In Situ Engineered Plastic–Crystal Interlayers Enable Li-Rich Cathodes in PVDF-HFP-Based All-Solid-State Polymer Batteries

All-solid-state lithium batteries (ASSLBs) have gained substantial attention because of their intrinsic safety and high energy density.1 However, the commercialization of ASSLBs has been stymied by insufficient ionic conductivity of solid-state electrolytes, significant interfacial challenges, as well as the large gap between fundamental research and practical engineering. Over the past several years, we have been dedicated to developing ASSLBs from solid electrolyte synthesis to interface design to engineering practical solid-state pouch cells. First, a wet-chemistry method with a low cost was proposed to produce solid-state electrolytes at the kilogram level with a high room-temperature ionic conductivity (> 1 mS.cm-1).2 Second, the interfacial challenges of ASSLBs have been well addressed via increasing the ionic conductivity of interfacial buffer layers,3 manipulating interfacial nanostructures,4, 5 using single-crystal cathodes,6 deciphering interfacial reaction mechanisms,7 and constructing artificial solid electrolyte interphases (SEI),8 which successfully boosted interfacial ion and electron transport kinetics.9 Resultantly, ASSLBs demonstrated superior electrochemical performance. Third, practical solid-state pouch cells with high energy density have been engineered. Recently, a solvent-free process was proposed to fabricate freestanding and ultrathin inorganic solid electrolyte membranes.10 Furthermore, a feasible solid-liquid transformable interface was devised to improve the solid-solid ionic contact and accommodate the significant volume change of solid-state pouch cells.11, 12 The resultant solid-state pouch cells successfully demonstrated high energy density and unparalleled safety. In summary, our research not only provides an in-depth understanding of solid electrolyte synthesis and rational interface design but also offers feasible strategies to commercialize ASSLBs with high energy density, low cost, and excellent safety. References C. Wang, J. Liang, Y. Zhao, M. Zheng, X. Li and X. Sun, Energy Environ. Sci., 2021, 14, 2577-2619.C. Wang, J. Liang, J. Luo, J. Liu, X. Li, F. Zhao, R. Li, H. Huang, S. Zhao, L. Zhang, J. Wang and X. Sun, Sci. Adv., 2021, 7, eabh1896.C. Wang, J. Liang, S. Hwang, X. Li, Y. Zhao, K. Adair, C. Zhao, X. Li, S. Deng, X. Lin, X. Yang, R. Li, H. Huang, L. Zhang, S. Lu, D. Su and X. Sun, Nano Energy, 2020, 72, 104686.C. Wang, X. Li, Y. Zhao, M. N. Banis, J. Liang, X. Li, Y. Sun, K. R. Adair, Q. Sun, Y. Liu, F. Zhao, S. Deng, X. Lin, R. Li, Y. Hu, T.-K. Sham, H. Huang, L. Zhang, R. Yang, S. Lu and X. Sun, Small Methods, 2019, 3, 1900261.C. Wang, J. Liang, M. Jiang, X. Li, S. Mukherjee, K. Adair, M. Zheng, Y. Zhao, F. Zhao, S. Zhang, R. Li, H. Huang, S. Zhao, L. Zhang, S. Lu, C. V. Singh and X. Sun, Nano Energy, 2020, 76, 105015.C. Wang, R. Yu, S. Hwang, J. Liang, X. Li, C. Zhao, Y. Sun, J. Wang, N. Holmes, R. Li, H. Huang, S. Zhao, L. Zhang, S. Lu, D. Su and X. Sun, Energy Storage Mater., 2020, 30, 98-103.C. Wang, S. Hwang, M. Jiang, J. Liang, Y. Sun, K. Adair, M. Zheng, S. Mukherjee, X. Li, R. Li, H. Huang, S. Zhao, L. Zhang, S. Lu, J. Wang, C. V. Singh, D. Su and X. Sun, Adv. Energy Mater., 2021, 11, 2100210.C. Wang, Y. Zhao, Q. Sun, X. Li, Y. Liu, J. Liang, X. Li, X. Lin, R. Li, K. R. Adair, L. Zhang, R. Yang, S. Lu and X. Sun, Nano Energy, 2018, 53, 168-174.C. Wang, K. Adair and X. Sun, Acc. Mater. Res., 2022, 3, 21-32.C. Wang, R. Yu, H. Duan, Q. Lu, Q. Li, K. R. Adair, D. Bao, Y. Liu, R. Yang, J. Wang, S. Zhao, H. Huang and X. Sun, ACS Energy Lett., 2022, DOI: 10.1021/acsenergylett.1c02261, 410-416.C. Wang, Q. Sun, Y. Liu, Y. Zhao, X. Li, X. Lin, M. N. Banis, M. Li, W. Li, K. R. Adair, D. Wang, J. Liang, R. Li, L. Zhang, R. Yang, S. Lu and X. Sun, Nano Energy, 2018, 48, 35-43.C. Wang, K. R. Adair, J. Liang, X. Li, Y. Sun, X. Li, J. Wang, Q. Sun, F. Zhao, X. Lin, R. Li, H. Huang, L. Zhang, R. Yang, S. Lu and X. Sun, Adv. Funct. Mater., 2019, 29, 1900392.

