Recent Tactics and Advances in the Application of Metal Sulfides as High-Performance Anode Materials for Rechargeable Sodium-Ion Batteries

The successful development of post-lithium technologies depends on two key elements: performance and economy. Because sodium-ion batteries (SIBs) can potentially satisfy both requirements, they are widely considered the most promising replacement for lithium-ion batteries (LIBs) due to the similarity between the electrochemical processes and the abundance of sodium-based resources. Among various SIB anode materials, metal sulfides are most extensively studied as materials for high-performance electrodes due to the versatility of their synthesis procedure, utilization potential, and high sodiation capacity. Herein, some of the most effective strategies aimed at effectively alleviating the performance shortcomings of these materials from the materials engineering/design perspective are summarized. In terms of facilitating ion transport in SIBs, which represents one of the most critical aspects of their performance, a specific family of strategies related to a particular operational mechanism is considered rather than categorizing based-on individual sulfide materials. In the foreseeable future, the development of highly functional SIBs electrode materials and utilization of metal sulfides will become highly relevant due to their stability and performance characteristics. Therefore, it is anticipated that this review will guide further research and facilitate the realization of various applications of sulfide-based high-performance rechargeable batteries.     

Highly Energy-Dissipative,Fast Self-Healing Binder for Stable Si Anode in Lithium-Ion Batteries

A double-wrapped binder has been rationally designed with high Young's modulus polyacrylic acid (PAA) inside and low Young's modulus bifunctional polyurethane (BFPU) outside to address the large inner stress of silicon anode with drastic volume changes during cycling. Harnessing the “hard to soft” gradient distribution strategy, the rigid PAA acts as a protective layer to dissipate the inner stress first during lithiation, while the elastic binder BFPU serves as a buffer layer to disperse residual stress, and thus avoids structural damage of rigid PAA. Moreover, the introduction of BFPU with fast self-healing ability can dynamically recover the microcracks arising from large stress, further ensuring the integrity of silicon anode. This multifunctional binder with smart design of double-wrapped structure provides enlightenment on enlarging the cycling life of high-energy-density lithium-ion batteries that suffer enormous volume change during the cycling process.     

Electrically Coupled Electrolyte Engineering Enables High Interfacial Stability for High-Voltage Sodium-Ion Batteries

Sodium-ion batteries (SIBs) suffer from severe capacity decay as the harmful substances caused by the violent decomposition of electrolyte under high voltages continue to erode the cathodes. Therefore, the design of high-voltage electrolyte and construction of robust cathode–electrolyte interface (CEI) are critical for long-life SIBs. Herein, an electrically coupled composite electrolyte that takes the merits of cross-linked gel polymers and s well-tuned antioxidant additive (4-trifluoromethylphenylboronic acid, TFPBA) is proposed. Through an electrical coupling effect, TFPBA can be anchored by the cross-linked polymer framework to immobilize the PF₆⁻ anion and adsorb onto cathode surface spontaneously, both of which promote the formation of a robust CEI layer to facilitate Na⁺ transportation and suppress subsequent side reactions and corrosive cracking. As a result, the cells integrating high-voltage P2/O3 cathode and well-tailored gel polymer electrolyte achieve stable cycling over 550 cycles within 1.8–4.2 V with a capacity retention of 71.0% and a high-rate discharge capacity of 77.4 mAh g⁻¹ at 5 C. The work paves the way for the development of functionalized quasi-solid electrolyte for practical next generation high-voltage SIBs.     

Low-Cost Zinc Substitution of Iron-Based Prussian Blue Analogs as Long Lifespan Cathode Materials for Fast Charging Sodium-Ion Batteries

