Advancing Sulfide Electrolyte/Silicon-Based Anode Systems in All-Solid-State Batteries: Interface Stability, Design, and Perspectives

Abstract

The rapid advancement of all-solid-state battery (ASSB) technology has positioned sulfide electrolyte/silicon-based anode systems as promising alternatives in both the academic and industrial sectors, with such systems receiving considerable attention recently. Given the high reactivity and strain accommodation challenges involved in this newly emerging system, ensuring its interface compatibility is highly important. This review presents an in-depth discussion of recent developments in the stability and design of the interface between sulfide electrolytes and silicon-based anodes, as well as related perspectives. Major interface behaviors and the mechanisms underlying chemical/electrochemical and mechanical instability at the interface are discussed, underscoring how these intertwined factors contribute to the complexity of interface failure. Moreover, sulfide electrolyte and silicon-based anode modification methods are highlighted. Advancements in in situ/operando advanced characterization methods in interface analysis are emphasized. Further breakthroughs require precise interface regulation, as well as the deployment of multimodal, multiscale, and advanced intelligent characterization techniques, which may provide new insights into interfacial phenomena. These advancements will inform rational material designs, increase interfacial compatibility, and accelerate the practical implementation of sulfide electrolyte/silicon-based anode ASSBs.

Graphical Abstract

This review provides a comprehensive overview of the interface failure mechanisms and modification strategies in sulfide electrolyte|silicon-based anode systems, aiming to improve interfacial compatibility. It also emphasizes the pivotal role of advanced intelligent interface characterization techniques in unveiling interfacial evolution processes and guiding the rational design of high-performance solid-state batteries.

Keywords

Sulfide electrolytes / Silicon-based anode / Interface failure mechanism / Surface and interface modification / Multidimensional characterization

References

[1] Armand M, Tarascon JM. Building better batteries. Nature, 2008, 451: 652-657.

[2] Hu YS. Batteries: getting solid. Nat. Energy, 2016, 1. 16042

[3] He X, Bresser D, Passerini S, et al. The passivity of lithium electrodes in liquid electrolytes for secondary batteries. Nat. Rev. Mater., 2021, 6: 1036-1052.

[4] Alsaç EP, Nelson DL, et al. Characterizing electrode materials and interfaces in solid-state batteries. Chem. Rev., 2025, 125: 2009-2119.

[5] Janek J, Zeier WG. Challenges in speeding up solid-state battery development. Nat. Energy, 2023, 8: 230-240.

[6] Gu JB, Liang ZT, Shi JW, et al. Electrochemo-mechanical stresses and their measurements in sulfide-based all-solid-state batteries: a review. Adv. Energy Mater., 2023, 13. 2203153

[7] Lee SY, Rawal J, Lee J, et al. Solid-state electrolytes and their interfacial properties: implications for solid-state lithium batteries. Electrochem. Energy Rev., 2025, 8: 9.

[8] Ketter L, Greb N, Bernges T, et al. Using resistor network models to predict the transport properties of solid-state battery composites. Nat. Commun., 2025, 16. 1411

[9] Liang YH, Liu H, Wang GX, et al. Challenges, interface engineering, and processing strategies toward practical sulfide-based all-solid-state lithium batteries. InfoMat, 2022, 4. e12292

[10] Bai X, Sun YZ, Li XF, et al. A deep dive into spent lithium-ion batteries: from degradation diagnostics to sustainable material recovery. Electrochem. Energy Rev., 2024, 7: 33.

[11] Asano S, Hata JI, Watanabe K, et al. Formation processes of a solid electrolyte interphase at a silicon/sulfide electrolyte interface in a model all-solid-state Li-ion battery. ACS Appl. Mater. Interfaces, 2024, 16: 7189-7199.

[12] Wang XY, He K, Li SY, et al. Realizing high-performance all-solid-state batteries with sulfide solid electrolyte and silicon anode: a review. Nano Res., 2023, 16: 3741-3765.

[13] Zheng Y, Shen YY, Guo JP, et al. Recent advances in solid-state lithium batteries based on anode engineering. Nano Res. Energy, 2024, 3. e9120118

[14] Zhang YX, Wu BR, Bi JY, et al. Facilitating prelithiation of silicon carbon anode by localized high-concentration electrolyte for high-rate and long-cycle lithium storage. Carbon Energy, 2024, 6. e480

[15] Yang JY, Cao Z, Chen YW, et al. Dry-processable polymer electrolytes for solid manufactured batteries. ACS Nano, 2023, 17: 19903-19913.

[16] Li JH, Cai YF, Wu HM, et al. Polymers in lithium-ion and lithium metal batteries. Adv. Energy Mater., 2021, 11. 2003239

[17] Li K, Wang JF, Song YY, et al. Machine learning-guided discovery of ionic polymer electrolytes for lithium metal batteries. Nat. Commun., 2023, 14. 2789

[18] Cheng XL, Pan J, Zhao Y, et al. Gel polymer electrolytes for electrochemical energy storage. Adv. Energy Mater., 2018, 8. 1702184

[19] Feng JW, Wang JY, Gu Q, et al. 1 µm-thick robust gel polymer electrolyte with excellent interfacial stability for high-performance Li metal batteries. Adv. Funct. Mater., 2025, 35: 2412287.

[20] Zhao Q, Stalin S, Zhao CZ, et al. Designing solid-state electrolytes for safe, energy-dense batteries. Nat. Rev. Mater., 2020, 5: 229-252.

[21] Jia LN, Zhu JH, Zhang X, et al. Li–solid electrolyte interfaces/interphases in all-solid-state Li batteries. Electrochem. Energy Rev., 2024, 7: 12.

[22] Xiao W, Wang JY, Fan LL, et al. Recent advances in Li_1+xAl_xTi_2−x(PO₄)₃ solid-state electrolyte for safe lithium batteries. Energy Storage Mater., 2019, 19: 379-400.

[23] Kim JS, Yoon G, Kim S, et al. Surface engineering of inorganic solid-state electrolytes via interlayers strategy for developing long-cycling quasi-all-solid-state lithium batteries. Nat. Commun., 2023, 14. 782

[24] Rosenbach C, Walther F, Ruhl J, et al. Visualizing the chemical incompatibility of halide and sulfide-based electrolytes in solid-state batteries. Adv. Energy Mater., 2023, 13. 2203673

[25] Yun J, Shin HR, Hoang TD, et al. Deciphering the critical degradation factors of solid composite electrodes with halide electrolytes: interfacial reaction versus ionic transport. Energy Storage Mater., 2023, 59. 102787

[26] Kwak H, Kim JS, Han D, et al. Boosting the interfacial superionic conduction of halide solid electrolytes for all-solid-state batteries. Nat. Commun., 2023, 14. 2459

[27] Huang R, Li RL, Li SB, et al. In-situ constructing 3D nanocarbon conduction conformal network on silicon anodes for high-performance sulfide-based all-solid-state batteries. Chem. Eng. J., 2025, 503. 158154

[28] Tan DHS, Chen YT, Yang HD, et al. Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytes. Science, 2021, 373: 1494-1499.

[29] Li S, Yang SJ, Liu GX, et al. A dynamically stable mixed conducting interphase for all-solid-state lithium metal batteries. Adv. Mater., 2024, 36: 2307768.

[30] Wang ZL, Shen XF, Chen SJ, et al. Large-scale fabrication of stable silicon anode in air for sulfide solid state batteries via ionic-electronic dual conductive binder. Adv. Mater., 2024, 36. 2405025

[31] Liu ZT, Chien PH, Wang S, et al. Tuning collective anion motion enables superionic conductivity in solid-state halide electrolytes. Nat. Chem., 2024, 16: 1584-1591.

[32] Hu X, Zhang ZJ, Zhang X, et al. External-pressure–electrochemistry coupling in solid-state lithium metal batteries. Nat. Rev. Mater., 2024, 9: 305-320.

[33] Cao DX, Sun X, Li YJ, et al. Long-cycling sulfide-based all-solid-state batteries enabled by electrochemo-mechanically stable electrodes. Adv. Mater., 2022, 34: 2200401.

