Flexible Solid Electrolyte Research Articles

Flexible Solid Electrolytes from Two-Dimensional Metal Carbide, Polymer, and Ionic Covalent Organic Frameworks

Flexible Solid Electrolytes from Two-Dimensional Metal Carbide, Polymer, and Ionic Covalent Organic Frameworks

Synthesis and Characterization of a Biocompatible, and Flexible Solid-Electrolyte for Zn-MnO2 Batteries

The new generation of flexible wearable electronics is becoming one of the most in-demand wearable tech in most parts of the world, be it for regular use or for medical reasons, which gives rise to the need for the development of safe and flexible rechargeable batteries. Some of the most basic requirements for such batteries constitute the ease of use, flexibility, mechanical strength, and environmental friendliness. This can be achieved by carefully designing the electrolyte for the battery such that it fulfills the mentioned properties without compromising the electrochemical performance of the battery. This study sheds light on the development of a safe, flexible, and environmentally friendly solid electrolyte film based on a biopolymer. The electrolyte film derived from Chitosan, which is a biocompatible biopolymer, offers various advantages over the conventional liquid electrolytes. When soaked in an alkaline liquid, KOH, this Chitosan-film can be used as an efficient electrolyte for Zn-MnO2 battery chemistry. According to optical imaging, the incorporation of freeze drying for the preparation of the solid electrolyte films provided a lamellar structure with a microporous morphology. Higher concentrations of Chitosan enabled the film to absorb and retain increased amount of KOH because of the hydrogen bonds present between the Chitosan molecules and KOH, which helped in enhancing the ionic conductivity (IC) of the freeze-dried electrolyte, i.e., 300-600 mS/cm, at a thickness of 150-170µm. Additionally, the obtained electrolyte demonstrated exceptional mechanical strength and flexibility which also makes it a promising solid electrolyte for Zinc metal batteries, as it has a potential to impede the progression of Zn dendrites during cycling, thereby improving the stability and lifespan of the battery.

Superhydrophobic and Highly Flexible Artificial Solid Electrolyte Interphase Inspired by Lotus Effect Toward Highly Stable Zn Anode

AbstractDue to their cost‐effectiveness, high safety, and environmental friendliness, aqueous zinc‐ion batteries (AZIBs) are among the most promising technologies for next‐generation energy storage systems. Nonetheless, dendrite growth, hydrogen evolution, and corrosion at zinc (Zn) anode severely hinder their practical application. In this study, a combination of molecular self‐assembly engineering, squeegee coating, and air spraying process is employed to create a superhydrophobic and highly flexible artificial solid‐electrolyte‐interface layer on Zn anode (denoted as SFM/Zn). Self‐assembled monolayer of triethoxy‐3‐aminopropylsilane optimizes Zn2+ migration kinetics. The superhydrophobic interface, formed by polydimethylsiloxane (PDMS) and trimethoxy(octadecyl)silane (OTS)‐modified nanosilicon dioxide particles, inhibits water‐related side reactions. Furthermore, the highly flexible PDMS serves as a dynamic adaptive interface for Zn anode, effectively alleviating the “tip effect”. Consequently, the SFM/Zn||SFM/Zn symmetrical cells enable reversible and stable Zn plating/stripping at both ultralow current density (0.2 mA cm−2) and ultrahigh current density (45 mA cm−2). The assembled Zn‐vanadium (SFM/Zn||NH4V4O10) cell deliver stable average Coulombic efficiency (nearly 100%) and ultralong cycling stability (135.5 mAh g−1 after 500 cycles at 5 A g−1 and 173.2 mAh g−1 after 1000 cycles at 2 A g−1). This innovative superhydrophobic three‐layered strategy sheds new light on designing highly durable Zn anode for high‐performance AZIBs.

LLZTO crosslinks form a highly stretchable self-healing network for fast healable all-solid lithium metal batteries

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 Li6.4La3Zr1.4Ta0.6O12 (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/LiFePO4 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.

