Manganese-based Layered Oxides Research Articles

Achieving a Deeply Desodiated Stabilized Cathode Material by the High Entropy Strategy for Sodium-ion Batteries.

Manganese-based layered oxides are currently of significant interest as cathode materials for sodium-ion batteries due to their low toxicity and high specific capacity. However, the practical applications are impeded by sluggish intrinsic Na+ migration and poor structure stability as a result of Jahn-Teller distortion and complicated phase transition. In this study, a high-entropy strategy is proposed to enhance the high-voltage capacity and cycling stability. The designed P2-Na0.67Mn0.6Cu0.08Ni0.09Fe0.18Ti0.05O2 achieves a deeply desodiation and delivers charging capacity of 158.1 mAh g-1 corresponding to 0.61 Na with a high initial Coulombic efficiency of 98.2 %. The charge compensation is attributed to the cationic and anionic redox reactions conjunctively. Moreover, the crystal structure is effectively stabilized, leading to a slight variation of lattice parameters. This research carries implications for the expedited development of low-cost, high-energy-density cathode materials for sodium-ion batteries.

A Li-rich layered oxide cathode with remarkable capacity and prolonged cycle life

Introducing a facile ion-exchange method coupled with low-temperature thermal treatment, we have developed a strategy to enhance the cycling performance of Lithium-rich manganese-based layered oxides (LLOs). This approach results in the formation of a thin spinel phase layer, which is covered by a fast-ion-conducting Li3PO4 phase on the surface of pristine 0.5Li2MnO3·0.5LiMn1/3Co1/3Ni1/3O2 secondary particles of aggregated original nanoparticles, and an increase in oxygen vacancies. After undergoing 200 cycles at a rate of 1 C, the resulting cathode exhibits a high capacity of 204.7 mAh/g with a retention rate of up to 94.4 %, which is significantly superior to that of the original materials. The long-term cycling stability of the modified cathode is also evident at higher rates such as 2, 5, and 8 C. The electrochemical analysis suggests that the surface modification and oxygen vacancies can enhance the Li+ diffusion coefficient, improve anion redox reversibility and increase the capacity contribution from spinel oxidation, thereby improving the electrochemical performance of the cathode during cycling.

Unraveling the functioning mechanism of fluorine-doping in Mn-based layered oxide cathodes toward enhanced sodium-ion storage performance

Manganese-based layered oxides with anionic redox activity are considered as one of the most promising cathode candidates for sodium-ion batteries (SIBs) owing to their abundant resources and high theoretical specific capacities. However, the severe Jahn-Teller (J-T) effect of Mn3+ and irreversible lattice oxygen loss result in rapid structural degradation and electrochemical performance deterioration. Herein, the functioning mechanism of F-doping in regulating the local and electronic structures of Mn-based layered oxides is unraveled. The introduction of the more electronegative F ions on one hand breaks the electronic symmetry of the MnO6 octahedra and effectively alleviates the J-T distortion, on the other hand suppresses the Zn ions migration through the strong Zn-F bonds and stabilizes the oxygen redox chemistry and facilitates the Na+ diffusion. The above reaction mechanisms are systematically validated by in-situ/ex-situ analyses and theoretical computations. As a result, the optimum P2-Na0.75Zn0.28Mn0.72O1.93F0.07 cathode demonstrates significantly improved rate capability (178.6 mAh g−1 at 0.1 C with 64.4 mAh g−1 at 10 C) and enhanced cycling durability (83.1 % capacity retention over 400 cycles at 3 C) compared to the un-doped P2-Na0.75Zn0.28Mn0.72O2 material. This study clarifies the F-doping mechanism in layered oxides and provides new perspectives for designing high-energy and high-stability cathodes for SIBs.

Solid-state synthesis of low-cost and high-energy-density sodium layered-tunnel oxide cathodes: Dynamic structural evolution, Na+/vacancy disordering, and prominent moisture stability

