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Solid-state electrolytes (SSE) are one of the fundamental components of the upcoming generation of batteries since they increase the operational safety and efficiency. In this work, composite solid electrolytes (CSE) based on Li 1.3 Al 0.3 Ti 1.7 (PO 4) 3 and a (PEO 2 -LiTFSI) polymer matrix are obtained via the pioneering Cold Sintering Process (CSP), with a drastic reduction of the conventional sintering temperature. The CSP is performed at only 150 °C and 700 MPa, for 90 min of sintering time, by using a 3 m acetic acid solution as the transient liquid phase (TLP). Here, the effect of the LATP particle size (d 50) is studied to tailor the final microstructure, which enables the fine-tuning of the ultimate electrical properties of the electrolyte. An optimum d 50 of 0.415 μm produces CSEs with 91 % of relative density, an ionic conductivity of 0.169 mS/cm, activation energy of 0.293 eV and electrical stability under 0.1 mA/cm2, thus leading to competitive properties. [Display omitted] [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]

Solid-state batteries (SSBs) have been widely studied as next-generation lithium-ion batteries (LiBs) for many electronic devices due to their high energy density, stability, nonflammability, and chemical stability compared to LiBs which consist of liquid electrolytes. However, solid electrolytes exhibit poor electrochemical characteristics due to their interfacial properties, and the sintering process, which necessitates high temperatures, is an obstacle to the commercialization of SSBs. Hence, the aim of this study was to improve the interfacial properties of the lithium tantalum phosphate (LTPO) solid electrolyte by adding succinonitrile (SN) on the interface of the LTPO particle to enhance ionic conductivity without the sintering process. Electrochemical impedance spectroscopy (EIS), the Li symmetric cell test, and the galvanostatic cycle test were performed to verify the performance of the SN-containing LTPO composite electrolyte. The LTPO composite solid electrolyte exhibited a high ionic conductivity of 1.93 × 10−4 S/cm at room temperature (RT) compared to the conventional LTPO. Also, it showed good cycle stability, and low interfacial resistance with Li metal, ensuring electrochemical stability. On the basis of our experimental results, the performance of solid electrolytes could be improved by adding SN and lithium salt. In addition, the SN can be used to fabricate the solid electrolytes without the sintering process at high temperatures. [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 electrolyte (CSE), especially the composite room temperature solid electrolyte (CRTSE), is emerging as the promising electrolyte for all-solid-state lithium batteries (ASSLB) due to their ability to combine the desirable properties of ceramic and polymer-based electrolytes and the room temperature operation condition. In this paper, the CRTSE with polyethylene oxide (PEO), bis(fluorosulfonyl)imide (LiTFSI), succinonitrile (SN), LLZTO inorganic fillers, and cross-linked ethoxylated trimethylolpropane triacrylate (ETPTA) was proposed. With the help of lithium dendrite suppression via cross-linked microscopic pore structure, enhancement of the ionic conductivity via LLZTO fillers, and wide electrochemical window via SN, the obtained LCSE showed high ionic conductivity (2.12 × 10−4 S cm−1), high Li+ transfer number (tLi+ = 0.55), and stable electrochemical window (5.0 V vs Li/Li+) at room temperature. The Li symmetrical cell with LCSE can cycle over 500 h stably with current density of 0.1 mA cm−2 and 0.5 mA cm−2 at room temperature. The full solid-state LiFePO4 cell can successfully work over 200 cycles with capacity retention ratio of about 70% at room temperature. [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.

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.

Solid-state batteries (SSBs) have been widely studied as next-generation lithium-ion batteries (LiBs) for many electronic devices due to their high energy density, stability, nonflammability, and chemical stability compared to LiBs which consist of liquid electrolytes. However, solid electrolytes exhibit poor electrochemical characteristics due to their interfacial properties, and the sintering process, which necessitates high temperatures, is an obstacle to the commercialization of SSBs. Hence, the aim of this study was to improve the interfacial properties of the lithium tantalum phosphate (LTPO) solid electrolyte by adding succinonitrile (SN) on the interface of the LTPO particle to enhance ionic conductivity without the sintering process. Electrochemical impedance spectroscopy (EIS), the Li symmetric cell test, and the galvanostatic cycle test were performed to verify the performance of the SN-containing LTPO composite electrolyte. The LTPO composite solid electrolyte exhibited a high ionic conductivity of 1.93 × 10−4 S/cm at room temperature (RT) compared to the conventional LTPO. Also, it showed good cycle stability, and low interfacial resistance with Li metal, ensuring electrochemical stability. On the basis of our experimental results, the performance of solid electrolytes could be improved by adding SN and lithium salt. In addition, the SN can be used to fabricate the solid electrolytes without the sintering process at high temperatures.

