrochemical impedance spectroscopy, and galvanostatic measurements. • The particle size of this Ga Rb LLZO material was reduced from 10.1 to 0.61 μm through ball-milling. • The LLZO-ball-milled pellet exhibited a high ionic conductivity of 1.58 × 10−3 S cm−1 at 25 °C • Composite solid electrolytes were prepared via PEO, Ga Rb LLZO and Li salts. • The LLZO-ball-milled was low and stable, even in the symmetric cell overvoltage. • In the coin cell test, LLZO-ball-milled has high discharge capacity and is stable in cycle retention rate and rate characteristics. [ABSTRACT FROM AUTHOR]

The commercialization of high-energy-density lithium metal batteries relies on the development of novel solid electrolytes with high ionic conductivity, appropriate mechanical strength, and excellent compatibility with electrodes. Herein, poly(ethylene oxide)-lithium bis(trifluoromethanesulfonyl)imide-Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 /Y@CeO 2 composite solid electrolyte (CSE) with significantly enhanced ionic conductivity (1.08 × 10−3 S cm−1 at 75 °C), mechanical strength, and electrochemical stability were fabricated using Y@CeO 2 nanotubes with abundant oxygen vacancies. The LiFePO 4 /CSE/Li cell performed well in terms of capacity, rate performance, and cycle stability. At 60 °C, it afforded a discharge capacity of 168.7 mAh g−1 at 0.1 C-rate and 122.5 mAh g−1 at 1 C-rate. Remarkably, even after 100 cycles of 1 C-rate charge/discharge, the coin cell retained 99.3% of its original capacity. The use of inorganic-organic composite solid electrolytes in all-solid-state lithium metal batteries is encouraged by the composite filler design, which combines the benefits of active ceramic filler nanoparticles and inert ceramic filler nanotubes with ample oxygen vacancies. [Display omitted] • Y@CeO 2 nanotubes with oxygen vacancies enhance Li+ transport effectively. • The synergistic effect between LLZTO and Y@CeO 2 nanotubes is demonstrated. • Significantly improved ionic conductivity, mechanical strength, cell performance. [ABSTRACT FROM AUTHOR]

Solid-state electrolytes with high ionic conductivities, great flexibility, and easy processability are needed for high-performance solid-state rechargeable lithium batteries. In this work, we synthesize nanosized cubic Li 6.25 Al 0.25 La 3 Zr 2 O 12 (LLZO) by solution combustion method and develop a flexible garnet-based composite solid electrolyte composed of LLZO, poly(ethylene carbonate) (PEC), poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP) and lithium bis(fluorosulfonyl)imide (LiFSI)). In the flexible composite solid electrolytes, LLZO nanoparticles, as ceramic matrix, have a positive effect on ionic conductivities and lithium ion transference number ( t Li+ ). PEC, as a fast ion-conducting polymer, possesses high t Li+ inherently. P(VdF-HFP), as a binder, can strengthen mechanical properties. Consequently, the as-prepared composite solid electrolyte demonstrates high t Li+ (0.82) and superb thermal stability (remaining LLZO matrix after burning). All-solid-state LiFePO 4 |Li cells assembled with the flexible composite solid electrolyte deliver a high initial discharge specific capacity of 121.4 mAh g −1 and good cycling stability at 55 °C. [ABSTRACT FROM AUTHOR]

The drive towards all solid state lithium ion batteries requires discovery of new methods for synthesis of true hybrid solid electrolytes in which organic and inorganic components are chemically associated to simultaneously maximize lithium ion conductivity and processability. Herein, the first mechanochemical milling synthesis of an ambient processable hybrid lithium aluminum germanium phosphate (Li 1.5 Al 0.5 Ge 1.5 (PO 4) 3)/polyethylene glycol (PEG) solid electrolyte is presented. Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA) provide evidence that the mechanochemical milling procedure impels a condensation reaction between the ceramic and organic phases which produces a surface product, water. Solid state nuclear magnetic resonance (NMR) spectroscopy confirms that protons from the polymer or associated surface water product are in bonding proximity to the Q2 metaphosphate sites of the glassy phase of the ceramic. This work thus establishes the viability of mechanochemical milling as a synthetic pathway for a class of promising ambient processable hybrid electrolytes. • Mechanochemical synthesis shown for hybrid solid electrolyte for Li-ion batteries. • They hybrid polymer/ceramic electrolyte is composed of moisture stable materials. • Polymer and ceramic are established to be in bonding proximity. [ABSTRACT FROM AUTHOR]