[34] Zhong YX, Yang XY, Guo RQ, et al. Protecting lithium metal anodes in solid-state batteries. Electrochem. Energy Rev., 2024, 7: 30.

[35] Hang BT, Ohnishi T, Osada M, et al. Lithium silicon sulfide as an anode material in all-solid-state lithium batteries. J. Power. Sources, 2010, 195: 3323-3327.

[36] Wenzel S, Leichtweiss T, Krüger D, et al. Interphase formation on lithium solid electrolytes: an in situ approach to study interfacial reactions by photoelectron spectroscopy. Solid State Ion., 2015, 278: 98-105.

[37] Huang YL, Shao BW, Wang Y, et al. Solid-state silicon anode with extremely high initial coulombic efficiency. Energy Environ. Sci., 2023, 16: 1569-1580.

[38] Matsuda R, Tanaka A, Yanagihara K, et al. Deterioration analysis of Si composite anodes for all-solid-state batteries during charge–discharge by auger electron spectroscopy and scanning electron microscopy with energy dispersive spectroscopy. J. Phys. Chem. C, 2023, 127: 16508-16514.

[39] Fan ZJ, Ding B, Li ZW, et al. In-situ prelithiation of electrolyte-free silicon anode for sulfide all-solid-state batteries. eTransportation, 2023, 18. 100277

[40] Huo HY, Bai Y, Benz SL, et al. Decoupling the effects of interface chemical degradation and mechanical cracking in solid-state batteries with silicon electrode. Adv. Mater., 2025, 37. 2415006

[41] Wang QC, Huang YL, Xu J, et al. Interface and mechanical degradation mechanisms of the silicon anode in sulfide-based solid-state batteries at high temperatures. Chin. Phys. B, 2024, 33. 088201

[42] Nagata H, Kataoka K. Influence of mechanochemical reactions between Si and solid electrolytes in the negative electrode on the performance of all-solid-state lithium-ion batteries. J. Power. Sources, 2024, 623. 235443

[43] Kim M, Kim MJ, Oh YS, et al. Design strategies of Li–Si alloy anode for mitigating chemo-mechanical degradation in sulfide-based all-solid-state batteries. Adv. Sci., 2023, 10. 2301381

[44] Cao DX, Ji TT, Singh A, et al. Unveiling the mechanical and electrochemical evolution of nanosilicon composite anodes in sulfide-based all-solid-state batteries. Adv. Energy Mater., 2023, 13: 2203969.

[45] Yamamoto M, Terauchi Y, Sakuda A, et al. Slurry mixing for fabricating silicon-composite electrodes in all-solid-state batteries with high areal capacity and cycling stability. J. Power. Sources, 2018, 402: 506-512.

[46] Lee J, Jin D, Kim JY, et al. Dry pre-lithiation for graphite-silicon diffusion-dependent electrode for all-solid-state battery. Adv. Energy Mater., 2023, 13: 2300172.

[47] Huo HY, Jiang M, Bai Y, et al. Chemo-mechanical failure mechanisms of the silicon anode in solid-state batteries. Nat. Mater., 2024, 23: 543-551.

[48] Kim JY, Choi J, Choi J, et al. Mechanical stress-tolerant diffusion-dependent electrode with well-dispersed silicon particles for high-performance all-solid-state batteries. Carbon Energy, 2025, 7. e70046

[49] Paz-Garcia JM, Taiwo OO, Tudisco E, et al. 4D analysis of the microstructural evolution of Si-based electrodes during lithiation: time-lapse X-ray imaging and digital volume correlation. J. Power. Sources, 2016, 320: 196-203.

[50] Sakka Y, Matsumoto M, Yamashige H, et al. Investigating plastic deformation between silicon and solid electrolyte in all-solid-state batteries using operando X-ray tomography. J. Electrochem. Soc., 2024, 171: 070536.

[51] Morino Y, Takase K, Kanazawa A, et al. In-situ internal observation of silicon composite anode in all-solid-state battery using X-ray CT. ACS Appl. Mater. Interfaces, 2025, 17: 23786-23794.

[52] Otoyama M, Terasaki N, Takeuchi T, et al. Visualization of local strain distributions in all-solid-state batteries with silicon negative electrodes using digital image correlation for operando/in situ microscopy images. ChemElectroChem, 2025, 12. e202400616

[53] Yamamoto M, Terauchi Y, Sakuda A, et al. Effects of volume variations under different compressive pressures on the performance and microstructure of all-solid-state batteries. J. Power. Sources, 2020, 473. 228595

[54] Vadhva P, Boyce AM, Patel A, et al. Silicon-based solid-state batteries: electrochemistry and mechanics to guide design and operation. ACS Appl. Mater. Interfaces, 2023, 15: 42470-42480.

[55] Ye LH, Lu Y, Wang YC, et al. Fast cycling of lithium metal in solid-state batteries by constriction-susceptible anode materials. Nat. Mater., 2024, 23: 244-251.

[56] Zhao LH, Feng M, Wu CS, et al. Imaging the evolution of lithium-solid electrolyte interface using operando scanning electron microscopy. Nat. Commun., 2025, 16. 4283

[57] Liu Y, Wang CC, Yoon SG, et al. Aluminum foil negative electrodes with multiphase microstructure for all-solid-state Li-ion batteries. Nat. Commun., 2023, 14: 3975.

[58] Su H, Li JR, Zhong Y, et al. A scalable Li–Al–Cl stratified structure for stable all-solid-state lithium metal batteries. Nat. Commun., 2024, 15. 4202

[59] Duan H, Wang CH, Yu RZ, et al. In situ constructed 3D lithium anodes for long-cycling all-solid-state batteries. Adv. Energy Mater., 2023, 13. 2300815

[60] Zhu JH, Luo JY, Li JY, et al. A porous Li–Al alloy anode toward high-performance sulfide-based all-solid-state lithium batteries. Adv. Mater., 2024, 36: 2407128.

[61] Wang CH, Liang JW, Zhao Y, et al. All-solid-state lithium batteries enabled by sulfide electrolytes: from fundamental research to practical engineering design. Energy Environ. Sci., 2021, 14: 2577-2619.

[62] Wu JH, Liu SF, Han FD, et al. Lithium/sulfide all-solid-state batteries using sulfide electrolytes. Adv. Mater., 2021, 33. 2000751

[63] Kamaya N, Homma K, Yamakawa Y, et al. A lithium superionic conductor. Nat. Mater., 2011, 10: 682-686.

[64] Fan CL, Tufail MK, Zeng CY, et al. A functional air-stable Li_9.8GeP_1.7Sb_0.3S_11.8I_0.2 superionic conductor for high-performance all-solid-state lithium batteries. ACS Appl. Mater. Interfaces, 2024, 16: 28342-28352.

[65] Deiseroth HJ, Kong ST, Eckert H, et al. Li₆PS₅X: a class of crystalline Li-rich solids with an unusually high Li⁺ mobility. Angew. Chem. Int. Ed., 2008, 47: 755-758.

[66] Hanghofer I, Gadermaier B, Wilkening HMR. Fast rotational dynamics in argyrodite-type Li₆PS₅X (X: Cl, Br, I) as seen by ³¹P nuclear magnetic relaxation: on cation–anion coupled transport in thiophosphates. Chem. Mater., 2019, 31: 4591-4597.

[67] Sung J, Lee HG, Jo YS, et al. Size-controlled wet-chemical synthesis of sulfide superionic conductors for high-performance all-solid-state batteries. Energy Storage Mater., 2024, 67. 103253

[68] Wang JC, Wang PF, Yi TF. Challenges and optimization strategies at the interface between sulfide solid electrolyte and lithium anode. Energy Storage Mater., 2023, 62. 102958

[69] Muramatsu H, Hayashi A, Ohtomo T, et al. Structural change of Li₂S–P₂S₅ sulfide solid electrolytes in the atmosphere. Solid State Ionics, 2011, 182: 116-119.