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]

Solid sodium ion batteries (SIBs) show a significant amount of potential for development as energy storage systems; therefore, there is an urgent need to explore an efficient solid electrolyte for SIBs. Na3Zr2Si2PO12 (NZSP) is regarded as one of the most potential solid-state electrolytes (SSE) for SIBs, with good thermal stability and mechanical properties. However, NZSP has low room temperature ionic conductivity and large interfacial impedance. F−doped NZSP has a larger grain size and density, which is beneficial for acquiring higher ionic conductivity, and the composite system prepared with epoxy can further improve density and inhibit Na dendrite growth. The composite system exhibits an outstanding Na+ conductivity of 0.67 mS cm−1 at room temperature and an ionic mobility number of 0.79. It also has a wider electrochemical stability window and cycling stability. [ABSTRACT FROM AUTHOR]

The safety concerns associated with power batteries have prompted significant interest in all−solid−state lithium batteries (ASSBs). However, the advancement of ASSBs has been significantly impeded due to their unsatisfactory electrochemical performance, which is attributed to the challenging interface between the solid−state electrolyte and the electrodes. In this work, an in situ polymerized composite solid−state electrolyte (LLZTO−PVC) consisting of poly(vinylene carbonate) (PVC) and Li6.4La3Zr1.4Ta0.6O12 (LLZTO) was successfully prepared by a γ−ray irradiation technique. The novel technique successfully solved the problem of rigidity at the interface between the electrode and electrolyte. The LLZTO−PVC electrolyte exhibited a notable ionic conductivity of 1.2 × 10−4 S cm−1 25 °C, along with good mechanical strength and flexibility and an electrochemical window exceeding 4.65 V. It was showed that the LiCoO2(LCO)/LLZTO−PVC/Li battery, which achieved in situ solidification via γ−ray irradiation, can steadily work at a current density of 0.2 C at 25 °C and maintain a retention rate of 92.4% over 100 cycles. The good interfacial compatibility between electrodes and LLZTO−PVC electrolyte designed via in situ γ−ray irradiation polymerization could be attributed to its excellent electrochemical performance. Therefore, the method of in situ γ−ray irradiation polymerization provides a vital reference for solving the interface problem. [ABSTRACT FROM AUTHOR]

Li–air battery-based solid electrolyte can better protect the lithium anode from the corrosion of other components and effectively block the risk of ignition and explosion caused by the lithium dendrite penetrating the dielectric layer. In this work, Li-containing ionic liquid (Li-IL) is absorbed in NH2-MIL-101(Cr) metal–organic frameworks (MOFs) to form a functional filler and further incorporated the filler into polyethylene oxide (PEO) to fabricate composite solid electrolyte (Li-IL@NH2-MIL-101(Cr)/PEO). The lithium anode and the air cathode were modified with Li-IL@NH2-MIL-101(Cr)/PEO, and the integrated solid-state Li–air batteries were prepared by roller pressing. Taking advantage of nanostructured Li-IL@NH2-MIL-101(Cr), fast lithium–ion transportation is achieved in the bulk and across the electrode/electrolyte interface. As a result, the ionic conductivity of the Li-IL@NH2-MIL-101(Cr)/PEO reaches 3.1 × 10–4 S/cm, the Li–air battery using the Li-IL@NH2-MIL-101(Cr)/PEO as solid electrolyte exhibited a high specific capacity of 11,682 mAh/g and remarkable cycling stability of 122 cycles. [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 All‐solid‐state Li metal batteries (ASSLMBs) have been considered the most promising candidates for next‐generation energy storage devices owing to their high‐energy density and safety. However, some obstacles such as thick solid electrolyte (SSEs) and unstable interface between the solid‐state electrolytes (SSEs) and the electrodes have restricted the practical application of ASSLBs. Here, the scalable polyimide (PI) film reinforced asymmetric ultra‐thin (~20 μm) composite solid electrolyte (AU‐CSE) with a ceramic‐rich layer and polymer‐rich layer is fabricated by a both‐side casting method and rolling process. The ceramic‐rich layer not only acts as a “securer” to inhibit the lithium dendrite growth but also redistributes Li‐ions uniform deposition, while the polymer‐rich layer improves the compatibility with cathode materials. As a result, the obtained AU‐CSE demonstrates an ionic conductivity of 1.44 × 10−4 S cm−1 at 35°C. The PI‐reinforced AU‐CSE enables Li/Li symmetric cell stable cycling over 1200 h at 0.2 mA cm−2 and 0.2 mAh cm−2. Li/LiNi0.6Co0.2Mn0.2O2 and Li/LiFePO4 ASSLMBs achieve superior performances at 35°C. This study provides a new way of solving the interface problems between SSEs and electrodes and developing high‐energy‐density ASSLMBs for practical applications.

