All-solid-state Batteries Research Articles

Combined Impedance and Electron Paramagnetic Resonance Spectroscopy for Investigating the Dynamics of Li/Solid Li‐ion Conductor Interfaces

AbstractElectrochemical impedance spectroscopy (EIS) is a widely used tool for the electrochemical characterization of all‐solid‐state batteries (ASSBs) with Li‐metal anodes. However, an unambiguous interpretation of the observed impedance response often requires additional independent information on the actual interfacial phenomena obtained. The measurement methodology presented in this study allows to conduct electron paramagnetic resonance (EPR) spectroscopy and EIS concurrently. Therefore, the informative power of EIS experiments can be significantly improved via monitoring of structural changes of paramagnetic lithium at the electrochemical interface. As the solid‐electrolyte‐lithium interface is a critical part of all‐solid‐state batteries, this study employs a model oxide solid electrolyte in contact with lithium metal. During the polarization of the cell with thin evaporated lithium electrodes, the ratio between positive and negative peaks (a/b) of the EPR signal momentarily rises, which indicates an accumulation of lithium on one side of the electrolyte. The peak ratio a/b then drops abruptly, accompanied by current irregularities. Both are indicative of a diminishing contact area, and as a result, finer lithium morphologies form. Shortly after that, a contact loss is observed. The change of the EPR signal shape before cell breakdown can hence be associated with the worsening Li‐electrolyte contact, providing a tool for physical in‐situ cell diagnostics.

Regulating Entanglement Networks of Fibrillatable Binders for Sub-20-µm Thick, Robust, Dry-Processed Solid Electrolyte Membranes in All-Solid-State Batteries.

Despite significant advancements in all-solid-state batteries (ASSBs), the reliance on thick solid electrolyte (SE) membranes hinders their commercial viability. Although the dry process using polytetrafluoroethylene (PTFE) binder is proposed for thin SE membranes, a comprehensive understanding of the correlation between PTFE fibrillation and SE membrane quality remains lacking. Here an important guidance is provided for producing durable SE membranes that can be reduced to sub-20-µm thickness by regulating the entanglement networks of PTFE. While establishing fabrication parameters; shear time and shear temperature, a dominant effect of the number-average molecular weight (Mn) on PTFE fibrillation is revealed for the first time. Moreover, the degree of PTFE fibrillation is quantified using systematic X-ray diffraction (XRD) analysis. The SE membrane utilizing the high-Mn PTFE binder that achieves a maximum fibrillation degree (≈98%) and thus forms highly entangled fibrous PTFE network interweaving SE particles, exhibited superior toughness. Consequently, the 18 µm thick SE membrane with 0.5wt% high-Mn PTFE shows a considerably higher areal conductance. The ASSB using this durable, ultrathin SE membrane outperforms its counterparts that used flimsy SE membranes or pure SE pellets. Finally, uniquely thin ASSBs demonstrate significantly improved cell-level energy densities, showcasing the promising potential for practical ASSB fabrication.

Understanding Electrochemical Reaction Mechanisms of All-Electrochem-Active Mg2Si Electrode in All-Solid-State Batteries.

To better understand the electrochemical reaction mechanism of the Mg2Si electrode in all-solid-state batteries (ASSBs), a rational all-electrochem-active Mg2Si electrode is first designed to minimize the inactive component-related interfacial degradation. This is due to its unique mixed conductivity properties, including a high electronic conductivity of up to 8.9 × 10-2 S cm-1 and an ionic conductivity of 9.7 × 10-5 S cm-1, which allow for fast charges transport. In ASSBs, the Mg2Si electrode exhibits a higher initial Coulombic efficiency of 83.5% at 300 mA g-1 compared with the Si electrode (72.3%). X-ray diffraction and X-ray photoelectron spectroscopy results demonstrate that intermediate products (LixMg2Si, Li-Si alloy, and Li-Mg alloy) can form when the Mg2Si electrode discharges to 0.01 V, and partial Mg2Si still does not react with lithium. This work provides valuable insights into the reaction mechanisms and guides optimization strategies for developing next-generation Si-based ASSBs.

