Inorganic Sodium Solid-State Electrolytes: Progress, Existing Issues, and Solutions Towards High-Performance all Solid-State Batteries

Abstract

Na-ion batteries (NIBs) have gained attention as a cost-effective option for large-scale energy storage, offering electrochemical properties similar to lithium-ion batteries (LIBs). To improve safety and energy density, solid-state electrolytes (SSEs) are being incorporated into NIBs, paving the way for high-performance all-solid-state sodium-ion batteries (ASSNIBs). This review summarises recent progress in Na-based SSEs, categorised into oxides, sulfides, and halides, with particular emphasis on their crystal structures, ion conduction mechanisms, and electrochemical performance. We then critically examine the key challenges facing ASSNIBs, including low ionic conductivity, unstable electrode/electrolyte interfaces, and the reliance on rare or costly materials. To gain deeper insights into these issues, we highlight advanced characterisation and modelling techniques, including cryogenic electron microscopy, in-situ/operando characterisation, and machine learning approaches—all of which contribute to understanding Na-ion transport mechanisms and interfacial dynamics more comprehensively, and comparing with conventional electrochemical tests, structural characterisation and modelling methods. Building on these insights, we explore promising strategies such as microstructural design, mixed-ion approaches, and interface engineering to overcome the current limitations in Na SSEs. Finally, we offer perspectives on future research directions to support the rational design and optimisation of Na SSEs, ultimately advancing the development of next-generation ASSNIBs. The advanced characterisation and machine learning methodologies emphasised herein will also prove valuable for broader applications in electrochemical energy storage systems.

Keywords

In-situ/operando techniques / Machine learning / Na solid-state electrolytes / All solid-state batteries / Ionic conductivity / Na dendrite / Mixed-ion strategy / Interface engineering

References

[1] Gibson L, Wilman EN, Laurance WF. How green is ‘green’ energy?. Trends Ecol. Evol., 2017, 32: 922-935

[2] Liu YS, Zhou Y, Wu WX. Assessing the impact of population, income and technology on energy consumption and industrial pollutant emissions in China. Appl. Energy, 2015, 155: 904-917

[3] Manisalidis I, Stavropoulou E, Stavropoulos Aet al.. Environmental and health impacts of air pollution: a review. Front. Public Health, 2020, 8 14

[4] Montzka SA, Dlugokencky EJ, Butler JH. Non-CO₂ greenhouse gases and climate change. Nature, 2011, 476: 43-50

[5] Nowotny J, Dodson J, Fiechter Set al.. Towards global sustainability: education on environmentally clean energy technologies. Renew. Sustain. Energy Rev., 2018, 81: 2541-2551

[6] Dang CC, Mu Q, Xie XBet al.. Recent progress in cathode catalyst for nonaqueous lithium oxygen batteries: a review. Adv. Compos. Hybrid Mater., 2022, 5: 606-626

[7] Davis SJ, Lewis NS, Shaner Met al.. Net-zero emissions energy systems. Science, 2018, 360 eaas9793

[8] Marino C, Nucara A, Pietrafesa Met al.. An energy self-sufficient public building using integrated renewable sources and hydrogen storage. Energy, 2013, 57: 95-105

[9] Liu CC, Wu BR, Liu Tet al.. Metal-organic frameworks and their composites for advanced lithium-ion batteries: synthesis, progress and prospects. J. Energy Chem., 2024, 89: 449-470

[10] Titirici M, Johansson P, Crespo Ribadeneyra Met al.. 2024 roadmap for sustainable batteries. J. Phys. Energy, 2024, 6 041502

[11] Goodenough JB, Park KS. The Li-ion rechargeable battery: a perspective. J. Am. Chem. Soc., 2013, 135: 1167-1176

[12] Cheng XB, Liu H, Yuan Het al.. A perspective on sustainable energy materials for lithium batteries. SusMat, 2021, 1: 38-50

[13] Harper G, Sommerville R, Kendrick Eet al.. Recycling lithium-ion batteries from electric vehicles. Nature, 2019, 575: 75-86

[14] Yoshino A. The birth of the lithium-ion battery. Angew. Chem. Int. Ed., 2012, 51: 5798-5800

[15] Huang C, Young NP, Zhang Jet al.. A two layer electrode structure for improved Li ion diffusion and volumetric capacity in Li ion batteries. Nano Energy, 2017, 31: 377-385

[16] Huang C, Kim A, Chung DJet al.. Multiscale engineered Si/SiO_x nanocomposite electrodes for lithium-ion batteries using layer-by-layer spray deposition. ACS Appl. Mater. Interfaces, 2018, 10: 15624-15633

[17] Huang C, Grant PS. Coral-like directional porosity lithium ion battery cathodes by ice templating. J. Mater. Chem. A, 2018, 6: 14689-14699

[18] Huang C, Dontigny M, Zaghib Ket al.. Low-tortuosity and graded lithium ion battery cathodes by ice templating. J. Mater. Chem. A, 2019, 7: 21421-21431

[19] Huang C, Leung CLA, Leung Pet al.. A solid-state battery cathode with a polymer composite electrolyte and low tortuosity microstructure by directional freezing and polymerization. Adv. Energy Mater., 2021, 11 2002387

[20] Risacher F, Fritz B. Origin of salts and brine evolution of Bolivian and Chilean salars. Aquat. Geochem., 2009, 15: 123-157

[21] Yaksic A, Tilton JE. Using the cumulative availability curve to assess the threat of mineral depletion: the case of lithium. Resour. Policy, 2009, 34: 185-194

[22] Koo BR, Lee YG, Lee SHet al.. One-pot spray engineering to design Na_0.44MnO₂ cathode electrodes for high-rate and cycle-stable Na-ion batteries. Batteries, 2022, 8 181

[23] Haridas AK, Huang C. Advances in strategic inhibition of polysulfide shuttle in room-temperature sodium-sulfur batteries via electrode and interface engineering. Batteries, 2023, 9 223

[24] Haridas AK, Huang C. Advances and challenges in tuning the reversibility & cyclability of room temperature sodium–sulfur and potassium–sulfur batteries with catalytic materials. Mater. Today Energy, 2023, 32 101228

[25] Kundu DP, Talaie E, Duffort Vet al.. The emerging chemistry of sodium ion batteries for electrochemical energy storage. Angew. Chem. Int. Ed., 2015, 54: 3431-3448

[26] Yabuuchi N, Kubota K, Dahbi Met al.. Research development on sodium-ion batteries. Chem. Rev., 2014, 114: 11636-11682

[27] Huang JW, Wu K, Xu Get al.. Recent progress and strategic perspectives of inorganic solid electrolytes: fundamentals, modifications, and applications in sodium metal batteries. Chem. Soc. Rev., 2023, 52: 4933-4995

[28] Usiskin R, Lu YX, Popovic Jet al.. Fundamentals, status and promise of sodium-based batteries. Nat. Rev. Mater., 2021, 6: 1020-1035

[29] Oh JAS, He LC, Chua Bet al.. Inorganic sodium solid-state electrolyte and interface with sodium metal for room-temperature metal solid-state batteries. Energy Storage Mater., 2021, 34: 28-44

