Li-rich Mn-based Oxides Research Articles

Near-surface reconstruction strategy stabilizing high-voltage redox reactions in single crystal Li-rich Mn-based oxides

Li-rich Mn-based oxides (LRMO) greatly increase its output energy density due to its additional oxygen redox activity. However, the inherent oxygen loss and irreversible phase transition induce low initial coulombic efficiency and serious voltage decay, further seriously impeding its industrial application. Herein, a near-surface in-situ reconstruction strategy has been proposed, which constructs the oxygen vacancies and spinel phase coating on the surface of single-crystal Li-rich Mn-based oxide (SC-LRMO) concurrently to improve Li+ storage performance via the oxalic acid induction method. Intensive exploration based on structure characterizations demonstrates that such a near-surface in-situ reconstruction strategy not only accelerates the transmission of Li+, but also stabilizes high-voltage redox reactions by trapping the escaping On− within the newly formed spinel phase coating. Impressively, the modified sample exhibit 91.1% capacity retention ratio after 300 cycles, superior to the SC-LRMO (74.5% capacity retention ratio after 300 cycles). Additionally, even at a high cut-off voltage of 5 V, the acid etched sample exhibits significantly enhanced cycling stability, delivering 200 mAh g−1 with a 94% capacity retention ratio after 300 cycles. This surface self-reconstruction strategy provides profound insights into regulating the surface structure of LRMO for high-energy-density lithium-ion batteries.

Local electronic structure modulation via S substitution enables fast-discharging capability for Li-rich Mn-based oxides cathodes

Anionic and cationic redox reaction contribute to the ultrahigh specific capacities of Li-rich Mn-based oxides cathodes (LMNC). However, the irreversible oxygen evolution and sluggish kinetics result in the continuous capacity decay and poor rate performance, which limited its application as cathode material in lithium-ion batteries. Herein, the local electronic structure of LMNC is appropriately modulated via S2− doping to alleviate oxygen release, stabilize the crystal structure stability, and facilitate Li+ diffusion via facile surface defect engineering. The effect of S2− doping site on the systematically energy is investigated by DFT. Under the guidance of this result, LNMC-S is prepared by co-precipitation and high-temperature solid-phase reaction method. The effect of doping concentration on electrochemical property of LMNC was systematically investigated. The results exhibit that S2− doping can effectively suppress the electronic insulation of Li2MnO3, enhance the transport dynamics of lithium ion and inhibit the phase transition of LMNC sample during charge-discharge process. Thereby, the modified sample exhibits superior electrochemical property, such as the 200th discharge capacity is 184.3 mAh·g−1 under 1C, with a capacity retention rate of 87.6 %. This paper is beneficial for enriching the existing theoretical findings and discoveries, providing theoretical guidance for the preparation of high-performance material.

Enhancing the stability of Li-Rich Mn-based oxide cathodes through surface high-entropy strategy

Li-rich Mn-based layered oxides (LMR) hold promise as cathode materials for lithium-ion batteries (LIBs) due to their high reversible capacity. However, issues such as oxygen release and structural degradation associated with oxygen redox cause voltage decay and capacity decline during cycling. In this study, a monodisperse Li1.2Ni0.13Co0.13Mn0.54O2 cathode material with surface high-entropy architecture (MZCN-LMR) was synthesized to enhance the overlap between the non-bonding orbitals of oxygen (|O2p) and the (TM-O)* occupied band. This enhancement enables regulation of the depth of oxygen oxidation, improving reversible oxygen redox and creating highly flexible structures, with mitigated anisotropic modulus and lattice strain evolution during (de)intercalation. Consequently, the developed MZCN-LMR cathode exhibits impressive capacity retention of 80.5 % after 400 cycles and minimal voltage decay of 0.7 mV per cycle with the voltage range of 2.1–4.6 V. This surface high-entropy strategy offers a universal approach to enhancing the redox stability of anions, contributing to the application of LMR.