Constructing Gradient Separator to Stabilize Bi‐electrodes Toward High‐Performance Zn Metal Batteries

AbstractAqueous zinc (Zn) metal batteries have considerable potential as large‐scale energy storage systems. However, cathodic metal ions dissolution and anodic dendrite growth constrain their further development. Here, an ion gradient separator is proposed to stabilize the bi‐electrodes of Zn metal batteries. The results show that the constructed low Zn2+ concentration region in the separator helps the NH4V4O10 (NVO) model cathode to maintain good electrolyte wettability and form a N/ZnS/ZnF2‐rich cathode‐electrolyte interphase (CEI), exhibiting a low vanadium (V) dissolution behavior. Meanwhile, the high Zn2+ concentration region in the separator and the flexible solid electrolyte interphase (SEI) inhibit the dendrite growth and parasitic reactions of the Zn metal anode and further prevent the diffusion of V ions. As a proof‐of‐concept, the NVO||Zn battery with gradient separator can achieve 88.1% capacity retention even after cycling over 800 cycles at 1 A g−1, while the ordinary separator only maintains 14.8%. This work presents an innovative gradient separator strategy for achieving high‐performance Zn metal batteries and sheds light on other rechargeable batteries.

Boosting lithium-ion conductivity of polymer electrolyte by selective introduction of covalent organic frameworks for safe lithium metal batteries

The demand for high-energy-density batteries has prompted exploration into advanced materials for enhancing the safety and performance of lithium metal batteries (LMBs). This study introduces a novel approach, incorporating two-dimensional (2D) pyrazine and imine-linked covalent organic frameworks (COFs) into a polyethylene oxide (PEO)-based solid electrolyte matrix. The synthesized COFs act as multifunctional additives, improving mechanical strength, ionic conductivity (reaching 1.86 ×10−3 S/cm at room temperature), electrochemical window (oxidation resistance up to 5 V vs. Li/Li+), and thermal stability (up to 400 °C). The unique electron-rich and polar functionalities of pyrazine and imine linkages facilitate strong interactions with lithium ions (Li+), resulting in a flexible composite solid electrolyte that mitigates dendrite formation and interface instability. Electrochemical performance of LMBs with LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode further confirm the enhanced Li+ conductivity, prolonged cycling stability, and a stable solid electrolyte interface, showcasing the potential of COFs in improving LMB performance. Overall, this study highlights the promising role of pyrazine and imine-linked COFs as effective additives for polymer-based solid electrolytes and their potential for developing safer and more efficient LMBs in the future.

The synergy mechanism of CsSnI3 and LiTFSI enhancing the electrochemical performance of PEO‐based solid‐state batteries

AbstractLithium metal solid‐state battery is the first choice of batteries for electromobiles and consumer electronic products because of the specific capacity of 3860 mAh g−1 and high electrochemical potential (−3.04 V) of Li metal. Flexible polymer solid electrolytes have become the optimal solution to produce high energy density lithium batteries with arbitrary size and shape. In this work, we introduce a halide perovskite, CsSnI3, into the polyethylene oxide/lithium bis‐(trifluoromethanesuphone)imide (PEO–LiTFSI) polymer matrix. The CsSnI3 could form a LixSn alloy with Li, leading to homogenization of the electric field and Li+‐flux at the interface, Sn atom also bonds with the TFSI− anion to provide more dissociated Li+. Besides that, the I atom could interact with Li to form an electronic insulation with a strong blocking effect on electron tunneling. As a proof of concept, the synergy mechanism of the PEO–LiTFSI–CsSnI3 electrolyte improves the stable cycle life of the symmetric battery to more than 500 h, and the Li+ conductivity raised to 6.1 × 10−4 S cm−1 at 60°C. The application of the “zwitter ions analog” halide perovskite in PEO–LiTFSI provides a new choice among various methods to improve the electrochemical performance of polymer solid‐state batteries.

Scalable Dry Process for Fabricating a Na Superionic Conductor-Type Solid Electrolyte Sheet.