[70] Fu JZ, Yang SG, Hou JH, et al. Modeling assisted synthesis of Zr-doped Li_3−xIn_1−xZr_xCl₆ with ultrahigh ionic conductivity for lithium-ion batteries. J. Power. Sources, 2023, 556. 232465

[71] Jiang ZL, Yu C, Chen SQ, et al. Ag/Br dual-doped Li₆PS₅Br electrolyte with superior conductivity for all-solid-state batteries. Scr. Mater., 2023, 227. 115303

[72] Li GY, Shen YQ, Tamerd MA, et al. One stone, three birds: Cu²⁺-substituted chloride electrolyte for high-performance all-solid-state lithium batteries. Energy Storage Mater., 2024, 71. 103673

[73] Liu H, Zhu QS, Liang YH, et al. Versatility of Sb-doping enabling argyrodite electrolyte with superior moisture stability and Li metal compatibility towards practical all-solid-state Li metal batteries. Chem. Eng. J., 2023, 462. 142183

[74] Liu YK, Yu T, Guo SH, et al. Designing high-performance sulfide-based all-solid-state lithium batteries: from laboratory to practical application. Acta Phys. Chim. Sin., 2023.

[75] Ma ZH, Shi J, Wu D, et al. Sn-doped thioantimonate superionic conductors with high air stability and enhanced Li-ion conduction for all-solid-state lithium batteries. J. Mater. Chem. A, 2023, 11: 23342-23353.

[76] Maithani V, Das S, Mukherjee S. Cooperative transport of lithium in disordered Li₁₀MP₂S₁₂ (M = Sn, Si) electrolytes for Li-ion batteries. Chem. Mater., 2024, 36: 10537-10551.

[77] Roh J, Lyoo J, Hong ST. Enhanced Li-ion conductivity and air stability of Sb-substituted Li₄GeS₄ toward all-solid-state Li-ion batteries. ACS Appl. Energy Mater., 2023, 6: 5446-5455.

[78] Seol K, Kaliyaperumal C, Uthayakumar A, et al. Enhancing the moisture stability and electrochemical performances of Li₆PS₅Cl solid electrolytes through Ga substitution. Electrochim. Acta, 2023, 441. 141757

[79] Shao QN, Yan CH, Gao MX, et al. New insights into the effects of Zr substitution and carbon additive on Li_3−xEr_1−xZr_xCl₆ halide solid electrolytes. ACS Appl. Mater. Interfaces, 2022, 14: 8095-8105.

[80] Wang DX, Shi HT, Wang S, et al. New insights into Li-argyrodite solid-state electrolytes based on doping strategies. Coord. Chem. Rev., 2024, 508. 215776

[81] Wang QT, Liu DX, Ma XF, et al. Sb-doped Li₁₀GeP₂S₁₂-type electrolyte Li₁₀SnP_2−xSb_xS₁₂ with enhanced ionic conductivity and lower lithium-ion migration barrier. J. Colloid Interface Sci., 2022, 627: 1039-1046.

[82] Wang QT, Liu DX, Ma XF, et al. Cl-doped Li₁₀SnP₂S₁₂ with enhanced ionic conductivity and lower Li-ion migration barrier. ACS Appl. Mater. Interfaces, 2022, 14: 22225-22232.

[83] Wang QT, Liu Q. Enhancement of ionic conductivity and air stability by co-doping Li₁₀SnP₂S₁₂ with Nb and O. J. Energy Storage, 2024, 104. 114505

[84] Wang X, Zhao EY, Guo WH. A dual-matrix hybridization strategy for synthesis of cationic-anionic double-doped Li_2.99Y_0.99Zr_0.01Br_1.6Cl_4.4 halide solid electrolyte. J. Solid State Electrochem., 2023, 27: 3597-3602.

[85] Yang J, Jiang ZL, Liu C, et al. Tin-based dual-modification enabling enhanced air stability and electrochemical performance for Li_5.5PS_4.5Cl_1.5 in all-solid-state lithium metal batteries. Chem. Eng. J., 2024, 500. 157027

[86] Yang ZD, Tang B, Ren DH, et al. Advancing solid-state sodium batteries: status quo of sulfide-based solid electrolytes. Mater. Today, 2024, 80: 429-449.

[87] Yu PW, Ahmad N, Zeng CY, et al. Tailored Li₇P₃S₁₁ electrolyte by In₂S₃ doping suppresses electrochemical decomposition for high-performance all-solid-state lithium–sulfur batteries. ACS Appl. Energy Mater., 2022, 5: 13429-13438.

[88] Zhang N, Wang L, Diao QY, et al. Mechanistic insight into La₂O₃ dopants with high chemical stability on Li₃PS₄ sulfide electrolyte for lithium metal batteries. J. Electrochem. Soc., 2022, 169. 020544

[89] Deck MJ, Chien PH, Poudel TP, et al. Oxygen-induced structural disruption for improved Li⁺ transport and electrochemical stability of Li₃PS₄. Adv. Energy Mater., 2024, 14. 2302785

[90] Li H, Lin QS, Wang JZ, et al. A cost-effective sulfide solid electrolyte Li₇P₃S_7.5O_3.5 with low density and excellent anode compatibility. Angew. Chem. Int. Ed., 2024, 63: e202407892.

[91] Arnold W, Shreyas V, Li Y, et al. Synthesis of fluorine-doped lithium argyrodite solid electrolytes for solid-state lithium metal batteries. ACS Appl. Mater. Interfaces, 2022, 14: 11483-11492.

[92] Ni Y, Huang C, Liu H, et al. A high air-stability and Li-metal-compatible Li_3+2xP_1−xBi_xS_4−1.5xO_1.5x sulfide electrolyte for all-solid-state Li–metal batteries. Adv. Funct. Mater., 2022, 32. 2205998

[93] Wang QT, Zhang P, Du PF, et al. Sb and O co-doping in Li₁₀SiP₂S₁₂ to reduce orthorhombic phase content and improve electrochemical performance. J. Alloys Compd., 2025, 1010. 178055

[94] Li DB, Liu XY, Li Y, et al. A versatile InF₃ substituted argyrodite sulfide electrolyte toward ultrathin films for all-solid-state lithium batteries. Adv. Energy Mater., 2024, 14. 2402929

[95] Jiang ZL, Yang J, Liu C, et al. Insights on Bi-O dual-doped Li_5.5PS_4.5Cl_1.5 electrolyte with enhanced electrochemical properties for all-solid-state lithium metal batteries. Nano Energy, 2024, 128: 109926.

[96] Li SL, Lin QQ, Yan H. Enhanced air stability and interface compatibility in Nb-O-doped Cl-rich Li-argyrodites for all-solid-state Li metal batteries. Electrochim. Acta, 2025, 509. 145341

[97] Tsukasaki H, Sano H, Igarashi K, et al. Deterioration process of argyrodite solid electrolytes during exposure to humidity-controlled air. J. Power. Sources, 2022, 524. 231085

[98] Naillou P, Boulineau A, De Vito E, et al. Evidencing phase transformations of Li₆PS₅Cl argyrodite under ambient air and dry room exposure. ACS Appl. Mater. Interfaces, 2024, 16: 53855-53863.

[99] Chen YT, Marple MAT, Tan DHS, et al. Investigating dry room compatibility of sulfide solid-state electrolytes for scalable manufacturing. J. Mater. Chem. A, 2022, 10: 7155-7164.

[100] Dandena BD, Su WN, Tsai DS, et al. Li–Sb alloy formation strategy to improve interfacial stability of all-solid-state lithium batteries. Small Methods, 2025, 9. 2400571

[101] Wang JC, Zhao LL, Zhang N, et al. Interfacial stability between sulfide solid electrolytes and lithium anodes: challenges, strategies and perspectives. Nano Energy, 2024, 123. 109361

[102] Hwang T, Bae JH, Lee SR, et al. Oxygen substitution to enhance chemo-mechanical stability at the cathode-sulfide electrolyte interface in all-solid-state batteries. ACS Nano, 2024, 18: 23320-23330.

