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[Display omitted] Benefiting from the extra contribution of O redox, Co-free Li-rich layered oxides (LRNMO) can satisfy the requirement of high specific capacities. However, during the high-voltage charging process, lattice oxygen being oxidized to O− or O 2 leads to a gradual transition of the structure from layered to spinel phase, capacity and voltage decline, hindering the practical application of LRNMO in the lithium-ion battery. Here, a surface modification strategy of Li 1.2 Ni 0.32 Mn 0.48 O 2-δ doped with Ta5+ ions is proposed, in which the Ta5+ ions occupy the lithium sites of the lattice structure on the surface layer of LRNMO and form a Ta 2 O 5 coating layer. The modified electrode exhibits excellent rate performance and cycling stability, with 94.9% and 85.5% capacity retention rate and voltage retention rate, respectively, after 200 cycles at 1C. Moreover, the initial coulomb efficiency and ionic conductivity of the modified electrode are also apparently enhanced. Simultaneously, the decreased Li/Ni mixing degree of the modified electrode reflects the improvement of the structural stability. Therefore, the modification strategy through strong metal–oxygen bonding to integrate the surface structure to regulate the oxygen activity provides a new direction for the design of high energy density Co-free Li-rich cathode materials. [ABSTRACT FROM AUTHOR]

[Display omitted] Benefiting from the extra contribution of O redox, Co-free Li-rich layered oxides (LRNMO) can satisfy the requirement of high specific capacities. However, during the high-voltage charging process, lattice oxygen being oxidized to O− or O 2 leads to a gradual transition of the structure from layered to spinel phase, capacity and voltage decline, hindering the practical application of LRNMO in the lithium-ion battery. Here, a surface modification strategy of Li 1.2 Ni 0.32 Mn 0.48 O 2-δ doped with Ta5+ ions is proposed, in which the Ta5+ ions occupy the lithium sites of the lattice structure on the surface layer of LRNMO and form a Ta 2 O 5 coating layer. The modified electrode exhibits excellent rate performance and cycling stability, with 94.9% and 85.5% capacity retention rate and voltage retention rate, respectively, after 200 cycles at 1C. Moreover, the initial coulomb efficiency and ionic conductivity of the modified electrode are also apparently enhanced. Simultaneously, the decreased Li/Ni mixing degree of the modified electrode reflects the improvement of the structural stability. Therefore, the modification strategy through strong metal–oxygen bonding to integrate the surface structure to regulate the oxygen activity provides a new direction for the design of high energy density Co-free Li-rich cathode materials. [ABSTRACT FROM AUTHOR]

Li-rich Mn-based cathode materials are one kind of the promising potential candidates to electric vehicles powered by high-energy density lithium-ion batteries due to its much higher theoretical energy density. Unfortunately, the rapid capacity fading and voltage decay are the most critical factors affecting its practical application. Herein, Li 1 · 17 Na 0 · 02 Mn 0 · 54 Ni 0 · 13 Co 0 · 13 O 2 (PN-LMNCO) is prepared via surface phase structure controlling and ion doping through an architecture strategy of surface lithium deficiency. It is found that the existence of lithium deficiencies can induce surface phase transformation, and thus resulting in an in-situ spinel surface conversion film, which can restrain the structure degradation during subsequent charge/discharge process. In addition, because of the larger ion radius than Li+, Na+ doping can effectively increase the spacing between Li layers, and thus improve the rate capacity. Accordingly, the as-prepared sample displays as a significantly higher initial coulombic efficiency (91.2%). After 200 cycles at 1 C, the PN-LMNCO can retain 94.7% discharge specific capacity. Furthermore, PN-LMNCO can still show a good discharge capacity of 214 mA h g−1 even at a high current rate of 5 C. Therefore, this work can preferably meet the need of the development of electric vehicle for high-energy density Lithium-ion battery. • Lithium deficiencies induce the in-situ spinel surface conversion film. • The interfacial reaction has been inhibited. • Na doping improves the diffusion kinetics of lithium ions. • There are any redundant synthesis steps and the cost be reduced. [ABSTRACT FROM AUTHOR]

The structure design strategy for LRO based on the reversible anionic redox and spinel-layered coherent structure is propitious to maintaining high specific capacity and improving the reversible anionic redox and stable cyclic performance of LRO. [Display omitted] • LRO cathode with reversible anionic redox and spinel-layered coherent structure is designed. • The specific capacity and initial Coulombic efficiency are enhanced by the introduction of S-anions. • Stable interface structure and enhanced electrochemical kinetics are realized by the spinel-layered coherent structure. • Improved specific capacity and excellent cyclic stability are revealed in the modified LRO. Initiating effective strategies to improve the reversibility of anionic redox and structural stabilization is crucial to the development and industrial application of Li-rich cathode materials (LRO), which are regarded as the preferred option of the cathode materials for the next-generation lithium-ion battery with high energy density. To remit the unexpected behavior of structural destruction and capacity attenuation, this paper proposes a strategy for maintaining high specific capacity and improving the reversible anionic redox and stable cyclic performance of LRO by introducing the spinel-layered coherent structure and S-anions. Proved by the ex-situ X-ray photoelectron spectroscopy, S-anions can regulate the anionic redox reversibility and thus enhance the reversible discharge capacity and initial Coulombic efficiency. Moreover, the structural stability is greatly improved by the introduction of spinel-layered coherent structure and S-anions in LRO, which has been confirmed by abundant structural characterizations. Besides, the results reveal that the optimized material exhibits a high reversible discharge capacity of 289.52 mAh/g and good cyclic performance with a retention rate of 88.21% after 200 cycles. Evidently, the structure design strategy for LRO based on the reversible anionic redox and spinel-layered coherent structure is a significant exploration, which will bring a new clew for the design of the cathode materials with high-energy–density and excellent electrochemical performance. [ABSTRACT FROM AUTHOR]