The cost reduction and mass production of oxide-based solid electrolytes are critical for the commercialization of all-solid-state batteries. In this study, an environmentally friendly, low-cost, and high-density oxide-based Na superionic conductor-type solid electrolyte sheet was fabricated via a dry process without the use of any solvent. The polytetrafluoroethylene (PTFE), used as a binder, was transformed into thin thread-like structures via shear force, resulting in a flexible solid electrolyte sheet. The solid electrolyte powder quantity was limited to 50 wt % for fabricating a uniform green sheet via the wet process. However, when the dry process was employed for green sheet fabrication, the solid electrolyte powder quantity could be increased to values exceeding 95 wt %. Therefore, the green sheets produced by using the dry process demonstrated a higher density than those fabricated by using the wet process. The binder content and particle size affected the ionic conductivity of a solid electrolyte sheet fabricated via a dry process. The sheet obtained via the blending of 3 wt % PTFE binder with a solid electrolyte powder, finely ground using a planetary ball mill, which exhibited the highest total ionic conductivity of 1.03 mS cm-1.

Gradual gradient distribution composite solid electrolyte for solid-state lithium metal batteries with ameliorated electrochemical performance

Composite solid electrolytes (CSEs) have emerged as promising contenders for tackling the safety concerns associated with lithium metal batteries and attaining elevated energy densities. Nonetheless, augmenting ion conductivity and curtailing the growth of lithium dendrites within the electrolyte remain pressing challenges. We have developed CSEs featuring a unique structure, in which Li6.4La3Zr1.4Ta0.6O12 (LLZTO) is distributed in a gradient decline from the center to both sides (GCSE). This distinctive arrangement encompasses heightened polymer content at the edges, thereby enhancing the compatibility between CSEs and electrode materials. Concurrently, the escalated LLZTO content at the center functions to impede the proliferation of lithium dendrites. The uniform gradient distribution state facilitates the consistent and rapid transport of lithium ions. At room temperature, GCSE exhibits an ionic conductivity of 1.5 × 10−4 S cm−1, with stable constant current cycling of lithium for over 1200 h. Furthermore, CR2032 coin batteries with a LiFePO4 (LFP)|GCSE|Li configuration demonstrate excellent rate performance and cycling stability, yielding a discharge capacity of 120 mA h g−1 at 0.5C and retaining 90 % capacity after 200 cycles at 60 °C. Flexible solid electrolytes with gradient structures offer substantial advantages in dealing with ion conductivity and inhibition of lithium dendrites, thereby expected to propel the practical application of lithium metal batteries.

Dual Interface Compatibility Enabled via Composite Solid Electrolyte with High Transference Number for Long-Life All-Solid-State Lithium Metal Batteries.

The development of solid-state electrolytes (SSEs) effectively solves the safety problem derived from dendrite growth and volume change of lithium during cycling. In the meantime, the SSEs possess non-flammability compared to conventional organic liquid electrolytes. Replacing liquid electrolytes with SSEs to assemble all-solid-state lithium metal batteries (ASSLMBs) has garnered significant attention as a promising energy storage/conversion technology for the future. Herein, a composite solid electrolyte containing two inorganic components (Li6.25Al0.25La3Zr2O12, Al2O3) and an organic polyvinylidene difluoride matrix is designed rationally. X-ray photoelectron spectroscopy and density functional theory calculation results demonstrate the synergistic effect among the components, which results in enhanced ionic conductivity, high lithium-ion transference number, extended electrochemical window, and outstanding dual interface compatibility. As a result, Li||Li symmetric battery maintains a stable cycle for over 2500h. Moreover, all-solid-state lithium metal battery assembled with LiNi0.6Co0.2Mn0.2O2 cathode delivers a high discharge capacity of 168mAhg-1 after 360 cycles at 0.1C at 25°C, and all-solid-state lithium-sulfur battery also exhibits a high initial discharge capacity of 912mAhg-1 at 0.1C. This work demonstrates a long-life flexible composite solid electrolyte with excellent interface compatibility, providing an innovative way for the rational construction of next-generation high-energy-density ASSLMBs.