[30] Lee B, Paek E, Mitlin Det al.. Sodium metal anodes: emerging solutions to dendrite growth. Chem. Rev., 2019, 119: 5416-5460

[31] Ma JL, Meng FL, Yu Yet al.. Prevention of dendrite growth and volume expansion to give high-performance aprotic bimetallic Li-Na alloy–O₂ batteries. Nat. Chem., 2019, 11: 64-70

[32] Zhao Y, Yang XF, Kuo L-Yet al.. High capacity, dendrite-free growth, and minimum volume change Na metal anode. Small, 2018, 14 1703717

[33] Ruan JF, Luo SN, Wang SFet al.. Enhancing the whole migration kinetics of Na⁺ in the anode side for advanced ultralow temperature sodium-ion hybrid capacitor. Adv. Energy Mater., 2023, 13 2301509

[34] Li HX, Xu M, Zhang ZAet al.. Engineering of polyanion type cathode materials for sodium-ion batteries: toward higher energy/power density. Adv. Funct. Mater., 2020, 30 2000473

[35] Tang B, Jaschin PW, Li Xet al.. Critical interface between inorganic solid-state electrolyte and sodium metal. Mater. Today, 2020, 41: 200-218

[36] Wu EA, Banerjee S, Tang HMet al.. A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries. Nat. Commun., 2021, 12 1256

[37] Hu SY, Huang C. Machine-learning approaches for the discovery of electrolyte materials for solid-state lithium batteries. Batteries, 2023, 9 228

[38] Huang C, Wilson MD, Cline Bet al.. Correlating lithium-ion transport and interfacial lithium microstructure evolution in solid-state batteries during the first cycle. Cell Rep. Phys. Sci., 2024, 5 101995

[39] Leung CLA, Wilson MD, Connolley Tet al.. Mapping of lithium ion concentrations in 3D structures through development of in situ correlative imaging of X-ray Compton scattering-computed tomography. J. Synchrotron Radiat., 2024, 31: 888-895

[40] Wheeler S, Hurlbutt K, Pasta M. A new solid-state sodium-metal battery. Chem, 2018, 4: 666-668

[41] Manthiram A, Yu XW, Wang SF. Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater., 2017, 2 16103

[42] Zheng XY, Bommier C, Luo Wet al.. Sodium metal anodes for room-temperature sodium-ion batteries: applications, challenges and solutions. Energy Storage Mater., 2019, 16: 6-23

[43] Yao YY, Kummer JT. Ion exchange properties of and rates of ionic diffusion in beta-alumina. J. Inorg. Nucl. Chem., 1967, 29: 2453-2475

[44] Goodenough JB, Hong HY, Kafalas JA. Fast Na⁺-ion transport in skeleton structures. Mater. Res. Bull., 1976, 11: 203-220

[45] Tanibata N, Deguchi M, Hayashi Aet al.. All-solid-state Na/S batteries with a Na₃PS₄ electrolyte operating at room temperature. Chem. Mater., 2017, 29: 5232-5238

[46] Park J, Son JP, Ko Wet al.. NaAlCl₄: new halide solid electrolyte for 3 V stable cost-effective all-solid-state Na-ion batteries. ACS Energy Lett., 2022, 7: 3293-3301

[47] Bu JF, Leung P, Huang Cet al.. Co-spray printing of LiFePO₄ and PEO-Li_1.5Al_0.5Ge_1.5(PO4)₃ hybrid electrodes for all-solid-state Li-ion battery applications. J. Mater. Chem. A, 2019, 7: 19094-19103

[48] Rankin GA, Merwin HE. The ternary system CaO-Al₂O₃-MgO. J. Am. Chem. Soc., 1916, 38: 568-588

[49] Beevers CA, Ross ΜAS. The crystal structure of “beta alumina” Na₂O11Al₂O₃. Z. Kristallogr. Crystalline Mater., 1937, 97: 59-66

[50] Ridgway RR, Klein AA, O’Leary WJ. The preparation and properties of so-called “beta alumina”. Trans. Electrochem. Soc., 1936, 70: 71-88

[51] Thery J, Briançon D. A new sodium aluminate NaAl₅O₈. C. R. Hebd. Seances Acad. Sci., 1962, 254: 2782-2784

[52] Chi C, Katsui H, Goto T. Effect of Li addition on the formation of Na-β/βʹʹ-alumina film by laser chemical vapor deposition. Ceram. Int., 2017, 43: 1278-1283

[53] De Vries RC, Roth WL. Critical evaluation of the literature data on beta alumina and related phases: I, phase equilibria and characterization of beta alumina phases. J. Am. Ceram. Soc., 1969, 52: 364-369

[54] Kummer JT. β-alumina electrolytes. Prog. Solid State Chem., 1972, 7: 141-175

[55] Lu XC, Xia GG, Lemmon JPet al.. Advanced materials for sodium-beta alumina batteries: status, challenges and perspectives. J. Power. Sources, 2010, 195: 2431-2442

[56] Wolf D. On the mechanism of diffusion in sodium beta alumina. J. Phys. Chem. Solids, 1979, 40: 757-773

[57] Skotniczny Z, Moscinski J, Rycerz Z. Computer simulation studies of cation migration mechanisms in sodium beta-alumina. J. Phys. C Solid State Phys., 1986, 19: 4781-4796

[58] Wang JC, Gaffari M, Choi SI. On the ionic conduction in β-alumina: potential energy curves and conduction mechanism. J. Chem. Phys., 1975, 63: 772-778

[59] Bates JB, Engstrom H, Wang JCet al.. Composition, ion-ion correlations and conductivity of beta″-alumina. Solid State Ionics, 1981, 5: 159-162

[60] Wang JC, Bates JB, Dudney NJet al.. Study of β- and β″-aluminas by means of potential energy calculations. Solid State Ion., 1981, 5: 35-40

[61] Briant JL, Farrington GC. Ionic conductivity in Na⁺, K⁺, and Ag⁺β″-alumina. J. Solid State Chem., 1980, 33: 385-390

[62] Li C, Li R, Liu KNet al.. NaSICON: a promising solid electrolyte for solid-state sodium batteries. Interdiscipl. Mater., 2022, 1: 396-416

[63] Li Y, Li M, Sun Zet al.. Recent advance on NASICON electrolyte in solid-state sodium metal batteries. Energy Storage Mater., 2023, 56: 582-599

[64] Zhang LX, Liu YM, You Yet al.. NASICONs-type solid-state electrolytes: the history, physicochemical properties, and challenges. Interdiscipl. Mater., 2023, 2: 91-110

[65] Guin M, Tietz F. Survey of the transport properties of sodium superionic conductor materials for use in sodium batteries. J. Power. Sources, 2015, 273: 1056-1064

[66] Uchida Y, Hasegawa G, Shima Ket al.. Insights into sodium ion transfer at the Na/NASICON interface improved by uniaxial compression. ACS Appl. Energy Mater., 2019, 2: 2913-2920

