Lithium-rich Cathode Materials Research Articles

Li1.2Mn0.54Ni0.13Co0.13O2 nanosheets with porous structure as a high-performance cathode material for lithium-ion batteries.

The morphological and structural optimizations of electrode materials are efficient ways to enhance their electrochemical performance. Herein, we report a facile co-precipitation and subsequent calcination method to fabricate Li1.2Mn0.54Ni0.13Co0.13O2 nanosheets consisting of interconnected primary nanoparticles and open holes through the full thickness. By comparing the nanosheets and the agglomerated nanoparticles, the effects of the morphology and structure on the electrochemical performance are investigated. Specifically, the nanosheets exhibit a discharge capacity of 210 mA h g−1 at 0.5C with a capacity retention of 85% after 100 cycles. The improved electrochemical performance could be attributed to their morphological and structural improvements, which may facilitate sufficient electrolyte contacts, short diffusion paths and good structural integrity during the charge/discharge process. This work provides a feasible approach to fabricate lithium-rich layered oxide cathode materials with 2D morphology and porous structure, and reveals the relationships between their morphology, structure and electrochemical performance.

Influence of Cu doping and high-pressure torsion on electrochemical performance of lithium-rich cathode material

Lithium-rich manganese based layered oxide yLi2MnO3∙(1-y)LiMO2 (M=Ni, Co and Mn) is one of the candidate materials for high-capacity cathodes in next-generation lithium-ion batteries. Ion doping with cation and introducing oxygen vacancy are regarded as two methods to change the electrochemical performance of Li-rich cathode materials. In this work, Li1.2Mn0.54Co0.13Ni0.13O2 was synthesized via one-step co-precipitation process, ion doping with low cost element Cu as well as high-pressure torsion were carried out to modify the Li-rich material. Results show that doping with Cu can slightly improve the specific discharge capacity as well as the coulombic efficiency which may be attributed to the lower cation mixing degree.

Anion Reactivity in Cation-Disordered Rocksalt Cathode Materials: The Influence of Fluorine Substitution

The global demand for energy storage technology has created a tremendous need for Li-ion batteries that are lightweight, low cost, and sustainable. Research in the field of lithium-rich cathode materials has led to the development a new class of lithium-excess, cation-disordered rocksalt (DRX) materials. DRX materials display exciting promise as potential cathodes in lithium-ion batteries, owing to their high capacity and resource-friendly composition. Despite these exciting characteristics, these materials suffer from capacity loss over extended cycling due to deleterious side reactions that occur at high potentials, such as O2 loss. It has been shown that oxygen loss can be suppressed by partial substitution of the lattice oxygen for fluorine, but the role of fluorine in the material remains unclear. In this study, we examine the impact of fluorination on the anionic reactivity of DRX materials. We first use Differential Electrochemical Mass Spectrometry (DEMS) and Titration Mass Spectrometry to map first-charge electrochemistry in DRX cathodes. Comparing the results of this analysis for a DRX oxide and a DRX oxyfluoride, we observe that fluorination increases the transition metal capacity and reduces the oxygen redox capacity. These two effects influence the total material capacity in opposite ways, shifting the balance between transition metal redox and oxygen redox without strongly affecting the total charge capacity. We also adapt an existing technique that couples DEMS with a fluoride-scavenging additive, using it for the first time to show that small amounts of fluorine dissolve from DRX oxyfluorides during charging to high potentials. Finally, we extend these techniques over the first several cycles to study the reversibility of the redox processes and the stability of the materials during cycling. We demonstrate that while oxygen redox remains mostly reversible from cycle to cycle, electrolyte degradation and fluoride dissolution also continue to occur to a diminishing extent during cycling. These conclusions motivate surface passivation to control interfacial reactivity as an important direction to improve cycling stability.