Effect of Ti3AlC2 MAX phase on electrochemical performance of thermo-responsive copolymer electrolyte for solid state zinc-ion battery

The solid-state zinc-ion battery (ZIB) is environmentally friendly, cost effective, and extremely safe, which are essential features for alternative sustainable energy storage systems. Herein, a polymer composite electrolyte (PCE) is successfully developed through a facile solution-casting approach from a thermo-responsive copolymer-based electrolyte and layered ternary carbide (Ti3AlC2). The thermo-responsive copolymer demonstrated synergistic mechanical properties through the addition of an appropriate plasticizer and a zinc salt. This combination suggests that the material possesses thermal self-protection capabilities due to its anti-Arrhenius ionic-conducting behavior. However, parasitic reactions and dendrite formation hindered the achievement of its full potential. The incorporation of Ti3AlC2 or MAX phase can mitigate the above obstacles, enhancing electrochemical performance with excellent flexibility and maintainable self-extinguishing. The solid-state ZIB benefits from the well-designed PCE with the expanding layer interspacing, delivering a remarkably high capacity (336 mAh g−1 at 0.1 A g−1) and energy density of 242 Wh kg−1. This is achieved due to the Ti3AlC2's ability to immobilize or entrap triflate anions via electrostatic forces. Therefore, the designed PCE is a promising step toward the development of flexible solid electrolytes in ZIBs.

Phenylboronic Acid Functionalized Calix[4]pyrrole-Based Solid-State Supramolecular Electrolyte.

Solid-state polymer electrolytes (SPEs) suffer from the low ionic conductivity and poor capability of suppressing lithium (Li) dendrites, which limits their utility in the preparation of all solid-state Li-metal batteries (LMBs). It is reported here a flexible solid supramolecular electrolyte that incorporates a new anion capture agent, namely a phenylboronic acid functionalized calix[4]pyrrole (C4P), into a poly(ethylene oxide) (PEO) matrix. The resulting solid-state supramolecular electrolyte demonstrates high ionic conductivity (1.9×10-3 Scm-1 at 60°C) and a high Li+ transference number ( =0.70). Furthermore, the assembled Li|C4P-PEO-LiTFSI|LiFePO4 cell allows for stable cycling over 1200 cycles at 1 C at 60°C, as well as good rate performance. The favorable performance of the C4P-PEO-LiTFSI SPE leads to suggest it can prove useful in the creation of high energy density solid-state LMBs.

G-C3N4 Boosting the Interfacial Compatibility of Solid-State Lithium-Sulfur Battery

The poor interfacial compatibility between solid electrolyte and lithium metal anode is one of the main obstacles to the development of solid lithium metal battery. Herein, the poly (1,3-dioxolane) (PDOL) polymer is combined with g-C3N4 powders to form a flexible and dense composite solid electrolyte film, which not only possesses high ionic conductivity of 3.7 × 10−4 S·cm−1, high ion migration number up to 0.86, and wide electrochemical stability window of 5.0 V, but also is helpful for inhibiting the growth of lithium dendrites to improve the interfacial stability of the lithium anode and close contact with cathode. The prepared S/g-C3N4-PDOL/Li battery exhibits good rate and cycle performances with a capacity of 550 mAh g−1 at 1 C, and 1150 mAh g−1 at 0.1 C with a capacity retention rate of 83% after 100 cycles. The dense Li3N layer generated by the reaction between g-C3N4 and Li gives g-C3N4/PDOL composite electrolyte a high inhibition ability of lithium dendrites. This composite solid electrolyte film with an interface modification function has good practical application prospects in lithium-sulfur batteries.

A multifunctional Janus layer for LLZTO/PEO composite electrolyte with enhanced interfacial stability in solid-state lithium metal batteries

Flexible composite solid electrolytes (CSEs) show great potential 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 inorganic fillers and polymer, which affects lithium-ion transport and electrochemical performances of CSEs. Herein, we design a Li6.4La3Zr1.4Ta0.6O12 (LLZTO) filler coated with 3-methacryloxypropyltrimethoxysilane (MEMO) Janus layer for poly(ethylene) oxide (PEO) electrolyte (denoted as MEMO@LLZTO-PEO). We demonstrate the effect of MEMO coating on ionic transport of CSEs by the combined experimental and theoretical methods. The MEMO Janus layer facilitates uniform dispersion of filler in polymer as well as dissociates more lithium salt, which leads to much improved ionic conductivity of MEMO@LLZTO-PEO (2.16 × 10−4 S cm−1 at 30 ℃). Besides, MEMO@LLZTO could immobilize lithium salt anions via hydrogen bonding interactions and F–O chemical bonding, leading to good lithium-ion transference number (0.53) of MEMO@LLZTO-PEO. Moreover, we prepare a nonwoven fabric (NF)-supported CSE (denoted as MEMO@LLZTO-PEO-NF) to further improve the mechanical strength and safety of CSEs. The MEMO@LLZTO-PEO-NF shows great cyclability over 4000 h in a lithium symmetrical cell at a current density of 0.1 mA cm−2 (areal capacity: 0.1 mAh cm−2, 60 ℃). When used in all-solid-state Li/LiFePO4 batteries with a high active mass loading (>4 mg cm−2), MEMO@LLZTO-PEO-NF cell shows much-enhanced cyclability and rate capability at 60 ℃. This work also provides a new strategy to achieve good interfacial compatibility between inorganic fillers and polymer matrix in composite solid electrolytes for all-solid-state lithium batteries.