For solid-state electrolyte in lithium-ion batteries, high crystal boundary impedance leads to tough electrolyte-electrode interfacial issues. Here, we introduce garnet Li6.4La3Zr1.4Ta0.6O12 (LLZTO) nanoparticles and succinonitrile (SN) into thermal polyurethane (TPU) to fabricate a composite solid-state electrolyte (TPU/LLZTO/SN), achieving high ionic conductivity of 6.452 × 10−4 S cm−1. The TPU polymer with specific soft and hard segments allows lithium ions fast transport and holds good mechanical strength as the electrolyte matrix. The ionic conductor LLZTO further improves the ionic conductivity and mechanical property of the composite electrolyte membrane. Additional SN supplies the electrolyte’ wide electrochemical stabilization window, and enhances the metallic lithium compatibility of the TPU matrix. As a result, the as prepared TPU/LLZTO/SN electrolyte presents high lithium ions transference number of 0.64, and also good mechanical property.

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]

Recently, all-solid-state lithium ion batteries (ASLBs) have emerged as the next generation lithium ion batteries due to safety issue for electric vehicles and energy storage system. This application can be achieved through layered structure cathode material of Li[Ni0.8Co0.1Mn0.1]O2, (NCM811) with high specific capacity and composite solid electrolyte. The composite solid electrolyte is composed by poly ethylene oxide (PEO) based polymer solid electrolyte and garnet type oxide based Li6.75La3Zr2Al0.25O12, (LLZO-Al) solid electrolyte. Here, in this article, we describe the effect of improved electrochemical performance on the controlling particle size of Ni-rich cathode material for ASLBs with oxide-based solid electrolyte. Therefore, the structure and electrochemical performance of Ni-rich cathode material in ASLBs were investigated by using powder X-ray diffraction analysis, Brunauer–Emmett–Teller adsorption experiments, electrochemical impedance spectroscopy, and galvanostatic measurements. [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]

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]

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.

Due to the intrinsically high ionic conductivity and good interfacial stability towards lithium, garnet-type solid electrolytes are usually introduced into polymer electrolytes as fillers to prepare polymer/garnet composite electrolytes, which can improve the ionic conductivity and enhance the mechanical strength to suppress Li dendrites. However, the surface Li2CO3 and/or LiOH passive layers which form when garnet is exposed to the air greatly reduce the enhancement effect of garnet on the composite electrolyte. Furthermore, compared with micro-size particles, nano-size garnet fillers exhibit a better effect on enhancing the performance of composite solid electrolytes. Nevertheless, inferior organic/inorganic interphase compatibility and high specific surface energy of nanofillers inevitably cause agglomeration, which severely hinders the effect of nanoparticles for promoting composite solid electrolytes. Herein, a cost-effective amphipathic 3-Aminopropyltriethoxysilane coupling agent is introduced to modify garnet fillers, which effectively expands the air stability of garnet and greatly improves the dispersion of garnet fillers in the polymer matrix. The well-dispersed garnet filler/polymer interface is intimate through the bridging effect of the silane coupling agent, resulting in boosted ionic conductivity (0.72 × 10−4 S/cm at room temperature) of the composite electrolyte, enhanced stability against lithium dendrites (critical current density > 0.5 mA/cm2), and prolonged cycling life of LFP/Li full cells. [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]