[67] Hong HY. Crystal structures and crystal chemistry in the system Na_1+xZr₂Si_xP_3-xO₁₂. Mater. Res. Bull., 1976, 11: 173-182

[68] Kohler H, Schulz H, Melnikov O. Composition and conduction mechanism of the NASICON structure X-ray diffraction study on two crystals at different temperatures. Mater. Res. Bull., 1983, 18: 1143-1152

[69] Boilot JP, Salanié JP, Desplanches Get al.. Phase transformation in Na_1+xSi_xZr2P_3−xO₁₂ compounds. Mater. Res. Bull., 1979, 14: 1469-1477

[70] von Alpen U, Bell MF, Wichelhaus W. Phase transition in nasicon (Na₃Zr₂Si₂PO₁₂). Mater. Res. Bull., 1979, 14: 1317-1322

[71] Jolley AG, Taylor DD, Schreiber NJet al.. Structural investigation of monoclinic-rhombohedral phase transition in Na₃Zr₂Si₂PO₁₂ and doped NASICON. J. Am. Ceram. Soc., 2015, 98: 2902-2907

[72] Oh JAS, He LC, Plewa Aet al.. Composite NASICON (Na₃Zr₂Si₂PO₁₂) solid-state electrolyte with enhanced Na⁺ ionic conductivity: effect of liquid phase sintering. ACS Appl. Mater. Interfaces, 2019, 11: 40125-40133

[73] Ma QL, Guin M, Naqash Set al.. Scandium-substituted Na₃Zr₂(SiO₄)₂(PO₄) prepared by a solution-assisted solid-state reaction method as sodium-ion conductors. Chem. Mater., 2016, 28: 4821-4828

[74] Jia HH, Peng LF, Yu Cet al.. Chalcogenide-based inorganic sodium solid electrolytes. J. Mater. Chem. A, 2021, 9: 5134-5148

[75] Guo XL, Halacoglu S, Chen Yet al.. Recent progress on dominant sulfide-type solid-state Na superionic conductors for solid-state sodium batteries. Small, 2024, 20 2311195

[76] Fuchs T, Culver SP, Till Pet al.. Defect-mediated conductivity enhancements in Na_3–xPn_1–xW_xS₄(pn = P, Sb) using aliovalent substitutions. ACS Energy Lett., 2020, 5: 146-151

[77] Jansen M, Henseler U. Synthesis, structure determination, and ionic conductivity of sodium tetrathiophosphate. J. Solid State Chem., 1992, 99: 110-119

[78] Hayashi A, Noi K, Sakuda Aet al.. Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries. Nat. Commun., 2012, 3 856

[79] Hayashi A, Noi K, Tanibata Net al.. High sodium ion conductivity of glass–ceramic electrolytes with cubic Na₃PS₄. J. Power. Sources, 2014, 258: 420-423

[80] Krauskopf T, Culver SP, Zeier WG. Local tetragonal structure of the cubic superionic conductor Na₃PS₄. Inorg. Chem., 2018, 57: 4739-4744

[81] Famprikis T, Kudu ÖU, Dawson JAet al.. Under pressure: mechanochemical effects on structure and ion conduction in the sodium-ion solid electrolyte Na₃PS₄. J. Am. Chem. Soc., 2020, 142: 18422-18436

[82] de Klerk NJJ, Wagemaker M. Diffusion mechanism of the sodium-ion solid electrolyte Na₃PS₄ and potential improvements of halogen doping. Chem. Mater., 2016, 28: 3122-3130

[83] Zhang DC, Cao XT, Xu Det al.. Synthesis of cubic Na₃SbS₄ solid electrolyte with enhanced ion transport for all-solid-state sodium-ion batteries. Electrochim. Acta, 2018, 259: 100-109

[84] Zhang L, Zhang DC, Yang Ket al.. Vacancy-contained tetragonal Na₃SbS₄ superionic conductor. Adv. Sci., 2016, 3 1600089

[85] Banerjee A, Park KH, Heo JWet al.. Na₃SbS₄: a solution processable sodium superionic conductor for all-solid-state sodium-ion batteries. Angew. Chem. Int. Ed., 2016, 55: 9634-9638

[86] Kim TW, Park KH, Choi YEet al.. Aqueous-solution synthesis of Na₃SbS₄ solid electrolytes for all-solid-state Na-ion batteries. J. Mater. Chem. A, 2018, 6: 840-844

[87] Wang H, Chen Y, Hood ZDet al.. An air-stable Na₃SbS₄ superionic conductor prepared by a rapid and economic synthetic procedure. Angew. Chem. Int. Ed., 2016, 55: 8551-8555

[88] Wang CH, Liang JW, Luo Jet al.. A universal wet-chemistry synthesis of solid-state halide electrolytes for all-solid-state lithium-metal batteries. Sci. Adv., 2021, 7 eabh1896

[89] Zhang L, Yang K, Mi JLet al.. Na₃PSe₄: a novel chalcogenide solid electrolyte with high ionic conductivity. Adv. Energy Mater., 2015, 5 1501294

[90] Wang Y, Richards WD, Bo S-Het al.. Computational prediction and evaluation of solid-state sodium superionic conductors Na₇P₃X₁₁ (X = O, S, Se). Chem. Mater., 2017, 29: 7475-7482

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

[92] Kandagal VS, Bharadwaj MD, Waghmare UV. Theoretical prediction of a highly conducting solid electrolyte for sodium batteries: Na₁₀GeP₂S₁₂. J. Mater. Chem. A, 2015, 3: 12992-12999

[93] Richards WD, Tsujimura T, Miara LJet al.. Design and synthesis of the superionic conductor Na₁₀SnP₂S₁₂. Nat. Commun., 2016, 7 11009

[94] Zhang Z, Ramos E, Lalère Fet al.. Na₁₁Sn₂PS₁₂: a new solid state sodium superionic conductor. Energy Environ. Sci., 2018, 11: 87-93

[95] Duchardt M, Ruschewitz U, Adams Set al.. Vacancy-controlled Na⁺ superion conduction in Na₁₁Sn₂PS₁₂. Angew. Chem. Int. Ed., 2018, 57: 1351-1355

[96] Oh K, Chang D, Park Iet al.. First-principles investigations on sodium superionic conductor Na₁₁Sn₂PS₁₂. Chem. Mater., 2019, 31: 6066-6075

[97] Yu ZX, Shang SL, Gao Yet al.. A quaternary sodium superionic conductor: Na_10.8Sn_1.9PS_11.8. Nano Energy, 2018, 47: 325-330

[98] Weng W, Wan HL, Liu GZet al.. Liquid-phase synthesis of nanosized Na₁₁Sn₂PS₁₂ solid electrolytes for room temperature all-solid-state sodium batteries. ACS Appl. Energy Mater., 2021, 4: 1467-1473

[99] Lee JE, Park KH, Kim JCet al.. Universal solution synthesis of sulfide solid electrolytes using alkahest for all-solid-state batteries. Adv. Mater., 2022, 34 2200083