A flexible and free-standing composite solid electrolyte with a pomegranate-like structure for solid-state sodium-ion batteries

Solid sodium-ion batteries have the advantages of high energy density and good safety and are considered promising candidates for the next generation of energy storage systems. However, the sizeable interfacial resistance and dendrite growth between sodium and solid electrolytes, especially at high current densities, severely limit their development. Polymer-ceramic composite electrolytes are considered one of the potential candidates for solid electrolytes with high ionic conductivity and soft interface contact. In this study, a flexible self-supporting composite solid electrolyte with a pomegranate structure was prepared by a simple solution casting method. The addition of Na3Zr2Si2PO12 filler significantly improved the mechanical strength and electrochemical stability of the composite polymer electrolyte (CPE). The electrochemical stability window increases to 4.8 V relative to Na/Na+, and the conductivity reaches 1.069 × 10−4 S cm−1 at room temperature. Solid-state Na3V2(PO4)3/Na batteries using this CPE exhibit high cycle stability, with a high capacity retention rate at 1C (95.13%, coulomb efficiency of >98% after 290 cycles). These results indicate that PVDF-based CPE doped with inorganic Na3Zr2Si2PO12 packing is a promising composite electrolyte for solid sodium-ion batteries.

Flexible and thin sulfide-based solid electrolyte sheet with Li+-ion conductive polymer network for all-solid-state lithium-ion batteries

All-solid-state lithium batteries (ASSLBs) with solid electrolytes are promising battery systems capable of improving the safety and energy density of current lithium-ion batteries. Reducing the thickness of the solid electrolyte while preventing the short circuit between the anode and cathode is imperative to increase the energy density of ASSLBs. Sulfide-based solid electrolytes have high ionic conductivities; however, they are brittle, difficult to be processed into a thin film, and challenging to form stable interfaces with electrodes of large volume change. In this study, flexible thin-solid electrolyte sheets with Li+-ion conductive polymer network were prepared and characterized for ASSLB applications. They exhibited higher ionic conductance and superior mechanical properties than those of pristine Li6PS5X (argyrodite) pellets. The all-solid-state lithium-ion cell (graphite/LiNi0.7Co0.15Mn0.15O2) with a solid electrolyte sheet delivered a high discharge capacity of 182.5 mAh g−1 and showed good cycling stability at 0.33 C and 25 ℃, demonstrating that flexible and thin sheets are promising solid electrolytes for ASSLBs operating at room temperature.

Replacing synthetic polymer electrolytes in energy storage with flexible biodegradable alternatives: sustainable green biopolymer blend electrolyte for supercapacitor device

Flexible free-standing blended solid biopolymer electrolytes (BSBEs) were developed using chitosan (CS) and potato starch (PS) as the host biopolymers for the biopolymer matrix. Potassium thiocyanate (KSCN) was used as the cation provider, while non-toxic glycerol (GCL) was employed as a plasticizer to reduce resistance and enhance the amorphousness of the BSBE films. The structural, morphological, and electrical analyses demonstrated encouraging properties for the BSBE films. The addition of GCL resulted in increased dissociation of KSCN. Deconvoluted Fourier transform infrared (FTIR) spectroscopy was utilized as an accurate method for extracting ion transport parameters. The highest ambient temperature conductivity of 1.40×10−3Scm−1 is recorded at 36 wt% of GCL. The best ion conducting film exhibited a wide potential stability of 2.72 V and an ion transference number (tion) close to unity, with a value of 0.978. The fabricated EDLC demonstrated approximately rectangular cyclic voltammetry (CV) performance and fast-rate charge-discharge behavior with a specific capacitance (Cspc) of 42.11Fg−1. The galvanostatic charge-discharge (GCD) test confirmed the capacitive characteristics of the cell, exhibiting good cyclic stability and excellent outcomes in terms of energy (Ed) and power (Pd) densities over numerous cycles.