Identification of Correlation between Cation Disordering and the Anionic Redox Chemistry in Li-Rich Layered Oxides

To satisfy our increasing dependence on the high energy storage electronics, Li-rich layered oxides (Li[LixM1-x]O2, M = Ni, Co, Mn, Ru, Ir, etc) have attracted significant attention as cathode materials for lithium-ion batteries in recent years. This class of cathode materials exhibit promising capacities, up to 300 mAh/g, due to accumulative transition metal and oxygen redox reaction1–5. Additional capacity in this class of Li-rich cathode material is due to the anionic redox which is irreversible or partially reversible oxygen evolution6,7 and reversible O2-/n- redox1,3,4,8. Luo el at.1 demonstrated that the localized electron holes on oxygen coordinated by Mn4+ and Li+ ions is promoted by the relatively more ionic interactions of O-(Mn/Li) than O-(Ni/Co) interactions at the result of the oxygen oxidation. In our previous study2, at least partially reversible oxygen evolution was observed in 0.4Li2MnO3-0.6LiMn0.5Ni0.5O2 by using Rietveld refinement of high resolution powder diffraction patterns. In the case of 4d (Ru) and 5d (Ir) transition metal-based Li-rich cathode materials, reversible anionic redox was confirmed by X-ray photoelectron spectroscopy (XPS)3,4. Even though the participation of oxygen in redox activity in Li2MnO3 results in partial oxygen evolution with irreversible structural changes9, oxygen redox reaction is stabilized by the reversible peroxo-dimers (O2 n-) formation in the Li2MO3-based (M = Ru, Ir) Li-rich cathode materials due to the high covalent metal-oxygen environment in Ru- and Ir-based lithium-rich cathode materials. However, Seo et al.10 identified the structural and chemical origin of the anionic redox activity which preferentially takes place along the Li-O-Li configurations (non-bonding O 2p states) in Li-rich layered oxides and cation-disordered oxides by using ab initio calculations based on DFT. The electrons in Li-O-Li states exist in the higher energy states than those in the other O 2p states owing to their unhybridized O 2p and Li 2s orbitals. Through these significant studies, anionic redox mechanism seems to be well established. In the case of Na2RuO3, extra anionic capacity is enabled in honeycomb-ordered Na2RuO3 due to the ordered intermediate Na1RuO3 phase which can accommodate the frontier orbital reorganization11, meanwhile, transition metal migration into the empty Li sites is closely associated with the anionic redox as a result of the structural disordering in Li1.17Ni0.21Co0.08Mn0.54O2 5 and Li2IrxSn1-xO3 systems12. It is still under debating whether such manifold anionic chemistry will be solved in terms of transition metals (3d, 4d, and 5d) or alkali metals (Li and Na) or bulk and local structure. In addition, the different reaction mechanism is confirmed between multivalent iridium redox (Ir4+/5.5+)12 and cumulative iridium (Ir4+/5+) and oxygen (O2-/n-) redox13 even in the same C2/m space group of Li2IrO3 materials.Herein, redox mechanism of Li2IrO3 was investigated as a model compound for Li-rich cathode material to understand the key structural differences that lead to anionic redox activity through the synchrotron-based analysis. The local environment, not the composition itself in Li-rich materials, is one of the major factors affecting the redox reaction. We demonstrate that the in-plane disordering in the transition metal layer play a critical role in cation migration and anionic redox, and that cation migration also can trigger the anionic redox reactions. These fundamental insights about Li-rich material family are critical for further development of anionic redox-based cathode materials. In-plane ordering in pristine state with the same composition of Li2IrO3 has a major impact on cation migration and reversible anion redox. Based on the experimental data, detailed findings and discussion will be presented in the PRiME 2020.References K. Luo et al., Nat. Chem., 8, 684–691 (2016)S. Muhammad et al., Nano Energy, 21, 172–184 (2016)M. Sathiya et al., Nat. Mater., 12, 827–835 (2013)E. McCalla et al., Science (80-. )., 350, 1516–1521 (2015).W. E. Gent et al., Nat. Commun., 8, 2091 (2017)A. R. Armstrong et al., J. Am. Chem. Soc., 128, 8694–8698 (2006).A. Boulineau, L. Simonin, J. F. Colin, C. Bourbon, and S. Patoux, Nano Lett., 13, 3857–3863 (2013).H. Koga et al., J. Electrochem. Soc., 160, 786–792 (2013).J. R. Croy et al., Chem. Mater., 26, 7091–7098 (2014).D. H. Seo et al., Nat. Chem., 8, 692–697 (2016)B. Mortemard de Boisse et al., Nat. Commun., 7, 11397 (2016)J. Hong et al., Nat. Mater., 18, 256–265 (2019)E. McCalla et al., Science (80-. )., 350, 1516–1521 (2015)

Enhanced electrochemical performances of cerium-doped Li-Rich Li1.2Ni0.13Co0.13Mn0.54O2 cathode materials

The effects of cerium doping and the formation of layered-spinel hetero-structure on the electrochemical properties of lithium-rich cathode material were studied. The doped sample with layered-spinel phase exhibited enhanced cycling rate capability and long-term cyclability, which achieved an initial discharge capacity of 265.4 mAh g−1 at 0.1 C and the capacity retention was 98.2% after 100 cycles at 1.0 C. The existence of layered-spinel hetero-structure in lithium-rich layered cathode material induced by cerium doping was believed to contribute to the remarkable improvement of cycling stability and rate capability. Cerium doping and the formation of spinel phase together facilitated lithium ion diffusion and inhibited the structural collapse during cycling.