Iron-based Prussian blue analogs (Fe-PBAs) are extensively studied as promising cathode materials for rechargeable sodium-ion batteries owing to their high theoretical capacity, low-cost and facile synthesis method. However, Fe-PBAs suffer poor cycle stability and low specific capacity due to the low crystallinity and irreversible phase transition during excess sodium-ion storage. Herein, a modified co-precipitation method to prepare highly crystallized PBAs is reported. By introducing an electrochemical inert element (Zn) to substitute the high-spin Fe in the Fe-PBAs (ZnFeHCF-2), the depth of charge/discharge is rationally controlled to form a highly reversible phase transition process for sustainable sodium-ion storage. Minor lattice distortion and highly reversible phase transition process of ZnFeHCF-2 during the sodium-ions insertion and extraction are proved by in-situ tests, which have significantly impacted the cycling stability. The ZnFeHCF-2 shows a remarkably enhanced cycling performance with capacity retention of 58.5% over 2000 cycles at 150 mA g⁻¹ as well as superior rate performance up to 6000 mA g⁻¹ (fast kinetics). Furthermore, the successful fabrication of the full cell on the as-prepared cathode and commercial hard carbon anode demonstrates their potential as high-performance electrode materials for large-scale energy storage systems.     

Unveiling the Anionic Redox Chemistry in Phosphate Cathodes for Sodium-Ion Batteries

Anionic redox chemistry has aroused increasing attention in sodium-ion batteries (SIBs) by virtue of the appealing additional capacity. However, up to now, anionic redox reaction has not been reported in the mainstream phosphate cathodes for SIBs. Herein, the ultrathin VOPO₄ nanosheets are fabricated as promising cathodes for SIBs, where the oxygen redox reaction is first activated accompanied by reversible ClO₄⁻ (from the electrolyte) insertion/extraction. As a result, the VOPO₄ cathode harvests a record-high capacity (168 mAh g⁻¹ at 0.1 C) among its counterparts ever reported. Moreover, the ClO₄⁻ insertion efficiently expands the interlayer spacing of VOPO₄ and accelerates the ion diffusion, enabling an unprecedentedly high rate performance (69 mAh g⁻¹ at 30 C). Via systematic ex situ characterizations and theoretical computations, the anionic redox chemistry and charge storage mechanism upon cycling are thoroughly elucidated. This study opens up a new avenue toward high-energy phosphate cathodes for SIBs by triggering anionic redox reactions.     

Unleashing the Potential of Sodium-Ion Batteries: Current State and Future Directions for Sustainable Energy Storage

Rechargeable sodium-ion batteries (SIBs) are emerging as a viable alternative to lithium-ion battery (LIB) technology, as their raw materials are economical, geographically abundant (unlike lithium), and less toxic. The matured LIB technology contributes significantly to digital civilization, from mobile electronic devices to zero electric-vehicle emissions. However, with the increasing reliance on renewable energy sources and the anticipated integration of high-energy-density batteries into the grid, concerns have arisen regarding the sustainability of lithium due to its limited availability and consequent price escalations. In this context, SIBs have gained attention as a potential energy storage alternative, benefiting from the abundance of sodium and sharing electrochemical characteristics similar to LIBs. Furthermore, high-entropy chemistry has emerged as a new paradigm, promising to enhance energy density and accelerate advancements in battery technology to meet the growing energy demands. This review uncovers the fundamentals, current progress, and the views on the future of SIB technologies, with a discussion focused on the design of novel materials. The crucial factors, such as morphology, crystal defects, and doping, that can tune electrochemistry, which should inspire young researchers in battery technology to identify and work on challenging research problems, are also reviewed.     

Optimized Cathode for High-Energy Sodium-Ion Based Dual-Ion Full Battery with Fast Kinetics

The most used systems based on the graphite-based cathode show unsatisfactory performance in dual-ion batteries. Developing new type cathode materials with high capacity for new type anions storage is an effective way to improve the total performance of dual-ion batteries. Herein, a protonated polyaniline (P-PANI) cathode is prepared to realize efficient and stable storage of ClO₄^–, and a high reversible capacity of 143 mAh g⁻¹ at 0.2 A g⁻¹ after 200 cycles can be obtained, which is competitive compared with common graphite cathodes. In addition, the highly reversible coordination storage mechanism between ClO₄⁻ and P-PANI cathode is indicated, rather than the labored intercalation reactions between PF₆⁻ and graphite. Subsequently, a full cell (P-PANI//N-PDHC) fabricated with a P-PANI cathode and hard carbon anode (N-PDHC) can deliver a high energy density of 284 Wh kg^–1 for 2000 cycles at 2 A g^–1, and the relevant pouch-type full cell can easily power a smartphone. In general, this work may promote the exploitation of sodium-based dual-ion batteries in practical application.     

