阴离子硫氧化还原与Li1-xNiO2-ySy的结构稳定性:第一性原理研究

引用本文: 鄢慧君, 李彪, 蒋宁, 夏定国. 阴离子硫氧化还原与Li_1-xNiO_2-yS_y的结构稳定性:第一性原理研究[J]. 物理化学学报, 2017, 33(9): 1781-1788. doi: 10.3866/PKU.WHXB201705041 shu

Citation: YAN Hui-Jun, LI Biao, JIANG Ning, XIA Ding-Guo. First-Principles Study:the Structural Stability and Sulfur Anion Redox of Li_1-xNiO_2-yS_y[J]. Acta Physico-Chimica Sinica, 2017, 33(9): 1781-1788. doi: 10.3866/PKU.WHXB201705041 shu

阴离子硫氧化还原与Li_1-xNiO_2-yS_y的结构稳定性:第一性原理研究

北京大学工学院, 先进电池材料理论与技术北京市重点实验室, 北京 100871
基金项目:
国家重点研发计划“新能源汽车”重点专项（2016YFB0100200）和国家自然科学基金（51671004）资助项目

摘要: 高镍层状氧化物是电动汽车高能量密度锂离子电池正极材料的首选。本文通过第一性原理计算模拟了Li_1-xNiO_2-yS_y材料的脱锂过程。通过GGA+U计算分析了体系费米能级处的电子结构，充电过程中的氧化还原机制和热稳定性。在Li_1-xNiO_2-yS_y脱锂过程中，首次发现硫参与电荷补偿，抑制过渡金属的迁移，降低晶格扭曲幅度和提高体系中氧的稳定性。这种基于硫阴离子氧化还原对锂离子电池阴极材料电化学行为的调制有助于设计高稳定性的高镍正极材料。

关键词:

English

First-Principles Study:the Structural Stability and Sulfur Anion Redox of Li_1-xNiO_2-yS_y

Beijing Key Laboratory of Theory and Technology for Advanced Batteries Materials, College of Engineering, Peking University, Beijing 100871, P. R. China
Received Date: 30 March 2017
Revised Date: 20 April 2017
Available Online: 04 May 2017
Fund Project:
The project was supported by the New Energy Project for Electric Vehicle of National Key Research and Development Program, China (2016YFB0100200) and National Natural Science Foundation of China (51671004).

Abstract: Ni-rich layered oxides are the preferred cathode materials for high-energy-density lithium-ion batteries currently used in electric vehicles. In this paper, we present a systematic first-principles evaluation of the deintercalation process in the Li_1-xNiO_2-yS_y. The partial density of states (PDOS) characters of the electrons near the Fermi level, redox behaviors, and thermal stability have been investigated within the GGA+U scheme. The results show that the introduction of sulfur alleviates the lattice distortion during charging, suppresses nickel migration, and enhances the stability of oxygen according to the contribution of sulfur anion redox to the charge compensation for the overcharged Li_1-xNiO_2-yS_y. This study provides a new insight on improving the stability of Ni-rich cathode materials by tuning of the electrochemical behaviors based on sulfur anion redox.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

阴离子硫氧化还原与Li_1-xNiO_2-yS_y的结构稳定性:第一性原理研究

English

First-Principles Study:the Structural Stability and Sulfur Anion Redox of Li_1-xNiO_2-yS_y

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

阴离子硫氧化还原与Li1-xNiO2-ySy的结构稳定性:第一性原理研究

English

First-Principles Study:the Structural Stability and Sulfur Anion Redox of Li1-xNiO2-ySy

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

阴离子硫氧化还原与Li_1-xNiO_2-yS_y的结构稳定性:第一性原理研究

First-Principles Study:the Structural Stability and Sulfur Anion Redox of Li_1-xNiO_2-yS_y

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