CoSb_3纳米热电材料的制备与性能研究
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摘要
热电发电系统能否实用化其关键是高性能热电材料的研究和开发，在中温领域(500～800K)，由于目前所使用的PbTe系热电材料存在性能指数低(ZT_(max)=0.9)，在使用过程中性能恶化及Pb对环境的污染等缺点，因此迫切需要研究和开发新型环境协调型高性能中温热电材料。CoSb_3方钴矿化合物作为一种具有潜在高热电性能指数的新型中温热电材料具有大的载流子移动度、高的电导率和较大的Seebeck系数，但由于热导率较大，因此要提高CoSb_3方钴矿化合物的热电性能，降低其热导率是当前研究的热点之一。本研究通过晶体结构纳米化来降低材料热导率，提高材料Seebeck系数，改善材料热电性能。
采用固相反应法合成了平均晶径约为3μm单相CoSb_3粉体，采用高能球磨法制备了纳米CoSb_3化合物粉体，研究了球磨参数(球料比、级配、转速和时间)对粉体颗粒尺寸的影响。在适当的参数条件下制备出平均颗粒尺寸约为50nm的纳米粉末。
以纳米和微米CoSb_3粉末为原料，用放电等离子烧结(SPS)方法制备CoSb_3块体材料，并探讨了烧结温度和时间对烧结体晶粒尺寸的影响。结果表明：随着烧结温度的增加和烧结时间的延长，烧结体的晶粒有明显长大。当烧结温度为625℃，烧结时间7min时，得到了最小平均晶粒尺寸为100nm的CoSb_3密实块体材料。
通过对一系列不同晶粒尺寸CoSb_3化合物的热导率、电导率和Seebeck系数的测定，讨论了晶粒尺寸大小对结构纳米化对热导率、电导率和Seebeck系数的影响，结果表明：随着CoSb_3化合物晶粒尺寸的减小，晶格热导率κ_L显著降低，从而导致CoSb_3化合物的热导率κ的降低；电导率σ也有一定的降低；以及Seebeck系数α显著增加。因此，晶粒尺寸对CoSb_3化合物的性能指数(ZT)影响很大，当晶粒尺寸为200nm时CoSb_3化合物的性能指数(ZT)最大，在700K时ZT可达到0.43。
In order to make thermoelectric generation system practicable, high-performance thermoelectric material should be developed. At present, in all of the middle- temperature thermoelectric materials, PbTe is used the most widely but it has a severe pollution to environment. And its thermoelectric performance figure (ZTmax=0.9) is still very low. Therefore it is necessary to develop new type high-performance and environment friendly middle-temperature thermoelectric materials. As a type of potentially good thermoelectric materials, CoSb3 compounds with the skutterudite crystal structure MX3 have attracted attention widely, because of their high carrier mobility, large electrical conductivities, and large Seebeck coefficients. However, the thermal conductivity of skutterudite is too large, so, ZT is low. Therefore reducing the thermal conductivity of CoSb3 has becomed a main research way at present. In this research, nano-structure CoSb3 was prepared and its thermoelectric performance figure is better than microm
eter structure CoSb3.
CoSb3 micrometer powder has been synthesized by solid-state reaction. CoSb3 nano-powders were prepared by high-energy ball-milling respectively. The influence of mass ratio of big balls and small balls, milling speed and time on particles size of CoSb3 powder, were investigated. In appropriate conditions, CoSb3 powders with particles size of 50nm were prepared.
CoSb3 nano-powders were used as starting materials, and bulk thermoelectric materials were prepared by Spark Plasma Sintering (SPS). We have investigated the influence of sintering temperature and sintering time on grains size. The results show that the grain size of CoSb3 grows with increasing sintering temperature or sintering time. When sintering temperature and sintering time are 625 C and 7min respectively, the densenfied bulk thermoelectric materials with mean grains size of 100nm were prepared.