Manganese-based layered oxides show promise as cathode materials for sodium-ion batteries (SIBs). However, several challenges including sluggish Na+ kinetics, complex phase transitions, and poor air stability hinder their practical application. Herein, we proposed a dual-function strategy that not only precisely manipulates dynamic structural evolution from layered to tunnel structure, but also effectively suppresses Na+/vacancy and charge ordering by inhibiting electron delocalization. A series of Ti-substituted Na2/3Mn1-xTixO2 (x=0, 1/9, 2/9, 1/3) as proof of concept materials were designed to demonstrate the dual-function strategy. As a result, the optimized Na2/3Mn8/9Ti1/9O2 cathode material delivers a high specific capacity of 202.9 mAh g−1 at 0.1 C within 1.5−4.3 V, equivalent to 536.6 Wh kg−1 of energy density, and exhibits 71.0% of capacity retention after 300 cycles at 1 C. Meanwhile, a highly reversible P2/Tunnel-OP4/Tunnel phase transition process and interlocking effect between the layered and tunnel structure as well as prominent moisture stability even after soak water treatment are further confirmed by in-situ charge and discharge XRD and other advanced characterization techniques. Noting that the electrode assembled with water-solution binder still displays a high capacity retention of 85.4% after 400 cycles at 1 C. Our dual-function strategy provides valuable guidance for developing high energy density and water stable practical SIB cathode materials.

Co/Al Co-Substituted Layered Manganese-Based Oxide Cathode for Stable and High-Rate Potassium-Ion Batteries.

Manganese-based layered oxides are promising cathode materials for potassium-ion batteries (PIBs) due to their low cost and high theoretical energy density. However, the Jahn-Teller effect of Mn3+ and sluggish diffusion kinetics lead to rapid electrode deterioration and a poor rate performance, greatly limiting their practical application. Here, we report a Co/Al co-substitution strategy to construct a P3-type K0.45Mn0.7Co0.2Al0.1O2 cathode material, where Co3+ and Al3+ ions occupy Mn3+ sites. This effectively suppresses the Jahn-Teller distortion and alleviates the severe phase transition during K+ intercalation/de-intercalation processes. In addition, the Co element contributes to K+ diffusion, while Al stabilizes the layer structure through strong Al-O bonds. As a result, the K0.45Mn0.7Co0.2Al0.1O2 cathode exhibits high capacities of 111 mAh g-1 and 81 mAh g-1 at 0.05 A g-1 and 1 A g-1, respectively. It also demonstrates a capacity retention of 71.6% after 500 cycles at 1 A g-1. Compared to the pristine K0.45MnO2, the K0.45Mn0.7Co0.2Al0.1O2 significantly alleviates severe phase transition, providing a more stable and effective pathway for K+ transport, as investigated by in situ X-ray diffraction. The synergistic effect of Co/Al co-substitution significantly enhances the structural stability and electrochemical performance, contributing to the development of new Mn-based cathode materials for PIBs.

Synergistic Effect of Co-Mo Pinning in Lay-Structured Oxide Cathode for Enhancing Stability toward Potassium-Ion Batteries.

Owing to the high economic efficiency and energy density potential, manganese-based layer-structured oxides have attracted great interests as cathode materials for potassium ion batteries. In order to alleviate the continuous phase transition and K+ re-embedding from Jahn-Teller distortion, the [Mn-Co-Mo]O6 octahedra are introduced into P3-K0.45 MnO2 herein to optimize the local electron structure. Based on the experimental and computational results, the octahedral center metal molybdenum in [MoO6 ] octahedra proposes a smaller ionic radius and higher oxidation state to induce second-order JTE (pseudo-JTE) distortion in the adjacent [MnO6 ] octahedra. This distortion compresses the [MnO6 ] octahedra along the c-axis, leading to an increased interlayer spacing in the K+ layer. Meanwhile, the Mn3+ /Mn4+ is balanced by [CoO6 ] octahedra and the K+ diffusion pathway is optimized as well. The proposed P3-K0.45 Mn0.9 Co0.05 Mo0.05 O2 cathode material shows an enhanced cycling stability and rate performance. It demonstrates a high capacity of 80.2mAhg-1 at 100mAhg-1 and 77.3mAhg-1 at 500mAhg-1 . Furthermore, it showcases a 2000 cycles stability with a 59.6% capacity retention. This work presents a promising solution to the challenges faced by manganese-based layered oxide cathodes and offers a deep mechanism understanding and improved electrochemical performance.

Slow-Released Cationic Redox Activity Promoted Stable Anionic Redox and Suppressed Jahn-Teller Distortion in Layered Sodium Manganese Oxides.