Oxide-ceramic based all-solid-state lithium batteries (ASSLB) can provide high intrinsic safety, extended operational temperature range, and high energy density. As the first two are intrinsic to the materials system, one prerequisite to obtain high energy densities with such ASSLBs is the manufacturing of composite cathodes. Preferably, cathode active material (CAM) and electrolyte should form an intertwined 3D-network with an intimate extended contact between two phases. The interface between the CAM and the electrolyte should feature high total surface area with a low impedance to enable an efficient charge transfer and transport and minimize the resistance losses in a battery.Composite solid cathode microstructures can be formed via a co-sintering of solid electrolyte and CAM powders. However, many CAMs such as Li[Ni1-x-yCoxMny]O2 (NMC), Li[Ni1-x-yCoxAly]O2 (NCA) or Li2NiMn3O8 (LMO) cannot withstand sintering temperatures required, for oxide class solid electrolytes as Li7La3Zr2O12 (LLZ) or Li1+xAlxTi2-x(PO4)3, to obtain sintered composite cathodes. Furthermore, the thermodynamic stability of CAMs significantly decreases in the presence of solid electrolytes. Still, several groups have demonstrated that thermodynamic limitations can be significantly lessened via a kinetic control of the process such as reduction of reaction times and a careful control of powder morphology during ceramic sintering process.Following this work, we now demonstrate that FAST/SPS enables fabrication of different solid-state battery components within minutes such as a dense LLZ separator layer with a high ionic conductivity, a dense dual LiCoCO2 (LCO)/LLZ composite cathode without any interfacial reactions, and an integrated cathode half-cell consisting of a composite cathode and a LLZ separator layer at temperatures as low as 675 – 800 °C. Analyzing the structure, morphology, and electrochemical performance of the obtained components, we conclude that the impurities (carbonates) on the surface of LLZ powder play a decisive role in the formation of high-quality interfaces and the minimization of porosity. Furthermore, these impurities decrease the ionic conductivity at low sintering temperature and deteriorate the cycling stability of an ASSLB. High areal capacity of up to 4.0 mA h/cm2 at 80 °C with a constant current of 50 µA/cm2 and a good utilization of LCO was achieved for ASSLB with LLZ powders free of surface impurities. FAST/SPS can therefore open new processing windows for ceramic-based ASSLBs to alleviate the problem of interphase formation.

Utmost limits of various solid electrolytes in all-solid-state lithium batteries: A critical review

