All-solid-state Lithium-sulfur Batteries Research Articles

Engineering Triple-Phase Interfaces with Hierarchical Carbon Nanocages for High-Areal-Capacity All-Solid-State Li-S Batteries.

All-solid-state lithium-sulfur batteries (ASSLSBs) have garnered widespread attention due to their advantages of high energy density and enhanced safety. However, the typical composite structure composed of solid-state electrolyte (SE), discrete conducting carbon black, and microsized sulfur (μ-S) with long-range Li+/e- conducting path and huge volume changes, suffers from sluggish charge transport and severe electrochemical-mechanical failure. In this work, a unique hierarchical carbon nanocage (hCNC) is applied as a continuous conducting network where nanosized sulfur are confined. Due to the synergistic effects of multi-dimensional (particle, interface, and electrode) structural engineering, this new sulfur-carbon composite cathode (S@hCNC39) can achieve uniform distribution of sulfur and carbon, and efficiently constructs triple-phase interfaces, showing enhanced charge-carrier transport and improved electrochemical-mechanical stability. Remarkable cycling performance of 89% after 300 cycles at 0.2C at 30°C is realized in ASSLSBs assembled with S@hCNC39. Notably, ASSLSBs achieve an ultrahigh areal capacity of 9.95 mAh cm-2 with stable cycling at 60°C with high sulfur contents of 40% and high sulfur loadings of 6mg cm-2. These results provide critical insights into the design of rational sulfur-carbon composites and offer a viable approach to enhance the overall performance of ASSLSBs.

Accelerating Lithium‐Ion Transfer and Sulfur Conversion via Electrolyte Engineering for Ultra‐Stable All‐Solid‐State Lithium–Sulfur Batteries

AbstractOffering ultrahigh energy density and exceptional safety, all‐solid‐state lithium–sulfur batteries (ASSLSBs) can be one of the most promising energy storage systems if their inherent challenges, including slow Li+ mass transport and insufficient sulfur utilization efficiency, are completely tackled. In this work, an amide‐based electrolyte additive with a high Gutmann donor number is used to construct a deep eutectic system, a “one‐stone‐two‐birds” solution to address these issues. In particular, an acetamide is used to interact with the insulative Li2S via a strong S─H bond and Li─O bond to boost the electrochemical reaction kinetics of lithium‐sulfur (Li─S) chemistry and sulfur utilization and simultaneously form a deep eutectic LiTFSI‐acetamide system to enhance ionic conductivity of solid polymer electrolytes (SPEs). Such a seamless integration of this system into the solid‐state LSBs helps deliver a high initial discharge specific capacity of 1012 mAh g−1 at 0.05 C and attain a stable cyclability for 1300 cycles at 0.1 C. This remarkable achievement in high performance and stability can effectively facilitate the commercialization of ASSLSBs.

(Invited) Understanding Electrochemical Reaction Mechanisms of Sulfur in All-Solid-State Batteries through Operando and Theoretical Studies

All-solid-state lithium-sulfur batteries (ASLSBs) have been considered a promising next-generation energy storage technology due to their remarkable safety and high energy density. In ASLSBs, the electrochemical pathways are intrinsically different from conventional Li-S batteries using liquid electrolytes. However, the mechanism still lacks clear identification and deep understanding. Herein, for the first time, we investigated the chemistries and explored the electrochemical reaction mechanism in ASLSBs through coupling operando Raman spectroscopy and ex-situ X-ray absorption spectroscopy. We proved that no long-chain lithium polysulfides (Li2Sn, 4≤n≤8) were formed during the redox reactions, but a short-chain polysulfide (Li2S2) intermediate phase formation was identified in the conversion between active material S8 and reduction product Li2S. This evidence explains the electrochemical behavior differences of Li-S batteries when using liquid and solid electrolytes. Moreover, there are partial S8 and Li2S2 remaining at the cathode even at fully lithiation stage, suggesting the sluggish reaction kinetics in the ASLSBs. This study revealed the generation of Li2S2 intermediates in ASLSBs, inspiring future research to further improve the performance of ASLSBs through completing the conversions and promoting reaction kinetics in ASLSBs.

All-Solid-State Lithium-Sulfur Batteries of High Cycling Stability and Rate Capability Enabled by a Self-Lithiated Sn-C Interlayer.