Manganese-based layered oxides are considered promising cathodes for sodium ion batteries due to their high capacity and low-cost manganese and sodium resources. Triggering the anionic redox reaction (ARR) can exceed the capacity limitation determined by conventional cationic redox. However, the unstable ARR charge compensation and Jahn-Teller distortion of Mn3+ ions readily result in structural degradation and rapid capacity fade. Here, we report a P2-type Na0.8Li0.2Mn0.7Cu0.1O2 cathode that shows a capacity retention of 84.5% at 200 mA/g after 200 cycles. Combining in situ X-ray diffraction and multi other ex situ characterizations, we reveal that the enhanced cycling stability is ascribed to a slow release of cationic redox activity which can well suppress the Jahn-Teller distortion and favor the ARR reversibility. Furthermore, density-functional theory calculations demonstrate that the inhibited interlayer migration and reduced band gap facilitate the stability and kinetic behavior of ARR. These findings provide a perspective for designing high-energy-density cathode materials with ARR activity.

Realizing high initial Coulombic efficiency in manganese-based layered oxide cathodes for sodium-ion batteries via P2/O′3 biphasic structure optimization

Realizing high initial Coulombic efficiency in manganese-based layered oxide cathodes for sodium-ion batteries via P2/O′3 biphasic structure optimization

Enhancing the power capability of lithium-rich manganese-based layered oxide cathodes by LaF3 modification

Lithium-rich manganese-based layered oxides, such as Li1.2Mn0.54Co0.13Ni0.13O2 (LNCM), are promising cathodes that possess both ultrahigh-specific capacity and high working voltage, yet they have not been commercialized due to intrinsic challenges. These challenges include sluggish Li-ion diffusion kinetics and structural degradation from the layered structure to a spinel-like form, leading to poor power capability and severe capacity fading. To address these challenges, we have developed a modification technique that involves fusing LaF3-decorated with La/F-doping. Protecting the electrode/electrolyte interface, inert LaF3 particles decorate on the LNCM surface impede interfacial side reactions. La-doping near the surface enlarges the Li layer spacing and facilitates Li-ion diffusion. A stronger TM-F bond is formed when F diffuses into the bulk phase and replaces O, thereby decreasing the migration of TM. The resulting LaF3-modified LNCM exhibits a high capacity of 256.1 mAh g−1 at 0.1C and a high-power capability of 3555 W kg−1 at 10C, which is 2.5 times higher than the pristine sample. We also elucidate the relationship between the structures (i.e., oxidation state of elements, bond energy, mechanical properties, and conductivity) and electrochemical behaviors (i.e., impedance and Li-ion diffusion) to explain why the modification of LaF3 improves the power property of the LNCM.

Effects of electrolyte/cathode ratio on investigation of their thermal behaviors using differential scanning calorimetry

Battery materials with high-energy density and good safety performance have been regarded as the ultimate target for larger-scale applications of lithium-ion batteries in electric transportation and grid energy storage. Thermal safety of high energy density cathode materials has been a hot topic for battery safety research in recent years. Differential scanning calorimetry (DSC) is widely used to investigate thermal reaction characteristics of battery materials, but the results are always affected by multiple variables, e.g., sample pre-processing and testing conditions. The variety of DSC results reported in literature have been perplexing the research community. Herein, the cathode-electrolyte system is chosen to reveal the changes of reaction mechanisms with different electrolyte/cathode ratios, since this system has been widely adopted to characterize thermal stability of cathodes and electrolytes in previous studies. Lithium-rich manganese-based layered oxide cathode and ester-based electrolyte are selected as representative samples. Our results reveal that flooded, sufficient, insufficient, and lean electrolyte conditions may lead to distinct thermal behaviors from probably different reaction routines, which may hold different reference values for battery-level safety analysis. This study also suggests the importance of systematic investigations on test conditions in battery material thermal safety research.

