Monitoring the phase evolution in LiCoO<sub>2</sub> electrodes during battery cycles using in‐situ neutron diffraction technique

Jena, Anirudha; Lee, Po‐Han; Pang, Wei Kong; Hsiao, Kuang‐Che; Peterson, Vanessa K.; Darwish, Tamim A.; Yepuri, Nageshwar R.; Wu, She‐Huang; Chang, Ho; Liu, Ru‐Shi

doi:10.1002/jccs.201900448

Cited by 17 publications

(4 citation statements)

References 46 publications

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“…Aside from the issues originated from bulk phase change and surface degradation, the inhomogeneous reaction leads to the uneven distribution of the state of charge (SOC) at the different particles and/or different parts of a particle, which causes gradual degradation of electrochemical performance with cycling. Liu et al [ 58 ] investigated the reaction mechanism and electrochemical behavior of two LiCoO 2 samples with different particle sizes by in situ neutron diffraction technique ( Figure 4 ). The LiCoO 2 with large particles displayed the inhomogeneous distribution of Li content due to sluggish Li diffusion, leading to a two‐phase reaction mechanism and poor rate performance.…”

Section: Failure Mechanisms Of Licoo2 At High Cutoff Voltagesmentioning

confidence: 99%

An Overview on the Advances of LiCoO₂ Cathodes for Lithium‐Ion Batteries

Lyu

Wu²,

Wang³

et al. 2020

Advanced Energy Materials

542

356

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LiCoO2, discovered as a lithium‐ion intercalation material in 1980 by Prof. John B. Goodenough, is still the dominant cathode for lithium‐ion batteries (LIBs) in the portable electronics market due to its high compacted density, high energy density, excellent cycle life and reliability. In order to satisfy the increasing energy demand of portable electronics such as smartphones and laptops, the upper cutoff voltage of LiCoO2‐based batteries has been continuously raised for achieving higher energy density. However, several detrimental issues including surface degradation, damages induced by destructive phase transitions, and inhomogeneous reactions could emerge as charging to a high voltage (>4.2 V vs Li/Li+), which leads to the rapid decay of capacity, efficiency, and cycle life. In this review, the history and recent advances of LiCoO2 are introduced, and a significant section is dedicated to the fundamental failure mechanisms of LiCoO2 at high voltages (>4.2 V vs Li/Li+). Meanwhile, the modification strategies and the development of LiCoO2‐based LIBs in industry are also discussed.

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Section: Failure Mechanisms Of Licoo2 At High Cutoff Voltagesmentioning

confidence: 99%

An Overview on the Advances of LiCoO₂ Cathodes for Lithium‐Ion Batteries

Lyu

Wu²,

Wang³

et al. 2020

Advanced Energy Materials

542

356

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show abstract

“…Nevertheless, the presence of an inhomogeneous Li-ion distribution and inactive chemical-state areas in a single LiCoO 2 particle during the cycling process was verified in a recent study 36 . Furthermore, the cycling performance of LiCoO 2 was found to depend on the particle size 56 . To address these issues, the morphology and size of the synthesized particles need to be controlled, and/or surface coating treatments should be applied.…”

Section: Resultsmentioning

confidence: 98%

Chemical-state distributions in charged LiCoO2 cathode particles visualized by soft X-ray spectromicroscopy

Zhang

Hosono

Asakura

et al. 2023

Sci Rep

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Lithium-ion deintercalation/intercalation during charge/discharge processes is one of the essential reactions that occur in the layered cathodes of lithium-ion batteries, and the performance of the cathode can be expressed as the sum of the reactions that occur in the local area of the individual cathode particles. In this study, the spatial distributions of the chemical states present in prototypical layered LiCoO2 cathode particles were determined at different charging conditions using scanning transmission X-ray microscopy (STXM) with a spatial resolution of approximately 100 nm. The Co L3- and O K-edge X-ray absorption spectroscopy (XAS) spectra, extracted from the same area of the corresponding STXM images, at the initial state as well as after charging to 4.5 V demonstrate the spatial distribution of the chemical state changes depending on individual particles. In addition to the Co L3-edge XAS spectra, the O K-edge XAS spectra of the initial and charged LiCoO2 particles are different, indicating that both the Co and O sites participate in charge compensation during the charging process possibly through the hybridization between the Co 3d and O 2p orbitals. Furthermore, the element maps of both the Co and O sites, derived from the STXM stack images, reveal the spatial distribution of the chemical states inside individual particles after charging to 4.5 V. The element mapping analysis suggests that inhomogeneous reactions occur on the active particles and confirm the existence of non-active particles. The results of this study demonstrate that an STXM-based spatially resolved electronic structural analysis method is useful for understanding the charging and discharging of battery materials.