All-solid-state lithium batteries (ASSLBs) have gained intensive attention because of their intrinsic safety and high energy density.1 However, significant interfacial challenges such as detrimental interfacial reactions, poor solid-solid ionic contact, and lithium dendrite growth have stymied the development of ASSLBs. Besides that, the large gap between fundamental research and practical engineering design has slowed down ASSLBs commercialization. Over the past five years, our group has been dedicated to the research and development of ASSLBs, with the aims of overcoming the interfacial challenges and pushing ASSLBs closer to commercialization. First, we have regulated the interfacial ion and electron transport via increasing the ionic conductivity of interfacial buffer layers,2 manipulating interfacial nanostructures,3, 4 using single-crystal cathodes,5 deciphering interfacial reaction mechanisms,6 and constructing artificial solid electrolyte interphases (SEI).7 Based on these advanced and innovative strategies, the large interfacial resistance was successfully eliminated. As a result, ASSLBs with sulfide electrolytes demonstrated both ultra-long cycling stability and high-rate performance. To transfer these viable technologies into practical application and bridging the large gap between laboratory research and practical full cells, we are committed to engineering solid-state pouch cells with competitive energy density and low cost. Recently, a solvent-free and cost-effective process was developed for fabricating ultra-thin inorganic solid electrolyte membranes as well as solid-state thick electrodes. Furthermore, a solid-liquid interface and a plastic crystal electrolyte were engineered to enable practical solid-state pouch cells with high energy density and excellent safety.8, 9 These works not only provide an in-depth understanding of interfacial mass and charge transport but also offer feasible strategies to commercialize practical solid-state pouch cells. References C. Wang, J. Liang, Y. Zhao, M. Zheng, X. Li, X. Sun*, Energy Environ. Sci. , 2021, doi:10.1039/d1ee00551k.C. Wang, J. Liang, S. Hwang, X. Li, Y. Zhao, K. Adair, C. Zhao, X. Li, S. Deng, X. Lin, X. Yang, R. Li, H. Huang, L. Zhang, S. Lu, D. Su and X. Sun*, Nano Energy , 2020, 72, 104686.C. Wang, X. Li, Y. Zhao, M. N. Banis, J. Liang, X. Li, Y. Sun, K. R. Adair, Q. Sun, Y. Liu, F. Zhao, S. Deng, X. Lin, R. Li, Y. Hu, T.-K. Sham, H. Huang, L. Zhang, R. Yang, S. Lu and X. Sun*, Small Methods , 2019, 3, 1900261.C. Wang, J. Liang, M. Jiang, X. Li, S. Mukherjee, K. Adair, M. Zheng, Y. Zhao, F. Zhao, S. Zhang, R. Li, H. Huang, S. Zhao, L. Zhang, S. Lu, C. V. Singh and X. Sun*, Nano Energy, 2020, 76, 105015.C. Wang, R. Yu, S. Hwang, J. Liang, X. Li, C. Zhao, Y. Sun, J. Wang, N. Holmes, R. Li, H. Huang, S. Zhao, L. Zhang, S. Lu, D. Su and X. Sun*, Energy Storage Mater ., 2020, 30, 98-103.C. Wang, S. Hwang, M. Jiang, J. Liang, Y. Sun, K. Adair, M. Zheng, S. Mukherjee, X. Li, R. Li, H. Huang, S. Zhao, L. Zhang, S. Lu, J. Wang, C. V. Singh, D. Su, X. Sun*. Adv. Energy Mater., 2021, 2100210. doi:10.1002/aenm.202100210.C. Wang, Y. Zhao, Q. Sun, X. Li, Y. Liu, J. Liang, X. Li, X. Lin, R. Li, K. R. Adair, L. Zhang, R. Yang, S. Lu and X. Sun*, Nano Energy, 2018, 53, 168-174.C. Wang, Q. Sun, Y. Liu, Y. Zhao, X. Li, X. Lin, M. N. Banis, M. Li, W. Li, K. R. Adair, D. Wang, J. Liang, R. Li, L. Zhang, R. Yang, S. Lu and X. Sun*, Nano Energy, 2018, 48, 35-43.C. Wang, K. R. Adair, J. Liang, X. Li, Y. Sun, X. Li, J. Wang, Q. Sun, F. Zhao, X. Lin, R. Li, H. Huang, L. Zhang, R. Yang, S. Lu and X. Sun*, Adv. Funct. Mater. , 2019, 29, 1900392.

Halide solid electrolytes (SEs), like Li3InCl6, are promising for high-energy all-solid-state lithium batteries (ASSLBs) due to their high ionic conductivity and compatibility with high-voltage cathodes. Although solvent-mediated synthesis offers a scalable route to phase-pure Li3InCl6, a lack of understanding of critical synthetic parameters, specifically crystallization kinetics, generally yields SE materials with inferior properties. This study systematically investigates the influence of evaporative crystallization temperature and environment on the phase purity, microstructure, defect chemistry of Li3InCl6 SE, and how these factors collectively impact its transport properties and electrochemical performance. It is revealed that slow crystallization under ambient conditions and moderate temperatures (20-60 °C) yields phase-pure Li3InCl6 with the highest ionic conductivity ever reported for the water-mediated route -3.97 mS cm-1 with carbon contact and 2.98 mS cm-1 without. In contrast, high temperature and non-ambient processing introduce structural defects, increase grain-boundary impedance, and promote impurity incorporation, leading to a significant drop in conductivity. Full cells incorporating the optimized Li3InCl6 deliver high capacity even at a low 20 °C, along with excellent stability (>95%) at high areal loading, supported by low and stable cathode interfacial impedance. This work addresses a critical knowledge gap in solvent-mediated synthesis of halide SEs, providing broadly applicable insights for designing phase-pure, high-conductivity materials for next-generation ASSLBs.

