Revealing the correlation between structure evolution and electrochemical performance of high-voltage lithium cobalt oxide

Wan, Jiajia; Zhu, Jianping; Xiang, Yuxuan; Zhong, Guiming; Liu, Xiangsi; Li, Yixiao; Zhang, Kelvin H. L.; Hong, Chen; Zheng, Jianming; Wang, Kai; Yang, Yong

doi:10.1016/j.jechem.2020.06.027

Cited by 47 publications

(19 citation statements)

References 44 publications

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“…After 150 cycles, the XRD data of LCO-HT electrode exhibits a split at (003) peak, indicating the appearance of the H1−3 phase. 23 Furthermore, the (018) peak is significantly enhanced, suggesting the deterioration of layered structure. 22,25 Thus, the phase transition of LCO-HT electrode is irreversible.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…For LCO-LT electrode, the similar XRD data at pristine state and the 150th cycled state indicate reversible phase transitions during 150 cycles (Figure S15). After 150 cycles, the XRD data of LCO-HT electrode exhibits a split at (003) peak, indicating the appearance of the H1–3 phase . Furthermore, the (018) peak is significantly enhanced, suggesting the deterioration of layered structure. , Thus, the phase transition of LCO-HT electrode is irreversible.…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, at high deintercalation state more lithium ions are released from the crystal lattice, causing structural instability of the near surface and inside of LiCoO 2 particles. , Furthermore, the dissolution of cobalt is accompanied by the release of oxygen, exacerbating the deterioration of cyclability. To improve the reversibility of LiCoO 2 phase transition, the fundamental strategy is doping, and the classic doping elements are Ti, Mg, Al, and La. − Zhang et al employed trace Ti–Mg–Al codoping to enable stable cycling LiCoO 2 batteries at 4.6 V . Specifically, Mg and Al elements were doped into the LiCoO 2 lattice, inhibiting the undesired phase transition at high cutoff voltage, while Ti elements enriched significantly on the surface, stabilizing the surface oxygen at high voltage.…”

Section: Introductionmentioning

confidence: 99%

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Enhancing the Reversibility of Lithium Cobalt Oxide Phase Transition in Thick Electrode via Low Tortuosity Design

Tian

et al. 2022

Nano Lett.

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Lithium cobalt oxide (LCO) is a widely used cathode material for lithium-ion batteries. However, it suffers from irreversible phase transition during cycling because of high cutoff voltage or huge concentration polarization in thick electrode, resulting in deteriorated cyclability. Here, we design a low tortuous LiCoO2 (LCO-LT) electrode by ice-templating method and investigate the reversibility of LCO phase transition. LCO-LT thick electrode shows accelerated lithium-ion transport and reduced concentration polarization, achieving excellent rate capability and homogeneous actual operating voltage. Moreover, LCO-LT thick electrode exhibits a durable phase transition between O2 and H1–3, mitigated volume expansion, and suppressed microcrack formation. LCO-LT electrode (25 mg cm–2) delivers improved capacity retentions of 94.4% after 200 cycles and 93.3% after 150 cycles at cutoff voltages of 4.3 and 4.5 V, respectively. This strategy provides a new concept to improve the reversibility of LCO phase transition in thick electrode by low tortuosity design.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Enhancing the Reversibility of Lithium Cobalt Oxide Phase Transition in Thick Electrode via Low Tortuosity Design

Tian

et al. 2022

Nano Lett.

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“…LiCoO 2 has been the dominant cathode material for lithiumion batteries in portable electronic products because of its high volumetric energy density [1,2]. Increasing the operating voltage of LiCoO 2 can effectively enhance its specific capacity; however, achieving stable cycling performance of LiCoO 2 at high voltage faces many challenges [3], including the adverse phase transition at an operating voltage above 4.5 V (vs. Li/Li + ) [4,5], the lattice distortion caused by internal mechanical strain, the loss of oxygen, dissolution of cobalt and side reactions with the electrolyte [6,7].…”

Section: Introductionmentioning

confidence: 99%

Li2TiO3 Dopant and Phosphate Coating Improve the Electrochemical Performance of LiCoO2 at 3.0–4.6 V

Shi

Feng

Liu

et al. 2022

Trans. Tianjin Univ.