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“…21 The uneven distribution of charge in each particle and in different parts of particles caused by the diffusion of lithium ions leads to the generation of stress and deformation, which generate the capacity fading. 22,23 In order to solve these issues, many efforts have been made to improve the stability and performance of LCO under high voltage, including ion doping and surface coating strategies. 24−29 Surface coating method has been identified to possess the advantages of blocking the contact between the LCO surface and the electrolyte, inhibiting side reaction and enhancing cyclic stability.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In addition, surface deterioration with the formation of cathode electrolyte interphase, particle cracks, loss of oxygen, and dissolution of cobalt also result in increased impedance of the LCO cathode, which no doubt decreases the electrochemical performance . The uneven distribution of charge in each particle and in different parts of particles caused by the diffusion of lithium ions leads to the generation of stress and deformation, which generate the capacity fading. , In order to solve these issues, many efforts have been made to improve the stability and performance of LCO under high voltage, including ion doping and surface coating strategies. − Surface coating method has been identified to possess the advantages of blocking the contact between the LCO surface and the electrolyte, inhibiting side reaction and enhancing cyclic stability. However, many coating materials are insulators for lithium ions, which inhibit the transport of lithium ions on the LCO surface and lead to poor electrochemical performances.…”

Section: Introductionmentioning

confidence: 99%

NASICON-Structured LiZr₂(PO₄)₃ Surface Modification Improves Ionic Conductivity and Structural Stability of LiCoO₂ for a Stable 4.6 V Cathode

Zhang

Peng

Zhao

et al. 2022

ACS Appl. Mater. Interfaces

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Lithium cobalt oxide (LCO) as a classic layered oxide cathode for lithium-ion batteries is limited by the cutoff voltage, which only delivers about half of the theoretical capacity (∼4.2 V, 140 mA h g–1). Recently, raising the cutoff voltage to 4.6 V has been considered to further improve its specific capacity. However, LCO suffers from serious phase transition of O3 to H1-3, which leads to dramatic volume change and loss of cobalt, finally resulting in rapid capacity decay. In this work, we introduce the NASICON-structured LiZr2(PO4)3 (LZP), an ion conductor for lithium ion, to modify the surface of LCO by a wet-chemical method. Such a surface modification improves lithium-ion diffusion between the interface of LCO and electrolyte and restrains the O3 to H1-3 phase transition. As a result, the optimized LCO with 1 wt % coating (denoted as LCO@LZP-1%) demonstrates enhanced electrochemical performance in both half-cell and full-cell. To be specific, LCO@LZP-1% delivers a high specific capacity of 161.3 mA h g–1 and increases the capacity retention from 37.8 to 75.1% within 100 cycles. Importantly, the full-cell assembled by LCO@LZP-1% and artificial graphite can exhibit an outstanding energy density of 345.5 W h kg–1 (based on the total mass of cathode and anode).

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Monitoring the phase evolution in LiCoO₂ electrodes during battery cycles using in‐situ neutron diffraction technique

Cited by 17 publications

References 46 publications

An Overview on the Advances of LiCoO₂ Cathodes for Lithium‐Ion Batteries

An Overview on the Advances of LiCoO₂ Cathodes for Lithium‐Ion Batteries

Chemical-state distributions in charged LiCoO2 cathode particles visualized by soft X-ray spectromicroscopy

NASICON-Structured LiZr₂(PO₄)₃ Surface Modification Improves Ionic Conductivity and Structural Stability of LiCoO₂ for a Stable 4.6 V Cathode

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Monitoring the phase evolution in LiCoO2 electrodes during battery cycles using in‐situ neutron diffraction technique

Cited by 17 publications

References 46 publications

An Overview on the Advances of LiCoO2 Cathodes for Lithium‐Ion Batteries

An Overview on the Advances of LiCoO2 Cathodes for Lithium‐Ion Batteries

Chemical-state distributions in charged LiCoO2 cathode particles visualized by soft X-ray spectromicroscopy

NASICON-Structured LiZr2(PO4)3 Surface Modification Improves Ionic Conductivity and Structural Stability of LiCoO2 for a Stable 4.6 V Cathode

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Monitoring the phase evolution in LiCoO₂ electrodes during battery cycles using in‐situ neutron diffraction technique

An Overview on the Advances of LiCoO₂ Cathodes for Lithium‐Ion Batteries

An Overview on the Advances of LiCoO₂ Cathodes for Lithium‐Ion Batteries

NASICON-Structured LiZr₂(PO₄)₃ Surface Modification Improves Ionic Conductivity and Structural Stability of LiCoO₂ for a Stable 4.6 V Cathode