Solid sodium ion batteries (SIBs) show a significant amount of potential for development as energy storage systems; therefore, there is an urgent need to explore an efficient solid electrolyte for SIBs. Na3Zr2Si2PO12 (NZSP) is regarded as one of the most potential solid-state electrolytes (SSE) for SIBs, with good thermal stability and mechanical properties. However, NZSP has low room temperature ionic conductivity and large interfacial impedance. F−doped NZSP has a larger grain size and density, which is beneficial for acquiring higher ionic conductivity, and the composite system prepared with epoxy can further improve density and inhibit Na dendrite growth. The composite system exhibits an outstanding Na+ conductivity of 0.67 mS cm−1 at room temperature and an ionic mobility number of 0.79. It also has a wider electrochemical stability window and cycling stability.

[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]

It is crucial to develop solid electrolyte with good mechanical and electrochemical stability for the application of lithium metal battery. In this work, a sandwich-structured composite solid electrolyte is designed and prepared based on the blend of polyvinylidene fluoride-hexafluoropropylene/polyacrylonitrile (PVDF-HFP/PAN) polymer, Li6.46La3Zr1.46Ta0.54O12 as filler, and a layer of PE film is introduced in the middle to act as a skeleton. The sandwich-structured PVDF-HFP/PAN-10%LLZTO-PE composite solid electrolyte displays a tensile strength of 66.58 MPa, high ionic conductivity of 2.28 × 10-4 S/m at 25 °C, wide electrochemical stable window of 4.8 V, and high lithium ion transfer number of 0.44. The LiFePO4 | PVDF-HFP/PAN-10%LLZTO-PE | Li coin battery shows a high specific capacity of 161.9 mAh/g and retains 150.2 mAh/g after 300 cycles at 1 C. Furthermore, the LiFePO4 | PVDF-HFP/PAN-10%LLZTO-PE | Li pouch battery shows excellent safety and functionality. [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]

In addition to the Li+ transport kinetics, the interface stability of the solid-state electrolyte is also critical for solid-state Li-metal batteries (SLMBs), especially for nickel-rich cathode-based ones. Herein, we develop an air-processable composite polymer electrolyte (CPE) using polyvinylidene difluoride (PVDF) as matrix, LiCF 3 SO 3 as Li-salt, Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 as fast Li-conductor and C 4 BLiO 8 (LiBOB) as additive. The presence of LiBOB suppress the defluorination reaction of PVDF in electrolyte solution, that reduce the corrosion reaction on LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) particles and enhance the intermolecular interactions between [Li(DMF) x ]+ and PVDF as well. Importantly, the formed H 3 BO 3 in CPE induce the in situ passivation of Li-B-O/B-O on surface of NCM811 and Li-metal, which impedes the crack of NCM811 particles and growth of Li-dendrites. Thus, NCM811/Li battery exhibits a high specific capacity up to 196.1 mAh g−1 (0.1C) and excellent long-term stability. Specifically, a capacity retention rate of 71.8 % (134.5/181.1 mAh g−1) and 78.7 % (132.1/167.9 mAh g−1) has been achieved at 0.2C and 0.5C after 500 cycles, respectively, which represent one of the best performances in the field. This strategy also greatly enhance the cyclic stability of LiFePO 4 /Li battery, which shows a capacity retention rate of 92 % (143.5 mAh g−1) after 700 cycles. [Display omitted] • A stable solid-state electrolyte based on PVDF/LiOTf is built. • NCM811/Li (LFP/Li) battery shows excellent cyclic stability for 500 (700) cycles. • Air-processable technique is applied for the fabrication of electrolyte membrane. • Both cathode and anode are in situ passivated by Li-B-O/B-O. [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]

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]