Insights into P-Type Iron- and Manganese-Based Layered Sodium Cathodes

Sodium-ion batteries are a low-cost alternative to lithium-ion batteries in large-scale electric energy storage applications due to the natural-abundant sodium resources and similar working principle to LIBs during cycling [1]. Until now, many different cathodes for SIBs have been studied, including layered transition metal oxides (NaxTMO2, x<1), Prussian blue-type compounds, polyanionic and organic compounds [2]. Among them, NaxTMO2 has been extensively reported, due to its layered structure, easy synthesis, promising electrochemical properties, and feasibility for commercial production [3]. According to the occupation of Na ions and oxygen stacking, NaxTMO2 can be classified into P2 and O3 types, where P2 structure contasins trigonal prismatic sites of sodium ions and ABBA oxygen stacking sequence and O3 structure represents octahedral sites of sodium ions and ABCABC oxygen stacking sequence [4]. At low potentials (<2.0V), there is a phase transition P2-P2’ connected with the manganese redox activity and the Jahn-Teller distortion [5]. Compared with O3-type structure, P2-type NaxTMO2 provides higher specific capacity and better structural stability due to the lower diffusion barriers through Na-ion prismatic sites [6].Iron- and manganese-based layered oxides for sodium-ion batteries have attracted renewed interest due to their low cost and environmental friendliness. However, the phase change at high voltage and the Jahn-Teller effect lead to shortening cycle life and poor rate capability. We design a structure optimization of the Na2/3Mn1/2Fe1/2O2 cathode through a partial substitution of Fe3+ to explore the mechanism of redox activity of P2-type Mn/Fe-based layered cathodes. We present the investigation of the effect of simultaneous cationic substitution on the electrochemical performance and structural stability of P2-Na2/3Mn1/2Fe1/2O2. The obtained material exhibits a solid solution mechanism during desodiation/resodiation process and delivers an initial discharge capacity of 168 mA h g-1 at 0.1C and a capacity retention of 80% after 50 cycles. The modified P2 composition has stable cycle performance in the potential window from 1.5V to 4.5V. The main focus here is to understand the fundamental electrochemical mechanism of this layered cathode material by exploring the redox processes of transition metal cations and oxygen anions upon cycling. In situ X-ray synchrotron radiation diffraction is used to explore the structural changes during cycling. In situ X-ray Absorption Near Edge Spectroscopy is used to elucidate the local electronic structure of Fe and Mn atoms as it evolves throughout this electrochemical process. 23Na solid-state nuclear magnetic resonance spectroscopy is used to investigate Na coordination environments during desodiation/resodiation. Ex situ soft X-ray absorption spectroscopy results reveal the participation of oxygen anions in the electrochemical reactions. Thus, we explore the redox reactions of transition metals and oxygen to explain the mechanism and the electrochemical performance for the P2-type Mn/Fe-based layered cathodes.

Effects of elemental doping on phase transitions of manganese-based layered oxides for sodium-ion batteries

Effects of elemental doping on phase transitions of manganese-based layered oxides for sodium-ion batteries

Entropy-Tuned Layered Oxide Cathodes for Potassium-Ion Batteries.

The manganese-based layered oxides as a promising cathode material for potassium ion batteries (PIBs) have attracted considerable interest owing to their simple synthesis, high specific capacity, and low cost. However, due to the irreversible phase transition and the Jahn-Teller distortion of the Mn3+ , its application in potassium ion batteries is limited, leading to slow potassium ion kinetics and severe capacity attenuation. Here, entropy-tuning by changing the content of cathode material composition is proposed to address the above challenges. Compared to low and high entropy variants of K0.45 Mnx Co(1- x )/4 Mg(1- x )/4 Cu(1- x )/4 Ti(1- x )/4 O2 , where x = 0.8, 0.6, and 0.4, the medium entropy K0.45 Mn0.6 Co0.1 Mg0.1 Cu0.1 Ti0.1 O2 shows more balanced electrochemical properties in the PIBs. Benefiting from entropy-tuned suppression of the Jahn-Teller distortion of the Mn3+ , the K0.45 Mn0.6 Co0.1 Mg0.1 Cu0.1 Ti0.1 O2 can achieve a high K+ ion transport rate and alleviated volume variation while retaining high specific capacity. Accordingly, the medium entropy K0.45 Mn0.6 Co0.1 Mg0.1 Cu0.1 Ti0.1 O2 cathode in the full cell exhibits a high capacity of 100 mAh g-1 at 50mA g-1 , delivers superior rate capability (65.8 mAh g-1 at 500mA g-1 ) and cycling stability (67.8 mAh g-1 after 350 cycles at 100mA g-1 ). The entropy-tuning strategy is expected to open new avenues in designing PIB cathode materials and beyond.

Sodium Layered/Tunnel Intergrowth Oxide Cathodes: Formation Process, Interlocking Chemistry, and Electrochemical Performance.

