Solid-state Lithium Batteries Research Articles

Constructing an All Solid-state Flexible Lithium-Manganese Battery with High Performance

Abstract Due to a lack of portable flexible power supply, flexible electronic products can still not be applied in a large scale, particularly in the high energy density devices. To resolve this issue, flexible solid-state lithium batteries with a high safety, excellent mechanical property, and high energy densit，is proposed. In this paper, a flexible solid-state lithium-manganese battery is developed, which is assembled with a lithium cloth composite anode, a composite solid-state electrolyte poly (vinylidene fluoride)-hexafluoropropylene (PVDF-HFP)/Li6.4La3Ta0.6O12 (LLZTO), and a composite cathode (Fe ion-doped MnO2-carbon cloth). To improve the conductivity and stability of cathode, a mixture of conductive carbon black (Super P) and sodium alginate (SA) is employed. To ensure the high capacity and low price, the MnO2-based cathode is used.The obtained solid state batteries can deliver an initial capacity of 275.9 mAh g-1 at a current density of 1 C and a capacity retention of 57.9% (159.7 mAh g-1 ) after 1000 cycles. Also the produced flexible punch cell can light up the light-emitting diode(LED), and its capacity is 0.58 mAh cm-2 after 100 cycles at current density of 0.2 C.

Co-doping strategies for advanced solid state electrolytes with lithium salt: a study on the structural and electrochemical properties of LATP

The commercialization of lithium-ion batteries has revolutionized the field of energy storage, yet their usage of organic electrolytes has led to significant safety concerns. Solid-state electrolytes have emerged as a promising solution to these issues, enabling the development of high-performance solid-state lithium batteries. The NASICON-type solid electrolyte Li1.3Al0.3Ti1.7P3O12 (LATP) has demonstrated excellent properties and significant potential. This study involves the solid-state synthesis of LATP electrolytes doped with Cobalt and Silicon. Furthermore, adding 8% LiBr into LATP-0.04 significantly enhanced ionic conductivity, reaching a value of 3.50 × 10−4 S cm−1. This can be linked to lithium salt filling vacant spaces between grains, resulting in a significant drop in grain boundary resistances. The electrochemical analysis through Linear Sweep Voltammetry (LSV) indicates that the investigated material demonstrates the capability to sustain stability and functionality even under the influence of elevated voltages, notably up to 5.45 V. These findings imply that optimal cobalt doping and Lithium salt contribute to superior ionic conductivity compared to pristine LATP.

SEI/dead Li-turning capacity loss for high-performance anode-free solid-state lithium batteries

Anode-free solid-state lithium metal batteries (AF-SSLBs) have the potential to deliver higher energy density and improved safety beyond lithium-metal batteries. However, the unclear mechanism for the fast capacity decay in AF-SSLBs, either determined by dead Li or solid electrolyte interface (SEI), limits the proposal of effective strategies to prolong cycling life. To clarify the underlying mechanism, herein, the evolution of SEI and dead Li is quantitatively analyzed by a solid-state nuclear magnetic resonance (ss-NMR) technology in a typical LiPF6-based polymer electrolyte. The results show that the initial capacity loss is attributed to the formation of SEI, while the dead Li dominates the following capacity loss and the growth rate is 0.141 mA h cm−2 cycle−1. To reduce the active Li loss, the combination of inorganic-rich SEI and self-healing electrostatic shield effect is proposed to improve the reversibility of Li deposition/dissolution behavior, which reduces the capacity loss rate for the initial SEI and following dead Li generation by 2.3 and 20.1 folds, respectively. As a result, the initial Coulombic efficiency (ICE) and stable CE increase by 15.1% and 15.3% in Li-Cu cells, which guides the rational design of high-performance AF-SSLBs.

Metal-Doped NASICON/Polymer Composite Solid Electrolyte for Lithium Titania Anode in Lithium-Ion Batteries.