All-solid-state lithium-sulfur batteries (ASSLSBs) have attracted intense interest due to their high theoretical energy density and intrinsic safety. However, constructing durable lithium (Li) metal anodes with high cycling efficiency in ASSLSBs remains challenging due to poor interface stability. Here, a compositionally stable, self-lithiated tin (Sn)-carbon (C) composite interlayer (LSCI) between Li anode and solid-state electrolyte (SSE), capable of homogenizing Li-ion transport across the interlayer, mitigating decomposition of SSE, and enhancing electrochemical/structural stability of interface, is developed for ASSLSBs. The LSCI-mediated Li metal anode enables stable Li plating/stripping over 7000h without Li dendrite penetration. The ASSLSBs equipped with LSCI thus exhibit excellent cycling stability of over 300 cycles (capacity retention of ≈80%) under low applied pressure (<8MPa) and demonstrate improved rate capability even at 3C. The enhanced electrochemical performance and corresponding insights of the designed LSCI broaden the spectrum of advanced interlayers for interface manipulation, advancing the practical application of ASSLSBs.

Insight into All‐Solid‐State Li–S Batteries: Challenges, Advances, and Engineering Design

AbstractThe advancement of conventional lithium–sulfur batteries (LSBs) is hindered by the shuttle effect and corresponding safety issues. All‐solid‐state lithium–sulfur batteries (ASSLSBs) substitute the liquid electrolytes with solid‐state electrolytes (SEs) to completely isolate the cathode and anode, thereby effectively suppressing polysulfide migration and growth while significantly enhancing energy density and safety. However, the development of ASSLSBs is accompanied by several challenges such as the formation of Li dendrites, electrode degradation, poor interfacial wettability, and sluggish reaction kinetics, etc. This review systematically summarizes the recent advancements made in ASSLSBs. First, a comprehensive overview of the research conducted on advanced cathodes utilizing sulfur (S) and lithium sulfide (Li2S) is displayed. Subsequently, the SEs are classified and discussed that have been implemented in ASSLSBs. Furthermore, the issues of interfaces and anodes in ASSLSBs are analyzed. Finally, based on current laboratory advancements, rational design guidelines are proposed for each component of ASSLSBs while also presenting four practical recommendations for facilitating early commercialization.

Developing Cathode Films for Practical All-Solid-State Lithium-Sulfur Batteries.

The development of all-solid-state lithium-sulfur batteries (ASSLSBs) toward large-scale electrochemical energy storage is driven by the higher specific energies and lower cost in comparison with the state-of-the-art Li-ion batteries. Yet, insufficient mechanistic understanding and quantitative parameters of the key components in sulfur-based cathode hinders the advancement of the ASSLSB technologies. This review offers a comprehensive analysis of electrode parameters, including specific capacity, voltage, S mass loading and S content toward establishing the specific energy (Wh kg-1) and energy density (Wh L-1) of the ASSLSBs. Additionally, this work critically evaluates the progress in enhancing lithium ion and electron percolation and mitigating electrochemical-mechanical degradation in sulfur-based cathodes. Last, a critical outlook on potential future research directions is provided to guide the rational design of high-performance sulfur-based cathodes toward practical ASSLSBs.

High-modulus solid electrolyte interphase layer with gradient composition enables long-cycle all-solid-state lithium-sulfur batteries

All-solid-state lithium-sulfur batteries (ASSLSBs) have become one of the most potential candidates for the next-generation high-energy systems due to their intrinsic safety and high theoretical energy density. However, PEO-based ASSLSBs face the dilemma of insufficient Coulombic efficiency and long-term stability caused by the coupling problems of dendrite growth of anode and polysulfide shuttle of cathode. In this work, 1,3,5-trioxane (TOX) is used as a functional additive to design a PEO-based composite solid-state electrolyte (denoted as TOX-CSE), which realizes the stable long-term cycle of an ASSLSB. The results show that TOX can in-situ decompose on the anode to form a composite solid electrolyte interphase (SEI) layer with rich-organic component. It yields a high average modulus of 5.0 GPa, greatly improving the mechanical stability of the SEI layer and thus inhibiting the growth of dendrites. Also, the robust SEI layer can act as a barrier to block the side reaction between polysulfides and lithium metal. As a result, a Li-Li symmetric cell assembled with a TOX-CSE exhibits prolonged cycling stability over 2000 h at 0.2 mA cm−2. The ASSLSB also shows a stable cycling performance of 500 cycles at 0.5 C. This work reveals the structure–activity relationship between the mechanical property of interface layer and the battery’s cycling stability.