Controlling Solvation and Solid-Electrolyte Interphase Formation to Enhance Lithium Interfacial Kinetics at Low Temperatures

Operation of lithium-based batteries at low temperatures (<0 °C) is challenging due to transport limitations as well as sluggish Li⁺ kinetics at the electrode interface. The complicated relationships among desolvation, charge transfer, and transport through the solid electrolyte interphase (SEI) at low temperatures are not well understood, hindering electrolyte development. Here, an ether/hydrofluoroether and fluoroethylene carbonate (FEC)-based ternary solvent electrolyte is developed to improve Li cycling at low temperatures (Coulombic efficiency of 93.3% at -40 °C), and the influence of the local solvation structure on interfacial Li⁺ kinetics and SEI chemistry is further revealed. The hydrofluoroether cosolvent allows for modulation of the solvation structure, thereby enabling facile Li⁺ desolvation while forming an inorganic-rich SEI, which are both beneficial for lowering Li⁺ kinetic barriers at the interface. This cosolvent also increases the oxidative stability of the electrolyte to over 4.0 V versus Li/Li⁺, thereby enabling cycling of NMC-based full cells at −40 °C. This study advances the understanding of the influence of Li⁺ solvation structure, SEI chemistry, and interfacial Li⁺ kinetics on Li electrochemistry at low temperatures, providing new design considerations for creating effective low-temperature electrolyte systems.     

On the Practical Applicability of Rambutan-like SiOC Anode with Enhanced Reaction Kinetics for Lithium-Ion Storage

Silicon oxycarbide (SiOC) possesses great potential in lithium-ion batteries owing to its tunable chemical component, high reversible capacity, and small volume expansion. However, its commercial application is restricted due to its poor electrical conductivity. Herein, rambutan-like vertical graphene coated hollow porous SiOC (Hp-SiOC@VG) spherical particles with an average diameter of 302 nm are fabricated via a hydrothermal treatment combined CH₄ pyrolysis strategy for the first time. As-prepared Hp-SiOC@VG exhibits a large reversible capacity of 729 mAh g⁻¹ at 0.1 A g⁻¹, remarkable cycling stability of 98% capacity retention rate after 600 cycles at 1.0 A g⁻¹ and high rate capability of 289 mAh g⁻¹ at 5.0 A g⁻¹ owing to the unique structure of the particles and the electrical conductivity of the vertical graphene. Density functional theory calculations reveal that the higher contents of SiO₃C and SiO₂C₂ structural units in the SiOC are beneficial to enhance the Li⁺ storage capacity. Additionally, the full-cell assembled with Hp-SiOC@VG and LiFePO₄ delivers up to 74% capacity retention rate after 100 cycles at 0.2 A g⁻¹. This work reports a new way for the facile preparation of template-free hollow porous materials and expands the application prospects of SiOC-based anode for lithium-ion batteries.     

Mn-Rich Phosphate Cathode for Sodium-Ion Batteries: Anion-Regulated Solid Solution Behavior and Long-Term Cycle Life

As a sodium superionic conductor, Mn-rich phosphate of Na_3.4Mn_1.2Ti_0.8(PO₄)₃ is considered as one of the promising cathodes for sodium-ion batteries owing to its good thermodynamic stability and high working voltage. However, Na_3.4Mn_1.2Ti_0.8(PO₄)₃ is faced with low electronic conductivity, poor cycling stability and complex phase transition caused by multi-electron transfers, which limits its practical application. Herein, an anion-regulated strategy is proposed to optimize the Mn-rich Na_3.4Mn_1.2Ti_0.8(PO₄)₃ phosphate cathode. After introducing F anions into the lattice, the rate performance is improved from 60.5 to 72.8 mAh g⁻¹ at 20 C. Ascribed to unique structure design, the reaction kinetics of Na_3.4Mn_1.2Ti_0.8(PO₄)₃ are significantly improved, as demonstrated by cyclic voltammetry at varied scan rates and galvanostatic intermittent titration technique. The generated M-F bond inhibits Jahn–Teller effect with an improved cycle stability (85.8 mAh g⁻¹ after 1000 cycles at 5 C with 94.3% capacity retention). Interestingly, reaction mechanism of Na_3.4Mn_1.2Ti_0.8(PO₄)₃ with the complex two-phase and solid solution reactions changes to the whole solid solution reaction after fluorine substitution, and leads to a smaller volume change of 5.41% during reaction processes, which is verified by in situ X-ray diffraction. This anion regulation strategy provides a new method for designing the high-performance phosphate cathode materials of sodium-ion batteries.     

