《厦门大学学报（自然科学版）》

锂-氧气电池氧电极催化的研究进展

林晓东,孙宗强,徐攀,范镜敏,袁汝明,郑明森,董全峰^*

(厦门大学化学化工学院,福建厦门 361005)

关键词：锂-氧气电池; 反应动力学; 催化; 氧电极催化剂

Research progress of oxygen electrode catalysis in lithium-oxygen batteries

LIN Xiaodong,SUN Zongqiang,XU Pan,FAN Jingmin,YUAN Ruming,ZHENG Mingsen,DONG Quanfeng^*

(College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)

DOI: 10.6043/j.issn.0438-0479.202009042

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锂-氧气电池由于具有极高的理论比能量而受到广泛关注,被认为是最具发展前景的下一代高比能二次电池体系.然而,其复杂的反应历程及迟滞的多相反应动力学使其充放电过程的极化严重,造成能量效率低下、倍率性能和循环性能较差等诸多问题,制约了其商业化应用进程.催化是改善反应动力学的关键,因此,氧电极催化剂的设计与开发成为锂-氧气电池的核心问题和研究重点.结合本课题组在这一体系的系统性研究工作,本文综述了近几年来锂-氧气电池氧电极催化的研究进展,分析了各类氧电极催化剂的优缺点,并展望了未来氧电极催化剂的研究方向.

Lithium-oxygen battery has received extensive attention due to its ultrahigh theoretical specific energy,and is regarded as the most promising next-generation high specific energy secondary battery system.However,the serious polarization of the charge-discharge process caused by its complicated reaction process and sluggish multiphase reaction kinetics results in many problems,such as low energy efficiency,poor rate performance and poor cycling performance,which restrict its commercial application.Catalysis is the key to improve the reaction kinetics.Therefore,the design and development of oxygen electrode catalysts become the core issue and research focus of lithium-oxygen batteries.By combining the systematic research work of our group on this system,this article reviews the research progress of oxygen electrode catalysis in lithium-oxygen batteries in recent years,and analyzes the advantages and disadvantages of various oxygen electrode catalysts.Besides,a future research direction in oxygen electrode catalysts is prospected.

引言
1 固相催化剂
2 液相催化剂
3 总结与展望

图1 非水系锂-氧气电池的原理示意图(a)和典型充放电曲线(b)<br/>Fig.1 Schematic diagram(a)and typical discharge-charge curve(b)of an aprotic Li-O2 battery

图1 非水系锂-氧气电池的原理示意图(a)和典型充放电曲线(b)
Fig.1 Schematic diagram(a)and typical discharge-charge curve(b)of an aprotic Li-O2 battery

图2 分级多孔石墨烯的扫描电子显微镜(SEM)图(a～b)及其电极的放电过程示意图(c)和在0.1 mA/cm2电流密度下的放电曲线图(d)[7]<br/>Fig.2 SEM images of hierarchically porous graphene(a-b), schematic diagram of discharge process of the hierarchically porous graphene electrode(c),and discharge curve of the hierarchically porous graphene electrode at a current density of 0.1 mA/cm2(d)[7]

图2 分级多孔石墨烯的扫描电子显微镜(SEM)图(a～b)及其电极的放电过程示意图(c)和在0.1 mA/cm2电流密度下的放电曲线图(d)[7]
Fig.2 SEM images of hierarchically porous graphene(a-b), schematic diagram of discharge process of the hierarchically porous graphene electrode(c),and discharge curve of the hierarchically porous graphene electrode at a current density of 0.1 mA/cm2(d)[7]

图3 rGO(a)和B-rGO(b)与Li5O6团簇结合的最优几何构型和相应的结合能,B-rGO基底从Li2O2获取电子的示意图(c),rGO和B-rGO在100 mA/g电流密度下的放电曲线(d),及其在电流密度为2 000 mA/g、限制容量为1 000 mAh/g条件下的充放电曲线(e)[13]
Fig.3 Optimized geometries and corresponding binding energy of rGO(a)and B-rGO(b)combined with Li5O6 cluster,schematic diagram of B-rGO as the substrate gaining electrons from the Li2O2(c), discharge curves of the rGO and B-rGO electrodes at a current density of 100 mA/g(d), charge-discharge curves of the rGO and B-rGO electrodes at a current density of 2 000 mA/g with a cutoff capacity of 1 000 mAh/g(e)[13]

图4 RuO2空心球的合成示意图(a),RuO2空心球氧电极的倍率性能(b)及其在500 mA/g电流密度下的充放电曲线(c)[22]<br/>Fig.4 Synthetic diagram of RuO2 hollow spheres(a), rate capability(b)and charge-discharge curves(c)of the RuO2 hollow sphere electrode at a current density of 500 mA/g[22]

图4 RuO2空心球的合成示意图(a),RuO2空心球氧电极的倍率性能(b)及其在500 mA/g电流密度下的充放电曲线(c)[22]
Fig.4 Synthetic diagram of RuO2 hollow spheres(a), rate capability(b)and charge-discharge curves(c)of the RuO2 hollow sphere electrode at a current density of 500 mA/g[22]

图5 不同形貌和种类的锰氧化物的SEM图(a)和循环性能(b)[34]<br/>Fig.5 SEM images(a)and cycling performances(b)of different morphologies and types of manganese oxides[34]