[103] Lin XZ, Li DB, Li YR, et al. ZnO substitution in argyrodite Li_5.5+3xZn_xP_1−xO_xS_4.5−xBr_1.5 electrolyte with enhanced interface performance for all-solid-state battery. Batter. Supercaps, 2024, 7. e202400048

[104] Luo QY, Liu C, Li L, et al. O-doping strategy enabling enhanced chemical/electrochemical stability of Li₃InCl₆ for superior solid-state battery performance. J. Energy Chem., 2024, 99: 484-494.

[105] Wei CC, Yu C, Wang R, et al. Sb and O dual doping of chlorine-rich lithium argyrodite to improve air stability and lithium compatibility for all-solid-state batteries. J. Power. Sources, 2023, 559. 232659

[106] Yan H, Yao JM, Ye ZR, et al. Al–F co-doping towards enhanced electrolyte-electrodes interface properties for halide and sulfide solid electrolytes. Chin. Chem. Lett., 2025, 36. 109568

[107] Luo M, Wang CH, Duan Y, et al. Surface coating enabling sulfide solid electrolytes with excellent air stability and lithium compatibility. Energy Environ. Mater., 2024, 7. e12753

[108] Serbessa GG, Nikodimos Y, Taklu BW, et al. Stabilizing the interface between Li₆PS₅Cl argyrodite sulfide solid electrolyte and Li via in situ formed LiF–Li₃Bi lithiophobic–lithiophilic bifunctional layer. Energy Storage Mater., 2025, 76. 104103

[109] Lu SJ, Zhang YX, Lv HJ, et al. A core-shell structured argyrodite-type electrolyte enabling elevated chemical/electrochemical stability. Angew. Chem. Int. Ed., 2025, 64. e202500388

[110] Li JW, Li YY, Cheng J, et al. In situ modified sulfide solid electrolyte enabling stable lithium metal batteries. J. Power. Sources, 2022, 518. 230739

[111] Wang GD, Lin CG, Gao CW, et al. Hydrolysis-resistant and anti-dendritic halide composite Li₃PS₄–LiI solid electrolyte for all-solid-state lithium batteries. Electrochim. Acta, 2022, 428. 140906

[112] Zhang WR, Wang ZY, Wan HL, et al. Revitalizing interphase in all-solid-state Li metal batteries by electrophile reduction. Nat. Mater., 2025, 24: 414-423.

[113] Chen Y, Gao X, Zhen Z, et al. The construction of multifunctional solid electrolyte interlayers for stabilizing Li₆PS₅Cl-based all-solid-state lithium metal batteries. Energy Environ. Sci., 2024, 17: 9288-9302.

[114] Muruganantham R, Wu HW, Lo Y, et al. Improving electrochemical stability by modifying the Li₆PS₅Cl entailed with the mixed phase of Li_6.4La₃Zr_1.4Ta_0.6O_1.2 composite solid electrolytes for all-solid-state lithium battery applications. Surf. Coat. Technol., 2024, 479: 130480.

[115] Qiao RH, Yu HL, Ben LB, et al. Utilizing hydrolysis resistance of compressed Li₃PS₄ films to eradicate surface hydroxyls and form conformal coatings through atomic layer deposition. Chem. Eng. J., 2024, 486. 149877

[116] Sheng OW, Jin CB, Ju ZJ, et al. Stabilizing Li₄SnS₄ electrolyte from interface to bulk phase with a gradient lithium iodide/polymer layer in lithium metal batteries. Nano Lett., 2022, 22: 8346-8354.

[117] Li Y, Arnold W, Thapa A, et al. Stable and flexible sulfide composite electrolyte for high-performance solid-state lithium batteries. ACS Appl. Mater. Interfaces, 2020, 12: 42653-42659.

[118] Huo HY, Jiang M, Mogwitz B, et al. Interface design enabling stable polymer/thiophosphate electrolyte separators for dendrite-free lithium metal batteries. Angew. Chem. Int. Ed., 2023, 62. e202218044

[119] Khomein P, Byeon YW, Liu DY, et al. Lithium phosphorus sulfide chloride–polymer composite via the solution–precipitation process for improving stability toward dendrite formation of Li-ion solid electrolyte. ACS Appl. Mater. Interfaces, 2023, 15: 11723-11730.

[120] Yuan HY, Lin WJ, Tian CH, et al. In-situ coating strategy to synthesize ultra-soft sulfide solid-state electrolytes for dendrite-free lithium metal batteries. Nano Energy, 2024, 128. 109835

[121] Du LM, Wu Z, Pang B, et al. Dendrite-free Li_5.5PS_4.5Cl_1.5-based all-solid-state lithium battery enabled by grain boundary electronic insulation strategy through in situ polymer encapsulation. ACS Appl. Mater. Interfaces, 2024, 16: 26288-26298.

[122] Liu MC, Hong JJ, Sebti E, et al. Surface molecular engineering to enable processing of sulfide solid electrolytes in humid ambient air. Nat. Commun., 2025, 16: 213.

[123] Yan JT, Yao JM, Zhao J, et al. Revealing the thermal stability of the Li/sulfide solid electrolyte interface at atomic scale via cryogenic electron microscopy. Adv. Funct. Mater., 2025, 35. 2421918

[124] Tan DHS, Wu EA, Nguyen H, et al. Elucidating reversible electrochemical redox of Li₆PS₅Cl solid electrolyte. ACS Energy Lett., 2019, 4: 2418-2427.

[125] Lu SJ, Zhang YX, Zhang XY, et al. Tailoring argyrodite electrolyte for enhanced interface compatibility with lithium anode. Chem. Eng. J., 2025, 507. 160455

[126] Wei CC, Xiao YJ, Wu ZK, et al. Construction of LiCl/LiF/LiZn hybrid SEI interface achieving high-performance sulfide-based all-solid-state lithium metal batteries. Sci. China Chem., 2024, 67: 1990-2001.

[127] Matsuda R, Muto H, Matsuda A. Air-stable Li₃SbS₄–LiI electrolytes synthesized via an aqueous ion-exchange process and the unique temperature dependence of conductivity. ACS Appl. Mater. Interfaces, 2022, 14: 52440-52447.

[128] Sun XL, Sun YM, Cao FT. Preparation, characterization and ionic conductivity studies of composite sulfide solid electrolyte. J. Alloys Compd., 2017, 727: 1136-1141.

[129] Zhu L, Wang YW, Wu YM, et al. Boron nitride-based release agent coating stabilizes Li_1.3Al_0.3Ti_1.7(PO₄)₃/Li interface with superior lean-lithium electrochemical performance and thermal stability. Adv. Funct. Mater., 2022, 32. 2201136

[130] Xu JR, Li YX, Lu PS. Water-stable sulfide solid electrolyte membranes directly applicable in all-solid-state batteries enabled by superhydrophobic Li⁺-conducting protection layer. Adv. Energy Mater., 2022, 12. 2102348

[131] Bi JY, Mu DB, Wu BR, et al. A hybrid solid electrolyte Li_0.33La_0.557TiO₃/poly(acylonitrile) membrane infiltrated with a succinonitrile-based electrolyte for solid state lithium-ion batteries. J. Mater. Chem. A, 2020, 8: 706-713.

[132] Guo YY, Liu K, Li C, et al. A sulfide-based solid electrolyte with high humid air tolerance for long lifespan all-solid-state sodium batteries. Adv. Energy Mater., 2024, 14. 2401504

[133] Yang H, Wu NQ. Ionic conductivity and ion transport mechanisms of solid-state lithium-ion battery electrolytes: a review. Energy Sci. Eng., 2022, 10: 1643-1671.

[134] Yang YH, Wu Q, Cui YH. Elastic properties, defect thermodynamics, electrochemical window, phase stability, and Li⁺ mobility of Li₃PS₄: insights from first-principles calculations. ACS Appl. Mater. Interfaces, 2016, 8: 25229-25242.

[135] Hood ZD, Mane AU, Sundar A. Multifunctional coatings on sulfide-based solid electrolyte powders with enhanced processability, stability, and performance for solid-state batteries. Adv. Mater., 2023, 35. 2300673

[136] Xia K, Yao ZY, Liu Z, et al. Hierarchical ionic networks in polymer electrolyte boost high-voltage solid-state Li batteries with stable interfaces and long cycling. Nano Res. Energy, 2026, 5. e9120181

[137] Zhang DM, Meng XL, Hou WY, et al. Solid polymer electrolytes: ion conduction mechanisms and enhancement strategies. Nano Res. Energy, 2023, 2: e9120050.