After testing thermal conductivity (K), electrical conductivity ( ) and See-beck coefficient (a), the results demonstrate that for CoSb3 nano-materials, with
decreasing in grains size lattice thermal conductivity falls, electrical conductivity decreases and Seebeck coefficient increases. Thermoelectric performance figure (ZT) CoSbs nano-compound with grains size of 200nm has reached 0.43.
采用固相反应法合成了平均晶径约为3μm单相CoSb_3粉体，采用高能球磨法制备了纳米CoSb_3化合物粉体，研究了球磨参数(球料比、级配、转速和时间)对粉体颗粒尺寸的影响。在适当的参数条件下制备出平均颗粒尺寸约为50nm的纳米粉末。
以纳米和微米CoSb_3粉末为原料，用放电等离子烧结(SPS)方法制备CoSb_3块体材料，并探讨了烧结温度和时间对烧结体晶粒尺寸的影响。结果表明：随着烧结温度的增加和烧结时间的延长，烧结体的晶粒有明显长大。当烧结温度为625℃，烧结时间7min时，得到了最小平均晶粒尺寸为100nm的CoSb_3密实块体材料。
通过对一系列不同晶粒尺寸CoSb_3化合物的热导率、电导率和Seebeck系数的测定，讨论了晶粒尺寸大小对结构纳米化对热导率、电导率和Seebeck系数的影响，结果表明：随着CoSb_3化合物晶粒尺寸的减小，晶格热导率κ_L显著降低，从而导致CoSb_3化合物的热导率κ的降低；电导率σ也有一定的降低；以及Seebeck系数α显著增加。因此，晶粒尺寸对CoSb_3化合物的性能指数(ZT)影响很大，当晶粒尺寸为200nm时CoSb_3化合物的性能指数(ZT)最大，在700K时ZT可达到0.43。
In order to make thermoelectric generation system practicable, high-performance thermoelectric material should be developed. At present, in all of the middle- temperature thermoelectric materials, PbTe is used the most widely but it has a severe pollution to environment. And its thermoelectric performance figure (ZTmax=0.9) is still very low. Therefore it is necessary to develop new type high-performance and environment friendly middle-temperature thermoelectric materials. As a type of potentially good thermoelectric materials, CoSb3 compounds with the skutterudite crystal structure MX3 have attracted attention widely, because of their high carrier mobility, large electrical conductivities, and large Seebeck coefficients. However, the thermal conductivity of skutterudite is too large, so, ZT is low. Therefore reducing the thermal conductivity of CoSb3 has becomed a main research way at present. In this research, nano-structure CoSb3 was prepared and its thermoelectric performance figure is better than microm
eter structure CoSb3.
CoSb3 micrometer powder has been synthesized by solid-state reaction. CoSb3 nano-powders were prepared by high-energy ball-milling respectively. The influence of mass ratio of big balls and small balls, milling speed and time on particles size of CoSb3 powder, were investigated. In appropriate conditions, CoSb3 powders with particles size of 50nm were prepared.
CoSb3 nano-powders were used as starting materials, and bulk thermoelectric materials were prepared by Spark Plasma Sintering (SPS). We have investigated the influence of sintering temperature and sintering time on grains size. The results show that the grain size of CoSb3 grows with increasing sintering temperature or sintering time. When sintering temperature and sintering time are 625 C and 7min respectively, the densenfied bulk thermoelectric materials with mean grains size of 100nm were prepared.
After testing thermal conductivity (K), electrical conductivity ( ) and See-beck coefficient (a), the results demonstrate that for CoSb3 nano-materials, with
decreasing in grains size lattice thermal conductivity falls, electrical conductivity decreases and Seebeck coefficient increases. Thermoelectric performance figure (ZT) CoSbs nano-compound with grains size of 200nm has reached 0.43.
引文
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3．李伟文，赵新兵，周邦昌，Skutterudite结构热电材料的研究进展，材料导报，16(2002)，19-21．
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