图5 不同形貌和种类的锰氧化物的SEM图(a)和循环性能(b)[34]
Fig.5 SEM images(a)and cycling performances(b)of different morphologies and types of manganese oxides[34]

表1 近几年来非贵金属基氧电极催化剂的性能对比<br/>Tab.1 Performance comparison of non-noble metal-based oxygen electrode catalysts in recent years

表1 近几年来非贵金属基氧电极催化剂的性能对比
Tab.1 Performance comparison of non-noble metal-based oxygen electrode catalysts in recent years

图6 剑麻状Co9S8氧电极的充放电过程示意图(a)、放电前(b)和放电后(c)的SEM图、倍率性能(d)及其在电流密度为50 mA/g、限制容量为1 000 mAh/g条件下的充放电曲线(e)[63]<br/>Fig.6 Schematic diagram of charge-discharge process(a),SEM images before(b)and after(c)discharge,rate capability of the sisal-like Co9S8 electrode(d),and its charge-discharge curves at a current density of 50 mA/g with a cutoff capacity of 1 000 mAh/g(e)[63]

图6 剑麻状Co9S8氧电极的充放电过程示意图(a)、放电前(b)和放电后(c)的SEM图、倍率性能(d)及其在电流密度为50 mA/g、限制容量为1 000 mAh/g条件下的充放电曲线(e)[63]
Fig.6 Schematic diagram of charge-discharge process(a),SEM images before(b)and after(c)discharge,rate capability of the sisal-like Co9S8 electrode(d),and its charge-discharge curves at a current density of 50 mA/g with a cutoff capacity of 1 000 mAh/g(e)[63]

图7 石墨烯内嵌式α-MnO2/RuO2复合氧电极的充放电曲线(a)和协同催化机理示意图(b～c)[71]<br/>Fig.7 Discharge-charge curves(a)and schematic diagram of synergistic catalytic mechanism(b-c)of the graphene-embedded α-MnO2/RuO2 composite[71]

图7 石墨烯内嵌式α-MnO2/RuO2复合氧电极的充放电曲线(a)和协同催化机理示意图(b～c)[71]
Fig.7 Discharge-charge curves(a)and schematic diagram of synergistic catalytic mechanism(b-c)of the graphene-embedded α-MnO2/RuO2 composite[71]

表2 石墨烯内嵌式α-MnO2/RuO2复合氧电极催化剂与其他氧电极催化剂的性能对比<br/>Tab.2 Performance comparison of graphene-embedded α-MnO2/RuO2 composite catalyst and other oxygen electrode catalysts

表2 石墨烯内嵌式α-MnO2/RuO2复合氧电极催化剂与其他氧电极催化剂的性能对比
Tab.2 Performance comparison of graphene-embedded α-MnO2/RuO2 composite catalyst and other oxygen electrode catalysts

图8 含RM的锂-氧气电池的反应机理示意图(a),以及含RM和不含RM的锂-氧气电池的充放电曲线(b)<br/>Fig.8 Schematic diagram of reaction mechanism of the RM-containing Li-O2 batteries(a),and charge-discharge curves of the Li-O2 batteries with and without RM(b)

图8 含RM的锂-氧气电池的反应机理示意图(a),以及含RM和不含RM的锂-氧气电池的充放电曲线(b)
Fig.8 Schematic diagram of reaction mechanism of the RM-containing Li-O2 batteries(a),and charge-discharge curves of the Li-O2 batteries with and without RM(b)

图9 含苯酚的锂-氧气电池的反应机理示意图(a)和充放电曲线(b)[93]<br/>Fig.9 Schematic diagram of reaction mechanism(a)and charge-discharge curves(b)of the phenol-containing Li-O2 batteries[93]

图9 含苯酚的锂-氧气电池的反应机理示意图(a)和充放电曲线(b)[93]
Fig.9 Schematic diagram of reaction mechanism(a)and charge-discharge curves(b)of the phenol-containing Li-O2 batteries[93]

图10 含RuPC(a)[97]和含PhIO(b)[98]的锂-氧气电池的反应机理示意图<br/>Fig.10 Schematic diagrams of reaction mechanisms of the RuPC-containing(a)[97] and PhIO-containing(b)[98] Li-O2 batteries

图10 含RuPC(a)[97]和含PhIO(b)[98]的锂-氧气电池的反应机理示意图
Fig.10 Schematic diagrams of reaction mechanisms of the RuPC-containing(a)[97] and PhIO-containing(b)[98] Li-O2 batteries

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《厦门大学学报（自然科学版）》于1931年创刊，是由教育部主管，厦门大学主办，国内外公开发行的综合性学术期刊（双月刊），是我国自然科学核心期刊。本刊以印刷版、网络版的方式同时出版。主要刊载自然科学各学科的最新研究成果，包括自然科学基础理论研究、应用基础研究、高新技术方面的学术论文。所刊载的论文分三大类型：（1）“快讯”：报道某前沿领域具有突破性的最新研究成果。（2）“研究论文”：刊载理工科基础理论研究与实验研究学术论文。（3）“研究简报”：刊载内容新颖、实用（或阶段性）的成果。更多>>

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引言

1 固相催化剂

2 液相催化剂

3 总结与展望

学报简介