[100] Liu GZ, Sun XR, Yu XQet al.. Na₁₀SnSb₂S₁₂: a nanosized air-stable solid electrolyte for all-solid-state sodium batteries. Chem. Eng. J., 2021, 420 127692

[101] Ramos EP, Zhang ZZ, Assoud Aet al.. Correlating ion mobility and single crystal structure in sodium-ion chalcogenide-based solid state fast ion conductors: Na₁₁Sn₂PnS₁₂ (pn = Sb, P). Chem. Mater., 2018, 30: 7413-7417

[102] Heo JW, Banerjee A, Park KHet al.. New Na-ion solid electrolytes Na_4−xSn_1−xSb_xS₄ (0.02≤x≤0.33) for all-solid-state Na-ion batteries. Adv. Energy Mater., 2018, 8 1702716

[103] Jia HH, Sun YL, Zhang ZRet al.. Group 14 element based sodium chalcogenide Na₄Sn_0.67Si_0.33S₄ as structure template for exploring sodium superionic conductors. Energy Storage Mater., 2019, 23: 508-513

[104] Duchardt M, Neuberger S, Ruschewitz Uet al.. Superion conductor Na_11.1Sn_2.1P_0.9Se₁₂: lowering the activation barrier of Na⁺ conduction in quaternary 1–4–5–6 electrolytes. Chem. Mater., 2018, 30: 4134-4139

[105] Zhang ZZ, Roy PN, Li Het al.. Coupled cation–anion dynamics enhances cation mobility in room-temperature superionic solid-state electrolytes. J. Am. Chem. Soc., 2019, 141: 19360-19372

[106] Liang CC. The self-discharge mechanism of the Li∕Lil∕Agl solid electrolyte cell. J. Electrochem. Soc., 1971, 118: 894

[107] Kanno R. Structure, ionic conductivity and phase transformation of double chloride spinels. Solid State Ion., 1988, 28: 1276-1281

[108] Zhao YS, Daemen LL. Superionic conductivity in lithium-rich anti-perovskites. J. Am. Chem. Soc., 2012, 134: 15042-15047

[109] Li XN, Liang JW, Yang XFet al.. Progress and perspectives on halide lithium conductors for all-solid-state lithium batteries. Energy Environ. Sci., 2020, 13: 1429-1461

[110] Xia W, Zhao Y, Zhao FPet al.. Antiperovskite electrolytes for solid-state batteries. Chem. Rev., 2022, 122: 3763-3819

[111] Wang YG, Wang QF, Liu ZPet al.. Structural manipulation approaches towards enhanced sodium ionic conductivity in Na-rich antiperovskites. J. Power. Sources, 2015, 293: 735-740

[112] Zhu JL, Wang YG, Li Set al.. Sodium ion transport mechanisms in antiperovskite electrolytes Na₃OBr and Na₄OI₂: an in situ neutron diffraction study. Inorg. Chem., 2016, 55: 5993-5998

[113] Nguyen H, Hy S, Wu Eet al.. Experimental and computational evaluation of a sodium-rich anti-perovskite for solid state electrolytes. J. Electrochem. Soc., 2016, 163: A2165-A2171

[114] Chen M, Liu L, Yin ZHet al.. Defect physics in Na₃OI antiperovskite solid electrolytes. J. Phys. Chem. C, 2024, 128: 9311-9316

[115] Wan TH, Lu ZH, Ciucci F. A first principle study of the phase stability, ion transport and substitution strategy for highly ionic conductive sodium antipervoskite as solid electrolyte for sodium ion batteries. J. Power. Sources, 2018, 390: 61-70

[116] Sun YL, Wang YC, Liang XMet al.. Rotational cluster anion enabling superionic conductivity in sodium-rich antiperovskite Na₃OBH₄. J. Am. Chem. Soc., 2019, 141: 5640-5644

[117] Tsai PC, Mair S, Smith Jet al.. Double paddle-wheel enhanced sodium ion conduction in an antiperovskite solid electrolyte. Adv. Energy Mater., 2023, 13: 2203284

[118] Xu Z, Liu Y, Sun Xet al.. Theoretical design of Na-rich anti-perovskite as solid electrolyte: the effect of cluster anion in stability and ionic conductivity. J. Solid State Chem., 2022, 316 123643

[119] Asano T, Sakai A, Ouchi Set al.. Solid halide electrolytes with high lithium-ion conductivity for application in 4 V class bulk-type all-solid-state batteries. Adv. Mater., 2018, 30 1803075

[120] Wang S, Bai Q, Nolan AMet al.. Lithium chlorides and bromides as promising solid-state chemistries for fast ion conductors with good electrochemical stability. Angew. Chem. Int. Ed., 2019, 58: 8039-8043

[121] Cheng JL, Sivonxay E, Persson KA. Evaluation of amorphous oxide coatings for high-voltage Li-ion battery applications using a first-principles framework. ACS Appl. Mater. Interfaces, 2020, 12: 35748-35756

[122] Kwak H, Lyoo J, Park Jet al.. Na₂ZrCl₆ enabling highly stable 3 V all-solid-state Na-ion batteries. Energy Storage Mater., 2021, 37: 47-54

[123] Wang K, Ren QY, Gu ZQet al.. A cost-effective and humidity-tolerant chloride solid electrolyte for lithium batteries. Nat. Commun., 2021, 12 4410

[124] Hu Y, Fu JM, Xu JBet al.. Superionic amorphous NaTaCl₆ halide electrolyte for highly reversible all-solid-state Na-ion batteries. Matter, 2024, 7: 1018-1034

[125] Huang Z, Yoshida S, Akamatsu Het al.. NaMCl₆ (M = Nb and Ta): a new class of sodium-conducting halide-based solid electrolytes. ACS Mater. Lett., 2024, 6: 1732-1738

[126] Niu XY, Dou XY, Fu CYet al.. Sodium halide solid state electrolyte of Na₃YBr₆ with low activation energy. RSC Adv., 2024, 14: 14716-14721

[127] Yu S, Kim K, Wood BCet al.. Structural design strategies for superionic sodium halide solid electrolytes. J. Mater. Chem. A, 2022, 10: 24301-24309

[128] Lian YX, Wu MS, Xu Bet al.. Phase-structure design for sodium chloride solid electrolytes with outstanding performance: a first-principles approach. J. Mater. Chem. A, 2023, 11: 1906-1919

[129] Qie Y, Wang S, Fu SJet al.. Yttrium–sodium halides as promising solid-state electrolytes with high ionic conductivity and stability for Na-ion batteries. J. Phys. Chem. Lett., 2020, 11: 3376-3383

[130] Wang S, Fu JM, Liu YSet al.. Design principles for sodium superionic conductors. Nat. Commun., 2023, 14 7615

[131] Park D, Kim K, Chun GHet al.. Materials design of sodium chloride solid electrolytes Na₃MCl₆ for all-solid-state sodium-ion batteries. J. Mater. Chem. A, 2021, 9: 23037-23045