1.89 $ kg-1 Lake-Water-Based Semisolid Electrolytes for Highly Efficient Energy Storage.

Solid electrolytes with fast ion kinetics and superior mechanical properties are critical to electrochemical energy devices; however, how to design low-cost, high-performance solid electrolytes has become a critical challenge in the energy field, and significant progress has not been achieved until now. Here, lake-water-based semisolid electrolytes with a low cost of 1.89 $ kg-1 have been put forward for the purpose of market promotion. By virtue of the palygorskite dopants and lake water source, the electrolytes display satisfying mechanical, electrical, and electrochemical properties as well as economic benefits. The application potential of electrolytes has been demonstrated by employing a polyelectrolyte with ionic conductivity of 0.82 × 10-4 S cm-1 in flexible supercapacitors. The as-assembled devices give a high energy density of 54.72 Wh kg-1 and excellent cycling stability with a capacity retention of 94.8% over 20 000 cycles. The flexibility of devices has been verified through 5000 repetitive bending tests. Our work presents insight into the design of flexible solid electrolytes based on cheap and green raw materials.

Semi-Solid Supramolecular Ionic Network Electrolytes Formed by Zwitterionic Liquids and Polyoxometalate Nanoclusters for High Proton Conduction.

Flexible electrolytes with solid self-supporting properties are highly desired in the fields of energy and electronics. However, traditional flexible electrolytes prepared by doping ionic liquids or salt solutions into a polymer matrix pose a risk of liquid component leakage during device operation. In this work, the development of supramolecular ionic network electrolytes using polyoxometalate nanoclusters as supramolecular crosslinkers to solidify bola-type zwitterionic liquids is reported. The resulting self-supporting electrolytes possess semi-solid features and show a high proton conductivity of 8.2×10-4 S cm-1 at low humidity (RH = 30%). Additionally, the electrolytes exhibit a typical plateau region in rheological tests, indicating that their dynamic network structures can contribute mechanical behavior similar to the entangled networks in covalent polymer materials. This work introduces a new paradigm for designing flexible solid electrolytes and expands the concept of reticular chemistry to noncrystalline systems.

Preparation of LLZO template by electrospinning and study on flexible composite solid electrolyte based on 3D Li6.4La3Zr2Al0.2O12 framework

In this work, we innovatively used the electrospinning method to prepare templates, which were then used in the template method to prepare Li6.4La3Zr2Al0.2O12(LLZO). By combining the advantages of electrospinning and template methods, we greatly expanded the source of template materials for the template method. Different template materials combined with electrospinning can obtain LLZO with different structures and performance. At the same time, we innovatively combined PVDF-based solid electrolyte with high concentration of LiTFSI with 3D LLZO framework. Using the complex formed by N-methyl pyrrolidone (NMP) and lithium ion (Li+) as a charge carrier, unique lithium ion migration channels formed by high-concentration LiTFSI, and the joint effect of high-content LLZO, we obtained a composite solid electrolyte with excellent performance. It has high mechanical strength (1.4 MPa) and high Young's modulus (6.4 MPa), which effectively inhibits the growth of lithium dendrites. In addition, the composite solid electrolyte exhibits excellent ion conductivity at room temperature (2.07 ×10−4 S cm−1), and a lithium symmetric battery can operate stably for at least 1000 h at 50 ℃. After 100 cycles at a current density of 0.5 C at 50 ℃, the remaining specific capacity of LiFePO4 | 3D LLZO·CSE | Li was 141.9 mAh g−1, and the capacity retention rate was 96.4%. Our research results show that this low-cost LLZO template manufacturing method, combined with the excellent performance of the obtained composite solid electrolyte, has great potential in energy storage direction.