• Construct Mn 3 O 4 protective shell to alleviate Jahn-Teller distortion. • Oxygen vacancy can effectively restrain the release of oxygen. • The designed LRNMO@Mn 3 O 4 cathode has higher electron/ion conductivity. • The Mn 3 O 4 -coated electrode exhibited excellent cycle stability. Herein, we put forward a feasible interfacial modification strategy in virtue of Mn 3 O 4 surface coating to construct protective shell and alleviate Jahn-Teller distortion during the charge/discharge process. It has been found that the increase of the oxygen vacancy on the surface of Li 1.2 Ni 0.27 Mn 0.54 O 2 of (LRNMO) after Mn 3 O 4 protective layer modification can effectively restrain the release of oxygen and enhancing rate capability, and thus improving its comprehensive electrochemical performances. In particular, the initial coulombic efficiency of the optimized LRNMO-1 electrode is improved from 72.3% to 84.3%. The capacity retention rate is up to 95.6% at 250 mA g−1 (1C) after 200 cycles. In addition, the LRNMO-1 electrode also has a good capacity retention rate (96.4% after 100 cycles) at a high current density of 5C. Moreover, the designed LRNMO@Mn 3 O 4 cathode exhibits higher ionic conductivity and better interface stability. As a result, this work offers a practicable and valuable exploration for the development and industrialization of Co-free Li-rich Mn-based cathode materials with high energy density. [ABSTRACT FROM AUTHOR]

• Co-free lithium-rich material was prepared by simple oxalate co-precipitation way. • The nano-micron combined structure was favorable to the infiltration of electrolyte. • The anions regulated the valence of surface transition metal ions. • The F-doped electrode exhibited excellent cycle stability. Co-free cathode materials are gradually attracted wide attention due to the low budget and environmental friendliness, but their application is still prevented by the poor rate performance and cyclic stability. Herein, the Co-free lithium-rich cathode materials (Li 1.2 Ni 0.2 Mn 0.6 O 2 , LRNMO) with a nano-micron combined morphology is prepared by a simple oxalate co-precipitation route and further modified by an anion doping strategy. It has been found that the F− anion doping can increase the content of Mn4+ in LRNMO, reduce the influence of the Jahn-Teller effect, and further impede the transition from layered phase to spinel phase. As a result, the as-obtained Li 1.2 Ni 0.2 Mn 0.6 O 2-x F x (x = 0.04, named as F4-LRNMO) shows an optimal electrochemical performance, for instance, high discharge capacity (243 mAh g−1) with a satisfactory initial coulombic efficiency of 84.37% at 0.1C. Meanwhile, the F4-LRNMO sample also can display high capacity retention of 92.2% after 200 cycles at 1C, and a remarkably high discharge capacity of 151 mAh g−1 with capacity retention of 95.4% after 100 cycles even at high rate of 5C. In consequence, this work can not only ameliorate the defects of poor stability and low initial coulomb efficiency, but also offer a meaningful exploration for the development of Co-free lithium-rich cathode materials with high capacity and high performance-price ratio. [ABSTRACT FROM AUTHOR]

The high theoretical energy density, high environmental adaptability and safety of lithium sulfide (Li 2 S)-oriented cathodes attract enough attention among lithium-sulfur batteries (LSBs). In this work, the lithium sulfide (Li 2 S)-oriented composite is fabricated via an in-situ carbothermic reduction method, in which lithium sulfate is reduced by CMK3 at an optimized temperature and subsequently the as-prepared Li 2 S is protected via the conformal carbon layer by carbonization of phenol-formaldehyde resin (PF). With the aid of the porous carbon structure of CMK3 and protection of PF-derived conformal carbon layer, the dispersity of Li 2 S and conductivity of cathode are availably enhanced. It has been found that the Li 2 S@CMK3-C prepared at optimum carbothermic reduction temperature of 835 °C has excellent electrochemical performance. The lithium-sulfur battery using Li 2 S@CMK3-C as cathode and metal Li as anode can deliver a high initial discharge capacity of 979 mAh g−1 at 0.1 C, the capacity retention after running at various current density is 94%, and the discharge specific capacity is still 530 mAh g−1 at 2 C after 450 cycles. Therefore, the preparation of CMK3-supported Li 2 S-based cathode material provides a new approach for the development and industrialization of new high-performance Li–S battery. Image 1 • An in-situ carbothermic reduction method is employed. • Lithium sulfide is in-situ formed inside cathode matrix as sulfur source. • The shuttle of polysulfides and activation energy barrier is suppressed. • The as-fabricated batteries deliver elevated electrochemical performance. [ABSTRACT FROM AUTHOR]