Synergistic effect of bulk phase doping and layered-spinel structure formation on improving electrochemical performance of Li-Rich cathode material

In this study, La was doped into the lithium layer of Li-rich cathode material and formed a layered-spinel hetero-structure. The morphology, crystal structure, element valence and kinetics of lithium ion migration were studied by field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The La doped lithium-rich cathode material exhibited similar initial discharge capacity of 262.8 mAh g−1 at 0.1 C compared with the undoped material, but the discharge capacity retention rate can be obviously improved to 90% after 50 cycles at 1.0 C. Besides that, much better rate capability and Li+ diffusion coefficient were observed. The results revealed that La doping not only stabilized the material structure and reduced the Li/Ni mixing degree, but also induced the generation of spinel phase to provide three-dimensional diffusion channels for lithium ion migration. Moreover, the porous structure of the doped samples also contributed to the remarkable excellent electrochemical performance. All of these factors combined to significantly improve the electrochemical performance of the material.

Sol-gel synthesis of nano Li1.2Mn0·54Ni0·13Co0·13O2 cathode materials using DL-lactic acid as chelating agent

Lithium-rich cathode materials Li1·2Mn0·54Ni0·13Co0·13O2 (LMNCO) are prepared by sol-gel method using dl-lactic acid as chelating agent. The effect of pH on crystal structures, morphologies, particle sizes, and electrochemical properties of cathode materials are studied by X-ray diffractometry (XRD), scanning electron microscopy (SEM), nanoparticle analysis, charge–discharge tests, and electrochemical analysis. The Li1·2Mn0·54Ni0·13Co0·13O2 cathodes exhibit well-ordered layered structures consisting of hexagonal LiMO2 and monoclinic Li2MnO3 with smooth surfaces and well-crystallized particles (100–500 nm). LMNCO-7.0 exhibits smaller particle sizes than LMNCO-5.5 and LMNCO-8.5 and better electrochemical performance. The first discharge capacity and Coulombic efficiency of LMNCO-7.0 are 232.31 mAh g−1 and 73.2%, respectively. After 50 cycles, discharge capacity of LMNCO-7.0 decrease to 194.93 mAh g−1. LMNCO-7.0 cathode shows superior discharge capacity and rate performance due to its low charge transfer impedance and small average quasi-spherical particle diameter.

Understanding the Structure-Performance Relationship of Lithium-Rich Cathode Materials from an Oxygen-Vacancy Perspective.

Li-rich layered oxide cathode materials are regarded as an attractive candidate of next-generation Li-ion batteries (LIBs) to realize an energy density of >300 Wh kg-1. However, challenges such as capacity fade, cycle life, oxygen release, and structural transformation still restrain its practical application. Micro/nanotechnology is one of the effective strategies to enhance its structural stability and electrochemical performance. An in-depth understanding of the relationship between micro/nanostructures and the electrochemical performance of Li-rich layered oxides is undoubtedly important for developing high-performance cathode materials. Herein, Li1.2Ni0.13Co0.13Mn0.54O2 with different micro/nanostructures including irregular particles, microspheres, microrods, and orthogonal particles are synthesized. Starting from the amount of surface oxygen vacancies in the different structures, the influence of oxygen vacancies on every step during the charge-discharge processes is analyzed by experimental characterizations and theoretical calculations. It is indicated that intrinsic oxygen vacancies can enhance the electrical conductivity and decrease the energy barrier for ion migration, which exerts a significant influence on promoting the kinetics and capacity. Among the different micro/nanostructures, microrods with abundant oxygen vacancies can not only promote lithium ion transport but also stabilize a cathode electrolyte interface (CEI) film by adjusting the distribution of surface elements with lower nickel content. The microrods deliver an initial discharge capacity of up to 306.1 mAh g-1 at 0.1C rate and a superior cycle performance with a capacity retention of 91.0% after 200 cycles at 0.2C rate.