Research on safe, high-energy density all-solid-state lithium batteries (ASSLBs) has been rapidly advancing to address the major safety and functional limitations of conventional batteries utilizing liquid electrolytes. The development of solid electrolytes with high ionic conductivity and a wide electrochemical stability window is therefore crucial for enabling high-performance ASSLBs. In this investigation, flexible polymer composite solid electrolyte (PCSE) membranes were fabricated via a solution casting method using a PEO polymer matrix with optimized LiTFSI salt content, and Li1.3Al0.3Ti1.7(PO4)3 (LATP) ceramic filler. The PCSE membrane containing 10 wt% LATP ceramic filler (10% LATP) exhibited an ionic conductivity of 0.19 × 10-3 S cm-1 at 60 °C. The electrochemical stability of the polymer membranes was assessed via lithium stripping-plating experiments at 0.1 mA cm-2. The 10% LATP PCSE membrane demonstrated notable stability for over 900 h without significant voltage fluctuations, confirming its superior interfacial robustness with lithium. The LFP/10% LATP/Li cell at 60 °C delivered a first cycle discharge capacity of 151.6 mAh g-1, compared to 143.4 mAh g-1 for the LFP/20% LiTFSI/Li cell at 0.1C. The cell also showed remarkable rate capability and cycling performance, retaining a high capacity of 103.9 mAh g-1 at 1C with 86.8% capacity retention after 150 cycles. Additionally, the optimized 10% LATP PCSE membrane was also tested with a high-voltage NMC622 cathode, demonstrating its potential applicability in high-voltage ASSLBs.

The all-solid-state lithium battery (ASSB) has received great attention due to its greater safety than the conventional lithium-ion battery (LIB). Sulfide-based inorganic solid electrolytes are an important component to fabricate the ASSB. But to attain a better performance, the ionic conductivity and electrochemical stability of the sulfide-based solid electrolytes need to be improved. In this work, we prepared the metal-oxide-doped/mixed Li7P2S8I0.75Br0.25 lithium superionic conductors by a dry ball-milling process. The high ionic conductivity was achieved by a low-temperature (200 °C) heat-treatment process. The metal-oxide-doped Li7P2S8I0.75Br0.25 solid electrolyte exhibited a higher ionic conductivity value of 7.3 mS cm-1 at room temperature than the bare Li7P2S8I0.75Br0.25 solid electrolyte. The structural characteristics of the prepared solid electrolytes were studied by solid NMR and laser Raman analysis. The electrochemical stability of the prepared solid electrolyte was studied by cyclic voltammetry and DC charge-discharge analysis. The addition of metal oxide increased the electrochemical stability and dry-air stability of the Li7P2S8I0.75Br0.25 solid electrolyte. The Ta2O5-doped Li7P2S8I0.75Br0.25 solid electrolyte was stable even after 300 charge-discharge DC cycles and also 100 h of dry-air exposure. Further, the Ta2O5-doped Li7P2S8I0.75Br0.25 solid electrolyte-based ASSB exhibited a high discharge capacity value of 184 mA h g-1 at 0.1 C rate with 66% initial cycle Coulombic efficiency.

As lithium rechargeable batteries are considered a potential candidate for large‐scale energy storage applications in devices such as electric vehicles (EVs) and smart grids, their safety has become of prime concern. This calls for the need to replace the flammable organic liquid electrolyte (LE) with an inorganic solid electrolyte (SE), and thus, develop bulk‐type all‐solid‐state lithium batteries (ASLBs), fabricated using a scalable process. Sulfide SEs are considered the most competitive candidate owing to their high conductivity at room temperature (10−3–10−2 S cm−1), which is comparable to that of LEs, and their ductility, which enables the fabrication of ASLBs simply using cold pressing. In the present review, issues and challenges to be faced for the fabrication of bulk‐type ASLBs using sulfide SEs are presented and discussed, with a special focus on the development of SEs, compatibility of the electrode materials with SEs, and structure of the composite electrodes. Recent progress made with the aim of addressing the aforementioned issues and challenges is also presented, to provide an outlook on the future of SEs and ASLBs.