[132] Huang H, Chi C, Zhang JYet al.. Fast ion transport mechanism and electrochemical stability of trivalent metal iodide-based Na superionic conductors Na₃XI₆ (X = Sc, Y, La, and In). ACS Appl. Mater. Interfaces, 2022, 14: 36864-36874

[133] Huang H, Wu HH, Chi Cet al.. Phase-structure-dependent Na ion transport in yttrium-iodide sodium superionic conductor Na₃YI₆. J. Mater. Chem. A, 2021, 9: 26256-26265

[134] Zhou CT, Bag S, Thangadurai V. Engineering materials for progressive all-solid-state Na batteries. ACS Energy Lett., 2018, 3: 2181-2198

[135] Liang JW, Li XN, Wang CHet al.. Current status and future directions in environmental stability of sulfide solid-state electrolytes for all-solid-state batteries. Energy Mater. Adv., 2023, 4 21

[136] Huang LJ, Barker K, Liu XZet al.. A mixed-anion strategy for constructing rapid ion-conducting Na solid-state electrolyte. Chem. Inorg. Mater., 2025, 6 100102

[137] Fan DS, Shen QY, Li Het al.. Redox couple modulation in NASICON phosphates toward high-performance cathodes for Na-ion batteries. Energy Mater. Adv., 2024, 5 73

[138] Zhu GL, Zhao CZ, Huang JQet al.. Fast charging lithium batteries: recent progress and future prospects. Small, 2019, 15 1805389

[139] Wang YY, Sun QY, Zou JLet al.. Simultaneous high ionic conductivity and lithium-ion transference number in single-ion conductor network polymer enabling fast-charging solid-state lithium battery. Small, 2023, 19 2303344

[140] Liu GZ, Yang J, Wu JHet al.. Inorganic sodium solid electrolytes: structure design, interface engineering and application. Adv. Mater., 2024, 36 2311475

[141] Banerjee A, Wang XF, Fang CCet al.. Interfaces and interphases in all-solid-state batteries with inorganic solid electrolytes. Chem. Rev., 2020, 120: 6878-6933

[142] Zhu YZ, He XF, Mo YF. Origin of outstanding stability in the lithium solid electrolyte materials: insights from thermodynamic analyses based on first-principles calculations. ACS Appl. Mater. Interfaces, 2015, 7: 23685-23693

[143] Richards WD, Miara LJ, Wang Yet al.. Interface stability in solid-state batteries. Chem. Mater., 2016, 28: 266-273

[144] Haruyama J, Sodeyama K, Han LYet al.. Space–charge layer effect at interface between oxide cathode and sulfide electrolyte in all-solid-state lithium-ion battery. Chem. Mater., 2014, 26: 4248-4255

[145] Shen YB, Zhang YT, Han SJet al.. Unlocking the energy capabilities of lithium metal electrode with solid-state electrolytes. Joule, 2018, 2: 1674-1689

[146] Chen RS, Li QH, Yu XQet al.. Approaching practically accessible solid-state batteries: stability issues related to solid electrolytes and interfaces. Chem. Rev., 2020, 120: 6820-6877

[147] Yang YX, Yang SM, Xue Xet al.. Inorganic all-solid-state sodium batteries: electrolyte designing and interface engineering. Adv. Mater., 2024, 36 2308332

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

[149] Tang WH, Qi RY, Wu JMet al.. Engineering, understanding, and optimizing electrolyte/anode interfaces for all-solid-state sodium batteries. Electrochem. Energy Rev., 2024, 7 23

[150] Ning ZY, Li GC, Melvin DLRet al.. Dendrite initiation and propagation in lithium metal solid-state batteries. Nature, 2023, 618: 287-293

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

[152] Hong YS, Li N, Chen HSet al.. In operando observation of chemical and mechanical stability of Li and Na dendrites under quasi-zero electrochemical field. Energy Storage Mater., 2018, 11: 118-126

[153] Wang SF, Xu HH, Li WDet al.. Interfacial chemistry in solid-state batteries: formation of interphase and its consequences. J. Am. Chem. Soc., 2018, 140: 250-257

[154] Lou SF, Zhang F, Fu CKet al.. Interface issues and challenges in all-solid-state batteries: lithium, sodium, and beyond. Adv. Mater., 2021, 33 2000721

[155] Rees GJ, Spencer Jolly D, Ning ZYet al.. Imaging sodium dendrite growth in all-solid-state sodium batteries using ²³Na T₂-weighted magnetic resonance imaging. Angew. Chem. Int. Ed., 2021, 60: 2110-2115

[156] Geng L, Xue DC, Yao JMet al.. Morphodynamics of dendrite growth in alumina based all solid-state sodium metal batteries. Energy Environ. Sci., 2023, 16: 2658-2668

[157] McCloskey BD. Attainable gravimetric and volumetric energy density of Li–S and Li ion battery cells with solid separator-protected Li metal anodes. J. Phys. Chem. Lett., 2015, 6: 4581-4588

[158] Haynes, W. M., Lide, D. R., Bruno, T. J.: Abundance of elements in the earth’s crust and in the sea. CRC Handbook of Chemistry and Physics, 97th ed., pp. 14–17. CRC Press, (2016–2017).

[159] Yang FZT, Peterson VK, Schmid S. Composition and temperature dependent structural investigation of the perovskite-type sodium-ion solid electrolyte series Na_1/2−xLa_1/2−xSr_2xZrO₃. J. Alloys Compd., 2021, 863 158500

[160] Lin XT, Zhao Y, Wang CHet al.. A dual anion chemistry-based superionic glass enabling long-cycling all-solid-state sodium-ion batteries. Angew. Chem. Int. Ed., 2024, 63 e202314181

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

[162] Cheng YF, Li MH, Yang XMet al.. Na–K alloy anode for high-performance solid-state sodium metal batteries. Nano Lett., 2022, 22: 9614-9620

[163] Nuwayhid RB, Kozen AC, Long DMet al.. Dynamic electrode–electrolyte intermixing in solid-state sodium nano-batteries. ACS Appl. Mater. Interfaces, 2023, 15: 24271-24283

[164] Liu DQ, Shadike Z, Lin RQet al.. Review of recent development of in situ/operando characterization techniques for lithium battery research. Adv. Mater., 2019, 31 1806620

[165] Huang C, Wilson MD, Cline Bet al.. Li⁺ concentration and morphological changes at the anode and cathode interphases inside solid-state lithium metal batteries. J. Phys. Energy, 2025, 7 025009

[166] Ma QL, Ortmann T, Yang AKet al.. Enhancing the dendrite tolerance of NaSICON electrolytes by suppressing edge growth of Na electrode along ceramic surface. Adv. Energy Mater., 2022, 12 2201680

[167] Xie G, Tang M, Xu SHet al.. Degradation at the Na₃SbS₄/Anode interface in an operating all-solid-state sodium battery. ACS Appl. Mater. Interfaces, 2022, 14: 48705-48714

[168] Zhang ZZ, Wenzel S, Zhu YZet al.. Na₃Zr₂Si₂PO₁₂: a stable Na⁺-ion solid electrolyte for solid-state batteries. ACS Appl. Energy Mater., 2020, 3: 7427-7437

