锌掺杂提高LiNi1/3Co1/3Mn1/3O2正极材料的电化学稳定性

引用本文: 李节宾, 徐友龙, 杜显锋, 孙孝飞, 熊礼龙. 锌掺杂提高LiNi_1/3Co_1/3Mn_1/3O₂正极材料的电化学稳定性[J]. 物理化学学报, 2012, 28(08): 1899-1905. doi: 10.3866/PKU.WHXB201205152 shu

Citation: LI Jie-Bin, XU You-Long, DU Xian-Feng, SUN Xiao-Fei, XIONG Li-Long. Improved Electrochemical Stability of Zn-Doped LiNi_1/3Co_1/3Mn_1/3O₂ Cathode Materials[J]. Acta Physico-Chimica Sinica, 2012, 28(08): 1899-1905. doi: 10.3866/PKU.WHXB201205152 shu

锌掺杂提高LiNi_1/3Co_1/3Mn_1/3O₂正极材料的电化学稳定性

基金项目:
国家自然科学基金(50902109)资助项目 (50902109)

摘要:

通过共沉淀法与固相法相结合制备了掺锌的高稳定性Li(Ni_1/3Co_1/3Mn_1/3)_1-xZn_xO₂ (x=0, 0.02, 0.05)正极材料. 循环伏安(CV)曲线表明Zn掺杂使氧化峰与还原峰的电势差减小到0.09 V, 电化学阻抗谱(EIS)曲线表明Zn掺杂使电极的阻抗从266 Ω减小到102 Ω. Li⁺嵌入扩散系数从1.20×10^-11 cm²·s^-1增大到 2.54×10^-11 cm²·s^-1. Li(Ni_1/3Co_1/3Mn_1/3)_0.98Zn_0.02O₂正极材料以0.3C充放电在较高的截止电压(4.6 V)下比其他两种材料的电化学循环性能更稳定, 其第二周的放电比容量为176.2 mAh·g^-1, 循环100周后容量几乎没衰减; 高温(55 °C)下充放电循环100周, 其放电比容量平均每周仅衰减0.20%, 远小于其他两种正极材料(LiNi_1/3Co_1/3Mn_1/3O₂平均每周衰减0.54%; Li(Ni_1/3Co_1/3Mn_1/3)_0.95Zn_0.05O₂平均每周衰减0.38%). Li(Ni_1/3Co_1/3Mn_1/3)_0.98Zn_0.02O₂正极材料以3C充放电时其放电比容量可达142 mAh·g^-1, 高于其他两种正极材料. 电化学稳定性的提高归因于Zn掺杂后减小了电极的极化和阻抗, 增大了锂离子扩散系数.

关键词:

English

Improved Electrochemical Stability of Zn-Doped LiNi_1/3Co_1/3Mn_1/3O₂ Cathode Materials

1.
1. Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education, International Center for Dielectric Research, Xi’an Jiaotong University, Xi’an 710049, P. R. China;
2. Shaanxi Applied Physics and Chemistry Research Institute; Xi'an 710061, P. R. China
Received Date: 15 March 2012
Available Online: 10 July 2012
Fund Project:
国家自然科学基金(50902109)资助项目

Abstract:

Highly stable Li(Ni_1/3Co_1/3Mn_1/3)_1-xZn_xO₂ (x=0, 0.02, 0.05) cathode materials doped with Zn are synthesized by solid-state reactions with co-precipitated precursors. Cyclic voltammetry (CV) curves reveal that the potential difference between oxidation and reduction decreases to 0.09 V, and from electrochemical impedance spectra (EIS) curves, the impedance of LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials is reduced from 266 to 102 Ω. The diffusion coefficients of Li⁺ ions in intercalation processes increase from 1.20×10^-11 to 2.54×10^-11 cm²·s^-1. Li(Ni_1/3Co_1/3Mn_1/3)_0.98Zn_0.02O₂ is stable at 0.3C (constant charge/discharge) at a high cut-off potential of 4.6 V vs Li/Li⁺. It has a second discharge capacity of 176.2 mAh·g^-1 at 0.3C and 142 mAh·g^-1 at 3C, and keep almost no decay after 100 cycles at room temperature. Furthermore, its average capacity loss per cycle at 55 °C is 0.20%, which is lower compared with 0.54% for LiNi_1/3Co_1/3Mn_1/3O₂ and 0.38% for Li(Ni_1/3Co_1/3Mn_1/3)_0.95Zn_0.05O₂ after 100 cycles. The improved electrochemical stability of Zn-doped LiNi_1/3Co_1/3Mn_1/3O₂ is attributed to the reduced electrode polarization and impedance values, and an increased Li+ ion diffusion coefficient.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

锌掺杂提高LiNi_1/3Co_1/3Mn_1/3O₂正极材料的电化学稳定性

English

Improved Electrochemical Stability of Zn-Doped LiNi_1/3Co_1/3Mn_1/3O₂ Cathode Materials

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