A Decade of Progress on Solid-State Electrolytes for Secondary Batteries: Advances and Contributions

Compared with conventional liquid batteries, all-solid-state batteries (ASSBs) show great promise for enabling higher safety in electric vehicles without compromising operational durability and range. As a key component of ASSBs, solid-state electrolytes (SSEs) need high ionic conductivity and favorable interfacial compatibility between electrodes and SSEs. In the recent decade, numerous efforts have been devoted to SSE advancement and fruitful achievements have been made, particularly regarding metal anode-oriented SSEs with high energy density. This review focuses on the historical process of SSEs employed in ASSBs. The new understanding and origins for the enhanced ionic conductivity and mechanical properties of SSEs are first summarized. As to the cathode/SSE interface, its decomposition mechanism and modification strategies are analyzed. As to the interfacial issues of SSEs with anodes, the mechanisms of dendrite formation and penetration into the SSEs are discussed in detail. Additionally, assisted by a library of big data sources, contributions are systematically highlighted from different countries, institutions, and corresponding authors to significantly advance SSE progress, and certain insights are provided into the underlying relationships between various items in a collective manner. Finally, current challenges and potential strategies are identified for the future development of SSEs in ASSBs.     

Enabling High-Performance NASICON-Based Solid-State Lithium Metal Batteries Towards Practical Conditions

Solid-state lithium metal batteries (SSLMBs) are promising next-generation high-energy rechargeable batteries. However, the practical energy densities of the reported SSLMBs have been significantly overstated due to the use of thick solid-state electrolytes, thick lithium (Li) anodes, and thin cathodes. Here, a high-performance NASICON-based SSLMB using a thin (60 µm) Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) electrolyte, ultrathin (36 µm) Li metal, and high-loading (8 mg cm⁻²) LiFePO₄ (LFP) cathode is reported. The thin and dense LAGP electrolyte prepared by hot-pressing exhibits a high Li ionic conductivity of 1 × 10⁻³ S cm⁻¹ at 80 °C. The assembled SSLMB can thus deliver an increased areal capacity of ≈1 mAh cm⁻² at C/5 with a high capacity retention of ≈96% after 50 cycles under 80 °C. Furthermore, it is revealed by synchrotron X-ray absorption spectroscopy and in situ high-energy X-ray diffraction that the side reactions between LAGP electrolyte and LFP cathode are significantly suppressed, while rational surface protection is required for Ni-rich layered cathodes. This study provides valuable insights and guidelines for the development of high-energy SSLMBs towards practical conditions.     

Advanced Electrolytes Enabling Safe and Stable Rechargeable Li-Metal Batteries: Progress and Prospects

Rechargeable Li-metal batteries (RLBs) can boost energy yet possess poor cycle stability and safety concerns when utilizing carbonate electrolytes. Countless effort has been invested in researching and developing electrolytes for RLBs to obtain stable and safe batteries. However, only few existing electrolytes meet the requirements for practical RLBs. In this perspective, the challenges of organic liquid electrolytes in the application in RLBs are summarized, and requirements for electrolytes for practical RLBs are proposed. This perspective briefly reviews the recent achievements of electrolytes (liquid- and solid-state) for RLBs and analyzes the corresponding drawbacks of each electrolyte. Further, possible solutions to the existing shortcomings of various electrolytes are proposed. In particular, this perspective outlines the development strategy of in situ gelation electrolytes, accompanied by a call for people using pouch cells to evaluate performance and paying more attention to battery safety research. This perspective aims to expound on the challenges and the possible research directions of RLBs electrolytes to promote practical RLBs better.     