This study reports five types of metal-doped (Co, Cu, Sn, V, and Zr) NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP)/polymer composite solid electrolytes (CSEs) enabling Li4Ti5O12 (LTO) anodes to have high rate capability and excellent cycling performance. The high Li+-conductivity LATP samples are successfully synthesized through a modified sol-gel method followed by thermal calcination. We find that the cation dopants clearly influence the substitution of Al for Ti, with the type of dopant serving as a crucial factor in determining the ionic conductivity and interfacial resistance of the solid electrolyte. The CSE containing poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and Sn-LATP shows an ionic conductivity of 1.88 × 10-4 S cm-1 at ambient temperature. The optimum conductivity can be attributed to alterations in the lattice parameters and Li+ transport pathways owing to Sn doping. The solid-state cell equipped with the LTO-supported CSE containing Sn-LATP fillers demonstrates both excellent high rate capability at 5 C (with a capacity retention of 86% compared to the value measured at 0.2 C) and superior cycling stability, maintaining high Coulombic efficiency (>99.0%) over 510 cycles. These findings indicate that the proposed CSE is highly promising for use in solid-state lithium batteries with desirable charge-discharge properties and high durability.

Realizing the dendrite-free sulfide-based all-solid-state Li metal battery by surface design

Although the ultrahigh ionic conductivity of sulfide-type solid electrolytes is comparable to that of liquid electrolytes, the low critical current density (CCD) limits the practical application of solid-state lithium (Li) metal batteries. The insufficient Li0 self-diffusion in solid Li leads to the voids that form at the interface at a large stripping current density, which results in interface contact loss and the increase of local current density. Herein, an artificial hybrid interphase layer dominated by Li3Sb and LiF was constructed on the Li surface to explore the Li plating/stripping behavior at the Li/Li6PS5Cl interface. The Li3Sb alloy provides a fast Li0 diffusion channel to avoid the interfacial voids formation and current focusing, while the electrically insulated LiF acts an electron blocking shield at the Li/Li6PS5Cl interface. Consequently, the symmetric cells reveal a significantly increased CCD of 1.8 mA cm−2 and a stable Li plating/stripping for 1472 h with a high current density of 2 mA cm−2 at 50 °C. Moreover, the all-solid-state Li-SPAN cell with Li3Sb/LiF interphase exhibits good capacity retention of 83.2 % after 120 cycles at 0.5 C, and it also delivers a superior rate performance of 400 mAh g−1 at 5C. The construction of lithium-alloy interphase is a promising alternative to solid-state lithium battery applications.

Multifunctional Additive Enables a "5H" PEO Solid Electrolyte for High-Performance Lithium Metal Batteries.

The solid-state battery with a lithium metal anode is a promising candidate for next-generation batteries with improved energy density and safety. However, the current polymer electrolytes still cannot fulfill the demands of solid-state batteries. In this work, we propose a "5H" poly(ethylene oxide) (PEO) electrolyte via introducing a multifunctional additive of tris(pentafluorophenyl)borane (TPFPB) for high-performance lithium metal batteries. The addition of TPFPB improves the ionic conductivity from 6.08 × 10-5 to 1.54 × 10-4 S cm-1 via reducing the crystallinity of the PEO electrolyte and enhances the lithium-ion transference number from 0.19 to 0.53 via anion trapping due to its Lewis acid nature. Furthermore, the fluorine and boron segments from TPFPB can optimize the composition of the solid-electrolyte interphase and cathode-electrolyte interphase, providing a high electrochemical stability window over 4.6 V of the PEO electrolyte along with significantly improved interface stability. At last, TPFPB can ensure improved safety through a self-extinguishing effect. As a result, the "5H" electrolyte enables the Li/Li symmetric cells to achieve a stable cycle over 2200 h at the current density of 0.2 mA cm-2 with a capacity of 0.2 mA h cm-2; the LiFePO4/Li full cells with a high LFP loading of 8 mg cm-2 exhibits decay-free capacity of 140 mA h g-1 (99% capacity retention) after 100 cycles; and the NCM811/Li cells exhibit a high capacity of 160 mA h g-1 after 50 cycles at 0.5 C. This work presents an innovative approach to utilizing a "5H" electrolyte for high-performance solid-state lithium batteries.

