HUANG Qing (1999-), male, Master candidate. E-mail: hq990907@126.com
Conventional lithium-ion batteries have been widely used in consumer electronics, electric vehicles, and energy storage systems. However, safety concerns such as the flammability of liquid electrolytes and the melting of separators at high temperatures have become increasingly prominent, limiting their further development in high-energy-density energy storage applications. In contrast, all-solid-state batteries (ASSBs), which use non-flammable solid electrolytes and high-temperature-resistant solid electrolyte membranes, offer advantages such as high safety and high energy density, making them a promising direction for next-generation battery technology.
Solid-state electrolytes (SSEs) are broadly classified as polymer, oxide, sulfide, and halide. Among them, halide SSEs have attracted particular interest owing to their combination of high oxidative stability with excellent processability and high Li+conductivity, making them ideal for high-energy-density ASSBs. When integrated into composite cathodes, they markedly improve electrochemical and thermal stability, rendering halides a leading choice of solid electrolyte for cathode composites. However, in halide-based composite cathodes, interface failure remains a significant challenge. The volume changes in the active material during cycling cause loss of interfacial contact, leading to rising impedance. Additionally, halide SSEs tend to oxidize at high potentials, generating insulating byproducts that hinder lithium-ion transport. The misalignment of energy bands at the interface also forms space charge layers, suppressing ion migration, which degrades battery performance.
In this review, recent research on the interfaces of halide-based composite cathodes is summarized, highlighting the progress in this field. The failure mechanisms at the cathode interface in halide-based ASSBs are discussed in detail, and strategies for achieving stable interfaces through materials design, interface engineering, and structural optimization are elaborated. On one hand, electrolyte optimization, including cation doping, anion substitution, high-entropy strategies, and surface coatings, can enhance intrinsic oxidative resistance. On the other hand, surface modification of the cathode, such as LiNbO3 coating or in-situ formation of LiF-rich electrolyte interface layers, can effectively block direct contact between the active material and electrolyte, thus suppressing interfacial side reactions. Moreover, the synergistic optimization of structural design and processing techniques (such as controlling component ratios, designing single-crystal cathodes, and employing dry pressing and solvent lamination) can further improve the ion/electron transport network and interfacial compactness of composite cathodes, significantly reducing interface impedance and extending cycling life. Through this systematic analysis, this review aims to provide a theoretical foundation and research direction for the optimization and industrialization of halide-based ASSBs materials, offering scientific guidance for the development of next-generation high-energy-density ASSBs systems.
Halide SSEs are regarded as ideal candidates for high-energy-density ASSBs owing to their high ionic conductivity, superior electrochemical stability, and good processability. Nevertheless, cathode interfacial instability remains a principal bottleneck in practical applications. Although notable advances have been achieved in materials optimization, interfacial engineering, and structural design, several scientific and engineering challenges remain unresolved.
1) Intrinsic materials stability. Under high-voltage operation, the chemical and electrochemical stability of halide SSEs are still limited. Anion substitution, cation doping, and high-entropy strategies can partially expand these windows, yet their action mechanisms and the governing rules for interfacial electronic-structure modulation are not fully elucidated. Future studies should integrate experiment and theory to establish quantitative links among chemical composition, electronic structure, and stability, considering density of states, space-charge layers, and band alignment at interfaces, to derive design principles for interfacial stabilization.
2) Construction and evolution of interfacial structures. Current efforts focus on electrolyte modification or cathode surface treatments, forming passivating layers from electrolyte decomposition or applying protective coatings to block direct contact between active materials and the electrolyte. Building on this, priority should be given to controllable synthesis that delivers nanoscale, uniform interfacial contact while avoiding byproducts and voids-key to enhancing electrochemical stability. Gradient architectures, core-shell designs, and in situ-formed interphases are promising, but their cycling evolution and mechanical matching require deeper investigation. In parallel, combining single-crystal cathodes with highly stable halide SSEs may offer a new balance between energy density and interfacial stability.
3) Processing and manufacturability. Halide-based ASSBs still face challenges in scalable fabrication and environmental sensitivity. Many halide electrolytes are extremely sensitive to moisture and polar solvents, limiting the direct use of conventional wet processes. Priority should be placed on developing coating, dry pressing, and lamination routes in low-polarity or non-solvent environments, and on mapping how processing parameters (pressure, temperature, atmosphere) affect interfacial structure and performance to unify electrochemical metrics with manufacturability.
In summary, halide SSEs present a compelling suite of advantages for ASSBs, yet cathode interfacial stability remains the key constraint on performance and deployment. Research on halide cathode interfaces is transitioning from mechanistic elucidation to controllable construction and engineering implementation. Future efforts should pursue coordinated advances in materials optimization, structural design, and process development to enable safe, high-energy-density storage. Through the integration of multiple strategies, halide ASSBs hold promise for achieving high energy density, long cycle stability, and industrial viability-advancing ASSBs technology and underpinning safer, more efficient energy-storage systems.
| 科 Family | 属数 Number of genus | 种数 Number of species | 占总种数比例 Percentage of total species (%) | 属 Genus | 种数 Number of species | 占总种数比例 Percentage of total species (%) |
|---|---|---|---|---|---|---|
| 鹅膏菌科Amanitaceae | 2 | 11 | 5.26 | 鹅膏菌属 Amanita | 10 | 4.78 |
| 小菇科 Mycenaceae | 2 | 12 | 5.74 | 丝盖伞属 Inocybe | 5 | 2.39 |
| 多孔菌科 Polyporaceae | 8 | 14 | 6.70 | 蜡蘑属 Laccaria | 5 | 2.39 |
| 红菇科 Russulaceae | 3 | 23 | 11.00 | 小皮伞属 Marasmius | 6 | 2.87 |
| 小菇属 Mycena | 11 | 5.26 | ||||
| 光柄菇属 Pluteus | 5 | 2.39 | ||||
| 红菇属 Russula | 17 | 8.13 | ||||
| 栓菌属 Trametes | 5 | 2.39 |