Battery safety is increasingly at the forefront of consumer concerns, especially regarding electric vehicles. Current lithium ion battery technology utilizes liquid electrolytes, which have very high ionic conductivities but are extremely flammable. To improve safety, researchers are investigating replacing liquid electrolytes in lithium ion batteries with solid electrolytes. A promising approach is the use of solid polymer composite electrolytes where lithium conductive ceramic powders are dispersed into polymer electrolyte matrix. These materials are intended to improve lithium conductivities and mechanical properties relative to pure polymer electrolyte, lower manufacturing and battery cell construction costs relative to using pure ceramic electrolytes, and eliminate volatile and flammable electrolyte solvents. Currently, the archetypal polymer matrix used in composite electrolytes is polyethylene oxide (PEO). When mixed with lithium salts, such as lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and ceramics, such as Li7La3Zr2O12 (LLZO), PEO based composites have conductivities (~10-7 S/cm at room temperature) that are still insufficient for today’s applications. In addition, PEO tends to crystallize and has poor oxidative stability (decomposition ca. 4V). We are exploring poly(polyethylene glycol methyl ether methacrylate) (PEGMA) and polyethylene carbonate (PEC) as alternatives to PEO to address issues with crystallization and oxidative stability, respectively. Composite electrolytes are fabricated by blending bulk polymer with LiTFSI and LLZO powders. We have formed rubbery PEGMA-based composites with comparable conductivities (~10-7 S/cm at room temperature, 70 vol% polymer, 10:1 ethylene oxide:lithium). Lithium symmetric cycling was observed to be stable over 250 hours at 1C. We have also recently formed stand-alone PEC based composites with high conductivities (~10-6 S/cm at room temperature, 60 vol% polymer, 10:1 ethylene carbonate:lithium). Investigations into the origin of this high conductivity and measurements of electrochemical stability are currently underway.

In situ transmission electron microscopy for understanding materials and interfaces challenges in all-solid-state lithium batteries

A simplified process to prepare solid electrolytes (SEs) that fulfill long cyclability, fast‐charging performance, and wide‐temperature feasibility in all‐solid‐state lithium batteries (ASSLBs) is important. Here, amorphous LiTaOCl4 (aLTOC) SE is synthesized within only four hours via a two‐step reaction by high‐energy ball milling method, which exhibits high ionic conductivity and excellent interfacial compatibility. A bilayer SE based on aLTOC and sulfide along with corresponding ASSLBs, are constructed. Furthermore, slight evolution of the unusual microstructure in the chloride/sulfur interfacial region is observed and analyzed. Density functional theory calculations show that S tends to displace O sites in TaO2Cl4 octahedra instead of Cl sites. As a result of the enhanced interfacial stability and reduced formation of ionically insulating phases, the assembled ASSLBs achieve superior rate performance and cyclability in a wide temperature range. Notably, the ASSLBs show capacity retention of 84.4% and 77.6% after 2000 and 1000 cycles at current density of 10C at 30 and 60 °C, respectively. Importantly, even under −20 °C, the cell works stably over 1600 cycles with capacity retention of 76.3% at 0.5C. The work pave the way for the massive production of high‐performance amorphous chloride electrolytes and the realization of fast‐charging ASSLBs with long cycle life.

All solid-state lithium batteries (ASSLBs) employing inorganic solid electrolytes or solid polymer electrolytes are attracting increasing interests for electrochemical energy storage devices due to their advantages of high energy density, high safety, wide operating temperature range and long cycle life. However, the large interfacial resistance originated from the insufficient solid-solid contact at electrolyte/electrode interface hinders the development of ASSLBs. In addition, the interfacial stability and compatibility also greatly affect the electrochemical performance of batteries. To realize the ASSLB’s application requires significant research in solid electrolyte materials and solid electrolyte/electrode interfaces. This review summarizes the research and development in solid electrolyte materials and the interfaces of solid electrolyte/electrode, paying special attention to the challenges and progress for the studies of interface issues in ASSLBs. Based on the overview, we attempt to propose approaches to the issue by interface engineering and prospective developments of ASSLBs.