Composite polymer electrolyte with vertically aligned garnet scaffolds for quasi solid-state lithium batteries

Structure design is of great importance for composite solid electrolytes to meet the high requirements for lithium batteries today. Herein, a novel composite polymer electrolyte with vertically aligned fast ion pathways has been constructed through the in-situ UV-induced polymerization of poly (butyl acrylate) (PBA) based gel polymer electrolyte inside the honeycomb-structure Li6.5La3Zr1.5Ta0.5012 (LLZTO) scaffolds by freeze casting. The addition of LLZTO enhances the anion adsorption through the Lewis-acid sites of the La ions and reduces the Li+ complexation by participating in the interaction of CO⋯Li+. Therefore, the interface of PBA and LLZTO scaffold serves as a continuous Li+ transport pathway and the resulting composite solid electrolyte exhibits a high ionic conductivity (5.098×10−4 S cm−1), near single-ion conducting characteristic (a transference number of 0.8) and high electrochemical stability window (5.15 V). Based on the above superior performance, the composite electrolyte promotes uniform distribution of lithium ion concentration and electrolyte potential. Thus, quasi-solid-state LiFePO4/Li cells exhibit excellent cycling performance (capacity retention of 91.7 % after 300 cycles at 0.5 C).

UV Curved PESF-LLZTO Composite Solid Electrolyte to In Situ Construct Ultrastable Interface for All Solid-State Lithium Battery

Abstract Optimizing interfacial contact between electrolyte and electrode is one of key factors to achieve stable all solid state lithium batteries (ASSLBs). In this work, UV curving technique is reported to produce ASSLBs by in situ constructing integrated interface between PESF-LLZTO composite solid electrolytes (CSEs) and LiFePO4 (LFP) cathode. Benefiting from the integral structure and ultrastable properties of the as-prepared CSE/LFP interface, the obtained ASSLBs delivers an initial discharge specific capacities of 162.8 mAh g-1 at 0.1C and 30 oC, and successfully runs over 520 cycles at 0.5 C with a discharge capacity retention ratio of 96.3 %.

Flexible High Lithium-Ion Conducting PEO-Based Solid Polymer Electrolyte with Liquid Plasticizers for High Performance Solid-State Lithium Batteries.

Lithium-ion secondary batteries (LIB) with high energy density have attracted much attention for electric vehicle (EV) applications. However, LIBs have a safety problem because these batteries contain a flammable organic electrolyte. As such, all-solid secondary batteries that are not flammable have been extensively reported recently. In this study, we have focused on polymer electrolytes, which is flexible and is expected to address the safety problem. However, the conventional polymer electrolytes have low electrial conductivity at room temperature. Various attempts have been made to solve this problem, such as the addition of inorganic fillers and ionic liquids; however, these composite polymer electrolytes have not yet reached a practical level of lithium-ion conductivity. In this study, high electrical conductivity and lithium dendrite formation-free PEO based composite electrolytes are developed with both a filler of Li6,4La3Zr1.4Ta0.6O12 and liquid plasticizers of tetraethylene glycol dimethyl ether and 1,2 dimethoxyethane. The proposed flexible polymer electrolyte shows a high electrical conduciviy of 6.01×10-4 S cm-1 at 25 °C.

Molecular-scale interaction between sub-1 nm cluster chains and polymer for high-performance solid electrolyte

Organic-inorganic interface in composite solid electrolyte could lead to increased ion transport for solid-state lithium batteries; however, most inorganic fillers have much larger size than polymer chains, which results in severe aggregation of inorganic fillers and poor ionic conductivity. Herein, functional sub-1 nm inorganic cluster chains were integrated with polymer chains to fabricate composite solid electrolyte with enhanced ionic conductivity. Different from all other inorganic fillers, the sub-1 nm inorganic cluster chains with diameter <1 nm have similar size and geometry compared with polymer chains, exhibiting polymer-like solution properties. A transparent sub-1 nm inorganic filler/polymer mixed solution was generated to realize monodispersion of cluster chains as functional fillers in polymer matrix. Meanwhile, abundant oxygen vacancies on cluster chains interact with polymer chains and lithium salts at molecular-scale, which decreases the complexation of polymer segments with Li+ and promote the dissociation of lithium salts, thereby improving Li+ transport. As a result, the composite solid electrolyte exhibits high ionic conductivity (0.4 mS cm−1) and large mobile Li+ distribution (50.8 %). This work pushes the size of nanofillers down to <1 nm, which is a unique approach to the molecular-scale interaction between nanofillers and polymers to boost ion transport in solid electrolytes.

Ion-Exchange-Induced Phase Transition Enables an Intrinsically Air Stable Hydrogarnet Electrolyte for Solid-State Lithium Batteries.

