Oxygen vacancy in Li-rich Mn-based cathode materials: origination, influence, regulation and characterization

Liu, Xinrui; Cheng, Jen Chan; Guan, Yunlong; Huang, Shih Chiang; Lian, Fang

doi:10.1039/d3qm00284e

Cited by 16 publications

(1 citation statement)

References 99 publications

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“…Moreover, the oxygen vacancy (Vo) actively introduced strategy has been proposed to regulate the structure evolution of LRMO in recent years . Vo mitigates the excessive oxidation of oxygen and suppresses the release of lattice oxygen, thereby enhancing the anionic redox reversibility and structural stability. − In addition, Vo induces a low coordination environment of TMs, thereby facilitating the reversible migration of TMs and promoting Li + diffusion. − Nakamura’s group utilized YSZ, an almost pure oxide ion conductor at higher temperatures, to facilitate the extraction of oxygen in the bulk of LRMO .…”

Section: Introductionmentioning

confidence: 99%

Jointly Improving Anionic–Cationic Redox Reversibility of Lithium-Rich Manganese-Based Cathode Materials by N Surface Doping

Liu,

Zhang,

et al. 2024

ACS Appl. Mater. Interfaces

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The lithium-rich manganese-based layer oxide (LRMO) with high specific capacity (∼300 mAh g −1 ) and economic feasibility is accepted as the cathode material for high energy density rechargeable batteries. Accompanied by the additional anionic redox reactions during the initial charging process, LRMO presents oxygen release, sluggish Li + diffusion, and irreversible transition metal ion (TM) migration, which is responsible for its severe structural deterioration and rapid capacity/voltage decay. Here, the N doping strategy is proposed via feasible treatment of oxygen-vacancycontaining Li 1.16 Ni 0.21 Mn 0.63 O 2−δ (LNMO) particles. The as obtained LNMO-N samples demonstrate doping N, partially reduced Mn/Ni cations, and oxygen vacancies on the surface. The DFT calculations and experimental results demonstrate that N replacing the crystal oxygen sites on the surface reduces the energy barrier for diffusion, thereby enhancing the kinetics of Li + diffusion and improving the reversibility of transition metal migration. Furthermore, N doping induces stacking faults and a more flexible structure. Therefore, LNMO-N exhibits a significantly improved anionic−cationic redox reaction reversibility with a high discharge specific capacity of 296.6 mAh g −1 at 20 mA g −1 within the range of 2.0 to 4.8 V and an impressive initial Coulombic efficiency of 85.9%. Moreover, the rate capability is obviously improved with a remarkable capacity of 215.1 mAh g −1 at 200 mA g −1 in 200 cycles with a capacity retention of 72.52% and exceptional performance of 141.4 mAh g −1 even at a higher current density of 1000 mA g −1 .

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Section: Introductionmentioning

confidence: 99%

Jointly Improving Anionic–Cationic Redox Reversibility of Lithium-Rich Manganese-Based Cathode Materials by N Surface Doping

Liu,

Zhang,

et al. 2024

ACS Appl. Mater. Interfaces

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Oxygen‐Vacancy‐Assisted Dual Functional Surface Coatings Suppressing Irreversible Phase Transition of Li‐Rich Layered Oxide Cathodes

Jiang,

Li,

Hao

et al. 2024

Adv Funct Materials

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Both lattice oxygen release and the migration of transition metal (TM) ions challenge the cyclability of Li‐rich Mn‐based layered oxide (LMO) cathodes by inducing irreversible phase transitions. In this work, the oxygen‐vacancy‐assisted dual functional surface coatings of Li‐rich layered oxide cathodes, including a spinel‐over‐phase and a Li3PO4 layer are fabricated for lithium‐ion batteries (LIBs). The functional role of the optimized interface is mainly focused. Specifically, during the process of reorganized surface structure, the oxygen vacancies function as active sites for migrating TM ions to form the spinel over‐phase and deliver the decreased binding energy of PO43− on the LMO surface. It is found that the Li3PO4 layer increases the migration energy barrier of TM ions to 13.38 eV (7.62 eV for LMO). As a result, both the spinel over‐phase and the Li3PO4 layer synergistically inhibited the irreversible phase transitions of LMO upon cycling to boost lithium storage of the cathodes. The optimized cathode maintained higher capacity retention of 95% at 0.2 C after 200 cycles in comparison to 67% for the pristine LMO. This study provides some understanding of the functional roles of the optimized dual surface coatings in suppressing the irreversible phase transition of LMO for LIBs.

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Advanced High Energy Density Secondary Batteries with Multi‐Electron Reaction Materials

Zhang,

Gao,

Huang

et al. 2024

Adv Funct Materials

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Nowadays, various types of electrical facilities and the elevated demand for the wider application of electronic devices in future smart cities are calling for next‐generation batteries of higher energy density, superior rate capability, and extended cycling performance. Multi‐electron systems, based on related reactions and materials, have been considered as promising battery systems for future applications, and massive attempts have been made to achieve their practical use. Therefore, a comprehensive realization of multi‐electron reactions is imperative for the exploitation of innovative multi‐electron materials and steps forward to higher battery performances. In this review, the fundamental conception of multi‐electron reactions and their application bottlenecks are given from both theoretical principles and practice. Multi‐electron materials generally face problems from both thermodynamics and kinetics, including material dissolution, low intrinsic conductivity, low ion transport, etcetera, which seriously hinder their future application. Given all this, current prioritization schemes are summarized, thus making a better understanding of the working mechanisms of the modification methods and inspiring prospects of practical multi‐electron materials.

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Oxygen vacancy in Li-rich Mn-based cathode materials: origination, influence, regulation and characterization

Abstract: Lithium-rich Mn-based oxides (LRMOs) with high specific capacity have been accepted as key cathode materials for the development of high energy density secondary batteries. The oxygen-involved redox reaction contributes extra...

Cited by 16 publications

References 99 publications

Jointly Improving Anionic–Cationic Redox Reversibility of Lithium-Rich Manganese-Based Cathode Materials by N Surface Doping

Jointly Improving Anionic–Cationic Redox Reversibility of Lithium-Rich Manganese-Based Cathode Materials by N Surface Doping

Oxygen‐Vacancy‐Assisted Dual Functional Surface Coatings Suppressing Irreversible Phase Transition of Li‐Rich Layered Oxide Cathodes

Advanced High Energy Density Secondary Batteries with Multi‐Electron Reaction Materials

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