2D Graphene‐Like Carbon Coated Solid Electrolyte for Reducing Inhomogeneous Reactions of All‐Solid‐State Batteries

AbstractRecent studies have identified an imbalance between the electronic and ionic conductivities as the drivers of inhomogeneous reactions in composite cathodes, which cause the rapid degradation of all‐solid‐state battery (ASSB). To mitigate localized overcharge and utilize isolated active materials, the study proposes the coating of an argyrodite‐type Li6PS5Cl solid electrolyte (SE) with graphene‐like carbon (GLC@LPSCl), a 2D conductive material, to offer a continuous three‐dimensionally connected electron pathway within the composite cathode to facilitate ion mobility and promote homogeneous reactions. Despite reducing the content of the conducting agent, it is observed that the GLC@LPSCl cell exhibits high initial Coulombic efficiency and discharge capacity, reducing the inhomogeneous reactivity after 200 cycles compared with when ordinary conductive agents are deployed. Additionally, the presence of GLC@LPSCI surface suppresses the interfacial reaction between SE–cathode material, thus imparting the cell with excellent capacity retention (≈90%) after 200 cycles. Furthermore, the cell performance improves even after a fourfold increase in the cathode loading amount, demonstrating the criticality of a well‐developed continuous electron pathway to cell performance and highlighting the key role of ensuring a balance between the electron and ion conductivities in the development of high‐energy‐density and high‐power ASSBs.

A Li-Rich Fluorinated Lithium Zirconium Chloride Solid Electrolyte for 4.8 V-Class All-Solid-State Batteries.

Chloride solid-state electrolytes (SEs) represent an important advance for applications in all-solid-state batteries (ASSBs). Among various chloride SEs, lithium zirconium chloride (Li2ZrCl6) is an attractive candidate considering the high natural abundance of Zr. However, Li2ZrCl6 meets the challenge in practical ASSBs because of its limited ionic conductivity and instability when paired with high-voltage cathodes. This is a major drawback, which can result in a high internal resistance, a low capacity utilization of cathode, and poor cycle stability, especially at high voltage. Existing methods cannot achieve simultaneous enhancement on both ionic conductivity and high-voltage stability due to a trade-off between lithium-ion migration and structural stability. Here a two-pronged strategy based on partial fluorination and incorporation of lithium ions in excess of stoichiometric ratios is introduced that enables high-voltage stability while increasing ionic conductivity concurrently. The Li-rich fluorinated halide SE (Li2.3ZrCl6.1F0.2) exhibits a significant advancement in performance, with an ionic conductivity that is double that of the pristine Li2ZrCl6 and much better high-voltage stability. By leveraging Li2.3ZrCl6.1F0.2 with the LiCoO2 cathode and the Li-In anode, the all-solid-state cell exhibits a remarkable initial specific capacity (198.0 mAh g-1 at 0.1 C) and a high capacity retention (78.5% after 150 cycles) within 3.0-4.8V.

High Configuration Entropy Promises Electrochemical Stability of Chloride Electrolytes for High‐Energy, Long‐Life All‐Solid‐State Batteries

Solid‐state electrolytes (SSEs) with high ionic conductivity, stability, and interface compatibility are indispensable for high‐energy‐density and long‐life all‐solid‐state batteries (ASSBs), yet there are scarce SSEs with sufficient ionic conductivity and electrochemical stability. In this study, with a high‐entropy SSE (HE‐SSE, Li2.9In0.75Zr0.1Sc0.05Er0.05Y0.05Cl6), we show the high configuration entropy has a thermodynamically positive relationship with the high‐voltage stability. As a result, the ASSBs with HE‐SSE and high‐voltage cathode materials exhibit superior high‐voltage and long‐cycle stability, achieving 250 cycles with 81.4% capacity retention when charged to 4.8 V (vs. Li+/Li), and even 5000 cycles if charged to 4.6 V (vs. Li+/Li). Experimental characterizations and density functional theory calculations confirm that the HE‐SSE greatly suppresses the high‐voltage degradation of SSE at the interface, promoting the high‐voltage stability coordinately through high entropy and interface stability. The high entropy design offers a general strategy to simultaneously improve the high‐voltage stability and ionic conductivity of SSEs, creating an avenue to building high‐energy and long‐life ASSBs.

High Configuration Entropy Promises Electrochemical Stability of Chloride Electrolytes for High-Energy, Long-Life All-Solid-State Batteries.