[138] Zheng LH, Ren GY, Wang S, et al. Li₄SnS₄ sulfide composite electrolyte for improved solid-state lithium batteries. J. Electron. Mater., 2024, 53: 7400-7408.

[139] Zou CF, Yang L, Luo KL, et al. Preparation and performances of poly(ethylene oxide)–Li₆PS₅Cl composite polymer electrolyte for all-solid-state lithium batteries. J. Electroanal. Chem., 2021, 900. 115739

[140] Li GY, Wu SP, Gao CL, et al. In situ polymerized polydioxolane interlayer enabled dendrite-free argyrodite-based solid-state batteries. Nano Energy, 2024, 127. 109786

[141] Zhang Q, Liu K, Liu K, et al. Study of a composite solid electrolyte made from a new pyrrolidone-containing polymer and LLZTO. J. Colloid Interface Sci., 2020, 580: 389-398.

[142] Grandjean M, Pichardo M, Biecher Y, et al. Matching silicon-based anodes with sulfide-based solid-state electrolytes for Li-ion batteries. J. Power. Sources, 2023, 580. 233386

[143] Yamamoto M, Takatsu M, Okuno R, et al. Nanoporous silicon fiber networks in a composite anode for all-solid-state batteries with superior cycling performance. Sci. Rep., 2023, 13. 17051

[144] Xu X, Sun Q, Li YY, et al. Nano silicon anode without electrolyte adding for sulfide-based all-solid-state lithium-ion batteries. Small, 2023, 19: 2302934.

[145] Chiku M, Kitade N, Hotehama C, et al. Si particle size blends to improve cycling performance as negative electrode for all-solid-state lithium-ion battery. Electrochim. Acta, 2024, 505. 144963

[146] Huang YT, Jing SH, Shen HQ, et al. An electrochemical-mechanical synergistic regulation by constructing a double-layer fully active silicon-based alloy anode in sulfide all-solid-state batteries. Acta Mater., 2025, 289. 120915

[147] Yan WL, Mu ZL, Wang ZX, et al. Hard-carbon-stabilized Li–Si anodes for high-performance all-solid-state Li-ion batteries. Nat. Energy, 2023, 8: 800-813.

[148] Jing SH, Lu Y, Huang YT, et al. High-performance sheet-type sulfide all-solid-state batteries enabled by dual-function Li_4.4Si alloy-modified nano silicon anodes. Adv. Mater., 2024, 36. 2312305

[149] Ji WX, Zhang XX, Liu M, et al. High-performance all-solid-state Li–S batteries enabled by an all-electrochem-active prelithiated Si anode. Energy Storage Mater., 2022, 53: 613-620.

[150] Kim J, Kim C, Jang I, et al. Si nanoparticles embedded in carbon nanofiber sheathed with Li₆PS₅Cl as an anode material for all-solid-state batteries. J. Power. Sources, 2021, 510. 230425

[151] Hu LY, Yan X, Fu ZF, et al. A “reinforced concrete” structure of silicon embedded into an in situ grown carbon nanotube scaffold as a high-performance anode for sulfide-based all-solid-state batteries. ACS Appl. Energy Mater., 2022, 5: 14353-14360.

[152] Sun F, Ma ZH, Xin SH, et al. Performance degradation mechanism of the Si@N,S-doped carbon anode in sulfide-based all-solid-state batteries. Small, 2025, 21. 2407284

[153] Choi J, Bak C, Kim JY, et al. Enhancing electrochemo-mechanical properties of graphite-silicon anode in all-solid-state batteries via solvent-induced polar interactions in nitrile binders. J. Energy Chem., 2025, 105: 514-524.

[154] Li ML, Xue DC, Rong ZY, et al. Stack pressure enhanced size threshold of Si anode fracture in all-solid-state batteries. Adv. Funct. Mater., 2025, 35. 2415696

[155] Kim KT, Woo J, Kim YS, et al. Ultrathin superhydrophobic coatings for air-stable inorganic solid electrolytes: toward dry room application for all-solid-state batteries. Adv. Energy Mater., 2023, 13: 2301600.

[156] Lv HJ, Chu XR, Zhang YX, et al. Self-healing solid-state polymer electrolytes for high-safety and long-cycle lithium-ion batteries. Mater. Today, 2024, 78: 181-208.

[157] Tang CK, Yu LY, Jiang QK, et al. Polymer-based electrolyte for lithium-based high-energy-density and safe energy storages devices: strategy and mechanisms. Renewables, 2024, 2: 297-340.

[158] Huang QQ, Song JX, Gao Y, et al. Supremely elastic gel polymer electrolyte enables a reliable electrode structure for silicon-based anodes. Nat. Commun., 2019, 10: 5586.

[159] Pan H, Wang L, Shi Y, et al. A solid-state lithium-ion battery with micron-sized silicon anode operating free from external pressure. Nat. Commun., 2024, 15: 2263.

[160] Yu MY, Ma J, et al. Stabilizing the SiO_x anode by a highly elastic quasi-solid polyether-based electrolyte via an in situ fabrication. ACS Appl. Mater. Interfaces, 2025, 17: 14097-14108.

[161] Kang YJ, Lin DL, Liu BX, et al. In situ engineering of a 3D branched polyimide/silver interface layer with dual ion-electron conductivity for superior structural integrity and long-cycle stability of silicon anodes. Adv. Funct. Mater., 2025, 35. 2504861

[162] Pei F, Wu L, Zhang Y, et al. Interfacial self-healing polymer electrolytes for long-cycle solid-state lithium–sulfur batteries. Nat. Commun., 2024, 15. 351

[163] Pei F, Huang YM, Wu L, et al. Multisite crosslinked poly(ether-urethane)-based polymer electrolytes for high-voltage solid-state lithium metal batteries. Adv. Mater., 2024, 36. 2409269

[164] He TY, Ding YY, et al. Self-healing SA@Borax binder for in situ tuning of the solid electrolyte interfaces for silicon anodes. ACS Sustain. Chem. Eng., 2025, 13: 4093-4107.

[165] Peng XL, Chen XJ, Tang CX, et al. Self-healing binder for high-voltage batteries. ACS Appl. Mater. Interfaces, 2023, 15: 21517-21525.

[166] Munaoka T, Yan XZ, Lopez J, et al. Ionically conductive self-healing binder for low cost Si microparticles anodes in Li-ion batteries. Adv. Energy Mater., 2018, 8: 1703138.

[167] Li JJ, Yang LP, Zhang HT, et al. Self-healing composite solid electrolytes with enhanced Li⁺ transport and mechanical properties for safe lithium metal batteries. Chem. Eng. J., 2022, 438. 135418

[168] Wang C, Wu H, Chen Z, et al. Self-healing chemistry enables the stable operation of silicon microparticle anodes for high-energy lithium-ion batteries. Nat. Chem., 2013, 5: 1042-1048.

[169] Gamo H, Nagai A, Matsuda A. Toward scalable liquid-phase synthesis of sulfide solid electrolytes for all-solid-state batteries. Batteries, 2023, 9: 355.

[170] Li JW, Li YY, Wang YX, et al. Preparation, design and interfacial modification of sulfide solid electrolytes for all-solid-state lithium metal batteries. Energy Storage Mater., 2025, 74. 103962

[171] Yuan K, Yuan LX, Chen J, et al. Methods and cost estimation for the synthesis of nanosized lithium sulfide. Small Struct., 2021, 2: 2000059.

[172] Wei YD, Zhao ZX, Qi L, et al. Low-cost preparation and purification of Li₂S for sulfide solid electrolytes. J. Energy Storage, 2024, 103. 114180

[173] Yang YT, Tian RZ, Zhang HZ, et al. Preparation of high-quality lithium sulfide by reducing lithium sulfate with hydrogen: a green and cost-effective method. Green Chem., 2024, 26: 7231-7245.

