All-solid-state sodium-ion batteries that operate at room temperature are attractive candidates for use in large-scale energy storage systems. However, materials innovation in solid electrolytes is imperative to fulfill multiple requirements, including high conductivity, functional synthesis protocols for achieving intimate ionic contact with active materials, and air stability. A new, highly conductive (1.1 mS cm(-1) at 25 °C, Ea =0.20 eV) and dry air stable sodium superionic conductor, tetragonal Na3 SbS4 , is described. Importantly, Na3 SbS4 can be prepared by scalable solution processes using methanol or water, and it exhibits high conductivities of 0.1-0.3 mS cm(-1) . The solution-processed, highly conductive solidified Na3 SbS4 electrolyte coated on an active material (NaCrO2 ) demonstrates dramatically improved electrochemical performance in all-solid-state batteries.

, 0.7Li(CB 9 H 10)−0.3Li(CB 11 H 12), 6.7 mS cm −1), [11,12] and halides (e.g., Li 3 YX 6 [X = Cl, Br], 0.51-1.7 mS cm −1). [13,14] Thus far, oxide and sulfide SEs have been the most commonly investigated candidates. However, their pros and cons counteract each other. Oxide SEs possess high intrinsic electrochemical oxidation stabilities and relatively acceptable chemical stabilities; however, owing to their brittle nature, it is difficult to integrate them in devices. [3,10,15-17] On the other hand, the most important advantage of sulfide SEs, that is, mechanical deformability, which enables scalable cold-pressing-based fabrication protocols, is offset by their poor (electro)chemical stabilities. [3,16,18-20] On exposing sulfide SEs to humid air, the evolution of toxic H 2 S gases occurs. [21-26] Moreover, sulfide SEs exhibit oxidative decomposition at <3 V (vs Li/Li +) and are also incompatible with conventional layered LiMO 2 (M = Ni, Co, Mn, and Al) cathodes. [16,19,27] This issue can be alleviated by using protective coatings, such as LiNbO 3 and Li 3−x B 1−x C x O 3 ; [7,27] however, this constitutes additional processing costs. Furthermore, the oxidative decomposition of sulfide SEs at the surface of conductive carbon additives is unavoidable. [28-31] Recently, through reinvestigations on halide SEs, several compounds exhibiting Li + conductivities exceeding 10 −4 S cm −1 have been identified. [13,32−36] Asano and coworkers reported that trigonal Li 3 YCl 6 and monoclinic Li 3 YBr 6 showed high Li + Owing to the combined advantages of sulfide and oxide solid electrolytes (SEs), that is, mechanical sinterability and excellent (electro)chemical stability, recently emerging halide SEs such as Li 3 YCl 6 are considered to be a game changer for the development of all-solid-state batteries. However, the use of expensive central metals hinders their practical applicability. Herein, a new halide superionic conductors are reported that are free of rare-earth metals: hexagonal close-packed (hcp) Li 2 ZrCl 6 and Fe 3+-substituted Li 2 ZrCl 6 , derived via a mechanochemical method. Conventional heat treatment yields cubic close-packed monoclinic Li 2 ZrCl 6 with a low Li + conductivity of 5.7 × 10 −6 S cm −1 at 30 °C. In contrast, hcp Li 2 ZrCl 6 with a high Li + conductivity of 4.0 × 10 −4 S cm −1 is derived via ball-milling. More importantly, the aliovalent substitution of Li 2 ZrCl 6 with Fe 3+ , which is probed by complementary analyses using X-ray diffraction, pair distribution function, X-ray absorption spectroscopy, and Raman spectroscopy measurements, drastically enhances the Li + conductivity up to ≈1 mS cm −1 for Li 2.25 Zr 0.75 Fe 0.25 Cl 6. The superior interfacial stability when using Li 2+x Zr 1−x Fe x Cl 6 , as compared to that when using conventional Li 6 PS 5 Cl, is proved. Furthermore, an excellent electrochemical performance of the all-solid-state batteries is achieved via the combination of Li 2 ZrCl 6 and single-crystalline LiNi 0.88 Co 0.11 Al 0.01 O 2 .

Moreover, sulfide SEs in contact with an inactive component of conductive carbon additives are oxidatively decomposed at the entire range of operating voltages of Li [Ni,Mn,Co]O 2 , leading to the lowered initial Coulombic efficiency (ICE) and gradual capacity fading upon cycling. [49] Owing to the incompressible feature of SEs, electrochemomechanical effects on the performance are also critical for allsolid-state batteries. [37,50,51] Even slight volumetric strains of a few percentages in LiMO 2 during charge and discharge induces loosening and/or loss of interfacial ionic contacts. [18,37,38,52] Moreover, very recently, our group demonstrated that commercial-grade LiNi 0.80 Co 0.10 Mn 0.10 O 2 , consisting of randomly oriented grains, was susceptible to severe disintegration of the secondary particles even at the initial charge and discharge due to the anisotropic volumetric strains, which led to poor electrochemical performance of low ICE and degradation of cycling retention. [37] In this regard, recently emerging research directions for cathodes in advanced LIBs based on LEs, the development of cracking-free single-crystalline Ni-rich layered oxides, [30,[53][54][55][56][57][58] could be in the same vein for the development of practical ASLBs.The recent discovery of halide SEs (Li 3 YX 6 (X = Cl, Br)) with Li + conductivities of over 10 −4 S cm −1 has opened new opportunities due to their excellent electrochemical oxidation stability (>4 V vs Li/Li + ) and much better chemical stability (more oxygen-resistant and no H 2 S evolution), compared to sulfide SEs, as well as deformability. [59,60] By exploration of the Li 3 YX 6 analogs, highly Li + conductive halide SEs of Li 3 InCl 6 (1.5 mS cm −1 ), [61] Li 3 ErCl 6 (0.33 mS cm −1 ), [62] Li 3 ScCl 6 (3.0 mS cm −1 ), [63,64] and Li 3−x M 1−x Zr x Cl 6 (M = Y, Er, 1.4 mS cm −1 ), [65] Li 2+x Zr 1−x Fe x Cl 6 (max. ≈ 1 mS cm -1 ) [66] were identified. By employing these new halide SEs, uncoated LiCoO 2 electrodes showed good electrochemical performance, which was attributed to their high electrochemical oxidation stability. [65,66,67] To date, reports on the application of halide SE for Ni-rich layered oxides are scarce. [64,66] The aforementioned advances in understanding the failure modes of Ni-rich layered oxides in terms of electrochemical and electrochemo-mechanical stabilities, advanced Ni-rich layered oxides with electrochemo-mechanically compliant microstructures, and new halide SEs led us, herein, to the rigorous investigation of all-solid-state cells with variations in Ni-rich layered oxides (single-crystalline LiNi 0.88 Co 0.11 Al 0.01 O 2 (single-NCA) vs conventional polycrystalline LiNi 0.88 Co 0.11 Al 0.01 O 2 (poly-NCA)) and SEs (halide SE Li 3 YCl 6 (LYC) vs conventional sulfide SE Li 6 PS 5 Cl 0.5 Br 0.5 (LPSX)). Notably, several critical counteracting pros and cons of two sets of NCAs and SEs, summarized in Figure 1a, pose intriguing questions on the type of factors that are critical from the viewpoint of designing ASLBs. First, compared to poly-...

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