Solid-state electrolytes (SSEs) with high ionic conductivity, stability, and interface compatibility are indispensable for high-energy-density and long-life all-solid-state batteries (ASSBs), yet there are scarce SSEs with sufficient ionic conductivity and electrochemical stability. In this study, with a high-entropy SSE (HE-SSE, Li2.9In0.75Zr0.1Sc0.05Er0.05Y0.05Cl6), we show the high configuration entropy has a thermodynamically positive relationship with the high-voltage stability. As a result, the ASSBs with HE-SSE and high-voltage cathode materials exhibit superior high-voltage and long-cycle stability, achieving 250 cycles with 81.4% capacity retention when charged to 4.8 V (vs. Li+/Li), and even 5000 cycles if charged to 4.6 V (vs. Li+/Li).Experimental characterizations and density functional theory calculations confirm that the HE-SSE greatly suppresses the high-voltage degradation of SSE at the interface, promoting the high-voltage stability coordinately through high entropy and interface stability. The high entropy design offers a general strategy to simultaneously improve the high-voltage stability and ionic conductivity of SSEs, creating an avenue to building high-energy and long-life ASSBs.

Infiltration-driven performance enhancement of poly-crystalline cathodes in all-solid-state batteries

All-solid-state batteries (ASSBs) with adequately selected cathode materials exhibit a higher energy density and better safety than conventional lithium-ion batteries (LIBs). Ni-rich layered cathodes are benchmark materials for traditional LIBs owing to their high energy density. Recent studies have highlighted the advantages of using crack-free, single-crystalline cathode materials in ASSBs. In this study, a scalable infiltration sheet-type process was used to fabricate composite electrodes with different cathode-material morphologies for ASSBs. Typically, crack-free single-crystalline materials exhibit better retention performance and lower rate capability (i.e., slower kinetics in charge‒discharge processes) than polycrystalline cathode materials. Li6PS5Cl-infiltrated polycrystalline electrodes showed excellent retention performance and rate capability. Galvanostatic intermittent titration technique analysis and transmission electron microscopy of the single-crystalline electrode confirmed severe polarization and the presence of a rock-salt-structure layer in the cathode particles; these results indicated side reactions within the layered structure of the material. In contrast, composite electrodes consisting of polycrystalline cathode materials infiltrated with the solid electrolyte Li6PS5Cl showed excellent electrochemical performance owing to intimate electrode–electrolyte interfacial contact. The result from this study confirmed the critical influence of interface engineering and material morphology on the overall performance and stability of ASSBs and could facilitate the development of high-performance ASSBs in the future.

Unraveling Asymmetric Electrochemical Kinetics in Low-Mass-Loading LiNi1/3Mn1/3Co1/3O2 (NMC111) Li-Metal All-Solid-State Batteries

In this study, we fabricated a Li-metal all-solid-state battery (ASSB) with a low mass loading of NMC111 cathode electrode, enabling a sensitive evaluation of interfacial electrochemical reactions and their impact on battery performance, using Li1.3Al0.3Ti1.7(PO4)3 (LATP) as the solid electrolyte. The electrochemical behavior of the battery was analyzed to understand how the solid electrolyte influences charge storage mechanisms and Li-ion transport at the electrolyte/electrode interface. Cyclic voltammetry (CV) measurements revealed the b-values of 0.76 and 0.58, indicating asymmetry in the charge storage process. A diffusion coefficient of 1.5 × 10−9 cm2⋅s−1 (oxidation) was significantly lower compared to Li-NMC111 batteries with liquid electrolytes, 1.6 × 10−8cm2⋅s−1 (oxidation), suggesting that the asymmetric charge storage mechanisms are closely linked to reduced ionic transport and increased interfacial resistance in the solid electrolyte. This reduced Li-ion diffusivity, along with the formation of space charge layers at the electrode/electrolyte interface, contributes to the observed asymmetry in charge and discharge processes and limits the rate capability of the solid-state battery, particularly at high charging rates, compared to its liquid electrolyte counterpart.