Enhanced Cycling Stability of All-Solid-State Lithium-Sulfur Battery through Nonconductive Polar Hosts.

All-solid-state lithium-sulfur batteries (ASSLSBs) are promising next-generation battery technologies with a high energy density and excellent safety. Because of the insulating nature of sulfur/Li2S, conventional cathode designs focus on developing porous hosts with high electronic conductivities such as porous carbon. However, carbon hosts boost the decomposition of sulfide electrolytes and suffer from sulfur detachment due to their weak bonding with sulfur/Li2S, resulting in capacity decays. Herein, we propose a counterintuitive design concept of host materials in which nonconductive polar mesoporous hosts can enhance the cycling life of ASSLSBs through mitigating the decomposition of adjacent electrolytes and bonding sulfur/Li2S steadily to avoid detachment. By using a mesoporous SiO2 host filled with 70 wt % sulfur as the cathode, we demonstrate steady cycling in ASSLSBs with a capacity reversibility of 95.1% in the initial cycle and a discharge capacity of 1446 mAh/g after 500 cycles at C/5 based on the mass of sulfur.

Regulate transportation of ions and polysulfides in all-solid-state Li-S batteries using ordered-MOF composite solid electrolyte.

A dilemma arises when striving to balance the maximum desired ion conductivity and minimize the undesired lithium polysulfide shuttling effect for all-solid-state lithium-sulfur batteries (ASSLSBs). Here, we introduce a strategy of using ordered MIL-125-NH2 as fillers for poly(ethylene oxide)-based electrolytes to simultaneously regulate the transportation of lithium ions and polysulfides. When compared to electrolytes lacking metal-organic frameworks (MOFs) and those containing disordered MOFs, the electrolyte featuring an ordered-MOF structure, denoted as three-dimensional (3D) MPPL composite solid electrolyte (CSE), exhibits the highest ion conductivity of 8.3 × 10-4 siemens per centimeter at 60°C. As a result, pouch-type ASSLSBs with 3D MPPL CSE maintains stable cycling for 400 cycles at 0.5 C at 60°C, showcasing the successful implementation of this strategy in simultaneously regulating ion and polysulfide transport. This approach opens up alternative avenues to achieve high-performance ASSLSBs with exceptional energy density.

In Situ Construction of LiF-Li3N-Rich Interface Contributed to Fast Ion Diffusion in All-Solid-State Lithium-Sulfur Batteries.

All-solid-state lithium-sulfur batteries (ASSLSBs) have attracted wide attention due to their ultrahigh theoretical energy density and the ability of completely avoiding the shuttle effect. However, the further development of ASSLSBs is limited by the poor kinetic properties of the solid electrode interface. It remains a great challenge to achieve good kinetic properties, by common strategies to substitute sulfur-transition metal and organosulfur composites for sulfur without reducing the specific capacity of ASSLSBs. In this study, a sulfur-(Ketjen Black)-(bistrifluoromethanesulfonimide lithium salt) (S-KB-LiTFSI) composite is constructed by introducing LiTFSI into the S-KB composite. The initial discharge capacity reaches up to 1483 mA h g-1, benefited from the improved ionic conductivity and diffusion kinetics of the S-KB-LiTFSI composite, where numerous LiF interphases with a Li3N component are in situ formed during cycling. Combined with DFT calculations, it is found that the migration barriers of LiF and Li3N are much smaller than that of the Li6PS5Cl solid electrolyte. The fast ionic conductors of LiF and Li3N not only enhance the Li+ transfer efficiency but also improve the interfacial stability. Therefore, the assembled ASSLSBs operate stably for 600 cycles at 200 mA g-1, and this study provides an effective strategy for the further development of ASSLSBs.

Constructing the Interconnected Charge Transfer Pathways in Sulfur Composite Cathode for All-Solid-State Lithium-Sulfur Batteries.