Stabilized Li-rich Mn-based oxide cathode particles with an artificial surface in-Situ-preprocessing

The heavy hybrid anion and cation redox contributes to high discharge capacity for Li-rich Mn-based cathode material, but also raises a number of issues including the low initial coulombic efficiency (ICE), rapid attenuation of capacity and voltage and so on, which have prevented its commercialization for more than a decade. Herein, solid-liquid impregnating is conducted to in-situ-build an artificial surface for Li1.2Mn0.54Ni0.13Co0.13O2 (FLLO) particles, which concurrently constructed a anion-redox-free LiMn1.5Ni0.5O4 (LNMO) shell during FLLO synthesis process that completely encloses the FLLO lattice (A-2%-LNMO-FLLO), presents as solid solution structure between FLLO and LNMO coating interface and exhibits stronger bonding between coatings and FLLO cathode material. DSC, TEM and industry computed tomography (ICT) evidence that LNMO coatings is effectiveness in stabilizing the crystal structure of FLLO from macro and micro aspects, leading to the excellent electrochemical properties, such as A-2%-LNMO-FLLO exhibits a discharge capacity of 278mAh/g under 0.1C, and the capacity retention is 98.5 % after 200 cycles under 1C. Furthermore, the enhancement mechanism on electrochemical properties is investigated from aspects of reaction process and crystal structure stability. This paper can provide a theoretical and experimental support for the practical application of FLLO cathode material.

An entanglement association polymer electrolyte for Li-metal batteries

To improve the interface stability between Li-rich Mn-based oxide cathodes and electrolytes, it is necessary to develop new polymer electrolytes. Here, we report an entanglement association polymer electrolyte (PVFH-PVCA) based on a poly (vinylidene fluoride-co-hexafluoropropylene) (PVFH) matrix and a copolymer stabilizer (PVCA) prepared from acrylonitrile, maleic anhydride, and vinylene carbonate. The entangled structure of the PVFH-PVCA electrolyte imparts excellent mechanical properties and eliminates the stress arising from dendrite growth during cycling and forms a stable interface layer, enabling Li//Li symmetric cells to cycle steadily for more than 4500 h at 8 mA cm−2. The PVCA acts as a stabilizer to promote the formation of an electrochemically robust cathode–electrolyte interphase. It delivers a high specific capacity and excellent cycling stability with 84.7% capacity retention after 400 cycles. Li1.2Mn0.56Ni0.16Co0.08O2/PVFH-PVCA/Li full cell achieved 125 cycles at 1 C (4.8 V cut-off) with a stable discharge capacity of ~2.5 mAh cm−2.

New exploration of water-soluble lithium polyacrylate/xanthan gum composite binder for Li-rich Mn-based cathode materials

Li-rich Mn-based oxides are considered promising cathode materials of Li-ion batteries with high specific capacity and operating voltage. However, Li-rich materials suffer from a high initial irreversible capacity loss and severe voltage attenuation during cycling. In this work, lithium polyacrylate (LiPAA) was crosslinked with xanthan gum (XG) to form a water-soluble binder for Li[Li0.2Co0.13Ni0.13Mn0.54]O2 electrode. The capacity retention was 78.3 % after 100 cycles at 0.2 C. LiPAA provided additional Li+ ions during cycling, while XG firmly bound to the surface of the active particles. Cost-effective binders provide a facile mean to improve the electrochemical performance of Li-rich cathode materials.

Stabilization of Li2MnO3 phase by Mg doping suppressing irreversible oxygen loss and Mn ions migration

Li-rich Mn-based oxide cathode material has attracted people’s attention in that their higher specific capacity, which is attributed to their unique biphasic structure. When the voltage is greater than 4.5V, the Li2MnO3 phase is activated to provide a high specific capacity. But during the cycling process, the Li2MnO3 phase is continuously activated. During this process, O2 will be released and transition metal (TM) ions will migrate, leading to structural phase transition, resulting in voltage decay and capacity loss. In this work, 2wt% Mg-doped Li1.18Mg0.02Mn0.54Co0.13Ni0.13O2 exhibits excellent electrochemical performance. After 100 cycles at 1C, the capacity retention rate is 87.83% By introducing Mg at the position of Li in the TM layer, a more stable Mg-O bond is introduced, in which the inert Mg is not involved in the redox reaction but is fixed in the TM layer. The Li2MnO3 phase is optimized by stabilizing the lattice oxygen to make the Li2MnO3 phase more stable, so as to suppress the irreversible oxygen loss and slow down the structural phase transition. Improved the issue of low initial Coulomb efficiency of materials, the voltage attenuation is alleviated, and the cycle stability is improved.