Manganese-based layered oxides are prospective cathode materials for sodium-ion batteries (SIBs) due to their low cost and high theoretical capacities. The biphasic intergrowth structure of layered cathode materials is essential for improving the sodium storage performance, which is attributed to the synergistic effect between the two phases. However, the in-depth formation mechanism of biphasic intergrowth materials remains unclear. Herein, the layered/tunnel intergrowth Na0.6MnO2 (LT-NaMO) as a model material was successfully prepared, and their formation processes and electrochemical performance were systematically investigated. In situ high-temperature X-ray diffraction displays the detailed evolution process and excellent thermal stability of the layered/tunnel intergrowth structure. Furthermore, severe structural strain and large lattice volume changes are significantly mitigated by the interlocking effect between the phase interfaces, which further enhances the structural stability of the cathode materials during the charging/discharging process. Consequently, the LT-NaMO cathode displays fast Na+ transport kinetics with a remarkable capacity retention of ∼70.5% over 300 cycles at 5C, and its assembled full cell with hard carbon also exhibits high energy density. These findings highlight the superior electrochemical performance of intergrowth materials due to interlocking effects between layered and tunnel structures and also provide unique insights into the construction of intergrowth cathode materials for SIBs.

Enhancing the operation stability of lithium-rich layered oxide Li1.2Ni0.2Mn0.6O2 by synergistic pinning effect and interface reconstruction for high-energy-density lithium-ion batteries

Lithium-rich manganese-based layered oxides are considered to be promising cathode materials for next-generation lithium-ion batteries (LIBs). However, their practical application is hindered due to both the rapid capacity attenuation and the unsatisfactory rate capability. In this work, to overcome these problems, layered oxide Li1.2Ni0.2Mn0.6O2 (LNMO) is modified via La3+ doping and perovskite type LaMnO3 coating layer, meanwhile, interface layer Li2MnO3 with monoclinic structure is formed between the doped-La3+ Li1.2Ni0.2Mn0.6O2 and LaMnO3 coating layer. The 0.02 wt% La modified Li1.2Ni0.2Mn0.6O2 can deliver much higher rate capability and cyclic stability than original LNMO, attributed that the LaMnO3 coating layer can not only isolate La-doped LNMO from the electrolyte to reduce the dissolution of manganese ions but also can reduces the polarization of electrode interface via inhibiting the continuous growth of SEI during the cycle. Besides, La3+ doping plays a pinning effect role in enhancing the structural stability of LNMO.

Durable lithium-ion insertion/extraction and migration behavior of LiF-encapsulated cobalt-free lithium-rich manganese-based layered oxide cathode

Lithium-rich manganese-based cathode has made a subject of intense scrutiny for scientists and application researchers due to their exceptional thermal stability, high specific capacity, high operating voltage, and cost-effectiveness. However, the inclusion of cobalt, as a crucial component in lithium-rich manganese-based cathode materials, has become a cause for concern due to its limited availability and non-renewable nature, which eventually limits the growth of the battery industry and increase costs. Considering the poor stability of cobalt-free cathode, this work proposes a coating strategy of LiF through a simple high-temperature melting method. Directly coating LiF on Li1.2Ni0.2Mn0.6O2 surface is found to be an effective way to protect the cathode material, decrease metal solubility, and inhibit irreversible phase transition processes, thus leading to an improved electrochemical performance. As a result, the battery employing LiF coated Li1.2Ni0.2Mn0.6O2 cathode can be stabilized over 280 cycles and maintain a capacity of 110 mAh g−1 at 1C. What’s more, the mechanisms of ion insertion/extraction behavior and ion migration process are also studied systematically. This study will open the avenue to develop a high-energy battery system with cobalt-free cathode.

Enhancing Ionic Transport and Structural Stability of Lithium-Rich Layered Oxide Cathodes via Local Structure Regulation.

Lithium-rich manganese-based layered oxides (LRM) have garnered considerable attention as cathode materials due to their superior performance. However, the inherent structural degradation and obstruction of ion transport during cycling lead to capacity and voltage decay, impeding their practical applications. Herein, an Sb-doped LRM material with local spinel phase is reported, which has good compatibility with the layered structure and provides 3D Li+ diffusion channels to accelerate Li+ transport. Additionally, the strong Sb-O bond enhances the stability of the layered structure. Differential electrochemical mass spectrometry indicates that highly electronegative Sb doping effectively suppresses the release of oxygen in the crystal structure and mitigates successive electrolyte decomposition, thereby reducing structural degradation of the material. As a result of this dual-functional design, the 0.5 Sb-doped material with local spinel phases exhibits favorable cycling stability, retaining 81.7% capacity after 300 cycles at 1C, and an average discharge voltage of 1.87mV per cycle, which is far superior to untreated material with retention values of 28.8% and 3.43mV, respectively. This study systematically introduces Sb doping and regulates local spinel phases to facilitate ion transport and alleviate structural degradation of LRM, thereby suppressing capacity and voltage fading, and improving the electrochemical performance of batteries.