All-solid-state lithium-sulfur batteries (ASSLSBs) have advantageous features, such as high energy, low costs, enhanced safety, and no polysulfide dissolution. However, the use of sulfur as an active material in all-solid-state batteries is difficult because of its ionic and electrical insulating properties. Herein, we introduce a flower-shaped composite material consisting of MoS2 nanoparticles and sulfur, designed to establish interconnected ionic and electrical conduction pathways at the cathode. As a host material, MoS2 nanoparticles with a large specific surface area can coconduct Li ions and electrons, possessing the potential for effectively utilizing sulfur. However, MoS2 nanoparticles are prone to physical-electrochemical isolation by being surrounded by sulfur due to their crumpling property in the process of mixing and impregnation with sulfur. This problem is addressed by mildly milling the MoS2 nanoparticles and sulfur, after which melt diffusion is applied to generate uniform MoS2/sulfur composite materials to establish an interconnected conducting pathway within the composite. A sulfide solid electrolyte (Li6PS5Cl)-based ASSLSB incorporating the proposed MoS2/sulfur composite demonstrates a stable operation over 1000 cycles with a Coulombic efficiency of nearly 100%. This study emphasizes the significance of the structural design of the sulfur composite material on top of the intrinsic properties of the material for high-performance ASSLSBs.

Synergistic Interfacial Optimization for High-Sulfur-Content All-Solid-State Lithium-Sulfur Batteries.

Improving the sulfur content in the cathode is essential for achieving high-energy-density all-solid-state lithium-sulfur batteries (ASSLSBs). However, the complex multiinterfaces, akin to the short wooden planks that consist of the cask, severely limit the performance of ASSLSBs with high sulfur content. Since singular approaches fail to optimize these interfaces simultaneously, we propose a synergistic approach using a dual-doped sulfide solid electrolyte (Y2S3 and LiI) and an SbSn alloy sulfur host in this work. The incorporation of Y2S3 in the solid electrolyte serves to improve the electrolyte-electrolyte interfaces and enhance the ionic conductivity, while the inclusion of LiI helps stabilize the electrolyte-anode interface and suppress dendrite formation. Meanwhile, the SbSn alloy sulfur host facilitates the transfer of Li+ at the electrolyte-cathode interfaces. Consequently, the solid-solid interfaces are significantly improved, leading to impressive specific capacities in ASSLSBs with high sulfur content (>44% in the cathode composite) at room temperature (1163.5 mAh g-1) and at 60 °C (1408.7 mAh g-1) during the 50th cycle at 0.05C. This work presents a promising strategy for achieving practical high-performance ASSLSBs.

Bridging the gap between academic research and industrial development in advanced all-solid-state lithium-sulfur batteries.

The energy storage and vehicle industries are heavily investing in advancing all-solid-state batteries to overcome critical limitations in existing liquid electrolyte-based lithium-ion batteries, specifically focusing on mitigating fire hazards and improving energy density. All-solid-state lithium-sulfur batteries (ASSLSBs), featuring earth-abundant sulfur cathodes, high-capacity metallic lithium anodes, and non-flammable solid electrolytes, hold significant promise. Despite these appealing advantages, persistent challenges like sluggish sulfur redox kinetics, lithium metal failure, solid electrolyte degradation, and manufacturing complexities hinder their practical use. To facilitate the transition of these technologies to an industrial scale, bridging the gap between fundamental scientific research and applied R&D activities is crucial. Our review will address the inherent challenges in cell chemistries within ASSLSBs, explore advanced characterization techniques, and delve into innovative cell structure designs. Furthermore, we will provide an overview of the recent trends in R&D and investment activities from both academia and industry. Building on the fundamental understandings and significant progress that has been made thus far, our objective is to motivate the battery community to advance ASSLSBs in a practical direction and propel the industrialized process.

Comb-like poly(β-amino ester)-integrated PEO-based self-healing solid electrolytes for fast ion conduction in lithium-sulfur batteries.

All-solid-state lithium-sulfur batteries (ASSLSBs) using poly(ethylene oxide) (PEO) electrolytes offer significant advantages in energy density and safety. However, their development is hampered by the slow Li+ conduction in solid polymer electrolytes and sluggish electrochemical conversion at the cathode-electrolyte interface. Herein, we fabricate a self-healing poly(β-amino ester) with a comb-like topological structure and multiple functional groups, synthesized through a Michael addition strategy. This material modifies the PEO-based solid-state electrolyte, creating fast Li+ transport channels and improving polysulfides conversion kinetics at the electrode surface. Consequently, both modified all-solid-state lithium symmetric cells and lithium-sulfur batteries exhibit improved electrochemical performance. This work demonstrates an expanded interpenetrating macromolecular engineering approach to develop highly ion-conductive solid polymer electrolytes for ASSLSBs.