Inferior air stability is a primary barrier for large-scale applications of garnet electrolytes in energy storage systems. Herein, a deeply hydrated hydrogarnet electrolyte generated by a simple ion-exchange-induced phase transition from conventional garnet, realizing a record-long air stability of more than two years when exposed to ambient air is proposed. Benefited from the elimination of air-sensitive lithium ions at 96h/48e sites and unobstructed lithium conduction path along tetragonal sites (12a) and vacancies (12b), the hydrogarnet electrolyte exhibits intrinsic air stability and comparable ion conductivity to that of traditional garnet. Moreover, the unique properties of hydrogarnet pave the way for a brand-new aqueous route to prepare lithium metal stable composite electrolyte on a large-scale, with high ionic conductivity (8.04×10-4Scm-1), wide electrochemical windows (4.95V), and a high lithium transference number (0.43). When applied in solid-state lithium batteries (SSLBs), the batteries present impressive capacity and cycle life (164mAhg-1 with capacity retention of 89.6% after 180 cycles at 1.0C under 50°C). This work not only designs a new sort of hydrogarnet electrolyte, which is stable to both air and lithium metal but also provides an eco-friendly and large-scale fabrication route for SSLBs.

Polyester-enhanced poly (cyclic carbonate-fluoride)-based polymer electrolyte for stable circulating solid lithium batteries

Polymer solid-state electrolytes have become one of the promising materials for constructing solid-state lithium batteries due to their excellent processability and good compatibility with electrode interfaces. However, their limited electrochemical performance and mechanical strength have hindered their widespread application. Through the adoption of an in-situ thermal curing method, we successfully prepared a poly(carbonate-fluoride) solid-state electrolyte, utilizing a polyester separator with abundant polar groups as a reinforcing framework. The introduction of ionic liquid into the solid polymer electrolyte not only enhances the mobility of polymer chain segments to improve ionic conductivity but also, in synergy with trifluoromethyl, promotes lithium salt dissociation while restricting the migration of lithium salt anions. Additionally, their reaction with the lithium metal anode generates the LiF-rich SEI, regulating the deposition of lithium dendrites. The resulting 31VPIF/OZ exhibited outstanding ionic conductivity (3.58 × 10−4 S cm−1 at 25 °C), Li-ion migration number (0.52), and electrochemical window (5.4 V). Li | 31VPIF/OZ | Li battery cycled for 1000 h at 0.1 mA cm−2 without short-circuiting. Importantly, Li | | LiFePO4 battery demonstrated a high capacity retention rate of 91.5 % after 600 cycles at 0.5C (25 °C). Thus, through the synergistic interplay of polymer structure design and fillers, we have successfully achieved stable cycling in solid-state lithium batteries, providing robust support for their application in rechargeable lithium battery technology.

In-situ electrochemical passivation for constructing high-voltage PEO-based solid-state lithium battery

Polyethylene oxide (PEO) is one of the promising substrates for polymer solid electrolyte. However, when coupled with high energy density nickel-rich layered cathode materials, PEO faces the risk of catalytic decomposition by delithium nickel-rich materials. In this work, the in-situ electrochemical passivation strategy is employed to obtain high voltage PEO-based solid-state lithium battery. Trace commercial liquid electrolyte was added on the surface of LiNi0.8Co0.1Mn0.1O2 (NCM811) electrode, and liquid electrolyte is prior to PEO electrolyte to react with the cathode during charge/discharge process, leading to the formation of cathode-electrolyte interface (CEI) layer. The CEI layer avoids the direct contact between PEO and NCM811, thus effectively prevents PEO from being decomposed by NCM811 under high voltage. As a result, the optimized NCM811||PEO||Li battery displays enhanced electrochemical performance, especially cycling performance. This simple but effective strategy not only simplifies the manufacturing process, but also has instructional guidance for high-voltage PEO-based battery.

Weak-Interaction Environment in a Composite Electrolyte Enabling Ultralong-Cycling High-Voltage Solid-State Lithium Batteries.