Polyether-b-Amide Based Solid Electrolytes with Well-Adhered Interface and Fast Kinetics for Ultralow Temperature Solid-State Lithium Metal Batteries

Solid-state lithium metal batteries (SSLMBs) are highly desirable for energy storage because of the urgent need for higher energy density and safer batteries. However, it remains a critical challenge for stable cycling of SSLMBs at low temperature. Here, a highly viscoelastic polyether-b-amide (PEO-b-PA) based composite solid-state electrolyte is proposed through a one-pot melt processing without solvent to address this key process. By adjusting the molar ratio of PEO-b-PA to lithium bis(trifluoromethanesulphonyl)imide (ethylene oxide:Li = 6:1) and adding 20 wt.% succinonitrile, fast Li⁺ transport channel is conducted within the homogeneous polymer electrolyte, which enables its application at ultra-low temperature (−20 to 25 °C). The composite solid-state electrolyte utilizes dynamic hydrogen-bonding domains and ion-conducting domains to achieve a low interfacial charge transfer resistance (<600 Ω) at −20 °C and high ionic conductivity (25 °C, 3.7 × 10⁻⁴ S cm⁻¹). As a result, the LiFePO₄|Li battery based on composite electrolyte exhibits outstanding electrochemical performance with 81.5% capacity retention after 1200 cycles at −20 °C and high discharge specific capacities of 141.1 mAh g⁻¹ with high loading (16.1 mg cm⁻²) at 25 °C. Moreover, the solid-state SNCM811|Li cell achieves excellent safety performance under nail penetration test, showing great promise for practical application.     

Challenges and Prospects of All-Solid-State Electrodes for Solid-State Lithium Batteries

In the development of all-solid-state lithium batteries (ASSLB), progress is made with solid-state electrolytes; however, challenges regarding compatibility and stability still exist with solid electrodes. These issues result in a low battery capacity and short cycle life, which limit the commercial application of ASSLBs. This review summarizes the recent research progress on solid-state electrodes in ASSLBs including the solid–solid interface phenomena such as the interface between electrode materials and electrolytes. The mechanical stability problems in solid electrodes, including fracture, brittleness, and deformation of electrode materials, are also discussed, and corresponding methods to measure the solid electrode stress are provided. In addition, strategies for mitigating stress-related issues are examined. Finally, the fabrication process of solid electrodes is introduced and their future developments, including the exploration of new electrode materials and the design of more intelligent electrode structures, are proposed.     

A Review on the Status and Challenges of Cathodes in Room-Temperature Na-S Batteries

The cathode materials for sodium-sulfur batteries have attracted great attention since cathode is one of the important components of the sodium-sulfur battery, and there are cathode materials that have high capacity, non-toxicity, and cost-efficiency. Nevertheless, due to their low Coulombic efficiency and proneness to cycling decay, the practical application of the sodium–sulfur battery has always been suppressed. In terms of the responsibility of these problems, the polysulfide shuttle and the sluggish kinetics are the main culprits. To address these issues, impeding the notorious reaction between polysulfide intermediates on the cathode and improve the kinetics reaction on the anode are extremely important. Herein, a comprehensive review is prepared of different approaches to increasing the electrochemical performance and strengthening the stability of cathodes. The influences of various choices and the consequent properties of the cathode in relation to the whole sodium–sulfur battery performance is investigated. Finally, the current research challenges related to cathodes for sodium–sulfur batteries and future perspectives are also discussed.     

A Hetero-Layered,Mechanically Reinforced,Ultra-Lightweight Composite Polymer Electrolyte for Wide-Temperature-Range,Solid-State Sodium Batteries

The practical use of polyethylene oxide polymer electrolyte in the solid-state sodium metallic batteries (SSMBs) suffers from the retard Na⁺ diffusion at the room temperature, mechanical fragility as well as the oxidation tendency at high voltages. Herein, a hetero-layered composite polymeric electrolyte (CPE) is proposed to enable the simultaneous interfacial stability with the high voltage cathodes (till 4.2 V) and Na metallic anode. Being incorporated within the polymer matrix, the sand-milled Na₃Zr₂Si₂PO₁₂ nanofillers and nanocellulose scaffold collectively endow the thin-layer (25 µm), ultralightweight (1.65 mg cm⁻²) CPE formation with an order of magnitude enhancement of the mechanical strength (13.84 MPa) and ionic conductivity (1.62 × 10⁻⁴ S cm⁻¹) as compared to the pristine polymer electrolyte, more importantly, the improved dimension stability up to 180 °C. Upon the integration of the hetero-layered CPE with the iron hexacyanoferrate FeHCF cathode (1 mAh cm⁻²) and the Na foil, the cell model can achieve the room-temperature cycling stability (93.73% capacity retention for 200 cycles) as well as the high temperature tolerance till 80 °C, which inspires a quantum leap toward the surface-wetting-agent-free, energy-dense, wide-temperature-range SSMB prototyping.     