[169] Wang Q, Yu C, Li LPet al.. Sc-doping in Na₃Zr₂Si₂PO₁₂ electrolytes enables preeminent performance of solid-state sodium batteries in a wide temperature range. Energy Storage Mater., 2023, 54: 135-145

[170] Gao ZH, Bai Y, Feng JRet al.. Controlling sodium dendrite growth via grain boundaries in Na₃Zr₂Si₂PO₁₂ electrolyte. Adv. Energy Mater., 2024, 14 2304488

[171] Ono T, Hiraoka K, Kobayashi Tet al.. Degradation analysis of oxide-based all-solid-state Na batteries by operando Raman spectroscopy. ACS Appl. Energy Mater., 2023, 6: 6194-6200

[172] Hiraoka K, Yamamoto K, Kobayashi Tet al.. Multi-scale analysis combined operando elemental/spectroscopic measurement techniques in oxide-type all-solid-state Na batteries. Energy Environ. Mater., 2025, 8 e12821

[173] Quérel E, Williams NJ, Seymour IDet al.. Operando characterization and theoretical modeling of Metal|Electrolyte interphase growth kinetics in solid-state batteries. part I: Experiments. Chem. Mater., 2023, 35: 853-862

[174] Oh JAS, Sun JG, Goh Met al.. A robust solid–solid interface using sodium–tin alloy modified metallic sodium anode paving way for all-solid-state battery. Adv. Energy Mater., 2021, 11 2101228

[175] Luo K, Zhou R, Martin SWet al.. Flexible doorway controlled Na⁺ ion diffusion in NaPSO glassy electrolytes from machine-learning force field simulations. J. Mater. Chem. A, 2024, 12: 33518-33525

[176] Liu Y, Wu LH, Yang ZWet al.. Descriptors divide-and-conquer enables multifaceted and interpretable materials structure–activity relationship analysis. Adv. Funct. Mater., 2025, 35 2421621

[177] Lee BD, Gavali DS, Kim Het al.. Discovering virtual Na-based argyrodites as solid-state electrolytes using DFT, AIMD, and machine learning techniques. J. Mater. Chem. A, 2025, 13: 10462-10474

[178] Kalnaus S, Amin R, Parish Cet al.. Effect of composition on mechanical properties and conductivity of the dual-ion conductor Na_1+xMn_x/2Zr_2–x/2(PO₄)₃ for solid-state batteries. ACS Appl. Energy Mater., 2021, 4: 11684-11692

[179] Fu ZZ, Zhang L, Gritton JEet al.. Probing the mechanical properties of a doped Li₇La₃Zr₂O₁₂ garnet thin electrolyte for solid-state batteries. ACS Appl. Mater. Interfaces, 2020, 12: 24693-24700

[180] Sun Z, Li L, Sun Cet al.. Active control of interface dynamics in NASICON-based rechargeable solid-state sodium batteries. Nano Lett., 2022, 22: 7187-7194

[181] Sun Z, Zhao YJ, Ni Qet al.. Solid-state Na metal batteries with superior cycling stability enabled by ferroelectric enhanced Na/Na₃Zr₂Si₂PO₁₂ interface. Small, 2022, 18 2200716

[182] Gao ZH, Yang JY, Li GCet al.. TiO₂ as second phase in Na₃Zr₂Si₂PO₁₂ to suppress dendrite growth in sodium metal solid-state batteries. Adv. Energy Mater., 2022, 12 2103607

[183] Zhang ZZ, Shao YJ, Lotsch Bet al.. New horizons for inorganic solid state ion conductors. Energy Environ. Sci., 2018, 11: 1945-1976

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

[185] Gao YR, Nolan AM, Du Pet al.. Classical and emerging characterization techniques for investigation of ion transport mechanisms in crystalline fast ionic conductors. Chem. Rev., 2020, 120: 5954-6008

[186] Wang CH, Wang S, Liu XDet al.. New insights into aliovalent substituted halide solid electrolytes for cobalt-free all-solid state batteries. Energy Environ. Sci., 2023, 16: 5136-5143

[187] Chen GY, Lu JC, Li Let al.. Microstructure control and properties of β″-Al₂O₃ solid electrolyte. J. Alloys Compd., 2016, 673: 295-301

[188] Shan SJ, Yang LP, Liu XMet al.. Preparation and characterization of TiO₂ doped and MgO stabilized Na-β″-Al₂O₃ electrolyte via a citrate sol–gel method. J. Alloys Compd., 2013, 563: 176-179

[189] Yang LP, Shan SJ, Wei XLet al.. The mechanical and electrical properties of ZrO₂–TiO₂–Na-β/β″-alumina composite electrolyte synthesized via a citrate sol–gel method. Ceram. Int., 2014, 40: 9055-9060

[190] Wang ZM, Feng XX, Zhang TFet al.. Preparation and characterization of CoO-doped and Li₂O-stabilized Na-β″-Al₂O₃ solid electrolyte via a solid-state reaction method. Ceram. Int., 2020, 46: 24668-24673

[191] Chen GY, Lu JC, Zhou XHet al.. Solid-state synthesis of high performance Na-β″-Al₂O₃ solid electrolyte doped with MgO. Ceram. Int., 2016, 42: 16055-16062

[192] Zhang GX, Wen ZY, Wu XWet al.. Sol–gel synthesis of Mg²⁺ stabilized Na-β″/β-Al₂O₃ solid electrolyte for sodium anode battery. J. Alloys Compd., 2014, 613: 80-86

[193] Zhu CF, Hong YF, Huang P. Synthesis and characterization of NiO doped beta-Al₂O₃ solid electrolyte. J. Alloys Compd., 2016, 688: 746-751

[194] Xu D, Jiang HY, Li Met al.. Synthesis and characterization of Y₂O₃ doped Na-β″-Al₂O₃ solid electrolyte by double zeta process. Ceram. Int., 2015, 41: 5355-5361

[195] Lu Y, Alonso JA, Yi Qet al.. A high-performance monolithic solid-state sodium battery with Ca²⁺ doped Na₃Zr₂Si₂PO₁₂ electrolyte. Adv. Energy Mater., 2019, 9 1901205

[196] Shen L, Yang J, Liu Get al.. High ionic conductivity and dendrite-resistant NASICON solid electrolyte for all-solid-state sodium batteries. Mater. Today Energy, 2021, 20 100691

[197] Yang J, Liu GZ, Avdeev Met al.. Ultrastable all-solid-state sodium rechargeable batteries. ACS Energy Lett., 2020, 5: 2835-2841

[198] Yu LL, Jiao Q, Liang Bet al.. Exceptionally high sodium ion conductivity and enhanced air stability in Na₃SbS₄ via germanium doping. J. Alloys Compd., 2022, 913 165229

[199] Feng XY, Fang H, Liu PCet al.. Heavily tungsten-doped sodium thioantimonate solid-state electrolytes with exceptionally low activation energy for ionic diffusion. Angew. Chem. Int. Ed., 2021, 60: 26158-26166