SeO2-infused grain boundaries effectively improve rate and stability performance of Li-rich manganese-based layered cathode materials

For polycrystalline lithium-rich manganese-based layered oxides (LMLO), the presence of porous microstructures always leads to the greater oxygen release and lower conductivity, impairing their rate and cycling stability performance for real applications. Here, by temperature-controlled annealing, we propose a facile and scalable method to infuse molten SeO2 into the intracrystalline grain boundary of the polycrystalline Li1.2Mn0.54Ni0.13Co0.13O2 (LMNCO) particles. Then the uniform surface and double nanolayer structure composed of interconnected Li2SeO4 and robust Li2NixCoyO4 are revealed on primary particles. Accordingly, SeO2-infused LMNCO(Se-LMNCO) gains an upraised rate performance with 97 % capacity retenting rate after charge and discharge under 0.1–5 C then returned to 0.1 C and an improved cycling stability with a capacity retention of 80.0 % over 200 cycles at 1 C (1 C=250 mAh g−1). Our work highlights the significance of surface engineering inside the secondary LMLO particles and the improvement of electrochemical rate and stability performance toward lithium-ion batteries with LMLO electrode.

Computational Understandings of Cation Configuration-Dependent Redox Activity and Oxygen Dimerization in Lithium-Rich Manganese-Based Layered Cathodes

Lithium-rich manganese-based layered oxides have emerged as a fresh paradigm for developing advanced cathode materials with high energy density for next-generation lithium-ion batteries. Understanding lattice oxygen dimerization is quite essential for the optimal design of lithium-rich manganese-based cathode materials. Herein, based on density functional theory (DFT) calculations, a local Ni-honeycomb Li–Ni–Mn cation configuration for the Li1.22Ni0.22Mn0.56O2 cathode was carefully examined, which may coexist with the well-known local Li-honeycomb structure in experimentally synthesized Li1.2Ni0.2Mn0.6O2 samples. The local Li–Ni–Mn cation configurations have significant impacts on oxygen redox activity, transition metal atom migration, and oxygen dimerization in the charging process of LixNi0.22Mn0.56O2. It is found that there is no correlation between high lattice oxygen redox activity and easy oxygen dimerization, such as Li-honeycomb structures simultaneously exhibiting higher oxygen redox activities and higher activation energy barriers for prohibiting oxygen dimerization than Ni-honeycomb structures. The structural regulations of the local Li–Ni–Mn cation configuration by avoiding the local Ni-honeycomb structures to inhibit Mn migration and ease lattice oxygen dimerization and by making full use of the local Li-honeycomb structures would maximize performance of Li-rich Mn-based layered oxides. Such fresh insights provide us a fresh strategy to optimally design the local honeycomb structure for high-performance Li-rich Mn-based cathode materials.

In Situ Formed Heterostructure Interface and Well-Tuned Electronic Structure Ensuring Long Cycle Stability for 4.9 V High-Voltage Li-Rich Layered Oxide Cathodes

High-voltage lithium-rich manganese-based layered oxides (LMLOs) are considered as the most competitive cathode materials for next-generation high-energy-density lithium-ion batteries (LIBs). However, LMLOs still suffer from irreversible lattice oxygen release, uncontrollable interface side reactions, and surface structural degradation. Herein, we propose an integration strategy combining La/Al codoping and LixCoPO4 nanocoating to improve the electrochemical performance of LMLOs comprehensively. La/Al codoping regulates the electronic structure to enhance the redox activity of anions and cations and inhibit structural degradation. The LixCoPO4 nanocoating formed by in situ reaction with the surface residual lithium can not only promote Li-ion migration but also reduce interfacial side reactions. The induced Layered@Rocksalt@LixCoPO4 heterostructure suppresses lattice volume variation and structural degradation during cycling. Under the synergistic effect of the heterostructure interface and well-tuned electronic structure, the capacity retention rate of comodified LMLO materials reaches 80.06% after 500 cycles (2.0-4.65 V) and 75.1% after 340 cycles at 1C under a high cut-off voltage of 4.9 V.