锂离子电池正极材料β-Li0.3V2O5 的电化学性能研究

doi:10.19799/j.cnki.2095-4239.2019.0222

摘要/Abstract

摘要：

随着金属锂电池和全固态锂电池的发展，具有高能量密度无锂/少锂正极材料逐渐受到大家的广泛关注。该文通过一步固相法合成了结晶良好的微米颗粒少锂正极材料β-Li_0.3V₂O₅，电子电导率为2.20×10^-4 S/cm。该材料具有良好的循环性能，在2.2~4.0 V区间，0.5C电流下可逆容量为247 mA·h/g，循环100周仍有204 mA·h/g；同时倍率性能优异，在10C下容量为160 mA·h/g。利用非原位XRD，研究了该材料在1.5~4.0 V区间锂的嵌入/脱出过程的相变化，具体过程为：β(0<x<0.27) → β'(0.57<x<0.75) → β₁ (0.57<x<1.92) → β₂(0.75<x<1.92) → β₃(1.92<x<2.52)。整个充放电过程中，体积形变较小，晶胞参数a最大形变为3.1%（β₂），晶胞参数c最大形变为4.5%（β₃）。

关键词: 高能量密度, 锂离子电池, 少锂正极材料, 钒酸锂, 相转变反应

Abstract:

With the development of lithium (Li) and all-solid-state batteries, high energy-density Li-free/deficient cathode materials have received considerable attention. In this study, well-crystallized micron-size Li-deficient cathode material β-Li_0.3V₂O₅ is synthesized via a one-step high-temperature solid-state reaction with an electronic conductivity of 2.20 × 10^-4 S/cm. This material exhibits good cycling performance. It delivers a specific capacity of 247 mA·h/g when charging/discharging at 0.5 C between 2.2 V and 4.0 V, with a residual specific capacity of 204 mA·h/g after 100 cycles. In addition, β-Li_0.3V₂O₅ shows excellent rate capabilities, i.e., 160 mA·h/g at 10C. Ex situ X-ray diffraction is applied to study phase transformations during the Li insertion/extraction process; five different phases exist in the voltage range of 1.5—4.0 V: β(0<x<0.27) → β′(0.57<x<0.75) → β₁(0.57<x<1.92) → β₂(0.75<x<1.92) → β₃(1.92<x<2.52). The volume undergoes a small change during the cycling

process

a increases by a maximum of 3.1% (β₂) and c increases by a maximum of 4.5% (β₃).

Key words: high energy density, lithium ion batteries, Li deficient cathodes, vanadium oxide bronzes, phase transformations

中图分类号:

TM 912.9

邹剑, 汪博筠, 杨家超, 牛晓滨, 王丽平. 锂离子电池正极材料β-Li_0.3V₂O₅ 的电化学性能研究[J]. 储能科学与技术, 2020, 9(2): 353-360.

ZOU Jian, WANG Bojun, YANG Jiachao, NIU Xiaobin, WANG Liping.

Electrochemical performance of β-Li_0.3V₂O₅ as a lithium-ion battery cathode material

[J]. Energy Storage Science and Technology, 2020, 9(2): 353-360.

图/表 5

图1

图2

图3

图4

图5

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锂离子电池正极材料β-Li_0.3V₂O₅ 的电化学性能研究

Electrochemical performance of β-Li_0.3V₂O₅ as a lithium-ion battery cathode material

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