Hollow spherical 0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2 prepared by facile molten salt method for enhanced long-cycle and rate capability of lithium-ion batteries

Molten salt method has been widely adopted in preparation of a series of battery materials. The formula of the molten salts has a great influence on the morphology and property of the product. In this work, a hollow spherical lithium-rich cathode material (0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2, LMO) was successfully prepared using a mixed molted salt method. The hollow LMO possesses a higher crystallinity and more Li+ diffusion channels in comparison with the LMO prepared using single salt or no salt, because the mixed salts have a much lower melting point. These structural features endow the hollow LMO with remarkably high initial discharge capacity (280.9 mAh g−1 at 0.1C) and coulombic efficiency, excellent rate performance as well as good cycling stability (500 cycles at 5C). Notably, the hollow LMO exhibits outstanding cycling stability at high temperature (60 °C at 1C over 100 cycles). Further kinetic analyses reveal that the Li+ diffusion coefficient is obviously enhanced, and the charge transfer resistance is reduced by the mixed molten salt method. This work proposes an effective strategy to improve the electrochemical performance of Li-rich cathode materials by regulating the formula of the molten salt method.

Reaction Mechanisms of Layered Lithium-Rich Cathode Materials for High-Energy Lithium-Ion Batteries.

Layered lithium-rich cathode materials have attracted extensive interest owing to their high theoretical specific capacity (320-350 mA h g-1 ). However, poor cycling stability and sluggish reaction kinetics inhibit their practical applications. After many years of quiescence, interest in layered lithium-rich cathode materials is expected to revive in answer to our increasing dependence on high-energy-density lithium-ion batteries. Herein, we review recent research progress and in-depth descriptions of the structure characterization and reaction mechanisms of layered lithium-rich manganese-based cathode materials. In particular, we comprehensively summarize the proposed reaction mechanisms of both the cationic redox reaction of transition-metal ions and the anionic redox reaction of oxygen species. Finally, we discuss opportunities and challenges facing the future development of lithium-rich cathode materials for next-generation lithium-ion batteries.

Rocksalt type Li2Nb0·15Mn0·85O3 without structure degradation or redox evolution upon cycling

Voltage and capacity decay problems of Li2MnO3-based lithium rich layered cathode materials are still unsolved, which are the major barriers for its practical application. Intensive investigations of their mechanisms have been proceeded in recent years, which clarify cation ordered arrangement and spinel deterioration are culprits in structural aspect. Herein, we conduct various analyses to a rocksalt type Li2Nb0·15Mn0·85O3, whose first charge process is along with primary oxygen redox as Li2MnO3, but subsequently shows much better capacity retention. This material suffers from severe voltage decay and overpotential during the cycle but hard X-ray diffraction indicates it can remain rocksalt structure without any tendency of spinel deterioration or cation ordering even with massive lithium vacancies. XAS results further show there is no evident oxygen redox activity from the second cycle, while the redox range of Mn nearly has no change during the cycle. Our results demonstrate that disordered lithium rich cathode materials could be promising to exhibit highly reversible capacity upon long cycling, and their voltage decay problem could be easier to be solved for different mechanism from layered one.

Structural, Electrical, and Electrochemical Characterization of Li1.2Ni0.6−xMgxCo0.3O2 Cathode Materials for Application in Lithium-Ion Batteries

Lithium-rich nickel cobalt magnesium oxide cathode materials with varying concentrations of nickel and magnesium have been synthesized using a solid-state reaction (SSR) method. The structural properties of the as-synthesized cathode materials were analyzed by x-ray diffraction (XRD), confirming their α-NaFeO2 layered structure in space group R3m. Scanning electron microscopy (SEM) study revealed the cube-like hexagonal structure of the prepared materials. Electrochemical impedance spectroscopy (EIS) was carried out in the frequency range from 1 Hz to 7 MHz with a voltage amplitude of 10 mV. At ambient temperature, the direct-current (DC) conductivity was found to be the highest for the Li1.2Ni0.6Co0.3O2 cathode material with a value of 3.64 × 10−4 S/cm. Various conducting mechanisms are proposed for the prepared cathode materials based on Jonscher’s power law. The activation energy is seen to increase with increasing Mg concentration, which helps to produce a defect-less or ordered homogeneous structure. Furthermore, the value of the power-law exponent n is found to decrease with increasing Mg concentration. For the Li1.2Ni0.3Mg0.3Co0.3O2 sample, the n value decreases with increasing temperature and is found to be less than 1 at higher temperatures, indicating the orderliness of the system. Cyclic voltammetry (CV) measurements confirmed that Mg substitution delayed the oxidation and reduction processes, thus enhancing the operating voltage of the electrochemical cell.

