Nacre-Inspired Composite Electrolytes for Load-Bearing Solid-State Lithium-Metal Batteries

Solid-state lithium-metal batteries with solid electrolytes are promising for next-generation energy-storage devices. However, it remains challenging to develop solid electrolytes that are both mechanically robust and strong against external mechanical load, due to the brittleness of ceramic electrolytes and the softness of polymer electrolytes. Herein, a nacre-inspired design of ceramic/polymer solid composite electrolytes with a “brick-and-mortar” microstructure is proposed. The nacre-like ceramic/polymer electrolyte (NCPE) simultaneously possesses a much higher fracture strain (1.1%) than pure ceramic electrolytes (0.13%) and a much larger ultimate flexural modulus (7.8 GPa) than pure polymer electrolytes (20 MPa). The electrochemical performance of NCPE is also much better than pure ceramic or polymer electrolytes, especially under mechanical load. A 5 × 5 cm² pouch cell with LAGP/poly(ether-acrylate) NCPE exhibits stable cycling with a capacity retention of 95.6% over 100 cycles at room temperature, even undergoes a large point load of 10 N. In contrast, cells based on pure ceramic and pure polymer electrolyte show poor cycle life. The NCPE provides a new design for solid composite electrolyte and opens up new possibilities for future solid-state lithium-metal batteries and structural energy storage.     

A Rational Reconfiguration of Electrolyte for High-Energy and Long-Life Lithium–Chalcogen Batteries

Lithium–chalcogen batteries are an appealing choice for high-energy-storage technology. However, the traditional battery that employs liquid electrolytes suffers irreversible loss and shuttle of the soluble intermediates. New batteries that adopt Li⁺-conductive polymer electrolytes to mitigate the shuttle problem are hindered by incomplete discharge of sulfur/selenium. To address the trade-off between energy and cycle life, a new electrolyte is proposed that reconciles the merits of liquid and polymer electrolytes while resolving each of their inferiorities. An in situ interfacial polymerization strategy is developed to create a liquid/polymer hybrid electrolyte between a LiPF₆-coated separator and the cathode. A polymer-gel electrolyte in situ formed on the separator shows high Li⁺ transfer number to serve as a chemical barrier against the shuttle effect. Between the gel electrolyte and the cathode surface is a thin gradient solidification layer that enables transformation from gel to liquid so that the liquid electrolyte is maintained inside the cathode for rapid Li⁺ transport and high utilization of active materials. By addressing the dilemma between the shuttle chemistry and incomplete discharge of S/Se, the new electrolyte configuration demonstrates its feasibility to trigger higher capacity retention of the cathodes. As a result, Li–S and Li–Se cells with high energy and long cycle lives are realized, showing promise for practical use.     

Single-Ion Polymer Electrolyte Based on Lithium-Rich Imidazole Anionic Porous Aromatic Framework for High Performance Lithium-Ion Batteries

The low ionic conductivity and Li⁺ transference number ($t_{L{i}^{+}}$) of solid polymer electrolytes (SPEs) seriously hinder their application in lithium-ion batteries (LIBs). In this study, a novel single-ion lithium-rich imidazole anionic porous aromatic framework (PAF-220-Li) is designed. The abundant pores in PAF-220-Li are conducive to the Li⁺ transfer. Imidazole anion has low binding force with Li⁺. The conjugation of imidazole and benzene ring can further reduce the binding energy between Li⁺ and anions. Thus, only Li⁺ moved freely in the SPEs, remarkably reducing the concentration polarization and inhibiting lithium dendrite growth. PAF-220-quasi-solid polymer electrolyte (PAF-220-QSPE) is prepared through solution casting of Bis(trifluoromethane)sulfonimide lithium (LiTFSI) infused PAF-220-Li and Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP), and possessed excellent electrochemical performance. The electrochemical property are further improved by preparing all-solid polymer electrolyte (PAF-220-ASPE) via pressing-disc method, which has a high Li⁺ conductivity of 0.501 mS cm⁻¹ and $t_{L{i}^{+}}$ of 0.93. The discharge specific capacity at 0.2 C of Li//PAF-220-ASPE//LFP reached 164 mAh g⁻¹, and the capacity retention rate is 90% after 180 cycles. This study provided a promising strategy for SPE with single-ion PAFs to achieve high-performance solid-state LIBs.     