Effect of Borophene on the Electrochemical Performances of Li7P3S11 based AllSolid-State Lithium Sulfur Batteries

This study has investigated the effect of 2-dimensional (2D) beta borophene as a cathode additive for all-solid-state lithium-sulfur batteries. The comparisons have been carried out regarding the impact on ionic conductivity based on borophene content. Although the studies of borophene's contributions in the literature on the anode component, this study focuses on the cathode contribution for the first time. While MoS2 has been selected as the cathode active material, carbon black has been selected as the electrical conductor, and Li7P3S11 solid electrolyte has been synthesized as an ionic conductor in all-solid-state lithium-sulfur cells. Borophene has been synthesized from boron powder by the exfoliation method. As a cathodeactive material, MoS2, containing sulfur, and its 2D material nature, eliminates many of the disadvantages that sulfur exhibits when used alone. To investigate the effect of borophene on ionic conductivity in all-solid-state lithium-sulfur cells, multicomponent composite cathodes were prepared in (MoS2 / Conductive Carbon / Li7P3S11 + Borophene) overall compositions. According to the results, the specific capacity of the cells is affected negatively, while the stability of the cell is affected positively when increased the borophene amount.

High-areal-capacity all-solid-state Li-S battery enabled by dry process technology

All-solid-state lithium-sulfur batteries (ASSLSBs) based on sulfide solid electrolyte (SSE) hold great promise as the next-generation energy storage technology with great potential for high energy density and improved safety. However, the development of practical ASSLSBs is restricted by the scalable fabrication of sulfur cathode sheets with outstanding electrochemical performance, which remains a complex and challenging endeavor. Herein, we employ dry electrode technology to fabricate free-standing sulfur cathode sheets with both high sulfur content and loading. By utilizing polytetrafluoroethylene (PTFE) binders with unique fibrous morphologies in the dry electrodes, we achieved sulfur cathode sheets with high flexibility without compromising ionic and electronic conductivity. Remarkably, even with thickened dry cathode sheets featuring high sulfur loading of 4.5 mg cm-2, the sulfur cathodes exhibit high initial discharge capacity of 1114.8 mAh g-1 with good cycle stability and rate capability. Additionally, we successfully demonstrate the construction of sheet-type all-solid-state Li3.75Si/SSE/S cells, showcasing favorable electrochemical performance with a high reversible capacity of 1067.4 mAh g-1 after 30 cycles even at a high sulfur loading of 4.5 mg cm-2 and high current density of 1 mA cm-2 (0.2C). Our findings represent a demonstration of batteries coupled with high-capacity sulfur cathode and lithiated silicon anode exhibiting exceptional electrochemical performance. It also underscores the significant potential of dry-process technology in addressing the critical challenges associated with the practical production of ASSLSBs. This contribution propels ongoing endeavors in the development of next-generation energy storage systems.

An Electron/Ion Dual Conductive Integrated Cathode Using Cationic/Anionic Redox for High‐Energy‐Density All‐Solid‐State Lithium‐Sulfur Batteries

AbstractAll‐solid‐state lithium‐sulfur batteries (ASSLSB), composed of sulfur cathode and lithium metal anode with high theoretical capacity, have a potentially higher energy density by weight than a typical lithium‐ion battery (LIB). However, due to insulating sulfur, a relatively large proportion of electronic (carbon) and ionic (solid electrolyte) conductors are mixed for cathode fabrication, leading to inferior practical capacity. Herein, we report a novel integrated cathode Li2S‐LiI‐MoS2 which has relatively high electronic and ionic conductivities (the order of 10−4 S cm−1) without any carbon and solid electrolyte. The ASSLSB with integrated Li2S‐LiI‐MoS2 cathode delivers a remarkably high energy density of 1020 Wh kg−1 at the cathode level at room temperature. By applying precise X‐ray diffraction, pair distribution function analysis and X‐ray computed tomography, it is found that the formation of an ionic conducting phase composed mainly of LiI during discharge is responsible for the high rate capability. Furthermore, X‐ray absorption fine structure (XAFS) has also revealed the charge compensation mechanism and ascertained the involvement of both Mo 3d and S 3p orbitals during the charging and discharging process. It is believed the strategy will pave the way for developing high practical energy density at room temperature for all‐solid‐state batteries.