Concentration-gradient of Li-rich Mn-based cathode materials with enhanced cycling retention

Lithium-rich layered Mn-based materials have attracted much attention because of their high specific capacity and high energy density, but they have the characteristics of irreversible capacity loss, low initial coulombic efficiency, and poor cycling performance. In this study, a core-shell structure, including Mn0.75Ni0.25C2O4 precursor as core and Li-rich Mn-based oxides (LRMO, Li1.2Mn0.54Ni0.13Co0.13O2) as shell layer respectively, was synthesized by co-precipitation and sol-gel method. After sintering at high temperatures, the element concentration-gradient oxides material (LRMO-G) was formed. The material was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) and its electrochemical performance was investigated by various electrochemical methods. The LRMO-G material exhibits a high initial discharge specific capacity of 268 mAh/g at 0.1 C, and extremely superior capacity retention (95.4 %) after 100 cycles at 1 C. The initial coulomb efficiency of the LRMO-G material increases to 85 %, which is 12 % higher than that of LRMO.

Achieving the High Capacity and High Stability of Li-Rich Oxide Cathode in Garnet-Based Solid-State Battery.

Solid-state batteries (SSBs) based on Li-rich Mn-based oxide (LRMO) cathodes attract much attention because of their high energy density as well as high safety. But their development was seriously hindered by the interfacial instability and inferior electrochemical performance. Herein, we design a three-dimensional foam-structured GaN-Li composite anode and successfully construct a high-performance SSB based on Co-free Li1.2 Ni0.2 Mn0.6 O2 cathode and Li6.5 La3 Zr1.5 Ta0.5 O12 (LLZTO) solid electrolyte. The interfacial resistance is considerably reduced to only 1.53 Ω cm2 and the assembled Li symmetric cell is stably cycled more than 10,000 h at 0.1-0.2 mA cm-2 . The full battery shows a high initial capacity of 245 mAh g-1 at 0.1 C and does not show any capacity degradation after 200 cycles at 0.2 C (≈100 %). The voltage decay is well suppressed and it is significantly decreased from 2.96 mV/cycle to only 0.66 mV/cycle. The SSB also shows a very high rate capability (≈170 mAh g-1 at 1 C) comparable to a liquid electrolyte-based battery. Moreover, the oxygen anion redox (OAR) reversibility of LRMO in SSB is much higher than that in liquid electrolyte-based cells. This study offers a distinct strategy for constructing high-performance LRMO-based SSBs and sheds light on the development and application of high-energy density SSBs.

Achieving the High Capacity and High Stability of Li‐Rich Oxide Cathode in Garnet‐Based Solid‐State Battery

AbstractSolid‐state batteries (SSBs) based on Li‐rich Mn‐based oxide (LRMO) cathodes attract much attention because of their high energy density as well as high safety. But their development was seriously hindered by the interfacial instability and inferior electrochemical performance. Herein, we design a three‐dimensional foam‐structured GaN−Li composite anode and successfully construct a high‐performance SSB based on Co‐free Li1.2Ni0.2Mn0.6O2 cathode and Li6.5La3Zr1.5Ta0.5O12 (LLZTO) solid electrolyte. The interfacial resistance is considerably reduced to only 1.53 Ω cm2 and the assembled Li symmetric cell is stably cycled more than 10,000 h at 0.1–0.2 mA cm−2. The full battery shows a high initial capacity of 245 mAh g−1 at 0.1 C and does not show any capacity degradation after 200 cycles at 0.2 C (≈100 %). The voltage decay is well suppressed and it is significantly decreased from 2.96 mV/cycle to only 0.66 mV/cycle. The SSB also shows a very high rate capability (≈170 mAh g−1 at 1 C) comparable to a liquid electrolyte‐based battery. Moreover, the oxygen anion redox (OAR) reversibility of LRMO in SSB is much higher than that in liquid electrolyte‐based cells. This study offers a distinct strategy for constructing high‐performance LRMO‐based SSBs and sheds light on the development and application of high‐energy density SSBs.

Unlocking the Potential of Li-Rich Mn-Based Oxides for High-Rate Rechargeable Lithium-Ion Batteries.