Enhancing the Stability of Lithium-Rich Manganese-Based Layered Cathode Materials for Li-Ion Batteries Application

Enhancing the Stability of Lithium-Rich Manganese-Based Layered Cathode Materials for Li-Ion Batteries Application

The effect on the properties of each element in the Li1.2Mn0.54Ni0.13Co0.13O2 material by the incorporation of Al

In this paper, a lithium-rich layered cathode material Li1.2Mn0.54Ni0.13Co0.13O2 was synthesized by improving the sol-gel method. Lithium-rich manganese-based cathode materials are one of the promising next-generation lithium-ion battery cathode materials. However, this material has problems of severe capacity reduction and poor rate performance. By adding a certain amount of Al to replace the metal element in the raw material, and then testing and analyzing various produced materials, it was found that adding a certain amount of Al to replace the lithium element in the raw material can improve the cycle performance and stability of the material. XRD and SEM results show that the incorporation of Al does not significantly change the structure and morphology of the material. The results of electrochemical tests show that the Al-doped sample LMNCAO-1 has good specific capacity and stability. LMNCAO-1 has a high initial specific capacity of 271.0 mAh/g at a voltage of 2–4.8 V and a current density of 0.1 C. The initial discharge specific capacity of the sample LMNCAO-1 was 185 mAh/g at 0.5 C, and the cycle retention rate was 97.3% after 100 cycles.

Microwave-assisted hydrothermal synthesis of lithium-rich layered oxide cathode materials with high stability

Lithium-rich layered oxides have the advantages of high specific capacity (> 250 mAh g−1) and high energy density, which make them highly competitive in the lithium-ion cathode material market. However, low efficiency, poor cycle stability, and poor rate performance severely constrained their development. In this paper, the spherical lithium-rich Li1.2Mn0.54Ni0.13Co0.13O2 compound was rapidly synthesized by microwave hydrothermal method, and the microwave hydrothermal time was optimized. The samples were characterized and analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy (Raman), and X-ray photoelectron spectroscopy (XPS). The prepared lithium-rich compound is porous spherical secondary particles, of which the size distributed between 2.5 and 3.5 μm, which makes materials have larger specific surface area and active potential and promotes the improvement of electrochemical kinetics. The results of 100 charge-discharge cycles show that the microwave hydrothermal 40-min cathode has good stability, and the capacity retention rate can reach 91.4%. Furthermore, it can still provide a discharge capacity of 160.5 mAh g−1 at a current density of 5 C.

Enhanced electrochemical performance of La-doped Li-rich layered cathode material

A series of promising lithium-rich cathode materials with excellent electrochemical properties were successfully synthesized by calcining precursors and lithium salts. The structure, morphology, element valence state, cyclic voltammetry and electrochemical impedance were used to study the properties of the materials. The doped La3+ had great influence on the structure and electrochemical properties of the materials. XRD results displayed that La3+ was incorporated into the material lattice resulted in the formation of layered-spinel hetero-structure, the decrease of cation mixing and the expansion of c lattice parameter. The discharge capacity decreased after La3+ was doped into Li[Li0.2Mn0.54Ni0.13Co0.13]O2, which was due to La3+ was non-electrochemical active element did not participate in the electrical reaction. Although the discharge capacity was reduced after La3+ doping, the initial coulombic efficiency, cycling performance and rate capability were all improved. Among the prepared samples, Li[Li0.2Mn0.54Ni0.13Co0.125]La0.005O2 delivered the best electrochemical performance and highest lithium ions diffusion coefficient, which can be ascribed to its stable and ordered layered-spinel hetero-structure.