Mixed-Valence Copper Selenide as an Anode for Ultralong Lifespan Rocking-Chair Zn-Ion Batteries: An Insight into its Intercalation/Extraction Kinetics and Charge Storage Mechanism

Environment-friendly and low-cost aqueous zinc-ion batteries (ZIBs) have received considerable attention for large-scale energy storage. However, the low coulombic efficiency and potential safety hazards of Zn-metal anodes severely hinder their practical implementations. Herein, for the first time, mixed-valence Cu_2−xSe is proposed as a new intercalation anode to construct Zn-metal-free rocking-chair ZIBs with a long lifespan. It is found that the introduction of low-valence Cu not only modify active sites for Zn²⁺ ion storage, but also optimizes the electronic interaction between the active sites and the intercalated Zn²⁺ ion, leading to a favorable intercalation formation energy (−0.68 eV) and reduced diffusion barrier, as demonstrated by first-principles calculation. Ex situ X-ray diffraction, ex situ transmission electron microscopy and galvanostatic intermittent titration technique measurements reveal the reversible insertion/extraction of Zn²⁺ in Cu_2−xSe via an intercalation reaction mechanism. Owing to the rigid host structure and facile Zn²⁺ diffusion kinetics, the Cu_2−xSe nanorod anode shows an enhanced coulombic efficiency (above 99.5%), outstanding rate capability and excellent cycling stability. The as-fabricated Zn_xMnO₂||Cu_2−xSe Zn-ion full battery exhibits an impressive electrochemical performance, particularly an ultralong cycle life of over 20 000 cycles at 2 A g⁻¹. This study is expected to provide new opportunities for developing high-performance rechargeable aqueous ZIBs.     

Stable Cycling of Phosphorus Anode for Sodium‐Ion Batteries through Chemical Bonding with Sulfurized Polyacrylonitrile

Sodium‐ion batteries are attracting increasing interests as a promising alternative to lithium‐ion batteries due to the abundant resource and low cost of sodium. Despite phosphorus (P) has extremely high theoretical capacity of 2595 mAh g^?1, its wide application for sodium‐ion battery is highly hampered by its fast capacity fading and low Coulombic efficiency as a result of large volume change upon cycling. Herein, a robust phosphorus anode with long cycle life for sodium‐ion battery via hybridization with functional conductive polymer is presented. To this end, the polyacrylonitrile is first dehydrogenated by sulfur via a facile thermal treatment, forming a conductive main chain embedded with C–S–S moieties. This functional conductive polymer enables the formation of P? S bonds between phosphorus and functional conductive matrix, leading to a robust electrode that can accommodate the large volume change upon substantial volume change in cycling. Consequently, this hybrid anode delivers a high capacity of ≈1300 mAh g^?1 at a current density of 520 mA g^?1 with high Coulombic efficiency (>99%) and good cycling performance (91% capacity retention after 100 cycles).     

Structure-Performance Relationship of Aromatic Polymer Binder for Silicon Anode in Lithium-Ion Batteries

Polymer binders are essential for Silicon (Si) anode-based lithium-ion batteries (LIBs). However, the synthetic guidance for aromatic polymer binder is relatively less explored compared to aliphatic polymer binders. In this study, polyimide-based aromatic polymer binders are developed that have strong binding affinity with Si particles, a conductive agent and copper (Cu) current collector, and they show an improved initial discharge capacity of 2663 mAh g⁻¹, which is 29% higher than that of Kapton-based one (2071 mAh g⁻¹). The copolymerization between “hard” and “soft” segments is crucial to achieve reversible volume expansion/contraction during the repeated charging/discharging process, resulting in the best cycle performance. The new binder ensures both excellent volume retention after full-delithiation and allowed volume expansion at least to some extent upon full-lithiation. This Study finds a power-law relationship between the capacity of Si anode and the mechanical properties of the binder, i.e., the tensile stress (σ) and strain (ɛ). The initial discharge capacity is proportional to σⁿ · ɛ (n = 2.3–2.7). Such an understanding of the relationships between polymer structure, mechanical properties of the polymer and binder performance clearly revealed the importance of the soft-hard polymer structure for aromatic binders used in Si-based high-capacity lithium storage materials.     

