钯催化剂对锂空气电池氧析出和氧还原反应的催化机理的研究

doi:10.15541/jim20180107

无机材料学报 ›› 2018, Vol. 33 ›› Issue (10): 1131-1135.DOI: 10.15541/jim20180107

所属专题：离子电池材料

钯催化剂对锂空气电池氧析出和氧还原反应的催化机理的研究

谷峰^1,2, 王有伟², 郑智慧^1,2, 刘建军², 陆文聪¹

1.上海大学化学系, 上海 200444;
2.中国科学院上海硅酸盐研究所, 上海 200050

收稿日期:2018-03-12 修回日期:2018-05-02 出版日期:2018-10-20 网络出版日期:2018-09-25
作者简介:谷峰(1992-), 男, 硕士研究生. E-mail: fenggu@student.sic.ac.cn
基金资助:
国家自然科学基金(51432010, 21573272);上海市科学技术委员会项目(16DZ2260600)

Catalytic Mechanism of Palladium Catalyst for the Oxidation Reduction and Evolution Reaction of Lithium-air Battery

GU Feng^1,2, WANG You-Wei², ZHENG Zhi-Hui^1,2, LIU Jian-Jun², LU Wen-Cong¹

1.Department of Chemistry Shanghai University, Shanghai 200444, China;
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2018-03-12 Revised:2018-05-02 Published:2018-10-20 Online:2018-09-25
About author:GU Feng. E-mail: fenggu@student.sic.ac.cn
Supported by:
National Natural Science Foundation of China (51432010, 21573272);Science and Technology Commission of Shanghai(16DZ2260600)

摘要/Abstract

摘要：

锂空气电池以其超高的能量密度而备受关注, 然而充、放电过电位高等问题严重限制了其实际应用。金属钯作为催化剂可而降低锂空气电池的充、放电过电位, 但其充、放电反应催化机制尚不完善。本研究运用第一原理计算方法, 建立了钯/氧气/过氧化锂(Pd/O₂/Li₂O₂)的三相界面催化模型, 从微观角度揭示钯催化剂在锂空气电池充、放电反应中的催化机制。研究表明, Pd/O基底通过促进Li₂O₂在界面处的电荷转移提高自身对LiO₂吸附作用, 从而加速放电产物在电极表面的形成, 有效降低了充电过电位0.43 V。

关键词: 钯催化剂, 过电位, 界面电荷转移, 第一原理

Abstract:

Rechargeable lithium-oxygen (Li-O₂) batteries have recently attracted great attention due to their superior energy storage density. However, its practical application is seriously limited by some problems such as high charging and discharging overpotential. Metal palladium as a catalyst can simultaneously reduce the charging and discharging overpotential in Li-O₂ batteries by enhancing catalytic activity of air electrode, but its catalytical mechanism is insufficient. Here, using first-principles calculations, a three-phase interface model which consists of Pd/O₂/Li₂O₂ is constructed to explore the mechanism of charge and discharge reaction. The result indicates that the Pd/O substrate enhances its adsorption of LiO₂ by promoting charge transfer between substrate and Li₂O₂, thereby accelerating discharge product formed on the electrode surface, and effectively reducing the charging overpotential by 0.43 V.

Key words: Li-O₂ batteries, Pd catalyst, overpotential, interfacial charge transfer, first-principles calculations

中图分类号:

TQ174

谷峰, 王有伟, 郑智慧, 刘建军, 陆文聪. 钯催化剂对锂空气电池氧析出和氧还原反应的催化机理的研究[J]. 无机材料学报, 2018, 33(10): 1131-1135.

GU Feng, WANG You-Wei, ZHENG Zhi-Hui, LIU Jian-Jun, LU Wen-Cong. Catalytic Mechanism of Palladium Catalyst for the Oxidation Reduction and Evolution Reaction of Lithium-air Battery[J]. Journal of Inorganic Materials, 2018, 33(10): 1131-1135.

图/表 3

图1 氧原子在Pd(111)面上Fcc、Hcp和Top位点的(a)俯视图和(b)侧视图, 以及(c)三个位点关于覆盖率的关系

Fig. 1 Fcc, Hcp and Top sites on the Pd (111) surface of oxygen atoms from (a) top view and (b) main view, and (c) relationship between three kinds of adsorption sites on the coverage rate

图2 (a) Li+→Li+→O2和Li+→O2→Li+两种不同路径的电压图和(b) Li+→Li+→O2和Li+→O2→Li+两种不同路径的对应结构示意图

Fig. 2 (a) Energy profiles of two different oxygen evolution reaction paths of Li2O2 for Li+→Li+→O2 with charge voltage of 2.85 V (black line) and Li+→O2→Li+ with charge voltage of 3.78 V (red line); (b) Sketch maps of Li+→Li+→O2 and Li+→O2→ Li+ oxygen evolution reaction paths of Li2O2 with red ball indicating O, blue ball indicating Pd, and purple ball indicating Li

图3 (a)三相界面Pd/O2/Li2O2的结构示意图、(b)在沉积Li2O2后对应结构中的O和Pd得到的电荷量, 及(c)在充电反应路径为Li+→Li+→O2下的电荷转移

Fig. 3 (a) Calculated structure of Pd(111)/ Li2O2/O2 interface with red ball indicating O, blue ball indicating Pd, and purple ball indicating Li; (b) Bader charge analysis of O and Pd with oxygen reduction reaction of Li2O2, the calculated O atoms and Pd atoms in charge transfer analysis correspond to labeled O atoms and Pd atoms in figure (a); (c) Bader charge analysis of O and Pd with the oxygen evolution reaction of Li2O2, the calculated O atoms and Pd atoms in charge transfer analysis correspond to labeled O atoms and Pd atoms in figure (a)

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钯催化剂对锂空气电池氧析出和氧还原反应的催化机理的研究

Catalytic Mechanism of Palladium Catalyst for the Oxidation Reduction and Evolution Reaction of Lithium-air Battery

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