Rechargeable Lithium Metal Batteries with an In-Built Solid-State Polymer Electrolyte and a High Voltage/Loading Ni-Rich Layered Cathode

Solid-state batteries enabled by solid-state polymer electrolytes (SPEs) are under active consideration for their promise as cost-effective platforms that simultaneously support high-energy and safe electrochemical energy storage. The limited oxidative stability and poor interfacial charge transport in conventional polymer electrolytes are well known, but difficult challenges must be addressed if high-voltage intercalating cathodes are to be used in such batteries. Here, ether-based electrolytes are in situ polymerized by a ring-opening reaction in the presence of aluminum fluoride (AlF₃) to create SPEs inside LiNi_0.6Co_0.2 Mn_0.2O₂ (NCM) || Li batteries that are able to overcome both challenges. AlF₃ plays a dual role as a Lewis acid catalyst and for the building of fluoridized cathode–electrolyte interphases, protecting both the electrolyte and aluminum current collector from degradation reactions. The solid-state NCM || Li metal batteries exhibit enhanced specific capacity of 153 mAh g⁻¹ under high areal capacity of 3.0 mAh cm⁻². This work offers an important pathway toward solid-state polymer electrolytes for high-voltage solid-state batteries.     

Thiol-Branched Solid Polymer Electrolyte Featuring High Strength,Toughness, and Lithium Ionic Conductivity for Lithium-Metal Batteries

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

Interfacial Interaction of Multifunctional GQDs Reinforcing Polymer Electrolytes For All-Solid-State Li Battery

Solid-state polymer electrolytes are highly anticipated for next generation lithium ion batteries with enhanced safety and energy density. However, a major disadvantage of polymer electrolytes is their low ionic conductivity at room temperature. In order to enhance the ionic conductivity, here, graphene quantum dots (GQDs) are employed to improve the poly (ethylene oxide) (PEO) based electrolyte. Owing to the increased amorphous areas of PEO and mobility of Li⁺, GQDs modified composite polymer electrolytes achieved high ionic conductivity and favorable lithium ion transference numbers. Significantly, the abundant hydroxyl groups and amino groups originated from GQDs can serve as Lewis base sites and interact with lithium ions, thus promoting the dissociation of lithium salts and providing more ion pathways. Moreover, lithium dendrite is suppressed, associated with high transference number, enhanced mechanical properties and steady interface stability. It is further observed that all solid-state lithium batteries assembled with GQDs modified composite polymer electrolytes display excellent rate performance and cycling stability.     

Improving Room-Temperature Li-Metal Battery Performance by In Situ Creation of Fast Li+ Transport Pathways in a Polymer-Ceramic Electrolyte

Composite polymer-ceramic electrolytes have shown considerable potential for high-energy-density Li-metal batteries as they combine the benefits of both polymers and ceramics. However, low ionic conductivity and poor contact with electrodes limit their practical usage. In this study, a highly conductive and stable composite electrolyte with a high ceramic loading is developed for high-energy-density Li-metal batteries. The electrolyte, produced through in situ polymerization and composed of a polymer called poly-1,3-dioxolane in a poly(vinylidene fluoride)/ceramic matrix, exhibits excellent room-temperature ionic conductivity of 1.2 mS cm⁻¹ and high stability with Li metal over 1500 h. When tested in a Li|electrolyte|LiFePO₄ battery, the electrolyte delivers excellent cycling performance and rate capability at room temperature, with a discharge capacity of 137 mAh g⁻¹ over 500 cycles at 1 C. Furthermore, the electrolyte not only exhibits a high Li⁺ transference number of 0.76 but also significantly lowers contact resistance (from 157.8 to 2.1 Ω) relative to electrodes. When used in a battery with a high-voltage LiNi_0.8Mn_0.1Co_0.1O₂ cathode, a discharge capacity of 140 mAh g⁻¹ is achieved. These results show the potential of composite polymer-ceramic electrolytes in room-temperature solid-state Li-metal batteries and provide a strategy for designing highly conductive polymer-in-ceramic electrolytes with electrode-compatible interfaces.     