A Trip to Oz and a Peak Behind the Curtain of Magnesium Batteries

The introduction of the Li‐ion battery has revolutionized the electronics industry due to its high energy density. Magnesium batteries may have the potential to exceed the energy densities of Li‐ion batteries. Herein, the major advancements in magnesium electrochemistry and the challenges that must be overcome to realize a practical magnesium battery are discussed. So too are the controversial realities of current magnesium battery research and their implications.     

High-Performance All-Solid-State Batteries Enabled by Intimate Interfacial Contact Between the Cathode and Sulfide-Based Solid Electrolytes

All-solid-state batteries (ASSBs) are considered the ultimate next-generation rechargeable batteries due to their high safety and energy density. However, poor Li-ion kinetics caused by the inhomogeneous distribution of the solid electrolytes (SEs) and complex chemo-mechanical behaviors lead to poor electrochemical properties. In this study, LiNi_0.8Co_0.1Mn_0.1O₂ (NCM) (core) – Li₆PS₅Cl (LPSCl) SEs (shell) particles (NCM@LPSCl) are prepared by a facile mechano-fusion method to improve the electrochemical properties and increase the energy density of ASSBs. The conformally coated thin SEs layer on the surface of NCM enables homogeneous distribution of SEs in overall electrode and intimate physical contact with cathode material even under volume change of cathode material during cycling, which leads to the improvement in Li-ion kinetics without the increase in solid electrolyte content. As a result, an ASSBs employing NCM@LPSCl with 4 mAh cm⁻¹ specific areal capacity exhibits robust electrochemical properties, including the improved reversible capacity (163.1 mAh g⁻¹), cycle performance (90.0% after 100 cycles), and rate capability (discharge capacity of 152.69, 133.80, and 100.97 mAh g⁻¹ at 0.1, 0.2, and 0.5 C). Notably, ASSBs employing NCM@LPSCl composite show reliable electrochemical properties with a high weight fraction of NCM (87.3 wt%) in the cathode.     

Elastic Interfacial Layer Enabled the High-Temperature Performance of Lithium-Ion Batteries via Utilization of Synthetic Fluorosulfate Additive

The key to producing high-energy Li-ion cells is ensuring the interfacial stability of Si-containing anodes and Ni-rich cathodes. Herein, 4-(allyloxy)phenyl fluorosulfate (APFS), a multi-functional electrolyte additive that forms a mechanical strain-adaptive solid electrolyte interphase (SEI) comprising LiF and polymeric species, and a thermally stable cathode–electrolyte interface containing S O and S F species. The radical copolymerization of vinylene carbonate (VC) with APFS via electrochemical initiation creates a spatially deformable polymeric SEI on the SiG-C (30 wt.% graphite + 70 wt.% SiC composite) anode, with large volume changes during cycling. Moreover, the APFS-promoted interfacial layers reduce Ni dissolution and deposition. Furthermore, APFS deactivates the Lewis acid PF₅, thereby inhibiting hydrolyses that produce unwanted HF. These results indicate that the combined use of VC with APFS allows capacity retentions of 72.5% with a high capacity of 143.5 mAh g⁻¹ in SiG-C/LiNi_0.8Co_0.1Mn_0.1O₂ full cells after 300 cycles at 45 °C.     

Critical Current Density in Solid-State Lithium Metal Batteries: Mechanism,Influences, and Strategies

Solid-state lithium (Li) metal batteries (SSLMBs) have become a research hotspot in the energy storage field due to the much-enhanced safety and high energy density. However, the SSLMBs suffer from failures including dendrite-induced short circuits and contact-loss-induced high impedance, which are highly related to the Li plating/stripping kinetics and hinder the practical application of SSLMBs. The maximum endurable current density of lithium battery cycling without cell failure in SSLMB is generally defined as critical current density (CCD). Therefore, CCD is an important parameter for the application of SSLMBs, which can help to determine the rate-determining steps of Li kinetics in solid-state batteries. Herein, the theoretical and practical meanings for CCD from the fundamental thermodynamic and kinetic principles, failure mechanisms, CCD identifications, and influence factors for improving CCD performances are systematically reviewed. Based on these fundamental understandings, a series of strategies and outlooks for future researches on SSLMB are presented, endeavoring on increasing CCD for practical SSLMBs.     

