Inhibition of oxygen release and stabilization of the bulk structure of lithium-rich layered oxides by strong Mo–O covalent binding

Yu, Huinan; Xue, Zhichen; Xue, Zhiyuan; Luo, Zhongyuan; Ding, Chenxi; Hu, Guorong; Peng, Zhongdong; Cao, Yanbing; Du, Ke

doi:10.1039/d3ta05649j

Cited by 9 publications

(1 citation statement)

References 43 publications

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“…Doping with high-valence Mo 6+ has been proven to significantly enhance the performance of various lithium-/sodium-ion battery cathode materials, including Li 3 V 2 (PO 4 ) 3 /C [ 21 ], LiNi 0.6 Co 0.2 Mn 0.2 O 2 [ 22 ], LiNi 0.5 Mn 1.5 O 4 [ 23 ], Na 3 V 2 (PO 4 ) 3 @C [ 24 , 25 , 26 ], Li 1.2 Ni 0.13 Fe 0.13 Mn 0.54 O 2 [ 27 ], and LiMn 0.6 Fe 0.4 PO 4 [ 28 ], etc. For example, Wen et al [ 28 ] enhanced the Li + diffusion rate in LiMn 0.6 Fe 0.4 PO 4 materials by doping with Mo 6+ , achieving discharge capacities of 153.2 mAh g −1 at 0.2 C and 94.2 mAh g −1 at 10 C, with a capacity retention rate of 91.4% after 100 cycles at 1 C. For polyanionic cathode materials, the performance enhancement achieved by Mo 6+ doping is not only attributed to the strong Mo-O bond energy (502 kJ/mol) [ 29 ], which can increase the structural stability, but also to the decrease in charge transfer impedance and the generation of vacancies, which enhance the ion/electron transport, thereby accelerating the ion transport rates [ 21 , 24 , 26 ]. Additionally, Kumar et al demonstrated that Mo doping in trimetallic oxides significantly enhances the redox activity by optimizing the energy barriers in the reaction steps and increasing the adsorption energy of intermediates, thereby improving the overall performance in zinc–air batteries [ 30 ].…”

Section: Introductionmentioning

confidence: 99%

Mo-Doped Na4Fe3(PO4)2P2O7/C Composites for High-Rate and Long-Life Sodium-Ion Batteries

Chen,

Han,

Jie

et al. 2024

Materials

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Na4Fe3(PO4)2P2O7/C (NFPP) is a promising cathode material for sodium-ion batteries, but its electrochemical performance is heavily impeded by its low electronic conductivity. To address this, pure-phase Mo6+-doped Na4Fe3−xMox(PO4)2P2O7/C (Mox-NFPP, x = 0, 0.05, 0.10, 0.15) with the Pn21a space group is successfully synthesized through spray drying and annealing methods. Density functional theory (DFT) calculations reveal that Mo6+ doping facilitates the transition of electrons from the valence to the conduction band, thus enhancing the intrinsic electron conductivity of Mox-NFPP. With an optimal Mo6+ doping level of x = 0.10, Mo0.10-NFPP exhibits lower charge transfer resistance, higher sodium-ion diffusion coefficients, and superior rate performance. As a result, the Mo0.10-NFPP cathode offers an initial discharge capacity of up to 123.9 mAh g−1 at 0.1 C, nearly reaching its theoretical capacity. Even at a high rate of 10 C, it delivers a high discharge capacity of 86.09 mAh g−1, maintaining 96.18% of its capacity after 500 cycles. This research presents a new and straightforward strategy to enhance the electrochemical performance of NFPP cathode materials for sodium-ion batteries.

