【作者】 王晨；

【导师】 邓超；

【作者基本信息】 哈尔滨师范大学 ， 物理化学， 2020， 硕士

【摘要】 为了响应国家号召,贴合政府政策方针,解决现代社会上日益增长的能源短缺问题和环境保护问题所带来的压力,我们为促进替代能源的转换和能量存储相关技术的发展在研究过程中付出了巨大的努力。在过去的研究中,人们不断探索,研究和发展更高能量密度、更经济、更安全的电池技术,促使了人们对改进可充电电池的发展进行了一系列的研究。锌-空气电池,由于成本低廉和环境友好性而被认为是未来发展所需要的环保型电池。对于锌-空气电池,碱性条件下氧的电化学还原（ORR）和析出（OER）是锌空气电池充放电的基本途径,所以反应中高活性、高耐久能力的电催化剂是必不可少的,为了实现锌空气电池高利用率和循环性,需要设计具有高活性和稳定性的双功能氧催化剂材料,进一步增强锌空气电池的性能,以提高电池的能量效率和使用寿命。本文在锌-空气电池空气阴极的最新双功能氧催化剂研究进展的基础上加以改性,对可充电锌空气电池的一些基本认识以及ORR和OER的电催化机理也作了简要的讨论。以生物质基质为前驱体的碳材料资源丰富,很多有机体都可以作为碳源,其价格也相对较低,并且易于获得,同时生物碳结构稳定,不易发生变化。优良的催化剂载体可以促进催化剂-载体协同作用,加快电化学反应。本文采取生活中常见的鱼鳞,柳絮作为生物碳的前驱体载钴,并分别对其电催化性能,充放电性能进行研究比较。由于过渡金属氧化物具有良好的导电性和稳定性。近年来含锰、钴、镍的尖晶石氧化物为主的过渡金属氧化物在研究中被认为是在碱性介质中促进ORR和OER过程的有效电催化剂,这种催化剂材料为ORR和OER提供了良好的电催化活性。本文使用固相研磨法分别合成了二元过渡金属氧化物MnCo₂O₄和NiCo₂O₄作为锌空气电池的催化剂,通过对其性能的测试分析讨论了两者的性能。最后,对块状结构的MnCo₂O₄进行了优化改性,合成了中空结构的MnCo₂O₄,并研究了其电极催化性能与在锌空气电池中的充放电性能。使用旋转圆盘电极测试了中空结构的MnCo₂O₄的线性扫描伏安曲线,同时比较了中空结构的MnCo₂O₄与块状结构的MnCo₂O₄线性扫描伏安曲线及所绘制的相应的K-L方程斜率及塔菲尔斜率。优化改性后所合成的中空结构的MnCo₂O₄催化剂材料表现出较好的充放电循环性能。总的来说,经过多次的实验结论,以及其他研究者的成果来看,锌空气电池具有良好的性能以及巨大的发展空间,有望成为储能及移动设备的主要能量来源。更多还原

【Abstract】 In order to respond to national calls,conform to government policy guidelines,and solve the pressure caused by the growing energy shortage and environmental protection in modern society,we have made great efforts in the research process to promote the conversion of alternative energy and the development of energy storage related technologies.In the past research,people continue to explore,research and develop higher energy density,more economical,safer battery technology,what’s more,promoted a series of studies on the development of improved rechargeable batteries.Zinc-air battery is considered to be an environmentally friendly battery for future development due to its low cost and environmental friendliness.For zinc-air batteries,the electrochemical reduction（ORR）and evolution（OER）of oxygen under alkaline conditions are the basic ways to the charge and discharge of zinc-air batteries.Therefore,an electrocatalyst with high activity and high durability in the reaction is indispensable.In order to achieve high utilization rate and cyclicity of zinc-air batteries,it is necessary to design dual-functional oxygen catalyst materials with high activity and stability to further enhance the performance of zinc-air batteries and improve the energy efficiency and service life of batteries.This paper is modified on the basis of the latest bifunctional oxygen catalyst research progress of the air cathode of the zinc-air battery,and some basic understanding of the rechargeable zinc-air battery and the electrocatalytic mechanism of ORR and OER are also briefly discussed.The carbon material with biomass as a precursor is rich in resources,many organisms can be used as carbon sources,its price is also relatively low and easy to obtain,and the bio-carbon structure is stable and not prone to change.Excellent catalyst carrier can promote catalyst-carrier synergy and speed up the electrochemical reaction.In this paper,the common fish scales and catkins in life are used as the precursor of bio-carbon to carry cobalt,and compare their electrocatalytic performance,charge and discharge performance.Due to the transition metal oxide has good conductivity and stability.In recent years,transition metal oxides which are mainly containing manganese,cobalt,and nickel have been considered as effective electrocatalysts to promote ORR and OER processes in alkaline media.This catalyst material provides good electrocatalytic activity for ORR and OER.In this paper,the solid-phase grinding method was used to synthesize binary transition metal oxides MnCo₂O₄ and NiCo₂O₄ respectively as catalysts for zinc-air batteries,the performance of the two was discussed through the test and analysis of their performance.Finally,the bulk structure of MnCo₂O₄ was optimized and modified,the hollow structure of MnCo₂O₄ was synthesized,and its electrode catalytic performance and charge-discharge performance in zinc-air batteries were studied.The linear scanning voltammogram of MnCo₂O₄ with hollow structure was tested using a rotating disk electrode,At the same time,the linear scanning voltammetry curves of the hollow structure MnCo₂O₄ and the bulk structure MnCo₂O₄ and the corresponding K-L equation slope and Tafel slope were plotted.The hollow-structured MnCo₂O₄ catalyst material synthesized after optimized modification showed good charge-discharge cycle performance.In general,after many experimental conclusions and the results of other researchers,zinc-air batteries have good performance and huge space for development,and are expected to become the main energy source for energy storage and mobile devices.更多还原