Overcoming Anode Instability in Solid-State Batteries through Control of the Lithium Metal Microstructure

Enabling the lithium metal anode (LMA) in solid-state batteries (SSBs) is the key to developing high energy density battery technologies. However, maintaining a stable electrode–electrolyte interface presents a critical challenge to high cycling rate and prolonged cycle life. One such issue is the interfacial pore formation in LMA during stripping. To overcome this, either higher stack pressure or binary lithium alloy anodes are used. Herein, it is shown that fine-grained (d = 20 µm) polycrystalline LMA can avoid pore formation by exploiting the microstructural dependence of the creep rates. In a symmetric cell set-up, i.e., LiǀLi_6.25Al_0.25La₃Zr₂O₁₂(LLZO)ǀLi, fine-grained LMA achieves > 11.0 mAh cm⁻² compared to ≈ 3.6 mAh cm⁻² for coarse-grained LMA (d = 295 µm) at 0.1 mA cm⁻² and at moderate stress of 2.0 MPa. Smaller diffusion lengths (≈ 20 µm) and higher diffusivity pathway along dislocations (D_d ≈ 10⁻⁷ cm² s⁻¹), generated during cell fabrication, result in enhanced viscoplastic deformation in fine-grained polycrystalline LMA. The electrochemical performances corroborate well with estimated creep rates. Thus, microstructural control of LMA can significantly reduce the required stack pressure during stripping. These results are particularly relevant for “anode-free” SSBs wherein both the microstructure and the mechanical state of the lithium are critical parameters.     

A Stable Polymer-based Solid-State Lithium Metal Battery and its Interfacial Characteristics Revealed by Cryogenic Transmission Electron Microscopy

Solid-state lithium metal batteries (SSLMBs) are a promising candidate for next-generation energy storage systems due to their intrinsic safety and high energy density. However, they still suffer from poor interfacial stability, which can incur high interfacial resistance and insufficient cycle lifespan. Herein, a novel poly(vinylidene fluoride‑hexafuoropropylene)-based polymer electrolyte (PPE) with LiBF₄ and propylene carbonate plasticizer is developed, which has a high room-temperature ionic conductivity up to 1.15 × 10⁻³ S cm⁻¹ and excellent interfacial stability. Benefitting from the stable interphase, the PPE-based symmetric cell can operate for over 1000 h. By virtue of cryogenic transmission electron microscopy (Cryo-TEM) characterization, the high interfacial compatibility between Li metal anode and PPE is revealed. The solid electrolyte interphase is made up of an amorphous outer layer that can keep intimate contact with PPE and an inner Li₂O-dominated layer that can protect Li from continuous side reactions during battery cycling. A LiF-rich transition layer is also discovered in the region of PPE close to Li metal anode. The feasibility of investigating interphases in polymer-based solid-state batteries via Cryo-TEM techniques is demonstrated, which can be widely employed in future to rationalize the correlation between solid-state electrolytes and battery performance from ultrafine interfacial structures.     

Fluoride-Rich Solid-Electrolyte-Interface Enabling Stable Sodium Metal Batteries in High-Safe Electrolytes