Nb1.60Ti0.32W0.08O5−δ as negative electrode active material for durable and fast-charging all-solid-state Li-ion batteries

Li-based all-solid-state batteries (ASSBs) are considered feasible candidates for the development of the next generation of high-energy rechargeable batteries. However, ASSBs are detrimentally affected by a limited rate capability and inadequate performance at high currents. To circumvent these issues, here we propose the use of Nb1.60Ti0.32W0.08O5-δ (NTWO) as negative electrode active material. NTWO is capable of overcoming the limitation of lithium metal as the negative electrode, offering fast-charging capabilities and cycle stability. Physicochemical and electrochemical characterizations of NTWO in combination with the Li6PS5Cl (LPSCl) solid-state electrolyte demonstrate that the formation of LiWS2 at the electrode|electrolyte interphase is the main responsible for the improved battery performance. Indeed, when an NTWO-based negative electrode and LPSCl are coupled with a LiNbO3-coated LiNi0.8Mn0.1Co0.1O2-based positive electrode, the lab-scale cell is capable of maintaining 80% of discharge capacity retention after 5000 cycles at 45 mA cm−2 at 60 °C and 60 MPa.

Enhancing Long Stability of Solid-State Batteries Through High-Energy Ball Milling-Induced Decomposition of Sulfide-Based Electrolyte to Sulfur.

Metal sulfides are increasingly favored as cathode materials in all-solid-state batteries (ASSBs) due to their high energy density, stability, affordability, and conductivity. Metal sulfides often exhibit capacities exceeding their theoretical limits, a phenomenon that remains not fully understood. In this study, it reveals that this phenomenon is primarily due to the sulfur decomposition from sulfide-based electrolyte. By employing the high-energy ball milling (HEBM) technique, the deposition of sulfide-based electrolyte onto sulfur is intentionally promoted, resulting in higher charge capacities compared to the discharge capacities and surpass theoretical limits of metal sulfides. Using chromium sulfide (Cr2S3) as the active material, the sulfur decomposed from sulfide-based electrolyte transforms into lithium sulfide (Li2S) after discharge, resulting in an increased capacity by ≈439.6 mAhg-1 and improved cycling stability. Consequently, it demonstrates a specific capacity surpassing 1200 mAh g-1 with a capacity retention of over 80% after 650 cycles, maintaining cycling stability for more than 1900 cycles and achieving a Coulombic efficiency exceeding 99.9%. This versatile HEBM approach enables the fabrication of ASSBs utilizing various transition metal sulfides, such as molybdenum disulfide (MoS2), niobium disulfide (NbS2), and iron disulfide (FeS2), all exhibiting over theoretical limited capacities and prolonged cycling capabilities.

Integrating Prelithiation and Interface Protection to Achieve High-Energy All-Solid-State Batteries.

All-solid-state batteries (ASSBs), particularly those with Li-free anodes or even anode-free configurations, have attracted extensive attention due to high safety and energy density. However, chemical-mechanical degradation typically deteriorates the cycle life and energy of Li-free anode ASSBs with the absence of Li inventory. Here, the prelithiation agent Li5FeO4 (LFO) coated Ni-rich layered oxide is developed as the cathode for Li-free anode ASSBs. The coated LFO acts as an interfacial protective layer to prevent the highly oxidizing Ni-rich cathode from reacting with sulfide solid-state electrolytes (SSEs), mitigating the structural degradation of Ni-rich cathodes and the decomposition of SSE, resulting in excellent cycle life. Beneficial from the coated LFO in the cathode of the Li-free anode ASSBs, the reversible capacity improves from 174.7 mAh g-1 to 199.7 mAh g-1, and the capacity retention is enhanced from 33.8% to 84.8% after 100 cycles. Additionally, an ultrahigh energy density of 440 Wh kg-1, based on the mass of the composite cathode, Li-free anode, and SSE, is obtained in a Li-free anode all-solid-state pouch cell equipped with the LFO-coated cathode.

Integrating Prelithiation and Interface Protection to Achieve High‐Energy All‐Solid‐State Batteries

All‐solid‐state batteries (ASSBs), particularly those with Li‐free anodes or even anode‐free configurations, have attracted extensive attention due to high safety and energy density. However, chemical‐mechanical degradation typically deteriorates the cycle life and energy of Li‐free anode ASSBs with the absence of Li inventory. Here, the prelithiation agent Li5FeO4 (LFO) coated Ni‐rich layered oxide is developed as the cathode for Li‐free anode ASSBs. The coated LFO acts as an interfacial protective layer to prevent the highly oxidizing Ni‐rich cathode from reacting with sulfide solid‐state electrolytes (SSEs), mitigating the structural degradation of Ni‐rich cathodes and the decomposition of SSE, resulting in excellent cycle life. Beneficial from the coated LFO in the cathode of the Li‐free anode ASSBs, the reversible capacity improves from 174.7 mAh g−1 to 199.7 mAh g−1, and the capacity retention is enhanced from 33.8% to 84.8% after 100 cycles. Additionally, an ultrahigh energy density of 440 Wh kg−1, based on the mass of the composite cathode, Li‐free anode, and SSE, is obtained in a Li‐free anode all‐solid‐state pouch cell equipped with the LFO‐coated cathode.

