New phases and phase transitions observed in over-charged states of LiCoO2-based cathode materials☆

Sun, Xiao‐Guang; Yang, Xiao‐Qing; McBreen, J.; Gao, Yuan; Yakovleva, M. V.; Xing, Xuanxuan; Daroux, M. L.

doi:10.1016/s0378-7753(01)00512-2

Cited by 39 publications

(28 citation statements)

References 4 publications

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“…Figure 2A plots the XRD spectra collected during the first charge at rate of C/4.5 in which phases H1, H2, O1a and O1 are observed as a function of cell voltage, where H1 is the fully lithiated phase at x = 1 and O1 is the completely delithiated phase at x = 0, the others are partially delithiated with 0<x<1. The phase-transformation steps are: H1→H2→O1a→O1 (Sun et al, 2001;Chung et al, 2006Chung et al, , 2007. The H1 and H2 have hexagonal lattice in space group (S.G.) R3m, with similar lattice parameter a, but different in c, c H1 = 14.089 A, c H2 = 14.370A respectively (Yang et al, 2000), therefore, the (003) peak shifted to the lower 2θ direction as lattice parameter c increased during the H1 to H2 phase transition; on the other hand, the positions of (101) and (102) are almost unchanged.…”

Section: Licoomentioning

confidence: 99%

Application of Operando X-ray Diffraction and Raman Spectroscopies in Elucidating the Behavior of Cathode in Lithium-Ion Batteries

Zhu

Liu²,

Paolella³

et al. 2018

Front. Energy Res.

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With the advances in characterization techniques, various operando/in-situ methods were applied in studying rechargeable batteries in order to improve the electrochemical properties of electrode materials, prolonging the battery life and developing new battery materials. In the present review, we focus on the characterization of electrode materials with operando/in-situ X-ray diffraction and Raman spectroscopies. By correlating the results obtained via these two techniques in different electrode chemistry: (a) intercalation materials, such as layered metal oxides and (b) conversion materials, such as elemental sulfur. We demonstrate the importance of using operando/in-situ techniques in examining the microstructural changes of the electrodes under various operating conditions, in both macro and micro-scales. These techniques also reveal the working and the degradation mechanisms of the electrodes and the possible side reactions involved. The comprehension of these mechanisms is fundamental for ameliorating the electrode materials, enhancing the battery performance and lengthening its cycling life.Keywords: operando/in-situ XRD, operando/in-situ Raman, lithium-sulfur, layered metal oxide, LiFePO 4 , spinel oxide Frontiers in Energy Research | www.frontiersin.org

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Section: Licoomentioning

confidence: 99%

Application of Operando X-ray Diffraction and Raman Spectroscopies in Elucidating the Behavior of Cathode in Lithium-Ion Batteries

Zhu

Liu²,

Paolella³

et al. 2018

Front. Energy Res.

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“…The two-phase and single-phase reactions accompanying with phase transition from H1 to O1 via H2 and O1a have been verified by many in situ and ex situ XRD investigations when charging LiCoO 2 to higher voltage ( > 4.8 V) [28][29][30][31] . The mechanism of capacity fading of LiCoO 2 and the effects of Al 2 O 3 or ZrO 2 coating when charged to higher voltage ( > 4.5 V) have been studies by Yang et al using synchrotron based in situ XRD [32][33][34] .…”

Section: Electrochemical In Situ Characterization Of Phase Transformamentioning

confidence: 98%

The application of synchrotron X-ray techniques to the study of rechargeable batteries

Gong

Yang

2018

Journal of Energy Chemistry

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“…Li insertion/removal-induced structural changes can be investigated through Raman spectroscopy, X-ray diffraction, neutron powder diffraction, and TEM analysis. [280,281] The H2a appearing in the composition range of x = 0-0.5 bridged the H1 and H2. [278] Two hexagonal phases (H1 and H2) and one monoclinic phase (M1) were observed with progressing Li removal.…”

Section: Stress Development Arising From the Cathode Sidementioning

confidence: 99%

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Liu

et al. 2019

Advanced Energy Materials

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The continuous depletion of fossil fuels, the increase of oil prices, and the need to decrease CO 2 emissions have stimulated intensive research on developing alternative renewable and clean energy sources. [1] Among these alternative energy sources, rechargeable Li-ion batteries (LIBs) are one of the promising candidates. To date, the LIBs basically consisting of a positive electrode (cathode), an electrolyte, and a negative electrode (anode) have widespread applications, such as portable electronic devices, pure electric vehicles (PEVs), and hybrid electric vehicles (HEVs). [2] The state-of-the-art electrolytes are usually the lithium salts (LiPF 6 , LiBF 4 , and LiCF 3 SO 3 ) dissolved in organic solvents, i.e., ethylene carbonate, propylene carbonate, polyethylene oxide, and dimethyl carbonate, [3] which exhibit excellent wetting of the electrodes and produce a fast transfer of Li + ions upon charging and discharging. However, they suffer from flammability, poor electrochemical stability, limited temperature range of operation, and low power density. [4] There is an ever-increasing demand for batteries with a higher energy and power density, although current LIBs offer volumetric and gravimetric energy densities up to 770 Wh L −1 and 260 Wh kg −1 , respectively. [5] To improve the energy/power density of LIBs, one way is to adopt high-potential cathode materials such as LiNi 0.5 Mn 1.5 O 4 (LNMO). The high-voltage plateau of LNMO (≈4.7 V vs Li/Li + ) makes its energy density 20-30% higher than the energy density of commercial LiCoO 2 and LiFePO 4 . [6] However, successful commercialization of the LNMO is restricted in high-energy LIBs due to electrolyte decomposition and side reaction of the cathodes and liquid electrolytes when operating at high voltages. [7,8] The other way to improve the energy/power density is to replace the conventional graphite anode with Li metal. The Li metal, with a low anode potential (−3.04 V vs standard hydrogen electrode) and high specific capacity (3862 mAh g −1 for the Li anode versus 372 mAh g −1 for the graphite anode), [9][10][11] has been considered as the "Holy Grail" of battery technologies. When paired with sulfur and oxygen, the theoretical energy density of Li-S (≈2567 Wh kg −1 ) and Li-O 2 (≈3505 Wh kg −1 ) batteries is far higher than the theoretical energy density of conventional LIBs (≈387 Wh kg −1 ). [12][13][14][15] When Li metal approaches the liquid electrolytes, however, unstable Li/electrolyte interface Rechargeable Li-ion batteries (LIBs) are electrochemical storage device widely applied in electric vehicles, mobile electronic devices, etc. However, traditional LIBs containing liquid electrolytes suffer from flammability, poor electrochemical stability, and limited operational temperature range. Replacement of the liquid electrolytes with inorganic solid-state electrolytes (SSEs) would solve this problem. However, several critical issues, such as poor interfacial compatibility, low ionic conductivity at ambient temperatures, etc., need to be surmounted befor...

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New phases and phase transitions observed in over-charged states of LiCoO2-based cathode materials☆

Cited by 39 publications

References 4 publications

Application of Operando X-ray Diffraction and Raman Spectroscopies in Elucidating the Behavior of Cathode in Lithium-Ion Batteries

Application of Operando X-ray Diffraction and Raman Spectroscopies in Elucidating the Behavior of Cathode in Lithium-Ion Batteries

The application of synchrotron X-ray techniques to the study of rechargeable batteries

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

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