Lithium-rich Mn-based oxides have gained significant attention worldwide as potential cathode materials for the next generation of high-energy density lithium-ion batteries. Nonetheless, the inferior rate capability and voltage decay issues present formidable challenges. Here, a Li-rich material equipped with quasi-three-dimensional (quasi-3D)Li-ion diffusion channels is initially synthesized by introducing twin structures with high Li-ion diffusion coefficients into the crystal and constructing a "bridge" between different Li-ion diffusion tunnels. The as-prepared material exhibits monodispersed micron-sized primary particles (MP), delivering a specific capacity of 303mAhg-1 at 0.1 C and an impressive capacity of 253mAhg-1 at 1 C. More importantly, the twin structure also serves as a "breakwater" to inhibit the migration of Mn ions and improve the overall structural stability, leading to cycling stability with 85% capacity retention at 1 Cafter 200 cycles. The proposed strategy of constructing quasi-3Dchannels in the layered Li-rich cathodes will open up new avenues for the research and development of other layered oxide cathodes, with potential applications in industry.

Rational construction of graphitic carbon nitride composited Li-rich Mn-based oxide cathode materials toward high-performance Li-ion battery

Li-rich Mn-based oxides (LRMOs) are considered as one of the most-promising cathode materials for next generation Li-ion batteries (LIBs) because of their high energy density. Nevertheless, the intrinsic shortcomings, such as the low first coulomb efficiency, severe capacity/voltage fade, and poor rate performance seriously limit its commercial application in the future. In this work, we construct successfully g-C3N4 coating layer to modify Li1.2Mn0.54Ni0.13Co0.13O2 (LMNC) via a facile solution. The g-C3N4 layer can alleviate the side-reaction between electrolyte and LMNC materials, and improve electronic conduction of LMNC. In addition, the g-C3N4 layer can suppress the collapse of structure and improve cyclic stability of LMNC materials. Consequently, g-C3N4 (4 wt%)-coated LMNC sample shows the highest initial coulomb efficiency (78.5%), the highest capacity retention ratio (78.8%) and the slightest voltage decay (0.48 V) after 300 loops. Besides, it also can provide high reversible capacity of about 300 and 93 mAh g−1 at 0.1 and 10C, respectively. This work proposes a novel approach to achieve next-generation high-energy density cathode materials, and g-C3N4 (4 wt%)-coated LMNC shows an enormous potential as the cathode materials for next generation LIBs with excellent performance.

Constructing a robust Li-rich Mn-based oxide cathode with oxygen vacancies and strong B-O bonds by BN treatment

Li-rich Mn-based oxide cathodes are one of the most promising cathode candidates for high energy density over 400 Wh kg−1, deriving from oxygen redox of Li-O-Li configuration. However, the deep oxygen oxidation would lead to the formation of peroxides and superoxides (O2n−, 0 < n ≤ 2) and even oxygen (O2), accompanied by crystal phase transformation and structure collapse. Herein, an integrative strategy of simultaneously regulating the right amount of oxygen vacancies (OVs) and B-atom doping is proposed to achieve differentially modification of both R-3 m and C2/m phases. Firstly, Rietveld refinement, HRTEM and in situ XRD results reveal that the linear increase of OVs content is achieved by regulating the amount of BN and the selective introduction of OVs inside the C2/m phase makes the oxygen partial pressure lower in the weak O-Li-O bonds of TM-layer and inhibits oxygen release at over 4.5 V. Meanwhile, kinetics test shows oxygen defects would accelerate the Li+ diffusion and reduce the electronic impedance driven by uneven local charge distribution. Secondly, lattice analysis shows the strong covalent B-O bonds located at the tetrahedral site not only prevent the overoxidation of the oxygen atoms at high voltage, but also hinder the migration of Mn atoms through tetrahedral sites, which effectively avoids the damage of the crystal structure. As a result, the modified cathode exhibits the excellent discharge specific capacity of 272 mA h g−1 at 0.1C, higher rate performance of 145 mA h g−1 at 5C, an outstanding capacity retention rate of 93% at 1C and lower voltage decay value of 0.43 V after 200 cycles. This promising strategy could simultaneously achieve both high energy density and superior cycling stability and help to advance industrial application of Li-rich Mn-based Cathodes.