Lithium garnets: Synthesis,structure, Li+ conductivity,Li+ dynamics and applications

Inorganic solid fast Li⁺ conductors based batteries are expected to overcome the limitations over safety concerns of flammable organic polymer electrolytes based Li⁺ batteries. Hence, an all-solid-state Li⁺ battery using non-flammable solid electrolyte have attracted much attention as next-generation battery. Therefore, in the development of all-solid-state lithium rechargeable batteries, it is important to search for a solid electrolyte material that has high Li⁺ conductivity, low electronic conductivity, fast charge transfer at the electrode interface and wide electrochemical window stability against potential electrodes and lithium metal. Hence, significant research effort must be directed towards developing novel fast Li⁺ conductors as electrolytes in all-solid-state lithium batteries. Among the reported inorganic solid Li⁺ conductive oxides, garnet-like structural compounds received considerable attention in recent times for potential application as electrolytes in all-solid-state lithium batteries. The focus of this review is to provide comprehensive overview towards the importance of solid fast lithium ion conductors, advantages of lithium garnets over other ceramic lithium ion conductors and understanding different strategies on synthesis of lithium garnets. Attempts have also been made to understand relationship between the structure, Li⁺ conduction and Li⁺ dynamics of lithium garnets. The status of lithium garnets as solid electrolyte in electrochemical devices like all-solid state lithium battery, lithium-air battery and sensor are also discussed.     

Performance Evaluation of Composite Electrolyte with GQD for All-Solid-State Lithium Batteries

The use a stabilized lithium structure as cathode material for batteries could be a fundamental alternative in the development of next-generation energy storage devices. However, the lithium structure severely limits battery life causes safety concerns due to the growth of lithium (Li) dendrites during rapid charge/discharge cycles. Solid electrolytes, which are used in high-density energy storage devices and avoid the instability of liquid electrolytes, can be a promising alternative for next-generation batteries. Nevertheless, poor lithium ion conductivity and structural defects at room temperature have been pointed out as limitations. In this study, through the application of a low-dimensional graphene quantum dot (GQD) layer structure, stable operation characteristics were demonstrated based on Li⁺ ion conductivity and excellent electrochemical performance. Moreover, the device based on the modified graphene quantum dots (GQDs) in solid state exhibited retention properties of 95.3% for 100 cycles at 0.5 C and room temperature (RT). Transmission electron microscopy analysis was performed to elucidate the Li⁺ ion action mechanism in the modified GQD/electrolyte heterostructure. The low-dimensional structure of the GQD-based solid electrolyte has provided an important strategy for stably-scalable solid-state lithium battery applications at room temperature. It was demonstrated that lithiated graphene quantum dots (Li-GQDs) inhibit the growth of Li dendrites by regulating the modified Li⁺ ion flux during charge/discharge cycling at current densities of 2.2–5.5 mA cm, acting as a modified Li diffusion heterointerface. A full Li GQD-based device was fabricated to demonstrate the practicality of the modified Li structure using the Li–GQD hetero-interface. This study indicates that the low-dimensional carbon structure in Li–GQDs can be an effective approach for stabilization of solid-state Li matrix architecture.     

Converting Nafion into Li+-Conductive Nanoporous Materials

Sulfonated polymers have long been used as proton-conducting materials in fuel cells, and their ionic transport features are highly attractive for electrolytes in lithium-ion/metal batteries (LIBs/LMBs). However, most studies are still based on a preconceived notion of using them directly as polymeric ionic carriers, which precludes exploring them as nanoporous media to construct efficient lithium ions (Li⁺) transport network. Here, effective Li⁺-conducting channels realized by swelling nanofibrous Nafion is demonstrated, which is a classical sulfonated polymer in fuel cells. The sulfonic acid groups, interact with LIBs liquid electrolytes to form porous ionic matrix of Nafion and assist partial desolvation of Li⁺-solvates to further enhance Li⁺ transport. Li-symmetric cells and Li-metal full cells (Li₄Ti₅O₁₂ or high-voltage LiNi_0.6Co_0.2Mn_0.2O₂ as a cathode) with such membrane show excellent cycling performance and stabilized Li-metal anode. The finding provides a strategy to convert the vast sulfonated polymer family into efficient Li⁺ electrolyte, promoting the development of high-energy–density LMBs.     