[174] Wu ZZ, Han C, Wang JS, et al. Low-cost synthesis of high-purity Li₂S for sulfide solid state electrolytes enabled by polyvinyl alcohol. J. Cent. South Univ., 2024, 31: 4449-4459.

[175] Cho H, Sim D, et al. Analysis of the detrimental impact of residual solvent in solid electrolyte membranes for sulfide all-solid-state batteries. ACS Appl. Energy Mater., 2025, 8: 13920-13928.

[176] Su ZK, Li G, Zhang JJ. Coaxial nanofiber binders integrating thin and robust sulfide solid electrolytes for high-performance all-solid-state lithium battery. Adv. Funct. Mater., 2025, 35. 2415409

[177] Li DB, Liu H, Wang C, et al. High ionic conductive, mechanical robust sulfide solid electrolyte films and interface design for all-solid-state lithium metal batteries. Adv. Funct. Mater., 2024, 34. 2315555

[178] Smith WH, Vaselabadi SA, Wolden CA. Synthesis of high-purity Li₂S nanocrystals via metathesis for solid-state electrolyte applications. J. Mater. Chem. A, 2023, 11: 7652-7661.

[179] Yang SJ, Hu XH, Xu SJ, et al. Synthesis of deliquescent lithium sulfide in air. ACS Appl. Mater. Interfaces, 2023, 15: 40633-40647.

[180] Han AG, Tian RZ, Fang LR, et al. A low-cost liquid-phase method of synthesizing high-performance Li₆PS₅Cl solid-electrolyte. ACS Appl. Mater. Interfaces, 2022, 14: 30824-30838.

[181] Liu H, Liang YH, Wang C, et al. Priority and prospect of sulfide-based solid-electrolyte membrane. Adv. Mater., 2023, 35. 2206013

[182] Chen ZY, Hou JB, Yang M, et al. Sulfide-based solid electrolyte and electrode membranes for all-solid-state lithium batteries. Chem. Eng. J., 2024, 502. 158136

[183] Ren DS, Lu LG, Hua R, et al. Challenges and opportunities of practical sulfide-based all-solid-state batteries. eTransportation, 2023, 18: 100272.

[184] Li R, Chen N, Liu SN, et al. Finely-tuned polar-nonpolar synergistic binder enables ultra-thin sulfide solid electrolyte membrane for all-solid-state batteries. Adv. Funct. Mater., 2024, 34: 2409403.

[185] Cao DX, Li Q, Sun X, et al. Amphipathic binder integrating ultrathin and highly ion-conductive sulfide membrane for cell-level high-energy-density all-solid-state batteries. Adv. Mater., 2021, 33. 2105505

[186] Zhang ZH, Wu LP, Zhou D, et al. Flexible sulfide electrolyte thin membrane with ultrahigh ionic conductivity for all-solid-state lithium batteries. Nano Lett., 2021, 21: 5233-5239.

[187] Su ZK, Zhou QZ, Jin JH, et al. Phase-transition-promoted interfacial anchoring of sulfide solid electrolyte membranes for high-performance all-solid-state lithium battery. Adv. Sci., 2024, 11: 2407798.

[188] Kim DH, Lee YH, Song YB, et al. Thin and flexible solid electrolyte membranes with ultrahigh thermal stability derived from solution-processable Li argyrodites for all-solid-state Li-ion batteries. ACS Energy Lett., 2020, 5: 718-727.

[189] Zhu GL, Zhao CZ, Peng HJ, et al. A self-limited free-standing sulfide electrolyte thin film for all-solid-state lithium metal batteries. Adv. Funct. Mater., 2021, 31. 2101985

[190] Li YH, Zhang ZY, Su PF, et al. Enhancing conductivity of Si anode enabled by selecting Si particle size for interface stabilized all-solid-state batteries. Ionics, 2024, 30: 3789-3798.

[191] Ji Y, Wang ZF, Zhao CT, et al. Diffusion-free all-solid-state batteries enabled by an ionic/electronic dual-conductive anode. Renewables, 2024, 2: 194-203.

[192] Zhang ZY, Sun ZF, Han X, et al. An all-electrochem-active silicon anode enabled by spontaneous Li–Si alloying for ultra-high performance solid-state batteries. Energy Environ. Sci., 2024, 17: 1061-1072.

[193] Ham SY, Sebti E, Cronk A, et al. Overcoming low initial coulombic efficiencies of Si anodes through prelithiation in all-solid-state batteries. Nat. Commun., 2024, 15: 2991.

[194] Okuno R, Yamamoto M, Kato A, et al. Performance improvement of nanoporous Si composite anodes in all-solid-state lithium-ion batteries by using acetylene black as a conductive additive. Electrochem. Commun., 2022, 138. 107288

[195] Kim KB, Dunlap NA, Han SS, et al. Nanostructured Si/C fibers as a highly reversible anode material for all-solid-state lithium-ion batteries. J. Electrochem. Soc., 2018, 165: A1903A1908.

[196] Jo YH, Lee YJ, Kim DW. Exploring the optimal binder content in composite electrodes for sulfide-based all-solid-state lithium-ion batteries. J. Electrochem. Soc., 2024, 171. 100525

[197] Rosner M, Cangaz S, Dupuy A, et al. Toward higher energy density all-solid-state batteries by production of freestanding thin solid sulfidic electrolyte membranes in a roll-to-roll process. Adv. Energy Mater., 2025, 15. 2404790

[198] Rosner M, Cangaz S, Hippauf F, et al. Analysis of the electrochemical stability of sulfide solid electrolyte dry films for improved dry-processed solid-state batteries. Adv. Funct. Mater., 2026, 36. e18517

[199] Li GB, Xue RJ, Chen LQ. The influence of polytetrafluorethylene reduction on the capacity loss of the carbon anode for lithium ion batteries. Solid State Ion., 1996, 90: 221-225.

[200] Wei ZQ, Kong DW, Quan LJ, et al. Removing electrochemical constraints on polytetrafluoroethylene as dry-process binder for high-loading graphite anodes. Joule, 2024, 8: 1350-1363.

[201] Kong DT, et al. Revealing the impact of the binder content on solvent-free PTFE-based SiO_x/C composite electrodes for high-energy-density lithium-ion batteries. ACS Appl. Energy Mater., 2025, 8: 15438-15447.

[202] Liu Y, Gao J, Qi HQ, et al. Ion-conducting polymeric binder enhances lithium-ion mobility in sulfide-based solid-state lithium-ion battery: synergistic effect of interfacial layer and in situ generated Li₃N–LiF. Chem. Eng. J., 2025, 519. 165465

[203] Liang XX, Ahmad N, Zhang BJ, et al. Research progress of robust binders with superior mechanical properties for high-performance silicon-based lithium-ion batteries. Mater. Chem. Front., 2024, 8: 1480-1512.

[204] He HP, Zhang MM, Hao MJ, et al. Synthesis of different aspect-ratios of fixed width gold nanorods. Acta Phys. Chim. Sin., 2024, 40. 2304043

[205] Long ZR, Mao SL, et al. Polymer coating enabling a durable conductive network for Si-based lithium-ion batteries. Nano Lett., 2025, 25: 9015-9023.

[206] Feng K, Li M, Liu WW, et al. Silicon-based anodes for lithium-ion batteries: from fundamentals to practical applications. Small, 2018, 14. 1702737

[207] Li QY, Liu H, Ye YS, et al. The critical importance of stack pressure in batteries. Nat. Energy, 2025, 10: 1064-1073.

[208] Tao JM, Han JJ, Wu YB, et al. Unraveling the performance decay of micro-sized silicon anodes in sulfide-based solid-state batteries. Energy Storage Mater., 2024, 64. 103082

[209] Chen XY, Mu YB, Liao ZF, et al. Advancing high-performance one-dimensional Si/carbon anodes: current status and challenges. Carbon Neutralization, 2024, 3: 199-221.

[210] Wu G, Gao YH, Weng Z, et al. Binder-induced inorganic-rich solid electrolyte interphase and physicochemical dual cross-linked network for high-performance SiO_x anode. Carbon Neutralization, 2024, 3: 857-872.