Effective Coupling of Amorphous Selenium Phosphide with High-Conductivity Graphene as Resilient High-Capacity Anode for Sodium-Ion Batteries

It is of great importance to develop high-capacity electrodes for sodium-ion batteries (SIBs) using low-cost and abundant materials, so as to deliver a sustainable technology as alternative to the established lithium-ion batteries (LIBs). Here, a facile ball milling process to fabricate high-capacity SIB anode is devised, with large amount of amorphous SeP being loaded in a well-connected framework of high-conductivity crystalline graphene (HCG). The HCG substrate enables fast transportation of Na ions and electrons, while accommodating huge volumetric changes of the active anode matter of SeP. The strong glass forming ability of NaxSeP helps prevent crystallization of all stable compounds but ultrafine nanocrystals of Na2Se and Na3P. Thus, the optimized anode delivers excellent rate performance with high specific capacities being achieved (855 mAh g⁻¹ at 0.2 A g⁻¹ and 345 mAh g⁻¹ at 5 A g⁻¹). More importantly, remarkable cycling stability is realized to maintain a steady capacity of 732 mAh g⁻¹ over 500 cycles, when the SeP in the SeP@HCG still remains 86% of its theoretical capacity. A high areal capacity of 2.77 mAh is achieved at a very high loading of 4.1 mg cm⁻² anode composite.     

The Restrained Li/Gel Polymer Electrolyte Interface Deterioration Enabled by the Synergetic Effect of Ultra-Lithiophilic Interphase and Interfacial Coupling Skeleton

Quasi-solid-state lithium metal batteries are deemed as one of the most promising next-generation energy storage devices due to their enhanced safety and high energy density. However, the Li/Gel polymer Electrolyte (GPE) interface deterioration induced by the side reactions, dendrite growth during Li plating, and contact loss during Li stripping will inevitably lead to the failure of the battery. Herein, a Li/Li₂₃Sr₆–Li₃N/Sr₂N anode structure (LSN) prepared by hot-rolling process is designed, where Sr₂N serves as an inert skeleton to retain the interfacial coupling and to avoid contact loss. At the same time, the Li₃N–Li₂₃Sr₆ interphase with high Li adsorption energy and fast Li⁺ transfer kinetics regulate the Li plating behavior. Benefitting from the design, when coupled with the carbonate-based GPE, the lifespan of the symmetric battery with the LSN is extended to 1300 h at 0.2 mA cm⁻²/0.2 mAh cm⁻². Furthermore, the LSN||LiFePO₄ (LFP) full cell exhibits a steady cycle with extremely low voltage polarization at 0.5 C after 200 cycles. This study provides a practical strategy to stabilize the Li/GPE interface and deepens the understanding of Li⁺ plating/stripping behaviors through the interphase.     

Rational Design of a Trifunctional Binder for Hard Carbon Anodes Showing High Initial Coulombic Efficiency and Superior Rate Capability for Sodium-Ion Batteries

Hard carbon (HC) has emerged as a promising anode material for sodium-ion batteries (SIBs), whereas it suffers from low initial Coulombic efficiency (ICE) and poor rate capability. Binders endowed with high electron/ion transport and strong mechanical integrity are expected to boost the practical application of HC anodes, which cannot be realized via the functional design of commercially available binders. Herein, a trifunctional sodium alginate (SA)/polyethylene oxide (PEO) binder with massive hydrophilic functional groups and abundant Na⁺ is synthesized via a feasible esterification reaction. The binder forms a passivation film on glucose-derived carbon (GC) to suppress the electrolyte decomposition and offer stronger adhesion strength. Furthermore, the sluggish Na⁺ conduction is improved via sufficient ionic transfer channels provided by PEO. Notably, effects of Na⁺ compensation and interfacial ionic transport of Na⁺-containing binder for HC anodes are revealed. Therefore, the SA/PEO binder for the GC anode delivers a high ICE up to 87% and a high capacity of 270 mA h g⁻¹ at 0.1 A g⁻¹, both 10% and 80 mA h g⁻¹ higher than that of poly(vinylidene fluoride) binder, respectively. Significantly, this SA/PEO binder can also be applied to coal-based and polymer-based carbon anodes, exhibiting universal applicability.     