A Single-Ion Conducting Borate Network Polymer as a Viable Quasi-Solid Electrolyte for Lithium Metal Batteries

Lithium-ion batteries have remained a state-of-the-art electrochemical energy storage technology for decades now, but their energy densities are limited by electrode materials and conventional liquid electrolytes can pose significant safety concerns. Lithium metal batteries featuring Li metal anodes, solid polymer electrolytes, and high-voltage cathodes represent promising candidates for next-generation devices exhibiting improved power and safety, but such solid polymer electrolytes generally do not exhibit the required excellent electrochemical properties and thermal stability in tandem. Here, an interpenetrating network polymer with weakly coordinating anion nodes that functions as a high-performing single-ion conducting electrolyte in the presence of minimal plasticizer, with a wide electrochemical stability window, a high room-temperature conductivity of 1.5 × 10⁻⁴ S cm⁻¹, and exceptional selectivity for Li-ion conduction (t_Li+ = 0.95) is reported. Importantly, this material is also flame retardant and highly stable in contact with lithium metal. Significantly, a lithium metal battery prototype containing this quasi-solid electrolyte is shown to outperform a conventional battery featuring a polymer electrolyte.     

Polymer electrolytes and interfaces in solid-state lithium metal batteries

The polymer electrolyte based solid-state lithium metal batteries are the promising candidate for the high-energy electrochemical energy storage with high safety and stability. Moreover, the intrinsic properties of polymer electrolytes and interface contact between electrolyte and electrodes have played critical roles for determining the comprehensive performances of solid-state lithium metal batteries. In this review, the development of polymer electrolytes with the design strategies by functional units adjustments are firstly discussed. Then the interfaces between polymer electrolyte and cathode/anode, including the interface issues, remedy strategies for stabilizing the interface contact and reducing resistances, and the in-situ polymerization method for enhancing the compatibilities and assembling the batteries with favorable performances, have been introduced. Lastly, the perspectives on developing polymer electrolytes by functional units adjustment, and improving interface contact and stability by effective strategies for solid-state lithium metal batteries have been provided.     

A closed-host bi-layer dense/porous solid electrolyte interphase for enhanced lithium-metal anode stability

Thanks to its high specific capacity and low electrochemical potential, lithium metal is an ideal anode for next-generation high-energy batteries. However, the unstable heterogeneous surface of lithium gives rise to safety and efficiency concerns that prevent it from being utilized in practical applications. In this work, the formation of a closed-host bi-layer solid electrolyte interphase (SEI) improves the stability of lithium metal anode. This is successfully realized by forming an interconnected porous LiF-rich artificial SEI in contact with Li metal, and a dense, stable in-situ formed upper layer SEI. The porous layer increases the number of Li/LiF interfaces, which reduces local volume fluctuations and improves Li⁺ diffusion along these interfaces. Additionally, the tortuous porous structure guides uniform Li⁺ flux distribution and mechanically suppresses dendrite propagation. The dense upper layer of the SEI accomplishes a closed-host design, preventing continuous consumption of active materials. The duality of a dense top layer with porous bottom layer led to extended cycle life and improved rate performance, evidenced with symmetric cell testing, as well as full cell testing paired with sulfur and LiFePO₄ (LFP) cathodes. This work is a good example of a rational design of the SEI, based on comprehensive consideration of various critical factors to improve Li-metal anode stability, and highlights a new pathway to improve cycling and rate performances of Li metal batteries.     

Weak-Coordination Electrolyte Enabling Fast Li+ Transport in Lithium Metal Batteries at Ultra-Low Temperature

