CoSb_3基方钴矿热电材料保护涂层研究进展  

A Survey on the Protective Coating Techniques for CoSb_3-based Skutterudite Thermoelectric Materials

作　　者：包鑫 柏胜强[2] 吴子华[1] 吴汀[2] 顾明[2] 谢华清[1] BAO Xin;BAI Shengqiang;WU Zihua;WU Ting;GU Ming;XIE Huaqing(School of Environmental and Materials Engineering,Shanghai Polytechnic University,Shanghai 201209;The State Key Laboratory of High Performance Ceramics and Superfine Microstructure,Shanghai Institute of Ceramics,Chinese Academy of Sciences,Shanghai 200050)

机构地区：[1]上海第二工业大学环境与材料工程学院,上海201209 [2]中国科学院上海硅酸盐研究所高性能陶瓷和超微结构国家重点实验室,上海200050

出　　处：《材料导报》2019年第5期784-790,共7页Materials Reports

基　　金：国家自然科学基金(51676117;51406111);上海市青年东方学者(QD2015052);上海第二工业大学研究生项目基金(EGD17YJ0036)~~

摘　　要：热电转换技术可以利用固体中载流子输运实现热能与电能之间的相互转换,该技术具备无污染、无传动、无噪声等一系列优势。在太阳能光热复合发电、工业生产余废热回收利用等方面都极具潜力,为缓解环境及能源压力提供了新的研究方向。热电转换技术的性能通过无量纲优值ZT来衡量,ZT=S^2σT/κ,其中S是塞贝克系数,σ是电导率,T是绝对温度,κ是热导率。但目前热电器件转换与普通热机发电效率存在较大的差距,相对较低的转换效率是由于材料热电转换性能较低,即ZT优值较低导致。理论研究表明,热电材料ZT优值达到1以上就具备了商业应用价值。作为典型电子晶体-声子玻璃热电材料之一,锑化钴(CoSb_3)基方钴矿热电材料具有优异的热电性能,在过去20多年被广泛研究。填充、掺杂、纳米复合等方式能有效提升CoSb_3基热电材料的性能,其ZT值从CoSb_3二元方钴矿的0.5左右提升到了填充方钴矿的1.7～2.0。CoSb_3基方钴矿成为了最具潜力的中温区(500～850 K)的发电热电材料之一,CoSb_3基方钴矿热电器件的设计、集成、服役行为也随之展开。相关研究显示,CoSb_3基方钴矿热电转换器件在高温服役过程中,材料的劣化(如材料的氧化,元素的升华以及服役期间界面扩散等)会导致整个器件性能的降低,严重阻碍了方钴矿材料的商业化应用。打破限制CoSb_3基方钴矿器件实际应用的技术壁垒,扩大其应用领域,解决CoSb_3基方钴矿材料本身高温劣化性问题是当前方钴矿器件研究的热点之一。本文综述了CoSb_3基方钴矿热电材料的氧化、Sb元素升华等导致材料及器件失效的主要形式和各种CoSb_3基方钴矿热电材料保护涂层的最新研究进展,如金属类涂层Ti、Mo、Pt等,非金属类涂层玻璃、陶瓷、气凝胶等,以及复合涂层对方钴矿基材料的保护性能,以期为CoSb_3基方钴矿热电器件材料劣化性�Thermoelectric conversion technology can take the advantage of the carrier transport in solids to realize the conversion between thermal energy and electrical energy.Owing to its superiority of no pollution,no transmission,and no noise,thermoelectric conversion technology shows great potential in solar and thermal combined power generation and industrial waste heat recovery technologies,which provides a new research direction for alleviating environmental and energy pressure.The performance of thermoelectric conversion technology is characterized by the dimensionless figure of merit ZT,ZT=S 2σT/κ,where S,σ,T andκrepresent the Seebeck coefficient,conductivity,absolute temperature,thermal conductivity,respectively.However,there is a big gap between the current thermoelectric device conversion efficiency and the general heat engine power generation efficiency.The relatively low conversion efficiency results from the lower thermoelectric conversion performance of the material,namely the lower ZT value.Theoretical researches illustrate that only ZT value exceeds 1 can thermoelectric material be applied commercially.As one of the typical electronic crystal-phonon glass thermoelectric materials,the CoSb 3-based skutterudite thermoelectric material exhibits excellent thermoelectric properties and has been extensively studied in the past two decades.Filling,doping,preparing nanocomposites and other methods have effectively improved the properties of CoSb 3-based thermoelectric materials,and its ZT has increased from about 0.5 for CoSb 3 binary skutterudite to about 1.7-2.0 for filled skutterudite.Therefore,CoSb 3-based skutterudite(SKD)is considered as one of the most promising thermoelectric(TE)material in medium temperature region(500-850 K).And the design,integration and service behavior of SKD based thermoelectric devices are carried out.Unfortunately,relative studies have shown that the degradation of materials(such as oxidation of materials,sublimation of elements and diffusion of interface during service)of SKD

关 键 词：热电材料 方钴矿 高温防护涂层 锑化钴(CoSb3) 失效 复合涂层 

分 类 号：TQ16[化学工程—高温制品工业]