The safety concerns associated with power batteries have prompted significant interest in all−solid−state lithium batteries (ASSBs). However, the advancement of ASSBs has been significantly impeded due to their unsatisfactory electrochemical performance, which is attributed to the challenging interface between the solid−state electrolyte and the electrodes. In this work, an in situ polymerized composite solid−state electrolyte (LLZTO−PVC) consisting of poly(vinylene carbonate) (PVC) and Li6.4La3Zr1.4Ta0.6O12 (LLZTO) was successfully prepared by a γ−ray irradiation technique. The novel technique successfully solved the problem of rigidity at the interface between the electrode and electrolyte. The LLZTO−PVC electrolyte exhibited a notable ionic conductivity of 1.2 × 10−4 S cm−1 25 °C, along with good mechanical strength and flexibility and an electrochemical window exceeding 4.65 V. It was showed that the LiCoO2(LCO)/LLZTO−PVC/Li battery, which achieved in situ solidification via γ−ray irradiation, can steadily work at a current density of 0.2 C at 25 °C and maintain a retention rate of 92.4% over 100 cycles. The good interfacial compatibility between electrodes and LLZTO−PVC electrolyte designed via in situ γ−ray irradiation polymerization could be attributed to its excellent electrochemical performance. Therefore, the method of in situ γ−ray irradiation polymerization provides a vital reference for solving the interface problem.

Abstract Composite solid electrolyte is a promising solution for the development of new generation of safe and high‐performance all‐solid‐state lithium batteries (ASSLBs). It combines both the advantages of inorganic electrolyte and organic polymer electrolyte, having high ionic conductivity, mechanical strength, good contact with the electrodes and high processability. In the recent decades, rare earth oxides have attracted wide attentions from researchers because of their high ionic conductivity. China is abundant in rare earth resources, so has a good chance to provide the world with high quality rare earth containing functional materials. This review paper focuses on the recent progress in the studies of composite solid electrolyte of polymer and rare earth containing lithium lanthanum zirconium and lithium lanthanum titanium oxides, and gains insights into the challenges in the field, and hopefully helps in the rational design of high performance electrolyte for the development of ASSLBs.

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.

As a high-efficiency energy storage and conversion device, lithium-ion batteries have high energy density, and have received widespread attention due to their good cycle performance and high reliability. However, currently commercial lithium batteries usually use organic solutions containing various lithium salts as liquid electrolytes. In practical applications, liquid electrolytes have many shortcomings and shortcomings, such as poor chemical stability, flammability, and explosion. Therefore, the liquid electrolyte has a great safety hazard. The use of solid electrolyte ensures the safety of lithium-ion batteries, and has the advantages of high energy density, good cycle performance, long life, and wide electrochemical window, making the battery safer and more durable, with higher energy density and simple battery Structural design. Solid electrolytes mainly include inorganic solid electrolytes and organic polymer solid electrolytes. Although both inorganic solid electrolytes and polymer solid electrolytes have their own advantages, as far as the existing research work is concerned, whether it is an inorganic system or a polymer system, a single-system solid electrolyte can never achieve the full performance of an ideal solid electrolyte. The composite solid electrolyte composed of active or passive inorganic filler and polymer matrix is considered as a promising candidate electrolyte for all-solid-state lithium batteries. Among many polymer systems, PEO-based is considered to be the most ideal polymer substrate. In this review article, we first introduced the structure, properties, and preparation methods of PEO-based polymer electrolytes. Furthermore, the researches related to the modification of PEO-based polymer solid electrolytes in recent years are summarized. The contribution of polymer structural modification and the introduction of additives to the ionic conductivity, electrochemical stability and mechanical properties of PEO-based solid electrolytes is described. Examples of different composite solid electrolyte design concepts were extensively discussed, such as inorganic inert nanoparticles/PEO, oxide/PEO, and sulfide/PEO. Finally, the future development direction of composite solid electrolytes was prospected.