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A sol–gel tandem with a solid-phase modification procedure was developed to synthesize Li2TiO3-doped LiCoO2 together with phosphate coatings (denoted as LCO-Ti/P), which possesses excellent high-voltage performance in the range of 3.0–4.6 V. The characterizations of X-ray diffraction, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy illustrated that the modified sample LCO-Ti/P had the dopant of monoclinic Li2TiO3 and amorphous Li3PO4 coating layers. LCO-Ti/P has an initial discharge capacity of 211.6 mAh/g at 0.1 C and a retention of 85.7% after 100 cycles at 1 C and 25 ± 1 °C between 3.0 and 4.6 V. Nyquist plots reflect that the charge transfer resistance of LCO-Ti/P after 100 cycles at 1 C is much lower than that of the spent LCO, which benefits Li-ion diffusion. Density functional theory calculations disclose the superior lattice-matching property of major crystal planes for Li2TiO3 and LiCoO2, the lower energy barriers for Li-ion diffusion in Li2TiO3, and the suppressed oxygen release performance resulting from phosphate adsorption. This work provides useful guidance on the rational design of the high-voltage performance of modified LiCoO2 materials in terms of lattice-matching properties aside from the phosphate coating to reduce the energy barriers of Li-ion diffusion and enhance cycling stability.

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“…Since being commercialized at 1991, Lithium‐ion batteries (LIBs) are widely used at the electric vehicles, portable devices, and energy storage systems [1–5] . Due to its high tap density and volumetric energy density, lithium cobalt oxide (LCO) cathode has attracted increasing attention both in industry and academia [6,7] . However, the actual discharge capacity and acceptable cyclic reversibility of LCO cathode are only about 170 mAh g −1 (Li 1‐x CoO 2 , X=about 0.63; 4.45 vs. Li/Li + ), which is far below its theoretical discharge capacity of 274 mAh g −1 [8–10] .…”

Section: Introductionmentioning

confidence: 99%

Glycerol Tris(2‐cyanoethyl) Ether as an Electrolyte Additive to Enhance the Cycling Stability of Lithium Cobalt Oxide Cathode at 4.5 V

et al. 2021

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High‐voltage lithium cobalt oxide batteries are considered the ideal power source for portable devices, owing to their high‐energy density and accessible specific capacity. However, it is still challenging to achieve long‐term cycling stability when charging to the high cut‐off voltages (≥4.5 V vs. Li/Li+), owing to the unavoidable parasitic reactions at the cathode/electrolyte interface. Herein, we report an organic nitrile‐based molecule, glycerol tris(2‐cyanoethyl) ether (GTCE), as a novel electrolyte additive to improve the cycling stability of LiCoO2 (LCO) batteries at 2.75–4.5 V. Impressively, the LCO||Li metal half‐cell using the GTCE‐containing electrolyte (2 wt % GTCE in the base electrolyte, 1.0 M LiPF6 in EC/DEC/EMC=1/1/1, v/v) exhibits an outstanding capacity retention of 79.3 % over 150 cycles, superior to the battery with base electrolyte (only 27.4 %) under the same test conditions. It represents a feasible and valuable method to stabilize the cathode/electrolyte interface of high‐voltage lithium‐ion batteries.

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Revealing the correlation between structure evolution and electrochemical performance of high-voltage lithium cobalt oxide

Cited by 47 publications

References 44 publications

Enhancing the Reversibility of Lithium Cobalt Oxide Phase Transition in Thick Electrode via Low Tortuosity Design

Enhancing the Reversibility of Lithium Cobalt Oxide Phase Transition in Thick Electrode via Low Tortuosity Design

Li2TiO3 Dopant and Phosphate Coating Improve the Electrochemical Performance of LiCoO2 at 3.0–4.6 V

Glycerol Tris(2‐cyanoethyl) Ether as an Electrolyte Additive to Enhance the Cycling Stability of Lithium Cobalt Oxide Cathode at 4.5 V

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