Lithium metal batteries (LMBs) are promising for next-generation high-energy-density batteries owing to the highest specific capacity and the lowest potential of Li metal anode. However, the LMBs are normally confronted with drastic capacity fading under extremely cold conditions mainly due to the freezing issue and sluggish Li⁺ desolvation process in commercial ethylene carbonate (EC)-based electrolyte at ultra-low temperature (e.g., below −30 °C). To overcome the above challenges, an anti-freezing carboxylic ester of methyl propionate (MP)-based electrolyte with weak Li⁺ coordination and low-freezing temperature (below −60 °C) is designed, and the corresponding LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathode exhibits a higher discharge capacity of 84.2 mAh g⁻¹ and energy density of 195.0 Wh kg⁻¹_cathode than that of the cathode (1.6 mAh g⁻¹ and 3.9 Wh kg⁻¹_cathode) working in commercial EC-based electrolytes for NCM811‖ Li cell at −60 °C. Molecular dynamics simulation, Raman spectra, and nuclear magnetic resonance characterizations reveal that rich mobile Li⁺ and the unique solvation structure with weak Li⁺ coordination are achieved in MP-based electrolyte, which collectively facilitate the Li⁺ transference process at low temperature. This work provides fundamental insights into low-temperature electrolytes by regulating solvation structure, and offers the basic guidelines for the design of low-temperature electrolytes for LMBs.     

Tuning the Anode–Electrolyte Interface Chemistry for Garnet-Based Solid-State Li Metal Batteries

Lithium (Li) metal is a promising candidate as the anode for high-energy-density solid-state batteries. However, interface issues, including large interfacial resistance and the generation of Li dendrites, have always frustrated the attempt to commercialize solid-state Li metal batteries (SSLBs). Here, it is reported that infusing garnet-type solid electrolytes (GSEs) with the air-stable electrolyte Li₃PO₄ (LPO) dramatically reduces the interfacial resistance to ≈1 Ω cm² and achieves a high critical current density of 2.2 mA cm⁻² under ambient conditions due to the enhanced interfacial stability to the Li metal anode. The coated and infused LPO electrolytes not only improve the mechanical strength and Li-ion conductivity of the grain boundaries, but also form a stable Li-ion conductive but electron-insulating LPO-derived solid-electrolyte interphase between the Li metal and the GSE. Consequently, the growth of Li dendrites is eliminated and the direct reduction of the GSE by Li metal over a long cycle life is prevented. This interface engineering approach together with grain-boundary modification on GSEs represents a promising strategy to revolutionize the anode–electrolyte interface chemistry for SSLBs and provides a new design strategy for other types of solid-state batteries.     

Carbonized Polymer Dots with Controllable N,O Functional Groups as Electrolyte Additives to Achieve Stable Li Metal Batteries

Electrolyte additive is an effective strategy to inhibit the uncontrolled growth of Li dendrites for lithium metal batteries (LMBs). However, most of the additives are complex synthesis and prone to decompose in cycling. Herein, in order to guide the homogeneous deposition of Li⁺, carbonized polymer dots (CPDs) as electrolyte additives are successfully designed and synthesized by microwave (M-CPDs) and hydrothermal (H-CPDs) approaches. The controllable functional groups containing N or O (especially pyridinic-N, pyrrolic-N, and carboxyl group) enable CPDs to keep stable in electrolytes for at least 3 months. Meanwhile, the clusters formed between CPDs and Li⁺ through electrostatic interaction effectively guide the uniform Li dispersion and limit the “tip effect” and dendrite formation. Moreover, as lithiophilic groups increase, the strong electrostatic interference for the solvation effect of Li⁺ in the electrolyte is formed, which induces faster Li⁺ diffusion/transfer. As expected, H-CPDs achieve the ultra-even Li⁺ transfer. The corresponding Li//LiFePO₄ full cell delivers a high capacity retention rate of 93.8% after 200 cycles, which is much higher than that of the cells without additives (61.2%) and with M-CPDs (83.7%) as additives. The strategy in this work provides a theoretical direction for CPDs as electrolyte additives used in energy storage devices.     

Composition Modulation and Structure Design of Inorganic‐in‐Polymer Composite Solid Electrolytes for Advanced Lithium Batteries

Owing to their safety, high energy density, and long cycling life, all‐solid‐state lithium batteries (ASSLBs) have been identified as promising systems to power portable electronic devices and electric vehicles. Developing high‐performance solid‐state electrolytes is vital for the successful commercialization of ASSLBs. In particular, polymer‐based composite solid electrolytes (PCSEs), derived from the incorporation of inorganic fillers into polymer solid electrolytes, have emerged as one of the most promising electrolyte candidates for ASSLBs because they can synergistically integrate many merits from their components. The development of PCSEs is summarized. Their major components, including typical polymer matrices and diverse inorganic fillers, are reviewed in detail. The effects of fillers on their ionic conductivity, mechanical strength, thermal/interfacial stability and possible Li⁺‐conductive mechanisms are discussed. Recent progress in a number of rationally constructed PCSEs by compositional and structural modulation based on different design concepts is introduced. Successful applications of PCSEs in various lithium‐battery systems including lithium–sulfur and lithium–gas batteries are evaluated. Finally, the challenges and future perspectives for developing high‐performance PCSEs are proposed.     