Sodium metal batteries (SMBs) are promising for large scale energy storage due to the remarkable capacity of sodium metal anode (SMA) and the natural abundance of Na-containing resources. However, multiple challenges exist with regards to the usage of SMBs, including dendritic Na growth, poor cyclability of SMA, and severe safety hazards stemming from the employment of the highly flammable liquid electrolytes. Herein, by introducing two functional fluorinated solvents, 1,1,2,2-tetra-fluoroethyl 2,2,3,3-tetrafluoropropyl ether (HFE) and fluoroethylene carbonate (FEC) into trimethyl phosphate (TMP)-based electrolyte, a SMA-compatible flame-retardant electrolyte is enabled, in which Na/Na symmetrical cells can cycle for 800 h at 1.0 mA cm⁻² or 3.0 mAh cm⁻². Specifically, the non-solvating HFE plays a critical role in increasing the local electrolyte concentration and reducing the unfavorable decomposition of TMP molecules. By introducing FEC as the co-solvent simultaneously, its preferential defluorination induces a fluoride-rich solid-electrolyte interphase that prevents Na metal surface against the continuous parasitic reactions. More importantly, the designed electrolyte is endowed with an intrinsic non-flammability, which manifests a prerequisite for the real-life application of SMBs.     

Incombustible Polymer Electrolyte Boosting Safety of Solid-State Lithium Batteries: A Review

Lithium-ion batteries with their portability, high energy density, and reusability are frequently used in today's world. Under extreme conditions, lithium-ion batteries leak, burn, and even explode. Therefore, improving the safety of lithium-ion batteries has become a focus of attention. Researchers believe using a solid electrolyte instead of a liquid one can solve the lithium battery safety issue. Due to the low price, good processability and high safety of the solid polymer electrolytes, increasing attention have been paid to them. However, polymer electrolytes can also decompose and burn under extreme conditions. Moreover, lithium dendrites are formed continuously due to the uneven charge distribution on the surface of the lithium metal anode. A short circuit caused by a lithium dendrite can cause the battery to thermal runaway. As a result, the safety of polymer solid-state batteries remains a challenge. In this review, the thermal runaway mechanism of the batteries is summarized, and the batteries abuse test standard is introduced. In addition, the recent works on the high-safety polymer electrolytes and the solution strategies of lithium anode problems in polymer batteries are reviewed. Finally, the development direction of safe polymer solid lithium batteries is prospected.     

Dynamic Supramolecular Polymer Electrolyte to Boost Ion Transport Kinetics and Interfacial Stability for Solid-State Batteries

The key hurdle to the practical application of polymeric electrolytes in high-energy-density solid lithium-metal batteries is the sluggish Li⁺ mobility and inferior electrode/electrolyte interfacial stability. Herein, a dynamic supramolecular polymer electrolyte (SH-SPE) with loosely coordinating structure is synthesized based on poly(hexafluoroisopropyl methacrylate-co-N-methylmethacrylamide) (PHFNMA) and single-ion lithiated polyvinyl formal. The weak anti-cooperative H-bonds between the two polymers endow SH-SPE with a self-healing ability and improved toughness. Meanwhile, the good flexibility and widened energy gap of PHFNMA enable SH-SPE with efficient ion transport and superior interfacial stability in high-voltage battery systems. As a result, the as-prepared SH-SPE exhibits an ionic conductivity of 2.30 × 10⁻⁴ S cm⁻¹, lithium-ion transference number of 0.74, electrochemical stability window beyond 4.8 V, and tensile strength up to 11.9 MPa as well as excellent adaptability with volume change of the electrodes. In addition, no major electrolyte decomposition inside batteries made from SH-SPE and LiNi_0.8Mn_0.1Co_0.1O₂ cathode can be observed in the in situ differential electrochemical mass spectrometry test. This study provides a new methodology for the macromolecular design of polymer electrolytes to address the interfacial issues in high-voltage solid batteries.     

Dendrite-Free and Long-Cycling Sodium Metal Batteries Enabled by Sodium-Ether Cointercalated Graphite Anode

Stable and dendrite-free Na metal plating–stripping is achieved on the graphite electrode. The sodium-ether cointercalated graphite exhibits ultrahigh Na deposition efficiency of 99.86% over 900 cycles at a current density of 2 mA cm⁻². The discharge process involves the [Na-ether]⁺ cointercalation and Na deposition. Density functional theory calculations demonstrate that the cointercalated graphite is critical for uniform Na deposition and stable Coulombic efficiency, which is ascribed to both the robust binding sites to Na by the diglyme molecules and a low lattice mismatch for Na growth on the cointercalated graphite. Also, a full cell consisting of Na₄Fe₃(PO₄)₂(P₂O₇) cathode and 0.5 mAh cm⁻² Na predeposited graphite anode shows excellent cycling stability. The full cell delivers a capacity of 95 mAh g⁻¹ based on the weight of cathode materials, with a high capacity retention of 91% over 300 cycles.     