Poly(vinylidene fluoride) (PVDF)-based solid electrolytes with a Li salt-polymer-little residual solvent configuration are promising candidates for solid-state batteries. Herein, we clarify the microstructure of PVDF-based composite electrolyte at the atomic level and demonstrate that the Li+-interaction environment determines both interfacial stability and ion-transport capability. The polymer works as a "solid diluent" and the filler realizes a uniform solvent distribution. We propose a universal strategy of constructing a weak-interaction environment by replacing the conventional N,N-dimethylformamide (DMF) solvent with the designed 2,2,2-trifluoroacetamide (TFA). The lower Li+ binding energy of TFA forms abundant aggregates to generate inorganic-rich interphases for interfacial compatibility. The weaker interactions of TFA with PVDF and filler achieve high ionic conductivity (7.0 × 10-4 S cm-1) of the electrolyte. The solid-state Li||LiNi0.8Co0.1Mn0.1O2 cells stably cycle 4900 and 3000 times with cutoff voltages of 4.3 and 4.5 V, respectively, as well as deliver superior stability at -20 to 45 °C and a high energy density of 300 Wh kg-1 in pouch cells.

The effect of garnet content on the microstructure and electrochemical properties of PEO/garnet composite electrolyte

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 Li6.25Ga0.25La3Zr2O12 (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/LiFePO4 (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.

Composition regulation of polyacrylonitrile-based polymer electrolytes enabling dual-interfacially stable solid-state lithium batteries

The polyacrylonitrile (PAN) is an attractive matrix of polymer electrolytes owing to its wide electrochemical window and strong coordination with Li salts. However, the PAN-based electrolytes undergo severe interfacial problems from both cathode and anode sides, including uneven ionic transfer induced by high rigidity of dry PAN-based polymer, as well as inferior stability against Li-metal anode. Herein, the composition regulation of PAN-based electrolytes is proposed by introducing succinonitrile (SN) plastic crystal and LiNO3 salt for the construction of interfacially stable solid-state lithium batteries. The plastic nature of SN enables the rapid ionic transfer in electrolytes, along with the establishment of conformally interfacial contacts. Meanwhile, a stable solid-electrolyte-interface (SEI) layer consisting of Li3N and LiNO2 is in-situ formed at Li/electrolyte interface, contributing to the inhibition of uncontrol reactions between PAN and Li-metal. Consequently, the resultant Li symmetric cell delivers an extended critical current density of 1.7 mA cm−2 and an outstanding cycling lifespan of 700 h at 0.1 mA cm−2. Moreover, the corresponding solid-state LiNi0.6Co0.2Mn0.2O2/Li full cell shows an initial discharge capacity of 161 mAh/g followed by an outstanding capacity retention of 88.7 % after 100 cycles at 0.1C. This work paves the way for application of PAN-based electrolytes in the field of solid-state batteries by facile composition regulation.

Solid-State Electrolytes by Electrospinning Techniques for Lithium Batteries.

Solid-state lithium batteries (SSLBs) are regarded as next-generation energy storage devices because of their advantages in terms of safety and energy density. However, the poor interfacial compatibility and low ionic conductivity seriously hinder their development. Electrospinning is considered as a promising method for fabricating solid-state electrolytes (SSEs) with controllable nanofiber structures, scalability, and cost-effectiveness. Numerous efforts are dedicated to electrospinning SSEs with high ionic conductivity and strong interfacial compatibility, but a comprehensive summary is lacking. Here, the history of electrospinning SSEs is overeviewed and introduce the electrospinning mechanism, followed by the manipulation of electrospun nanofibers and their utilization in SSEs, as well as various methods to improve the ionic conductivity of SSEs. Finally, new perspectives aimed at enhancing the performance of SSEs membranes and facilitating their industrialization are proposed. This review aims to provide a comprehensive overview and future perspective on electrospinning technology in SSEs, with the goal of guiding the further development of SSLBs.

Interfacial self-healing polymer electrolytes for Long-Cycle silicon anodes in High-Performance solid-state lithium batteries