[200] Hayashi A, Masuzawa N, Yubuchi Set al.. A sodium-ion sulfide solid electrolyte with unprecedented conductivity at room temperature. Nat. Commun., 2019, 10 5266

[201] Tsuji F, Nasu A, Sakuda Aet al.. Mechanochemical synthesis and characterization of Na3–P1–W S4 solid electrolytes. J. Power. Sources, 2021, 506 230100

[202] Yubuchi S, Ito A, Masuzawa Net al.. Aqueous solution synthesis of Na₃SbS₄–Na₂WS₄ superionic conductors. J. Mater. Chem. A, 2020, 8: 1947-1954

[203] Rao RP, Chen HM, Wong LLet al.. Na_3+xM_xP_1−xS₄ (M = Ge⁴⁺, Ti⁴⁺, Sn⁴⁺) enables high rate all-solid-state Na-ion batteries Na_2+2δFe_2−δ(SO₄)₃|Na_3+xM_xP_1−xS₄|Na₂Ti₃O₇. J. Mater. Chem. A, 2017, 5: 3377-3388

[204] Zhu ZY, Chu IH, Deng Zet al.. Role of Na⁺ interstitials and dopants in enhancing the Na⁺ conductivity of the cubic Na₃PS₄ superionic conductor. Chem. Mater., 2015, 27: 8318-8325

[205] Yu ZX, Shang S-L, Seo JHet al.. Exceptionally high ionic conductivity in Na₃P_0.62As_0.38S₄ with improved moisture stability for solid-state sodium-ion batteries. Adv. Mater., 2017, 29: 1605561

[206] Shang SL, Yu ZX, Wang Yet al.. Origin of outstanding phase and moisture stability in a Na₃P_1−xAs_xS₄ superionic conductor. ACS Appl. Mater. Interfaces, 2017, 9: 16261-16269

[207] Jia HH, Peng LF, Zhang ZRet al.. 2020 Na_3.8[Sn_0.67Si_0.33]_0.8Sb_0.2S₄: a quinary sodium fast ionic conductor for all-solid-state sodium battery. J. Energy Chem., 2020, 48: 102-106

[208] Jia HH, Liang XM, An Tet al.. Effect of halogen doping in sodium solid electrolytes based on the Na–Sn–Si–P–S quinary system. Chem. Mater., 2020, 32: 4065-4071

[209] Weng W, Liu GZ, Shen Let al.. High ionic conductivity and stable phase Na_11.5Sn₂Sb_0.5Ti_0.5S₁₂ for all-solid-state sodium batteries. J. Power. Sources, 2021, 512 230485

[210] Kraft MA, Gronych LM, Famprikis Tet al.. Structure and sodium ion transport in Na_11+xSn_2+x(Sb_1–yP_y)_1–xS₁₂. Chem. Mater., 2020, 32: 6566-6576

[211] Moon CK, Lee HJ, Park KHet al.. Vacancy-driven Na⁺ superionic conduction in new Ca-doped Na₃PS₄ for all-solid-state Na-ion batteries. ACS Energy Lett., 2018, 3: 2504-2512

[212] Park KH, Kaup K, Assoud Aet al.. High-voltage superionic halide solid electrolytes for all-solid-state Li-ion batteries. ACS Energy Lett., 2020, 5: 533-539

[213] Shao QN, Yan CH, Gao MXet 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

[214] Chen RJ, Leung CLA, Huang C. Exploring the properties of disordered rocksalt battery cathode materials by advanced characterization. Adv. Funct. Mater., 2024, 34 2308165

[215] Huang LJ, Zhang L, Bi JYet al.. An insight into halide solid-state electrolytes: progress and modification strategies. Energy Mater. Adv., 2024, 4: 92

[216] Chen Y, Huang C. Realising higher capacity and stability for disordered rocksalt oxyfluoride cathode materials for Li ion batteries. RSC Adv., 2023, 13: 29343-29353

[217] Schlem R, Banik A, Eckardt Met al.. Na_3–xEr_1–xZr_xCl₆: a halide-based fast sodium-ion conductor with vacancy-driven ionic transport. ACS Appl. Energy Mater., 2020, 3: 10164-10173

[218] Ridley P, Nguyen LHB, Sebti Eet al.. Amorphous and nanocrystalline halide solid electrolytes with enhanced sodium-ion conductivity. Matter, 2024, 7: 485-499

[219] Fu JM, Wang S, Liang JWet al.. Superionic conducting halide frameworks enabled by interface-bonded halides. J. Am. Chem. Soc., 2023, 145: 2183-2194

[220] Yin YC, Yang JT, Luo JDet al.. A lacl₃-based lithium superionic conductor compatible with lithium metal. Nature, 2023, 616: 77-83

[221] Fu CY, Li YF, Xu WJet al.. Lacl₃-based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries. Nat. Commun., 2024, 15 4315

[222] Chi XW, Zhang Y, Hao Fet al.. An electrochemically stable homogeneous glassy electrolyte formed at room temperature for all-solid-state sodium batteries. Nat. Commun., 2022, 13 2854

[223] Bo SH, Wang Y, Ceder G. Structural and Na-ion conduction characteristics of Na₃PS_xSe_4−x. J. Mater. Chem. A, 2016, 4: 9044-9053

[224] Krauskopf T, Muy S, Culver SPet al.. Comparing the descriptors for investigating the influence of lattice dynamics on ionic transport using the superionic conductor Na₃PS_4–xSe_x. J. Am. Chem. Soc., 2018, 140: 14464-14473

[225] Krauskopf T, Pompe C, Kraft MAet al.. Influence of lattice dynamics on Na⁺Transport in the solid electrolyte Na₃PS_4–xSe_x. Chem. Mater., 2017, 29: 8859-8869

[226] Zhang SM, Zhao FP, Chang LYet al.. Amorphous oxyhalide matters for achieving lithium superionic conduction. J. Am. Chem. Soc., 2024, 146: 2977-2985

[227] Hu L, Wang JZ, Wang Ket al.. A cost-effective, ionically conductive and compressible oxychloride solid-state electrolyte for stable all-solid-state lithium-based batteries. Nat. Commun., 2023, 14 3807

[228] Zhang SM, Xu Y, Wu Het al.. A universal self-propagating synthesis of aluminum-based oxyhalide solid-state electrolytes. Angew. Chem. Int. Ed., 2024, 63 e202401373

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

[230] Hu L, Li H, Chen Fet al.. Overcoming the Na-ion conductivity bottleneck for the cost-competitive chloride solid electrolytes. J. Energy Chem., 2024, 95: 1-8

[231] Wu EA, Kompella CS, Zhu ZYet al.. New insights into the interphase between the Na metal anode and sulfide solid-state electrolytes: a joint experimental and computational study. ACS Appl. Mater. Interfaces, 2018, 10: 10076-10086

[232] Uematsu M, Yubuchi S, Tsuji Fet al.. Suspension synthesis of Na_3–xPS_4–xCl_x solid electrolytes. J. Power. Sources, 2019, 428: 131-135