In situ construction of cubic 3D Li+ channels enabling stable electrochemical topology in a Li-rich layered solid-state oxide-based lithium-ion battery

Solid-state Li-ion batteries (SSLIBs) are expected to become the next-generation energy storage devices due to their high energy density and safe reliability. While the use of conventional cathodes in SSLIBs clearly cannot meet the increasing energy density demands of electric vehicles (EVs). A Li-rich Mn-based oxide (LRMO) has been extensively studied in liquid-state electrolytes (LEs) due to its higher capacity density (≥250 mAh g−1). However, the further application of LRMO in SSLIBs is rarely reported due to its extremely low electronic conductivity (10−11 S cm−1) and gas evolution at high voltage (≥4.3 V). This work demonstrates a novel in situ synthetic strategy for preparing enhanced cubic 3D Li+ channel buffered LRMO cathodes packaged with Li6.75La3Zr1.75Nb0.25O12 (LLZNO) solid electrolyte (SE) for use in SSLIBs. The stable electrochemical topology contributes to good initial discharge capacities (IDC, 0.1 C, 183.1 mAh g−1) and stable cycling retention (0.1 C, 300 cycles, 73.4%) at room temperature (RT, 25 °C). In situ tests analysis and first-principles calculations (DFT) results demonstrated the promising industrial prospects for using the LZM cathode in SSLIBs.

Boosting the electrochemical performance of Li-rich Mn-based cathode materials via oxygen vacancy and spinel phase integration

Li-rich Mn-based oxide cathodes (LMOs) are regarded as one of the most prospective high energy density cathodes due to the reversible anion redox reaction, which gives them a very high capacity. However, LMOs materials usually have problems like low initial coulombic efficiency (ICE) and poor cycling performance during cycling, which are associated with irreversible surface O2 release and unfavourable electrode/electrolyte interface side reactions. Herein, an innovative and scalable NH4Cl-assisted gas–solid interfacial reaction treatment technique is employed to construct oxygen vacancies and spinel/layered heterostructures simultaneously on the surface of LMOs. The synergistic effect of the oxygen vacancy and the surface spinel phase can not only effectively enhance the redox properties of the oxygen anion and inhibit irreversible oxygen release, but also effectively mitigate the side reactions at the electrode/electrolyte interface, inhibit the formation of CEI films and stabilize the layered structure. The electrochemical performance of the treated NC-10 sample improved significantly, showing an increase in ICE from 77.4 % to 94.3 % and excellent rate capability and cycling stability, with a capacity retention of 77.9 % after 400 cycles at 1 C. This oxygen vacancy and spinel phase integration strategy offers an exciting prospect and avenue for improving the integrated electrochemical performance of LMOs.

Exceptional Li‐Rich Mn‐Based Cathodes Enabled by Robust Interphase and Modulated Solvation Microstructures Via Anion Synergistic Strategy

AbstractCoupling Li‐rich Mn‐based oxide (LRMO) cathodes with lithium metal anodes is crucial to enabl high‐energy batteries. However, capacity decline of LRMO caused generally by unexpected parasitic reactions needs to be solved. Herein, an anion synergistic strategy is developed to manipulate the solvation structure to boost the electrochemical performance of high‐voltage lithium batteries. Multi‐salt electrolytes containing TFSI−, DFOB−, and DFBOP− anions are formulated via facilitating a distinctive aggregate, Li+‐(DFBOP−)0.10(DFOB−)0.49(TFSI−)0.51EC0.63EMC2.49DEC0.77, which can reduce the penetration of other anions into the first solvation sheath and strengthen the interaction between Li+ ions and solvent molecules simultaneously. The solvation structure is studied by molecular dynamics (MD) and its feature is found to be able to enhance the transport kinetics of Li+ effectively and favor the formation of an inorganic‐rich interphase. Corrosion of the Al collector is retarded effectively by a cathode−electrolyte interphase (CEI) constructed by the decomposition of DFBOP−, thereby enhancing the cyclability. In addition, Li||LRMO cell can retain its 85% initial capacity after 650 cycles at 1 C. This study provides a guideline to formulate high‐voltage electrolytes with excellent kinetics by regulating the microstructures of solvation and interphases via anion formulation engineering.