[211] Wang HL, Zhang H, Wang L, et al. Mediating solid electrolyte interphase formation kinetics on SiO_x anodes using proton acceptors. Angew. Chem. Int. Ed., 2025, 64. e202505832

[212] Tian K, Zhang W, Zeng J, et al. In situ reconstruction and anion blocking interphase strategy for high-performance silicon-based anodes in liquid and solid-state batteries. Adv. Funct. Mater., 2025, 35. 2424137

[213] Shi YR, Li QH, Hu XF, et al. A tailored dual-layer electronic shielding interface enables highly stable and dendrite-free solid-state lithium metal batteries. Nano Energy, 2024, 120. 109150

[214] Peng LF, Lei TY, Cheng SJ, et al. Synergistic fluorine–nitrogen interfaces enabling stable high-voltage sulfide-based all-solid-state lithium metal batteries. Nano Res., 2025, 18. 94907614

[215] Xu C, Jing P, Xia PF, et al. Tailoring a multilayer fine-grained solid electrolyte interphase by pulse electrochemical activation maneuver for stable Si/C anodes. Energy Environ. Sci., 2025, 18: 7060-7070.

[216] Wei YN, Wang M, Zhang MM, et al. Advancements, challenges, and future trajectories in advanced battery safety detection. Electrochem. Energy Rev., 2025, 8: 10.

[217] Nomura Y, Yamamoto K. Advanced characterization techniques for sulfide-based solid-state lithium batteries. Adv. Energy Mater., 2023, 13: 2203883.

[218] Alt CD, Müller NUCB, Riegger LM, et al. Quantifying multiphase SEI growth in sulfide solid electrolytes. Joule, 2024, 8: 2755-2776.

[219] Li YY, Gao ZH, Hu F, et al. Advanced characterization techniques for interface in all-solid-state batteries. Small Meth., 2020, 4: 2000111.

[220] Zhao FP, Zhang SM, Li YG, et al. Emerging characterization techniques for electrode interfaces in sulfide-based all-solid-state lithium batteries. Small Struct., 2022, 3: 2100146.

[221] Gao T, Han Y, Fraggedakis D, et al. Interplay of lithium intercalation and plating on a single graphite particle. Joule, 2021, 5: 393-414.

[222] Jin XY, Huang D, et al. Operando optical microscopy for visualization of dendrite growth in an argyrodite LPSCl–polymer composite electrolyte. ACS Energy Lett., 2025, 10: 1953-1957.

[223] Yadav NG, Folastre N, Bolmont M. Study of failure modes in two sulphide-based solid electrolyte all-solid-state batteries via in situ SEM. J. Mater. Chem. A, 2022, 10: 17142-17155.

[224] Zhang CC, Feng YZ, Han Z, et al. Electrochemical and structural analysis in all-solid-state lithium batteries by analytical electron microscopy: progress and perspectives. Adv. Mater., 2020, 32. 1903747

[225] Tsukasaki H, Otoyama M, Mori Y, et al. Analysis of structural and thermal stability in the positive electrode for sulfide-based all-solid-state lithium batteries. J. Power. Sources, 2017, 367: 42-48.

[226] Wang LL, Xie RC, Chen BB, et al. In-situ visualization of the space-charge-layer effect on interfacial lithium-ion transport in all-solid-state batteries. Nat. Commun., 2020, 11. 5889

[227] Lee JZ, Wynn TA, Schroeder MA, et al. Cryogenic focused ion beam characterization of lithium metal anodes. ACS Energy Lett., 2019, 4: 489-493.

[228] Cheng DY, Wynn TA, Wang XF, et al. Unveiling the stable nature of the solid electrolyte interphase between lithium metal and LiPON via cryogenic electron microscopy. Joule, 2020, 4: 2484-2500.

[229] Liang KY, Yuan XT. A beginner’s guide to cryo-EM for battery research. Nano Lett., 2025, 25: 7210-7223.

[230] Huang W, Wang JY, Braun MR, et al. Dynamic structure and chemistry of the silicon solid-electrolyte interphase visualized by cryogenic electron microscopy. Matter, 2019, 1: 1232-1245.

[231] Kasemchainan J, Zekoll S, Spencer Jolly D. Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells. Nat. Mater., 2019, 18: 1105-1111.

[232] Ning ZY, Jolly DS, Li GC. Visualizing plating-induced cracking in lithium-anode solid-electrolyte cells. Nat. Mater., 2021, 20: 1121-1129.

[233] Huo HY, Huang K, Luo W, et al. Evaluating interfacial stability in solid-state pouch cells via ultrasonic imaging. ACS Energy Lett., 2022, 7: 650-658.

[234] Deng Z, Lin X, Huang ZY, et al. Recent progress on advanced imaging techniques for lithium-ion batteries. Adv. Energy Mater., 2021, 11: 2000806.

[235] Zhao ZQ, Li Q. Magnetometry characterization techniques in energy electrochemistry research. Renewables, 2023, 1: 169-189.

[236] Wang Y, Li ZY, Li XQ, et al. Catalyzing battery materials research via lab-made, sub-ampere-hour-scale pouch cells, and long-term electrochemical monitoring by a reparable reference electrode. Adv. Energy Mater., 2024, 14. 2304512

[237] Xia G, Jiang W, Li H. In-situ detection of electrolyte defects in lithium-ion batteries using ultrasonic imaging and analysis of formation patterns. Energy Rep., 2024, 12: 4686-4695.

[238] Bommier C, Chang W, Lu YF, et al. In operando acoustic detection of lithium metal plating in commercial LiCoO₂/graphite pouch cells. Cell Rep. Phys. Sci., 2020, 1. 100035

[239] Shen Y, Zou BC, Zhang ZD, et al. In situ detection of lithium-ion batteries by ultrasonic technologies. Energy Storage Mater., 2023, 62. 102915

[240] Zheng SP, Jiang SP, Luo Y, et al. Guided wave imaging of thin lithium-ion pouch cell using scanning laser Doppler vibrometer. Ionics, 2021, 27: 643-650.

[241] Cui H, Song YZ, Ren DS, et al. Electrocapillary boosting electrode wetting for high-energy lithium-ion batteries. Joule, 2024, 8: 29-44.

[242] Wood KN, Steirer KX, Hafner SE, et al. Operando X-ray photoelectron spectroscopy of solid electrolyte interphase formation and evolution in Li₂S–P₂S₅ solid-state electrolytes. Nat. Commun., 2018, 9. 2490

[243] Cao DX, Zhang YX, Ji TT, et al. Li dynamics in mixed ionic-electronic conducting interlayer of all-solid-state Li-metal batteries. Nano Lett., 2024, 24: 1544-1552.

[244] Lu SJ, Zhang XY, Yang ZL, et al. Toward ultrastable metal anode/Li₆PS₅Cl interface via an interlayer as Li reservoir. Nano Lett., 2023, 23: 10856-10863.

[245] Huang JQ, Boles ST, Tarascon JM. Sensing as the key to battery lifetime and sustainability. Nat. Sustain., 2022, 5: 194-204.

[246] Shuchi SB, D’Acunto G, Sayavong P. Cryogenic X-ray photoelectron spectroscopy for battery interfaces. Nature, 2025, 646: 850-855.

[247] Wang SH, Li SW, et al. Depth-resolved probing of native solid electrolyte interphase formation and dynamics in Li metal batteries by cryogenic X-ray photoelectron spectroscopy. J. Am. Chem. Soc., 2025, 147: 38069-38077.

[248] Caspar M, Biecher Y, Tison Y, et al. Study of the cathode/electrolyte interface in an all-sulfide-solid-state battery using lithium-rich transition metal sulfide. ACS Appl. Mater. Interfaces, 2025, 17: 7142-7150.

[249] Huang CH, Feng ZJ, Pei F, et al. Understanding protection mechanisms of graphene-encapsulated silicon anodes with operando Raman spectroscopy. ACS Appl. Mater. Interfaces, 2020, 12: 35532-35541.