[233] Gamo H, Phuc NHH, Muto Het al.. Effects of substituting S with Cl on the structural and electrochemical characteristics of Na₃SbS₄ solid electrolytes. ACS Appl. Energy Mater., 2021, 4: 6125-6134

[234] Feng XY, Chien PH, Zhu ZYet al.. Studies of functional defects for fast Na-ion conduction in Na_3−yPS_4−xCl_x with a combined experimental and computational approach. Adv. Funct. Mater., 2019, 29: 1807951

[235] Lu Y, Li L, Zhang Qet al.. Electrolyte and interface engineering for solid-state sodium batteries. Joule, 2018, 2: 1747-1770

[236] Liu QR, Chen QQ, Tang YBet al.. Interfacial modification, electrode/solid-electrolyte engineering, and monolithic construction of solid-state batteries. Electrochem. Energy Rev., 2023, 6 15

[237] Wu Z, Li XH, Zheng Cet al.. Interfaces in sulfide solid electrolyte-based all-solid-state lithium batteries: characterization, mechanism and strategy. Electrochem. Energy Rev., 2023, 6 10

[238] Chen KZ, Xia XM, Ma HGet al.. Sodiophilic V₂O₃-inducing layer for long lifespan and dendrite-free sodium metal anodes. Energy Mater. Adv., 2023, 4: 63

[239] Gao XR, Xing Z, Wang MYet al.. Comprehensive insights into solid-state electrolytes and electrode-electrolyte interfaces in all-solid-state sodium-ion batteries. Energy Storage Mater., 2023, 60 102821

[240] Yao YW, Wang XX, Dong CLet al.. Constructing effective interface for room-temperature Beta-Al₂O₃ based sodium metal batteries. J. Power. Sources, 2022, 523 231034

[241] Xiang L, Jiang DC, Gao Yet al.. Self-formed fluorinated interphase with Fe valence gradient for dendrite-free solid-state sodium-metal batteries. Adv. Funct. Mater., 2024, 34: 2301670

[242] Shen FC, Ma QL, Tietz Fet al.. In situ atomic-scale investigation of structural evolution during sodiation/desodiation processes in Na₃V₂(PO₄)₃-based all-solid-state sodium batteries. Adv. Sci., 2023, 10: 2301490

[243] Yu TH, Huang CY, Wu MCet al.. Atomic-scale investigation of Na₃V₂(PO4)₃ formation process in chemical infiltration via in situ transmission electron microscope for solid-state sodium batteries. Nano Energy, 2021, 87 106144

[244] Yang JY, Gao ZH, Ferber Tet al.. Guided-formation of a favorable interface for stabilizing Na metal solid-state batteries. J. Mater. Chem. A, 2020, 8: 7828-7835

[245] Helaley A, Liang XH. Solid-state sodium-ion batteries with composite polymer electrolytes and ALD-modified Na_0.7MnO₂ cathodes. Chem. Eng. J., 2025, 514 163173

[246] Hu P, Zhang Y, Chi XWet al.. Stabilizing the interface between sodium metal anode and sulfide-based solid-state electrolyte with an electron-blocking interlayer. ACS Appl. Mater. Interfaces, 2019, 11: 9672-9678

[247] Miao XG, Di HX, Ge XLet al.. AlF₃-modified anode-electrolyte interface for effective Na dendrites restriction in NASICON-based solid-state electrolyte. Energy Storage Mater., 2020, 30: 170-178

[248] Li R, Jiang DC, Du Pet al.. Negating Na‖Na₃Zr₂Si₂PO₁₂ interfacial resistance for dendrite-free and “Na-less” solid-state batteries. Chem. Sci., 2022, 13: 14132-14140

[249] Yu XL, Yao YW, Wang XXet al.. Rapid ultrasound welding toward compact Na/Beta-Al₂O₃ interface realizing room-temperature solid-state sodium metal battery. Energy Storage Mater., 2023, 54: 221-226

[250] Huang C, Zhang J, Snaith HJet al.. Engineering the membrane/electrode interface to improve the performance of solid-state supercapacitors. ACS Appl. Mater. Interfaces, 2016, 8: 20756-20765

[251] Huang C, Zhang J, Young NPet al.. Solid-state supercapacitors with rationally designed heterogeneous electrodes fabricated by large area spray processing for wearable energy storage applications. Sci. Rep., 2016, 6 25684

[252] Huang C, Young NP, Grant PS. Spray processing of TiO₂ nanoparticle/ionomer coatings on carbon nanotube scaffolds for solid-state supercapacitors. J. Mater. Chem. A, 2014, 2: 11022

[253] Wan HL, Mwizerwa JP, Qi XGet al.. Core–shell Fe_1–xS@Na_2.9PS_3.95Se_0.05 nanorods for room temperature all-solid-state sodium batteries with high energy density. ACS Nano, 2018, 12: 2809-2817

[254] Yue J, Zhu XY, Han FDet al.. Long cycle life all-solid-state sodium ion battery. ACS Appl. Mater. Interfaces, 2018, 10: 39645-39650

[255] Fan XL, Yue J, Han FDet al.. High-performance all-solid-state Na–S battery enabled by casting-annealing technology. ACS Nano, 2018, 12: 3360-3368

[256] Tufail MK, Zhai PB, Jia MYet al.. Design of solid electrolytes with fast ion transport: computation-driven and practical approaches. Energy Mater. Adv., 2023, 4: 15

[257] Xu GF, Luo L, Liang JWet al.. Origin of high electrochemical stability of multi-metal chloride solid electrolytes for high energy all-solid-state lithium-ion batteries. Nano Energy, 2022, 92 106674

[258] Barker K, McKinney SL, Artal Ret al.. The importance of A-site cation chemistry in superionic halide solid electrolytes. Nat. Commun., 2024, 15 7501

[259] Xu SJ, Cheng XB, Yang SJet al.. Performance enhancement of the Li₆PS₅Cl-based solid-state batteries by scavenging Lithium dendrites with LaCl₃-based electrolyte. Adv. Mater., 2024, 36 2310356

[260] Li MY, Dixit M, Shevchenko Pet al.. Pore-filling induced solid electrolyte failure of Ti-doped Na₃Zr₂Si₂PO₁₂ characterized by operando synchrotron X-ray tomography. Batteries Supercaps, 2025, 8 e202400429

[261] Song YM, Bhargava B, Stewart DMet al.. Electrochemical-mechanical coupling measurements. Joule, 2023, 7: 652-674

[262] Porzio J, Scown CD. Life-cycle assessment considerations for batteries and battery materials. Adv. Energy Mater., 2021, 11 2100771

[263] Puls S, Nazmutdinova E, Kalyk Fet al.. Benchmarking the reproducibility of all-solid-state battery cell performance. Nat. Energy, 2024, 9: 1310-1320

[264] Li GT, Su J, Huang C. Battery cathode with vertically aligned microstructure fabricated by directional ice templating. Small Sci., 2025, 5 2500198

Funding

Engineering and Physical Sciences Research Council(EP/Y009908/1)

Faraday Institution(FIRG060)

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