One-pot K+ and PO43− co-doping enhances electrochemical performance of Li-rich Li1.2Ni0.13Co0.13Mn0.54O2 cathode for Li-ion battery

The high specific capacity and voltage of Li-rich Mn-based oxides make them promising cathode materials for high-energy-density lithium-ion batteries (LIBs). However, the problems such as low initial coulombic efficiency, fast capacity and voltage fading, poor kinetics, large voltage hysteresis, and poor safety performance hamper their fast commercialization. Herein, we report one-pot K+ and PO43− co-doping Li-rich Mn-based oxides Li1.2Ni0.13Co0.13Mn0.54O2 cathode material to improve the electrochemical performance of the lithium-ion battery. On the one hand, K+ doping can stabilize the bulk structure and enlarge the Li slabs to facilitate the diffusion of Li+, resulting in enhanced cycling and rate performance. On the other hand, PO43− doping changes the electronic structure of the material and weakens the covalency of TM-O, decreasing the irreversible loss of lattice oxygen and stabilizing the structure. As a result, the K+ and PO43− co-doping can effectively alleviate the capacity and voltage decay and the modified sample shows better cycling stability (88.6%@0.5 C@250 cycles) and rate performance (155.5 mAh g −1@5 C) compared to the pristine material. Our strategy here provides a facile one-pot method to modify Li-rich Mn-based oxides cathode material for high-performance LIBs.

Modulating the local electronic structure via Al substitution to enhance the electrochemical performance of Li-rich Mn-based cathode materials

The performance degradation caused by irreversible O2 release and structural collapse has seriously hindered the commercialization of Li-rich Mn-based oxide cathode materials (LMOs). Herein, a Li-rich Mn-based cathode material Li1.2Ni0.2Mn0.6−xAlxO2 (x = 0.02, 0.04, 0.06) via the substitution of Mn by Al was designed. By introducing additional strong Al-O bonds into the local atomic coordination around O and transition metal (TM) to modulate the local electronic structure, the TM 3d-O 2p and non-bonding O-2p band are transferred to lower energy, thus increasing the redox reaction potential. The substitution of Al also enhances the interaction with oxygen and increases the oxygen vacancy formation energy, which stabilizes the lattice oxygen framework and ultimately further inhibits the structural transition (layered → spinel phase) caused by the reduction of TM ions during the cycling process and improves the stability of the layered structure. The results show that the voltage decay of the Al-doped sample is only 0.349 V after 300 cycles, which is much lower than the 0.578 V of the pristine sample. Assembled as a full cell using LMNA2 as the cathode and commercial graphite as the anode, it exhibited a specific energy density of 454.3 Wh kg−1 at 0.1 C, with a capacity retention rate of over 86% after 100 cycles. This research provides a novel idea for the future development of LMOs for high voltage and energy density applications.

Fabricating Heterostructures for Boosting the Structure Stability of Li-Rich Cathodes.

Li-rich Mn-based oxides are regarded as the most promising new-generation cathode materials, but their practical application is greatly hindered by structure collapse and capacity degradation. Herein, a rock salt phase is epitaxially constructed on the surface of Li-rich Mn-based cathodes through Mo doping to improve their structural stability. The heterogeneous structure composed of a rock salt phase and layered phase is induced by Mo6+ enriched on the particle surface, and the strong Mo-O bonding can enhance the TM-O covalence. Therefore, it can stabilize lattice oxygen and inhibit the side reaction of the interface and structural phase transition. The discharge capacity of 2% Mo-doped samples (Mo 2%) displays 279.67 mA h g-1 at 0.1 C (vs 254.39 mA h g-1 (pristine)), and the discharge capacity retention rate of Mo 2% is 79.4% after 300 cycles at 5 C (vs 47.6% (pristine)).

Eliminating interfacial O-involving degradation in Li-rich Mn-based cathodes for all-solid-state lithium batteries.

In the pursuit of energy-dense all-solid-state lithium batteries (ASSBs), Li-rich Mn-based oxide (LRMO) cathodes provide an exciting path forward with unexpectedly high capacity, low cost, and excellent processibility. However, the cause for LRMO|solid electrolyte interfacial degradation remains a mystery, hindering the application of LRMO-based ASSBs. Here, we first reveal that the surface oxygen instability of LRMO is the driving force for interfacial degradation, which severely blocks the interfacial Li-ion transport and triggers fast battery failure. By replacing the charge compensation of surface oxygen with sulfite, the overoxidation and interfacial degradation can be effectively prevented, therefore achieving a high specific capacity (~248 mAh g-1, 1.1 mAh cm-2; ~225 mAh g-1, 2.9 mAh cm-2) and excellent long-term cycling stability of >300 cycles with 81.2% capacity retention at room temperature. These findings emphasize the importance of irreversible anion reactions in interfacial failure and provide fresh insights into constructing stable interfaces in LRMO-based ASSBs.