Advances and Prospects in Improving the Utilization Efficiency of Lithium for High Energy Density Lithium Batteries

Lithium-ion batteries have attracted much attention in the field like portable devices and electronic vehicles. Due to growing demands of energy storage systems, lithium metal batteries with higher energy density are promising candidates to replace lithium-ion batteries. However, using excess amounts of lithium can lower the energy density and cause safety risks. To solve these problems, it is crucial to use limited amount of lithium in lithium metal batteries to achieve higher utilization efficiency of lithium, higher energy density, and higher safety. The main reasons for the loss of active lithium are the side reactions between electrolyte and electrode, growth of lithium dendrites, and the volume change of electrode materials during the charge and discharge process. Based on these issues, much effort have been put to improve the utilization efficiency of lithium such as mitigating the side reactions, guiding the uniform lithium deposition, and increasing the adhesion between electrolyte and electrode. In this review, strategies for high utilization efficiency of lithium are presented. Moreover, the remaining challenges and the future perspectives on improving the utilization of lithium are also outlined.     

Linking Solid Electrolyte Degradation to Charge Carrier Transport in the Thiophosphate-Based Composite Cathode toward Solid-State Lithium-Sulfur Batteries

Solid-state lithium-sulfur batteries (SSLSBs) have the potential to cause a paradigm shift in energy storage. The use of emerging highly-conductive solid electrolytes enables high energy and power densities. However, the need for an intimate mixture of electrolyte and conductive additives to compensate for the insulating nature of cathode active materials S₈ and Li₂S induces intense electrolyte degradation. Thus, it is paramount to understand better the electrochemical and transport properties of the cathode composite with extremely high interface density among cathode components. Here, by utilizing a ball-milled composite of the lithium argyrodite Li₆PS₅Cl and carbon as a model electrode, the stability, reversibility, and transport in the composite as functions of cathode loading, the volume fraction of conducting phase, temperature, and applied potentials are comprehensively investigated. Comparing the onset potentials of electrolyte degradation and the sharp drop in the effective ionic conductivity of the composite determined through transmission-line model analysis, successful enhancement of the capacity retention of SSLSBs is demonstrated by balancing between the attainable capacity and effective carrier transport, achieving a high areal capacity of 3.68 mAh cm⁻² after 100 cycles at room temperature. The here-observed analysis is applicable to any solid-state composite with electrically insulating active materials.     

A Progress Report on Metal–Sulfur Batteries

Nonaqueous conversion‐reaction sulfur chemistry has been attracting increasing attention over the past decade for the development of next‐generation lithium‐based batteries. Li–S batteries are currently approaching a nexus stage from lab‐scale experiments to possible pragmatic applications. Inspired by the success of Li–S chemistry, other metal–sulfur batteries with a variety of metallic anodes, such as sodium, potassium, magnesium, calcium, and aluminum, have also started to attract attention. In comparison to lithium, Na, Mg, Al, K, and Ca are naturally more abundant and affordable. The Na‐S, Mg‐S, Al‐S, K‐S, and Ca‐S battery systems provide a great potential for improving the volumetric energy density of sulfur‐based batteries. The multivalent metal‐sulfur systems, Mg‐S, Al‐S, and Ca‐S, offer better safety features as well. However, the research and development on Na‐S, Mg‐S, Al‐S, K‐S, and Ca‐S batteries is far behind the Li–S system due to many critical challenges. In this progress report, the fundamental principles of various metal–sulfur chemistries are first presented and compared. Then, the historical progress, recent advances, and key challenges of the Li–S, Na‐S, Mg‐S, Al‐S, K‐S, and Ca‐S systems are summarized and discussed. Finally, future efforts and directions for both the fundamental and practical research are prospected.