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Section: Introductionmentioning

confidence: 99%

Mo-Doped Na4Fe3(PO4)2P2O7/C Composites for High-Rate and Long-Life Sodium-Ion Batteries

Chen,

Han,

Jie

et al. 2024

Materials

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Comprehensive Review of Li‐Rich Mn‐Based Layered Oxide Cathode Materials for Lithium‐Ion Batteries: Theories, Challenges, Strategies and Perspectives

Chen,

Xia,

2024

ChemSusChem

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Lithium‐rich manganese‐based layered oxide cathode materials (LLOs) have always been considered as the most promising cathode materials for achieving high energy density lithium‐ion batteries (LIB). However, LLOs often face some key problems, such as low initial coulombic efficiency, capacity/voltage decay, poor rate performance and poor cycle stability. It seriously shortens the lifespan of lithium‐ion batteries and hinder the large‐scale commercial application of LLOs. Herein, firstly, the basic theories of LLOs were systematically reviewed, including the structural characteristics, the working mechanism of LLOs, the preparation methods of LLOs (liquid phase co‐precipitate method, sol‐gel method, hydrothermal synthesis method, solid phase method, low heat solid phase method etc,.), and electrochemical characteristics of LLOs (first charge discharge characteristics and reversible efficiency, cycling performance, high and low temperature performance and thermal stability etc,.). Then, key challenges faced by LLOs were systematically discussed. Finally, the LLOs modification strategies used to address these challenges (element doping, surface modification, defect engineering, structural and morphological control etc,.) were elaborated in detail. This important review provides potential insights and directions for further improving electrochemical performance of LLOs, and provides necessary theoretical basis for accelerating the large‐scale commercial application of LLOs. It possesses important scientific research value and far‐reaching social significance.

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Band Structure Engineering Promotes Anionic Redox Reversibility of Cobalt‐Free Li‐Rich Layered Oxides Cathodes

Gao,

Guo,

et al. 2024

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Li‐rich layered oxides cathodes (LLOs) have prevailed as the promising high‐energy‐density cathode materials due to their distinctive anionic redox chemistry. However, uncontrollable anionic redox process usually leads to structural deterioration and electrochemical degradation. Herein, a Mo/Cl co‐doping strategy is proposed to regulate the relative position of energy band for modulating the anionic redox chemistry and strengthening the structural stability of Co‐free Li1.16Mn0.56Ni0.28O2 cathodes. The incorporation of Mo with high d state orbit and Cl with low electronegativity can narrow the band energy gap between bonding and antibonding bands via increasing the filled lower‐Hubbard band (LHB) and decreasing the non‐bonding O 2p energy bands, promoting the anionic redox reversibility. In addition, strong covalent Mo─O and Mn─Cl bonding further increases the covalency of Mn─O band to further stabilize the O2n− species and enhance the reversible distortion of MnO6 octahedron. The strengthening electronic conductivity, together with the epitaxial structure Li2MoO4 facilitates the fast Li+ kinetics. As a result, the dual doping material exhibits enhanced anionic redox reversibility and suppressed oxygen release with increased cyclic stability and excellent rate performance. This strategy provides some guidance to design high‐energy‐density LLOs with desirable anionic redox reversibility and stable crystal structure via band structure engineering.

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Inhibition of oxygen release and stabilization of the bulk structure of lithium-rich layered oxides by strong Mo–O covalent binding

Abstract: Strongly covalent Mo–O stabilizes the lattice oxygen, which inhibits the activation of Mn redox pairs, stabilizes the bulk phase structure, and forms a stable CEI at the surface.

Cited by 9 publications

References 43 publications

Mo-Doped Na4Fe3(PO4)2P2O7/C Composites for High-Rate and Long-Life Sodium-Ion Batteries

Mo-Doped Na4Fe3(PO4)2P2O7/C Composites for High-Rate and Long-Life Sodium-Ion Batteries

Comprehensive Review of Li‐Rich Mn‐Based Layered Oxide Cathode Materials for Lithium‐Ion Batteries: Theories, Challenges, Strategies and Perspectives

Band Structure Engineering Promotes Anionic Redox Reversibility of Cobalt‐Free Li‐Rich Layered Oxides Cathodes

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