For all-solid-state lithium-ion batteries (ASSLIBs), silicon (Si) stands out as an appealing anodes material due to its high energy density and improved safety compared to lithium metal. However, the substantial volume changes during cycling result in poor solid-state physical contact and electrolyte–electrode interface issues, leading to unsatisfactory electrochemical performance. In this study, we employed in-situ polymerization to construct an integrated Si anodes/self-healing polymer electrolyte for ASSLIBs. The polymer chain reorganization stems from numerous dynamic bonds in the constructed self-healing dynamic supermolecular elastomer electrolyte (SHDSE) molecular structure. Notably, SHDSE also serves as a Si anodes binder with enhanced adhesive capability. As a result, the well-structured Li|SHDSE|Si-SHDSE cell generates subtle electrolyte–electrode interface contacts at the molecular level, which can offer a continuous and stable Li+ transport pathway, reduce Si particle displacement, and mitigate electrode volume expansion. This further enhances cyclic stability (>500 cycles with 68.1 % capacity retention and >99.8 % Coulombic efficiency). More practically, the 2.0 Ah wave-shaped Si||LiCoO2 soft-pack battery with in-situ cured SHDSE exhibits strongly stabilized electrochemical performance (1.68 Ah after 700 cycles, 86.2 % capacity retention) in spite of a high operating temperatures up to 100 °C and in various bending tests. This represents a groundbreaking report in flexible solid-state soft-pack batteries containing Si anodes.

A three-dimensional co-continuous network structure polymer electrolyte with efficient ion transport channels enabling ultralong-life all solid-state lithium metal batteries

Solid polymer electrolytes (SPEs) have emerged as one of the most promising candidates for the construction of solid-state lithium batteries due to their excellent flexibility, scalability, and interface compatibility with electrodes. Herein, a novel all-solid polymer electrolyte (PPLCE) was fabricated by the copolymer network of liquid crystalline monomers and poly(ethylene glycol) dimethacrylate (PEGDMA) acts as a structural frame, combined with poly(ethylene glycol) diglycidyl ether short chain interspersed serving as mobile ion transport entities. The preparaed PPLCEs exhibit excellent mechanical property and outstanding electrochemical performances, which is attributed to their unique three-dimensional co-continuous structure, characterized by a cross-linked semi-interpenetrating network and an ionic liquid phase, resulting in a distinctive nanostructure with short-range order and long-range disorder. Remarkably, the addition of PEGDMA is proved to be critical to the comprehensive performance of the PPLCEs, which effectively modulates the microscopic morphology of polymer networks and improves the mechanical properties as well as cycling stability of the solid electrolyte. When used in a lithium-ion symmetrical battery configuration, the 6 wt%-PPLCE exhibites super stability, sustaining operation for over 2000 h at 30 °C, with minimal and consistent overpotential of 50 mV. The resulting Li|PPLCE|LFP solid-state battery demonstrates high discharge specific capacities of 160.9 and 120.1 mA h g−1 at current densities of 0.2 and 1 C, respectively. Even after more than 300 cycles at a current density of 0.2 C, it retaines an impressive 73.5% capacity. Moreover, it displayes stable cycling for over 180 cycles at a high current density of 0.5 C. The super cycle stability may promote the application for ultralong-life all solid-state lithium metal batteries.

Mof-derived ionic conductor enhancing the performance of polymer electrolyte for solid-state lithium batteries

The solid-state electrolyte is an important component of solid-state batteries and significantly influences the performance of batteries. However, pure solid-state polymer electrolyte has challenges such as low ionic conductivity, weak mechanical strength and poor ability to inhibit lithium dendrites. Therefore, a unique nano porous structural material based on a metal–organic framework (MOF) was proposed as a filler to enhance the polymer electrolyte, which is lithium ionic liquid (Li-IL) immersed into the MIL-125 framework to transform MIL-125 from an inert conductor to an efficient ionic conductor to obtain MIL-125-Li. MIL-125-Li not only has Lewis acid nature, but also provides a more definite and continuous transport pathway for the rapid migration of Li+. The composite polymer electrolytes (CPEs), containing 15 wt% of MIL-125-Li, exhibit an ionic conductivity of 3.9 × 10-4 S cm−1 at 28 °C. Furthermore, the CPEs demonstrate excellent interfacial stability with the lithium metal electrode, effectively inhibiting the growth of lithium dendrites. The assembled symmetric Li/PL-15 % MIL-125/Li battery can be stably cycled for more than 700 h at 0.1 mA cm−2 at 28 °C. Applying the composite polymer electrolyte to LiFePO4/Li batteries, the discharge specific capacity achieves ∼130 mAh g-l with a capacity retention rate of 83.9 % after cycling for 500 cycles at 0.5C. This simple modification method provides a novel design idea for all solid-state lithium batteries with excellent electrochemical performance.