Novel Amorphous Nitride‐Halide Solid Electrolytes with Enhanced Performance for All‐Solid‐State Batteries

Solid electrolytes (SEs) in all‐solid‐state batteries (ASSBs) are garnering considerable attention for their potential applications in next‐generation energy storage systems. Amorphous SEs with dual‐anion hold great promise for achieving favorable performance, such as high ionic conductivity and good compatibility with electrodes within ASSBs. Here, we discover a family of amorphous nitride‐halide SEs, Li3xMClyNx (M = Ta or La, 1 ≤ 3x ≤ 1.4, y = 5 or 3), which can achieve ionic conductivities up to 7.34 mS cm‒1 at 30 °C. The amorphous properties and local structures are investigated using powder X‐ray diffraction, cryogenic transmission electron microscopy, and atomic pair distribution function analysis. Impressively, ASSBs employing amorphous Li3xTaCl5Nx have demonstrated good performance at high rates and charging voltages, as well as at low temperature.

Novel Amorphous Nitride-Halide Solid Electrolytes with Enhanced Performance for All-Solid-State Batteries.

Solid electrolytes (SEs) in all-solid-state batteries (ASSBs) are garnering considerable attention for their potential applications in next-generation energy storage systems. Amorphous SEs with dual-anion hold great promise for achieving favorable performance, such as high ionic conductivity and good compatibility with electrodes within ASSBs. Here, we discover a family of amorphous nitride-halide SEs, Li3xMClyNx (M = Ta or La, 1 ≤ 3x ≤ 1.4, y = 5 or 3), which can achieve ionic conductivities up to 7.34 mS cm‒1 at 30 °C. The amorphous properties and local structures are investigated using powder X-ray diffraction, cryogenic transmission electron microscopy, and atomic pair distribution function analysis. Impressively, ASSBs employing amorphous Li3xTaCl5Nx have demonstrated good performance at high rates and charging voltages, as well as at low temperature.

Dual-Seed Strategy for High-Performance Anode-Less All-Solid-State Batteries.

Interest in all-solid-state batteries (ASSBs), particularly the anode-less type, has grown alongside the expansion of the electric vehicle (EV) market, because they offer advantages in terms of their energy density and manufacturing cost. However, in most anode-less ASSBs, the anode is covered by a protective layer to ensure stable lithium (Li) deposition, thus requiring high temperatures to ensure adequate Li ion diffusion kinetics through the protective layer. This study proposes a dual-seed protective layer consisting of silver (Ag) and zinc oxide (ZnO) nanoparticles for sulfide-based anode-less ASSBs. This dual-seed-based protective layer not only facilitates Li diffusion via multiple lithiation pathways over a wide range of potentials, but also enhances the mechanical stability of the anode interface through the in situ formation of a Ag-Zn alloy with high ductility. The capacity retention during full-cell evaluation is 80.8% for 100 cycles when cycled at 1mA cm-2 with 3 mAh cm-2 at room temperature. The dual-seed approach provides useful insights into the design of multi-seed concepts in which, from a mechanochemical perspective, various lithiophilic materials synergistically impact upon the anode-less interface.

Exploring Chemical and Electrochemical Limitations in Sulfide Solid State Electrolytes: A Critical Review on Current Status and Manufacturing Scope.