Solid-state batteries (SSBs) promise improved safety and energy density by using solid electrolytes (SEs) and high-voltage cathodes. However, the SEs are unstable at high voltages, leading to oxidative chemical decomposition at the SE/CAM (cathode active material) interface, resulting in the formation of an insulating cathode-electrolyte interface (CEI) on CAM particles [1]. The layered oxide cathodes (LiNixMnyCozO2; NMC), when cycled at elevated voltages (>4.3V), undergo irreversible structural and chemical deformations, including the formation of kinetically less active phases (spinel and rock-salt), oxygen evolution, and mechanical degradation (intergranular or intraparticle cracking) [2]. The instability of the SE, CAM particles, and SE/CAM interface, collectively, results in inferior electrochemical performance, including low initial Coulombic efficiency (CE), increased cell polarization and impedance, reduced rate capability, and capacity fade during extended cycling.Therefore, it is crucial to stabilize the SE/CAM interface and preserve the CAM structure in SSB cathodes, particularly during high-voltage cycling. This is primarily achieved by developing a protective coating on CAM particles. Niobium (Nb)-based coatings are promising to protect the SE/CAM interface, mostly developed by wet chemical and solid-state processing routes that involve high-temperature annealing. On the other hand, atomic layer deposition (ALD) is a powerful technique for coatings, providing precise thickness and composition control [3]. Unfortunately, these coatings may have ‘hot spots’ for local current focusing (crystalline defects, i.e., grain boundaries) and oxygen release (pinholes at particle-particle contacts) [4].In the present study, we developed an Nb-based thin conformal amorphous coating on single crystal NMC CAM particles using ALD equipped with a rotary bed attachment. Unlike traditional stationary ALD reactors, ALD with a rotary bed attachment ensures a pinhole-free continuous coating on CAM powders. The low-temperature ALD process results in an amorphous coating (chemically and structurally isotropic), which is expected to effectively withstand the volumetric changes occurring in CAM particles during repetitive charge/discharge cycling. Comparing the performance of uncoated and coated samples tested at high voltages (≥4.5V) shows that the coated cathodes display significant improvements, including high initial Coulombic efficiency (91% vs. 83%), enhanced rate capability (10x higher accessible capacity at a 2C rate), and improved capacity retention during extended cycling (99.4% after 500 cycles). These enhancements are attributed to reduced cell polarization and interfacial impedance in coated samples. Post-mortem electron microscopy and XRD analysis confirm that the coating remains intact, inhibiting oxygen release from the CAM structure and the formation of inactive phases (spinel and rock-salt), thereby preventing CAM particle cracking. These findings pave the way for stable and high-performance SSBs with high-voltage cathodes.Keywords: Solid-state batteries, composite cathodes, Nb-based coating, atomic layer deposition (ALD), high voltage stability.Reference: Xiao et al. Understanding interface stability in solid-state batteries. Nat. Rev. Mater. 5 (2020) 105.Wang et al. Single crystal cathodes enabling high-performance all-solid-state lithium-ion batteries. Energy Storage Mater. 30 (2020) 98.Koshtyal et al. Applications and Advantages of Atomic Layer Deposition for Lithium-Ion Batteries Cathodes: Review. Batteries 8 (2022) 184.Cheng et al. Materials Design Principles of Amorphous Cathode Coatings for Lithium-Ion Battery Applications. J. Mater. Chem. A 10 (2022) 22245.

Enabling high-performance all-solid-state lithium batteries with high ionic conductive sulfide-based composite solid electrolyte and ex-situ artificial SEI film

All-solid-state lithium batteries (ASSLBs) have attracted increasing attention due to their high safety and energy density. Among all corresponding solid electrolytes, sulfide electrolytes are considered to be the most promising ion conductors due to high ionic conductivities. Despite this, many challenges remain in the application of ASSLBs, including the stability of sulfide electrolytes, complex interfacial issues between sulfide electrolytes and oxide electrodes as well as unstable anodic interfaces. Although oxide cathodes remain the most viable electrode materials due to high stability and industrialization degrees, the matching of sulfide electrolytes with oxide cathodes is challenging for commercial use in ASSLBs. Based on this, this review will present an overview of emerging ASSLBs based on sulfide electrolytes and oxide cathodes and highlight critical properties such as compatible electrolyte/electrode interfaces. And by considering the current challenges and opportunities of sulfide electrolyte-based ASSLBs, possible research directions and perspectives are discussed.