Amorphous Li2ZrO3 nanoparticles coating Li[Li0·17Mn0·58Ni0.25]O2 cathode material for enhanced rate and cyclic performance in lithium ion storage

The low-cost and eco-friendly cobalt free Mn–Ni-based layered compounds are attractive as potential cathode materials for high energy lithium ion batteries. To improve the stability of Mn–Ni-based cathode materials during charging/discharging, surface coating may hinder the side reactions on the interphase between active material and electrolyte. In this work, Li[Li0·17Mn0·58Ni0.25]O2 coated by amorphous Li2ZrO3 nanoparticles are synthesized, the coating quantity and morphologies are studied in detail aiming to find out an efficient approach to enhance electrochemical properties. LMO/LZO2 with an appropriate quantity of Li2ZrO3 coating layer delivers capacity of 253 mAh g−1 at the 1st cycle and remains 87% of the initial capacity after 100 cycles at 0.1 C-rate, moreover, it delivers highest capacity of 145 mAh g−1 at 5 C-rate. Construction a proper coating layer of Li2ZrO3 not only plays the key role in improving the conductivity and lithium ions diffusion ability through the interphase between active material and electrolyte, but also hinders the dissolution of Mn element of lithium-rich cathode material.

Suppressing the voltage decay of lithium-rich cathode for Li-Ion batteries via Pt nanoparticles surface modification

Lattice oxygen undergoes redox reaction to achieve high specific capacity of the material in lithium-rich cathode oxides. However, irreversible oxygen loss causes a change in the crystal structure, and the cations migrate in the transition metal layer, resulting in a rearrangement of the electronic structure and ultimately a severe voltage decay. Herein, we introduce Pt nanoparticles with good catalytic activity and electrical conductivity into lithium-rich cathode materials to improve the loss of lattice oxygen for the first time. We have revealed that the evolution of the lattice structure after the lattice oxygen redox reaction is relatively stable in the lithium-rich oxide with Pt nanoparticles, which is in stark contrast to the apparently deformed crystal structure in the lithium-rich oxide without Pt. Pt-containing electrodes exhibit excellent high-capacity retention rate (more than 80% after 200 cycles), and voltage decay is significantly reduced (less than 0.4 V after 200 cycles). Our results highlight the role of Pt nanoparticles in alleviating the loss of lattice oxygen and stabilizing the crystal structure, which opens up the field of vision for the design of high-energy-density lithium rich cathode oxides with stable structure.

Inhibition of transition metals dissolution in cobalt-free cathode with ultrathin robust interphase in concentrated electrolyte

The low Coulombic efficiency during cycling hinders the application of Cobalt-free lithium-rich materials in lithium-ion batteries. Here we demonstrated that the dissolution of iron, rather than traditionally acknowledged manganese, is mainly responsible for the low Coulombic efficiency of the iron-substituted cobalt-free lithium-rich material. Besides, we presented an approach to inhibit the dissolution of transition metal ions by using concentrated electrolytes. We found that the cathode electrolyte interphase (CEI) layer formed in the concentrated electrolyte is a uniform and robust LiF-rich CEI, which is a sharp contrast with the uneven and fragile organic-rich CEI formed in the dilute electrolyte. The LiF-rich CEI not only effectively inhibits the dissolution of TMs but also stabilizes the cathode structure. The Coulombic efficiency, cycling stability, rate performance, and safety of the Fe-substituted cobalt-free lithium-rich cathode material in the concentrated electrolyte have been improved tremendously.

Enhanced Structural Stability of Boron-Doped Layered@Spinel@Carbon Heterostructured Lithium-Rich Manganese-Based Cathode Materials

Layered Li-rich 3d-transition-metal cathode materials, xLi2MnO3·(1–x)LiMO2, have increasingly triggered immense interest for their use in Li-ion batteries due to their advantages in terms of energy density. Nevertheless, poor cycle and rate performances cause limitations in practical commercial applications. We modified the material with boron bulk doping and carbon surface modification to form a B-doped layered@spinel@carbon heterostructure. Herein, B-doping can increase the lattice spacing favorable for Li+ insertion/extraction and inhibit oxygen loss successfully. The spinel layer and carbon on the surface can protect the material from corrosion due to electrolyte decomposition, which can accelerate Li+ and electron conduction and lessen the phase transition. The co-modified material reveals outstanding cycle and rate capability. Especially, it not only shows superior thermal stability at the high temperature of 45 °C, with a capacity retention rate of 83.3%, but also shows a higher discharge capacity of 108.9 mAh g–1 at the low temperature of −20 °C. Furthermore, the mechanism of the Li-rich cathode material with improved performance was also detected systematically. The proposed facile synthesis and co-modification of the boron-doped layered@spinel@carbon heterostructure can shed light on the design direction for cathode materials of lithium-ion batteries to solve the problem of electrochemical performance degradation caused by structural instability.