Modulating Ionic Transport and Interface Chemistry via Surface-Modified Silica Carrier in Nano Colloid Electrolyte for Stable Cycling of Li-Metal Batteries

Tailoring the Li⁺ microenvironment is crucial for achieving fast ionic transfer and a mechanically reinforced solid–electrolyte interphase (SEI), which administers the stable cycling of Li-metal batteries (LMBs). Apart from traditional salt/solvent compositional tuning, this study presents the simultaneous modulation of Li⁺ transport and SEI chemistry using a citric acid (CA)-modified silica-based colloidal electrolyte (C-SCE). CA-tethered silica (CA-SiO₂) can render more active sites for attracting complex anions, leading to further dissociation of Li⁺ from the anions, resulting in a high Li⁺ transference number (≈0.75). Intermolecular hydrogen bonds between solvent molecules and CA-SiO₂ and their migration also act as nano-carrier for delivering additives and anions toward the Li surface, reinforcing the SEI via the co-implantation of SiO₂ and fluorinated components. Notably, C-SCE demonstrated Li dendrite suppression and improved cycling stability of LMBs compared with the CA-free SiO₂ colloidal electrolyte, hinting that the surface properties of the nanoparticles have a huge impact on the dendrite-inhibiting role of nano colloidal electrolytes.     

Double‐Layer Polymer Electrolyte for High‐Voltage All‐Solid‐State Rechargeable Batteries

No single polymer or liquid electrolyte has a large enough energy gap between the empty and occupied electronic states for both dendrite‐free plating of a lithium‐metal anode and a Li⁺ extraction from an oxide host cathode without electrolyte oxidation in a high‐voltage cell during the charge process. Therefore, a double‐layer polymer electrolyte is investigated, in which one polymer provides dendrite‐free plating of a Li‐metal anode and the other allows a Li⁺ extraction from an oxide host cathode without oxidation of the electrolyte in a 4 V cell over a stable charge/discharge cycling at 65 °C; a poly(ethylene oxide) polymer contacts the lithium‐metal anode and a poly(N‐methyl‐malonic amide) contacts the cathode. All interfaces of the flexible, plastic electrolyte remain stable with no visible reduction of the Li⁺ conductivity on crossing the polymer/polymer interface.     

Simultaneous High Ionic Conductivity and Lithium-Ion Transference Number in Single-Ion Conductor Network Polymer Enabling Fast-Charging Solid-State Lithium Battery

Developing solid-state electrolyte with sufficient ionic conduction and flexible-intimate interface is vital to advance fast-charging solid-state lithium batteries. Solid polymer electrolyte yields the promise of interfacial compatibility, yet its critical bottleneck is how to simultaneously achieve high ionic conductivity and lithium-ion transference number. Herein, single-ion conducting network polymer electrolyte (SICNP) enabling fast charging is proposed to positively realize fast lithium-ion locomotion with both high ionic conductivity of 1.1 × 10⁻³ S cm⁻¹ and lithium-ion transference number of 0.92 at room temperature. Experimental characterization and theoretical simulations demonstrate that the construction of polymer network structure for single-ion conductor not only facilitates fast hopping of lithium ions for boosting ionic kinetics, but also enables a high dissociation level of the negative charge for lithium-ion transference number close to unity. As a result, the solid-state lithium batteries constructed by coupling SICNP with lithium anodes and various cathodes (e.g., LiFePO₄, sulfur, and LiCoO₂) display impressive high-rate cycling performance (e.g., 95% capacity retention at 5 C for 1000 cycles in LiFePO₄|SICNP|lithium cell) and fast-charging capability (e.g., being charged within 6 min and discharged over than 180 min in LiCoO₂|SICNP|lithium cell). Our study provides a prospective direction for solid-state electrolyte that meets the lithium-ion dynamics for practical fast-charging solid-state lithium batteries.