[250] Tardif S, Pavlenko E, Quazuguel L, et al. Operando Raman spectroscopy and synchrotron X-ray diffraction of lithiation/delithiation in silicon nanoparticle anodes. ACS Nano, 2017, 11: 11306-11316.

[251] Loaiza LC, Salager E, Louvain N, et al. Understanding the lithiation/delithiation mechanism of Si_1–xGe_x alloys. J. Mater. Chem. A, 2017, 5: 12462-12473.

[252] Chen Y, Huang L, Zhou DL, et al. Elucidating and minimizing the space-charge layer effect between NCM cathode and Li₆PS₅Cl for sulfide-based solid-state lithium batteries. Adv. Energy Mater., 2024, 14: 2304443.

[253] Zhang ZH, Wang J, Jin YM, et al. Insights on lithium plating behavior in graphite-based all-solid-state lithium-ion batteries. Energy Storage Mater., 2023, 54: 845-853.

[254] Wang ZX, Mu ZL, Ma TH, et al. In situ formed Li₃N networks by soft carbon–Si₃N₄ for superior all-solid-state lithium-metal batteries. Adv. Energy Mater., 2024, 14. 2400003

[255] Raj H, Neveu A, Jordy C, et al. Incorporation of halogens (Cl, Br, and I) in an Li–P–S–O system for exploring new sulfide solid electrolytes with high conductivity and superior electrochemical performance in solid-state batteries. J. Mater. Chem. A, 2024, 12: 31405-31423.

[256] Lu Y, Zhao CZ, Huang JQ. The timescale identification decoupling complicated kinetic processes in lithium batteries. Joule, 2022, 6: 1172-1198.

[257] Wang HH, Zhang BT, et al. Advances in the application of fiber optic sensors for high spatial resolution monitoring of lithium-ion batteries. ACS Appl. Electron. Mater., 2025, 7: 5743-5756.

[258] Yang JH, Lu XB, Du HT, et al. A miniaturized, low-cost interrogator via intrapulse wavelength demodulation for operando fiber-optic sensing in batteries. IEEE Trans. Instrum. Meas., 2025, 74: 7009613.

[259] Yu YF, Vincent T, Sansom J, et al. Distributed internal thermal monitoring of lithium ion batteries with fibre sensors. J. Energy Storage, 2022, 50. 104291

[260] Jeong W, Kim SO, Lim H, et al. High-resolution thermal monitoring of lithium-ion batteries using Brillouin scattering based fiber optic sensor with flexible spatial arrangement of sensing points. J. Energy Storage, 2024, 104. 114558

[261] Huang JQ, Albero Blanquer L, Bonefacino J, et al. Operando decoding of chemical and thermal events in commercial Na(Li)-ion cells via optical sensors. Nat. Energy, 2020, 5: 674-683.

[262] Li K, Huang Y, Han GC, et al. Real-time electrochemical-strain distribution and state-of-charge mapping via distributed optical fiber for lithium-ion batteries. J. Power. Sources, 2024, 624. 235526

[263] Hedman J, Björefors F. Fiber optic monitoring of composite lithium iron phosphate cathodes in pouch cell batteries. ACS Appl. Energy Mater., 2022, 5: 870-881.

[264] Fan JB, Liu CC, Li N, et al. Wireless transmission of internal hazard signals in Li-ion batteries. Nature, 2025, 641: 639-645.

[265] Kazyak E, Garcia-Mendez R, LePage WS, et al. Li penetration in ceramic solid electrolytes: operando microscopy analysis of morphology, propagation, and reversibility. Matter, 2020, 2: 1025-1048.

[266] Nelson DL, Sandoval SE, Pyo J, et al. Fracture dynamics in silicon anode solid-state batteries. ACS Energy Lett., 2024, 9: 6085-6095.

[267] Pei JH, Bai XS, Xue PC, et al. All-solid-state battery safety in abnormal thermal situations: crack propagation and lithium dendrite growth. Nano Res. Energy, 2025, 4. e9120155

[268] Wang Y, Shi JS, Gao HW, et al. Study of void evolution in lithium solid-state batteries: integrating high-throughput phase-field modeling, experimental validation, and machine learning. Adv. Energy Mater., 2025, 15: 2501616.

[269] Kwon O, Kim TY, Kim T, et al. Intelligent stress-adaptive binder enabled by shear-thickening property for silicon electrodes of lithium-ion batteries. Adv. Energy Mater., 2024, 14. 2304085

[270] Yang CT, Qi Y. Maintaining a flat Li surface during the Li stripping process via interface design. Chem. Mater., 2021, 33: 2814-2823.

[271] Hu TP, Tian JX, Dai FZ, et al. Impact of the local environment on Li ion transport in inorganic components of solid electrolyte interphases. J. Am. Chem. Soc., 2023, 145: 1327-1333.

[272] Tian HK, Liu Z, Ji YZ, et al. Interfacial electronic properties dictate Li dendrite growth in solid electrolytes. Chem. Mater., 2019, 31: 7351-7359.

[273] Li ZZ, Cong JL, Ding Y, et al. Strategies for intelligent detection and fire suppression of lithium-ion batteries. Electrochem. Energy Rev., 2024, 7: 32.

[274] Golov A, Carrasco J. Molecular-level insight into the interfacial reactivity and ionic conductivity of a Li-argyrodite Li₆PS₅Cl solid electrolyte at bare and coated Li-metal anodes. ACS Appl. Mater. Interfaces, 2021, 13: 43734-43745.

[275] Ren FC, Wu YQ, Zuo WH, et al. Visualizing the SEI formation between lithium metal and solid-state electrolyte. Energy Environ. Sci., 2024, 17: 2743-2752.

[276] Fu FJ, Wang XX, Zhang LF, et al. Unraveling the atomic-scale mechanism of phase transformations and structural evolutions during (de)lithiation in Si anodes. Adv. Funct. Mater., 2023, 33: 2303936.

[277] Zhang BW, Ma T, He ND, et al. Machine learning driven insights into lithiation mechanisms at the silicon-graphite interface within composite electrode. Acta Mater., 2025, 292. 121072

[278] Gao YZ, Zhang K, Du XH, et al. Wood-derived closed pore hard carbon encapsulated micro-sized silicon anode design for long-term practical lithium-ion battery. Chem. Eng. J., 2025, 508. 160846

[279] Wen TQ, Zhang LF, Wang H, et al. Deep potentials for materials science. Mater. Futures, 2022, 1. 022601

[280] Choi YS, Jeong J, Lee Y, et al. Li-ion transport mechanisms in Ge/Cl dual-doped Li₁₀GeP₂S₁₂ solid electrolytes: synergistic insights from experimental structural characterization and machine-learning-assisted atomistic modeling. Carbon Energy, 2024, 6. e594

[281] Shanbhag D, Gautam A, Salager E. Bromine-rich argyrodites compositions: enhancing lithium-ion conductivity for improved solid-state battery performance. J. Power. Sources, 2025, 657. 238175

[282] Dutra ACC, Goldmann BA, Islam MS. Understanding solid-state battery electrolytes using atomistic modelling and machine learning. Nat. Rev. Mater., 2025, 10: 566-583.

[283] Wang RY, Guo MY, Gao YX. A pre-trained deep potential model for sulfide solid electrolytes with broad coverage and high accuracy. npj Comput. Mater., 2025, 11: 266.

[284] Fitzhugh W, Chen X, Wang YC. Solid–electrolyte-interphase design in constrained ensemble for solid-state batteries. Energy Environ. Sci., 2021, 14: 4574-4583.

[285] Yang D, Xu PC, Xu CG. Highly stable silicon oxycarbide all-solid-state batteries enabled by machined learning accelerated screening of oxides and sulfides electrolytes. J. Colloid Interface Sci., 2025, 677: 130-139.

Funding

National Key Research and Development Program of China(2024YFF0505900)

SINOPEC project(Grant No. 223128)

China Postdoctoral Science Foundation General Fund(No. 77)

Postdoctoral Fellowship Program of CPSF(GZC20252688)

Rights & permissions

Shanghai University and Periodicals Agency of Shanghai University