Due to the intrinsically high ionic conductivity and good interfacial stability towards lithium, garnet-type solid electrolytes are usually introduced into polymer electrolytes as fillers to prepare polymer/garnet composite electrolytes, which can improve the ionic conductivity and enhance the mechanical strength to suppress Li dendrites. However, the surface Li2CO3 and/or LiOH passive layers which form when garnet is exposed to the air greatly reduce the enhancement effect of garnet on the composite electrolyte. Furthermore, compared with micro-size particles, nano-size garnet fillers exhibit a better effect on enhancing the performance of composite solid electrolytes. Nevertheless, inferior organic/inorganic interphase compatibility and high specific surface energy of nanofillers inevitably cause agglomeration, which severely hinders the effect of nanoparticles for promoting composite solid electrolytes. Herein, a cost-effective amphipathic 3-Aminopropyltriethoxysilane coupling agent is introduced to modify garnet fillers, which effectively expands the air stability of garnet and greatly improves the dispersion of garnet fillers in the polymer matrix. The well-dispersed garnet filler/polymer interface is intimate through the bridging effect of the silane coupling agent, resulting in boosted ionic conductivity (0.72 × 10−4 S/cm at room temperature) of the composite electrolyte, enhanced stability against lithium dendrites (critical current density > 0.5 mA/cm2), and prolonged cycling life of LFP/Li full cells.

With high safety and good flexibility, polymer-based composite solid electrolytes are considered to be promising electrolytes and are widely investigated in solid lithium batteries. However, the low conductivity and high interfacial impedance of polymer-based solid electrolytes hinder their industrial applications. Herein, a composite solid-state electrolyte containing graphene (PVDF-LATP-LiClO4-Graphene) with structurally stable and good electrochemical performance is explored and enables excellent electrochemical properties for lithium-ion batteries. The ionic conductivity of the composite electrolyte membrane containing 5 wt% graphene reaches 2.00 × 10−3 S cm−1 at 25 °C, which is higher than that of the composite electrolyte membrane without graphene (2.67 × 10−4 S cm−1). The electrochemical window of the composite electrolyte membrane containing 5 wt% graphene reaches 4.6 V, and its Li+ transference numbers reach 0.84. Assembling this electrolyte into the battery, the LFP/PVDF-LATP-LiClO4-Graphene /Li battery has a specific discharge capacity of 107 mAh g−1 at 0.2 C, and the capacity retention rate was 91.58% after 100 cycles, higher than that of the LiFePO4/PVDF-LATP-LiClO4/Li (LFP/PLL/Li) battery, being 94 mAh g−1 and 89.36%, respectively. This work provides a feasible solution for the potential application of composite solid electrolytes.

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.

Commercial lithium-ion batteries have safety risks due to the use of electrolyte-containing flammable organic solvents. The development of all solid-state lithium ion batteries with solid electrolyte is a feasible technical way to improve the safety of batteries. In this work, PVDF-based composite solid-state electrolytes (CSEs) were prepared by coupling Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and polyvinylidene fluoride (PVDF). The electrochemical performance and interfacial compatibility between composite electrolyte and electrode were improved by the combination of appropriate amount of Li-ion-conducting particles and the insulating polymer. The corresponding solid-state battery of LiFePO4 |PVDF-LLZTO-CSE| Li is fabricated and delivers initial discharge capacity of 162.4 mAh g-1, and coulomb efficiency is approximately 98.5%. And the solid-state battery exhibits satisfactory rate capability and cycling stability at room temperature. This study suggests that a combination of the lithium garnet particles and insulating polymer is one of the promising methods to solve the problem of liquid electrolyte. [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.

High room-temperature ionic conductivity and mechanical property are essential for the application of solid electrolyte. In this work, a poly(vinylidene fluoride) (PVDF)-based composite polymer solid electrolyte membrane (CSE) incorporated with Li7La3Zr2O12 (LLZO) fillers and high-strength porous skeleton was prepared. The introduction of LLZO increased the ionic conductivity of PVDF at room temperature by reducing the crystallinity of PVDF matrix, and the addition of skeleton greatly improved the mechanical property of electrolyte membrane and inhibited the growth of lithium dendrites. The prepared PVDF-LLZO CSE has a room-temperature ionic conductivity of 1.75 × 10−4 S/cm, and the tensile strength reaches 95 MPa, which greatly enhanced the ability of lithium dendrite suppression. The assembled LiNi0.6Co0.2Mn0.2O2 (NCM622)/CSE/Li cell shows an initial capacity of 151 mAh/g with a retention capacity of 108 mAh/g after 100 cycles at the current density of 0.5 C. This ultrathin PVDF/LLZO CSE has a great application prospect in solid-state lithium batteries. [ABSTRACT FROM AUTHOR]