Lithium-ion batteries (LIBs) have gained recognition for their high energy density and cost-effectiveness. However, issues such as safety concerns, dendrite formation, and limited operational temperatures necessitate alternative solutions. A promising approach involves replacing flammable liquid electrolytes with non-flammable solid electrolytes (SEs). SEs represent a transformative shift in battery technology, offering stability, safety, and expanded temperature ranges. They effectively mitigate dendrite growth, enhancing battery reliability and lifespan. SEs also improve energy density, making them crucial for applications like portable gadgets, electric vehicles, and renewable energy storage. However, challenges such as ionic conductivity, chemical and thermal stability, mechanical strength, and manufacturability must be addressed. This review paper briefly identifies SE types, discusses their advantages and disadvantages, and explores ion transport fundamentals and all-solid-state batteries (ASSBs) production challenges. It comprehensively analyzes sulfide SEs (SSEs), focusing on recent advancements, chemical and electrochemical challenges, and potential future improvements. Electrochemical reactions, electrolyte materials, compositions, and cell designs are critically assessed for their impact on battery performance. The review also addresses challenges in ASSB production. The objective is to provide a comprehensive understanding of SSEs, laying the groundwork for advancing sustainable and efficient energy storage systems.

Exploring the Optimal Binder Content in Composite Electrodes for Sulfide-Based All-Solid-State Lithium-Ion Batteries

All-solid-state batteries (ASSBs) are promising next-generation batteries owing to their improved safety compared with lithium-ion batteries using flammable liquid electrolytes. Among various solid electrolytes, sulfide-based electrolytes exhibit high ionic conductivities, and their ductile properties allow them to be easily processed without high-temperature sintering. In sulfide-based ASSBs, a polymer binder is essential for achieving a good cycling performance by maintaining strong interfacial contacts in the composite electrodes during cycling. In this study, we prepared a composite Si-C anode and a LiNi0.82Co0.1Mn0.08O2 cathode using a nitrile-butadiene rubber binder for ASSB applications, and investigated the effect of the binder content on the mechanical properties and electrochemical performance. The binder content significantly influenced the physical and electrochemical characteristics of the composite electrodes, and the ASSB prepared with 1.5 wt% binder showed the best cycling performance considering capacity retention and rate capability. Furthermore, we investigated how the excess binder adversely affected the cycling performance through time-of-flight secondary ion mass spectrometry analysis.

Quantitative pre-lithiation modulation of aluminum foil anode kinetics enables high rate and stable cycling of high-loading all-solid-state batteries

Aluminum (Al) foil holds great promise as a pure alloy anode for all-solid-state batteries (ASSBs) due to its suitable potential, high theoretical capacity, and excellent electronic conductivity. However, it remains challenging to achieve high reversibility and stability of the Al foil anode for ASSBs. Herein, we investigate the morphological and lithium (Li) kinetics evolutions of the Al foil anode paired with sulfide solid-state electrolyte (SSE). We identify that the significant reversible capacity loss stems from diminished Li kinetics at low Li contents (LixAl, 0 < x < 0.5), where the accumulation of pores and pure delithiated Al phase obstructs Li diffusion, increasing interfacial resistance and overpotential. Conversely, the Al foil anode with high Li contents (LixAl, 0.5 < x < 1) demonstrates reversible structures and rapid Li kinetics. Through precise pre-lithiation control, ASSBs with LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes exhibit outstanding rate capabilities and cycling stability, achieving over 4,000 cycles with 82.1 % capacity retention at 5C and demonstrating long-term cycling over 1,000 cycles with nearly 100 % capacity retention at ultra-high loadings. This work offers a viable strategy for advancing practical-level ASSBs with enhanced performance and longevity, contributing valuable insights to future battery technology.

Bulk/Interfacial Structure Design of Li-Rich Mn-Based Cathodes for All-Solid-State Lithium Batteries.

Li-rich Mn-based cathode materials (LRMO) are promising for enhancing energy density of all-solid-state batteries (ASSBs). Nonetheless, the development of efficient Li+/e- pathways is hindered by the poor electrical conductivity of LRMO cathodes and their incompatible interfaces with solid electrolytes (SEs). Herein, we propose a strategy of in-situ bulk/interfacial structure design to construct fast and stable Li+/e- pathways by introducing Li2WO4, which reduces the energy barrier for Li+ migration and enhances the stability of the surface oxygen structure. The reversibility of oxygen redox was improved, and the voltage decay of the LRMO cathode was addressed significantly. As a result, the bulk structure of the LRMO cathodes and the high-voltage solid-solid interfacial stability are improved. Therefore, the ASSBs achieve a high areal capacity (∼3.15 mAh/cm2) and outstanding cycle stability of ≥1200 cycles with 84.1% capacity retention at 1 C at 25 °C. This study offers new insights into LRMO cathode design strategies for ASSBs, focusing on ultrastable high-voltage interfaces and high-loading composite electrodes.