Rate dependent structural changes, cycling stability, and Li-ion diffusivity in a layered–layered oxide cathode material after prolonged cycling

Kaewmala, Songyoot; Limphirat, Wanwisa; Yordsri, Visittapong; Nash, Jeffrey; Srilomsak, Sutham; Kesorn, Aniwat; Limthongkul, Pimpa; Meethong, Nonglak

doi:10.1039/d1ta02293h

Cited by 11 publications

(6 citation statements)

References 51 publications

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“…Similar to the cycling stability test result, the sample with 20 minutes of microwave treatment shows the optimum rate capability, which can be related to the high c/a ratio of this sample. A high c/a ratio enlarges the layer spacing, facilitating a facile Li ion diffusion and providing a large capacity at the high current density [46].…”

Section: Resultsmentioning

confidence: 99%

Improving the Structural Ordering and Particle-Size Homogeneity of Li-Rich Layered Li1.2Ni0.13Co0.13Mn0.54O2 Cathode Materials through Microwave Irradiation Solid-State Synthesis

et al. 2022

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Li1.2Ni0.13Co0.13Mn0.54O2 (LNCM) has been intensively investigated owing to its high capacity and large voltage window. However, despite its high performance, the synthesis of LNCM can be challenging as it usually contains structural disorders and particle-size inhomogeneities, especially via a solid-state method. This work introduces microwave irradiation treatment on the LNCM fabricated via a solid-state method. The as-treated LNCM has low structural disorders, as indicated by the smaller cation mixing, better hexagonal ordering, and higher c/a ratio compared to the non-treated LNCM. Furthermore, the particle-size homogeneities of as-treated LNCM improved, as characterized by scanning electron microscopy (SEM) and particle size analyzer (PSA) measurements. The improved structural ordering and particle-size homogeneity of the treated sample enhances the specific capacity, initial Coulombic efficiency, and rate capability of the cathode material. The LNCM sample with 20 minutes of microwave treatment exhibits an optimum performance, showing a large specific capacity (259.84 mAh/g), a high first-cycle Coulombic efficiency (81.45%), and good rate capability. It also showed a stable electrochemical performance with 80.57% capacity retention after 200 cycles (at a charge/discharge of 0.2C/0.5C), which is 13% higher than samples without microwave irradiation.

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Section: Resultsmentioning

confidence: 99%

Improving the Structural Ordering and Particle-Size Homogeneity of Li-Rich Layered Li1.2Ni0.13Co0.13Mn0.54O2 Cathode Materials through Microwave Irradiation Solid-State Synthesis

et al. 2022

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“…This indicates that the activation of Li 2 MnO 3 to form an LiMnO 2 phase can induce a spinel-like phase transition during cycling. Previous reports revealed that the degree of Li 2 MnO 3 activation was largely determined by the Li 2 MnO 3 domain size and current rate 33,42,43 . A small Li 2 MnO 3 domain size and low current rate could facilitate activation of the Li 2 MnO 3 phase and subsequently cause a large initial irreversible capacity and a spinel-like phase transition, leading to poor cyclability.…”

Section: Electrochemical Characterizationmentioning

confidence: 99%

Impacts of Mg doping on the Structural Properties and Degradation Mechanisms of a Li and Mn Rich Layered Oxide Cathode for Lithium-ion Batteries

Kaewmala

Kamma

Buakeaw³

et al. 2023

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The Li- and Mn-rich layered oxide cathode material class is a promising cathode material type for high energy density lithium-ion batteries. However, this cathode material type suffers from layer to spinel structural transition during electrochemical cycling, resulting in energy density losses during repeated cycling. Thus, improving structural stability is an essential key for developing this cathode material family. Elemental doping is a useful strategy to improve the structural properties of cathode materials. This work examines the influences of Mg doping on the structural characteristics and degradation mechanisms of a Li1.2Mn0.4Co0.4O2 cathode material. The results reveal that the prepared cathode materials are a composite material, exhibiting phase separation of the Li2MnO3 and LiCoO2 components. Li2MnO3 and LiCoO2 domain sizes decreased as Mg content increased, altering the electrochemical mechanisms of the cathode materials. Moreover, Mg doping can retard phase transition, resulting in reduced structural degradation. Li1.2Mn0.36Mg0.04Co0.4O2 with optimal Mg doping demonstrated improved electrochemical performance. The current work provides deeper understanding about the roles of Mg doping on the structural characteristics and degradation mechanisms of Li-and Mn-rich layered oxide cathode materials, which is an insightful guideline for the future development of high energy density cathode material for lithium-ion batteries.

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“…It was found that the more time spent at high potentials, the more structural defects that were formed. Yin et al [148] also studied the structural evolution of the material during a constant voltage of 5 h after being fully charged to 4.8 V and found a new phase produced under continuous oxidation at this stage, which aggravated the migration of Mn and the deterioration of capacity and voltage.…”

Section: Regulating Activationmentioning

confidence: 99%

Multi-dimensional correlation of layered Li-rich Mn-based cathode materials

Yang¹,

Zheng²,

Wei³

et al. 2022

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Lithium-rich manganese-based cathode materials are expected to promote the commercialization of lithium-ion batteries to a new stage by virtue of their ultrahigh specific capacity and energy density advantages. However, they are still restricted by complex phase transitions and electrochemical performance degradation caused by labile anion charge compensation. A deep understanding of the electrochemical properties contained in their intrinsic structures and the key driving factors of structural deterioration during cycling are crucial to guide the preparation and optimization of lithium-rich materials. Considering recent progress, this review introduces the intrinsic properties of Li-rich manganese-based cathode materials from interatomic interactions to particle morphology at multiple scales in the spatial dimension. The charge compensation mechanism and energy band reorganization of the initial charge and discharge, the structural evolution during cycling and the electrochemical reaction kinetics of the materials are analyzed in the temporal dimension. Based on the relationship between structure and electrochemical performance, preparation methods and modification methods are introduced to guide and design cathode materials. Effective characterization methods for studying anion charge compensation behavior are also demonstrated. This review provides important guidance and suggestions for making full use of the high specific capacity in these materials derived from anion redox and the maintaining of its stability.

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Rate dependent structural changes, cycling stability, and Li-ion diffusivity in a layered–layered oxide cathode material after prolonged cycling

Abstract: Li-rich layered oxide (LLO) cathode materials, xLi2MnO3·(1-x)LiCoO2 (0<x<1, M= Mn, Ni, Co, etc.) are considered promising cathode materials in Li-ion batteries for large scale applications.

Cited by 11 publications

References 51 publications

Improving the Structural Ordering and Particle-Size Homogeneity of Li-Rich Layered Li1.2Ni0.13Co0.13Mn0.54O2 Cathode Materials through Microwave Irradiation Solid-State Synthesis

Improving the Structural Ordering and Particle-Size Homogeneity of Li-Rich Layered Li1.2Ni0.13Co0.13Mn0.54O2 Cathode Materials through Microwave Irradiation Solid-State Synthesis

Impacts of Mg doping on the Structural Properties and Degradation Mechanisms of a Li and Mn Rich Layered Oxide Cathode for Lithium-ion Batteries

Multi-dimensional correlation of layered Li-rich Mn-based cathode materials

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