Investigation of the Reaction Mechanism of All-Solid-State Lithium-Sulfur Batteries by Operando in Situ Raman Spectroscopy

In recent years, all-solid-state lithium-sulfur batteries (ASSLSBs) with sulfide-based solid electrolytes have become a leading energy storage system due to their high ionic conductivity, ultra-high energy density, high safety, and low cost. There have been many challenges with the practical applications of Li-S batteries, however, as a result of the sluggish redox kinetics of lithium polysulfide (LPS) and its shuttling effects. Single-atom catalysts (SACs) with atomically dispersed metal-based sites have proven to be promising electrocatalysts in Li-S batteries. To construct the ASSLSBs, we design and develop MoS2/SnS2 and Fe SACs with MoS2/SnS2 cathodes, Li5.4PS4.4Cl1.6 sulfide-based solid electrolytes, and Li-In anode. In the current study, in situ Raman spectroscopy is used to determine the LPS species in the sulfur cathode with SACs and without SACs during the ASSLSBs cycling. The aim is to understand the charge-discharge mechanism and the influence of SACs on the dissolution of sulfur and poly-sulfides. As compared to the MoS2/SnS2 cathode, the Fe@MoS2/SnS2 cathode exhibit the highest catalytic LPS conversion. In addition, the Fe@MoS2/SnS2 cathode delivers a high discharge capacity and long-cycling performance with high coulombic efficiency in ASSLSBs. In operando in situ Raman studies, SACs provide important new insights into the charge-discharge reaction mechanism for the next generation of ASSLSBs.

Synergistic Defect Engineering and Interface Stability of Activated Carbon Nanotubes Enabling Ultralong Lifespan All-Solid-State Lithium-Sulfur Batteries.

Due to the high energy density, high safety, and low cost of sulfur, all-solid-state lithium-sulfur batteries (ASSLSBs) are considered one of the most promising next-generation energy storage devices. Nevertheless, the insufficient interfacial contact between solid electrolytes (SEs) and the active material of sulfur leads to inadequate electronic and ionic conduction, which increases interfacial resistance and capacity decay. In this paper, commercial carbon nanotubes (CNTs) are activated to form porous-CNTs (P-CNTs), which are used as sulfur-bearing matrix, forming S@P-CNTs-based composite cathodes for ASSLSBs. Compared with CNTs, P-CNTs possess a larger specific surface area and more oxygen-containing groups, providing enhanced interfacial contact and stability between S@P-CNTs and Li6PS5Cl SE, which are confirmed by scanning electron microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. Moreover, P-CNTs can form a 3D conductive network in the composite cathodes, facilitating the migration of electrons and the diffusion of ions, as well as improving the utilization of sulfur. As a result, the S@P-CNTs-based ASSLSBs display excellent electrochemical performances, especially rarely reported ultralong lifespan, which deliver a capacity of 1099.2 mA h g-1 at a current density of 1.34 mA cm-2, and remarkably maintain 70.4% of the initial capacity over 1400 cycles.

Insight into the role of crystallinity in oxide electrolytes enabling high-performance all-solid-state lithium-sulfur batteries

All-solid-state lithium-sulfur batteries (ASSLSBs) would be a promising candidate for the next-generation batteries due to the utilization of energy-dense electrodes and the non-flammable oxide solid-state electrolytes (SSEs), but still face great challenges such as low ionic conductivity of SSEs, poor interfacial contact and lithium (Li) dendrite propagation. Herein, we regulated the crystallinity degrees of the large-scale-fabricated Li1.5Al0.5Ge1.5(PO4)3 (LAGP) SSEs and explored the critical role of crystallinity optimization in reinforcing the basic properties of LAGP, developing a fundamental explanation for the inherent relation between the crystallinity and the performance of ASSLSBs. Benefiting from the optimized crystallinity (∼99.9 %), the large-scale-fabricated LAGP not only realizes the low surface roughness and high ionic conductivity (2.11 × 10−4 S cm−1) to improve interfacial contact and reduce resistance in ASSLSBs, but also possesses the dense internal structure with low porosity (1.49 %) to physically resist dendritic propagation and penetration. Consequently, the ASSLSB with the optimized LAGP delivers a high reversible capacity of 647.9 mAh/g even after 150 cycles at 0.1 C. This work confirms the significance of crystallinity in understanding the working mechanisms of oxide SSEs and developing future high-performance ASSLSBs.