Highly Symmetrical Six-Transition Metal Ring Units Promising High Air-Stability of Layered Oxide Cathodes for Sodium-Ion Batteries

Layered oxides are the most prevalent cathodes for sodium-ion batteries (SIBs), but their poor air stability significantly limits their practical application owing to the rapid performance degradation of aged materials and the cost increase for material storage and transportation. Here, an effective strategy of constructing stable transition metal (TM) layers with a highly symmetrical six-TM ring is suggested to enhance structure stability, thus hindering ambient air corrosion. The density functional theory calculations reveal that the higher symmetry ensures a higher thermodynamic energy for H₂O insertion into Na layer. The combined analyses of selected area electron diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and chemical titration indicate that the six-TM ring structure can effectively suppress the series of aging processes including water insertion, the spontaneous loss of lattice sodium, TM valence increment and residual alkali formation. Benefiting from the overall suppression of aging process, the strategy results in an excellent improvement in capacity retention after air exposure from 13.57% to 95.59%, and exhibits a good universality for both P2- and O3-cathodes, which are the two most common structures of Na-based layered oxides with different aging mechanism. These findings provide new insight to design high-performance cathodes for SIBs.     

Understanding the Critical Role of Binders in Phosphorus/Carbon Anode for Sodium‐Ion Batteries through Unexpected Mechanism

Polymer binders that combine active materials with conductive agents have played a critical role in maintaining the structural integrity of phosphorus anodes with a huge volume change upon sodiation/desodiation. Herein, the role of binders on the structural/chemical stability of phosphorus/carbon anode is spectroscopically uncovered through unexpected mechanism. Surprisingly, the selection of different binders is found to determine the oxidation degree of active phosphorus in various electrodes, which correlate well with their electrochemical properties. At a high oxidation degree, the electrode applying a conventional poly(vinylidene difluoride) binder displays the worst electrochemical properties, while the electrode using a sodium alginate binder delivers the best electrochemical performance (a highly reversible capacity of 1064 mAh g^?1 with a 90.1% capacity retention at 800 mA g^?1 after 200 cycles and an outstanding rate capability of 401 mAh g^?1 at 8000 mA g^?1) for its negligible oxidation. Additionally, the emergence/decomposition of surface intermediates, including (PO₂)^3? and (PO₄)^3? species, are observed in the discharging/charging processes via the ex situ P K‐edge X‐ray absorption spectroscopies. This novel discovery of the unique role of binders in phosphorus anodes, not only provides an opportunity to ameliorate their electrochemical properties, but also enables their practical applications in high‐energy sodium‐ion batteries.     

Engineering Wavy‐Nanostructured Anode Interphases with Fast Ion Transfer Kinetics: Toward Practical Li‐Metal Full Batteries

Fast Li‐metal depletion and severe anode pulverization are the most critical obstacles for the energy‐dense Li‐metal full batteries using thin Li‐metal anodes (<50 µm). Here, a wavy‐nanostructured solid electrolyte interphase (SEI) with fast ion transfer kinetics is reported, which can promote high‐efficiency Li‐metal plating/stripping (>98% at 4 mAh cm^?2) in conventional carbonate electrolyte. Cryogenic transmission electron microscopy (cryo‐TEM) further reveals the fundamental relationship between wavy‐nanostructured SEI, function, and the electrochemical performance. The wavy SEI with greatly decreased surface diffusion resistance can realize grain coarsening of Li‐metal deposition and exhaustive dissolution of active Li‐metal during the stripping process, which can effectively alleviate “dead Li” accumulation and anode pulverization problems in practical full cells. Under highly challenging conditions (45 µm Li‐metal anodes, 4.3 mAh cm^?2 high capacity LiNi_0.8Mn_0.1Co_0.1O₂ cathodes), full cells exhibit significantly improved cycling lifespan (170 cycles; 20 cycles for control cells) via the application of wavy SEI.     

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.