CN109659427A - 一种过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法 - Google Patents
一种过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法 Download PDFInfo
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 39
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 29
- 238000005253 cladding Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 21
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 239000002608 ionic liquid Substances 0.000 claims abstract description 10
- 239000011258 core-shell material Substances 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims abstract 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- -1 transition metal salt Chemical class 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910017971 NH4BF4 Inorganic materials 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 3
- HATAYPMPBZNIEE-UHFFFAOYSA-N CC(=O)C.[Cl-].[NH4+] Chemical compound CC(=O)C.[Cl-].[NH4+] HATAYPMPBZNIEE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000013557 residual solvent Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910000385 transition metal sulfate Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000006298 dechlorination reaction Methods 0.000 claims 1
- 238000007772 electroless plating Methods 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 9
- 230000005619 thermoelectricity Effects 0.000 abstract description 9
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910021205 NaH2PO2 Inorganic materials 0.000 abstract description 3
- 239000012928 buffer substance Substances 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 2
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- 206010070834 Sensitisation Diseases 0.000 abstract 1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 118
- 239000011787 zinc oxide Substances 0.000 description 58
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
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- 239000004065 semiconductor Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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- H—ELECTRICITY
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
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Abstract
本发明公开了一种过渡金属包覆In2O3(ZnO)5核‑壳结构热电材料的制备方法,属于新能源材料技术领域。其特征是,首先合成[bmim]BF4离子液体,后将In2O3(ZnO)5粉末经过敏化、活化,以金属酸盐作为金属源,以NiSO4作为Ni源为例,NaH2PO2·H2O为还原剂,H3BO3为缓冲物质,调节镀镍溶液pH至9,后将活化的样品倒入该溶液中,水浴60℃加热。水浴加热后的样品静置、分离、干燥,所获得粉体采用放电等离子烧结技术烧结。该方法中Ni2+离子通过用无电沉积而被还原包覆在In2O3(ZnO)5陶瓷上,从而促进了Ni在In2O3(ZnO)5陶瓷粉体表面上的沉积,制成的粉体样品形成核‑壳结构。ZT值从纯In2O3(ZnO)5的0.12增加到Ni包覆的In2O3(ZnO)5核‑壳体材料的0.39,为增强ZnO‑In2O3陶瓷的热电性能提供了一种新的制备方法协同掺杂策略。
Description
技术领域
本发明属于材料技术领域,具体涉及一种过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法。
背景技术
随着社会经济的不断发展,环境和能源问题越来越被人类所重视。目前人类能源利用率低,超过55%能源以废热形式被排放到环境中,热电材料(又称温差电材料),能够利用固体内部载流子和声子的输运及其相互作用,且热电器件无污染、结构轻便、体积小、寿命长,有可效地将热能转换为电能,故得到越来越多的重视。以热电器件为核心元件的热电模块在半导体制冷、温差电池等方面有着广泛的应用前景。热电材料的性能以无量纲热电优值ZT来表征,,α为塞贝克系数,σ为电导率,κ为热导率,T为绝对温度;α2称为功率因子,用于表征热电材料的电传输性能。由于决定材料热电性能的三个重要参数α、σ、κ之间是相互耦合的,如何实现这些参数的独立调控(或协同调控)是提高热电性能的核心。
氧化物热电材料由于其高温稳定性(化学稳定及结构稳定)、制备原料储量丰富、成本低、无污染、无毒性、使用寿命长等优点,在中高温区热电材料领域受到越来越多的重视。ZnO是具有纤锌矿结构的氧化物半导体,在热电、光电等领域具有广泛的应用;In2O3是另外一种比较有潜力的热电材料,它的晶体结构为锐钛矿结构,并且能经过简单的掺杂得到n型高导电的半导体材料。In2O3(ZnO)k是一种具有层状结构,由InO1.5、(ZnIn)O2.5、ZnO原子层沿c轴周期堆垛而成的自然超晶格材料,其具有低的热导率和较高的电子迁移率,是一种潜在的高温热电转换材料。Hirano等[Mizoguchi H, Hirano M, Fujitsu S, et al.Applied Physics Letters, 2002, 80(7):1207-1209.]通过冷等静压烧结和热压烧结制备了In2O3(ZnO)9,且在1073K取得最大ZT值0.18,Y取代In2O3(ZnO)5在1073K取最大ZT值有0.33。ZT值较低是氧化物热电材料的掣肘。近年来,有研究者试图通过掺杂或者低维化等方式来提高In2O3(ZnO)k体系的热电性能。Liang等人[Liang X, Shen L.Nanoscale, 2018(6269).]通过Al掺杂In2O3(ZnO)4,并在800℃,1.6 mol% Al掺杂量的条件下取得最大ZT值为0.22。Jia等人[Jia J, Owyang C, Akmehmet G I, et al. Journal of VacuumScience & Technology A Vacuum Surfaces & Films, 2016, 34(4):041507.]则通过制备In2O3(ZnO)5薄膜,并在670℃下获得其最大功率因子为1.3×10-4 W/mK2。
发明内容
本发明的目的在于提供一种过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法。
本发明的目的是这样实现的,所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法是以固相法合成In2O3(ZnO)5粉末,研磨过筛,然后采用溶液法,以过渡金属盐作为过渡金属源制备得到核壳结构粉体,再通过放电等离子烧结制备得到目标物过渡金属包覆In2O3(ZnO)5核-壳结构热电材料。
本发明采用固相反应法,溶液镀镍法以及放电等离子烧结技术,获得Ni均匀包覆的In2O3(ZnO)5粉体及Ni/ In2O3(ZnO)5核-壳结构的块体样品,且获得热电优值ZT从纯In2O3(ZnO)5的0.12增加到Ni/In2O3(ZnO)5复合材料的0.39。
本发明提供一种溶液法沉淀过程的机理模型,并观察到[bmim]BF4添加剂更容易吸附In2O3(ZnO)5表面的突起和尖端,抑制Ni的快速形核和晶体生长,可以获得均匀的Ni包覆的In2O3(ZnO)5粉体。随后通过放电等离子体烧结烧结合成的核-壳结构粉体以产生Ni包覆的In2O3(ZnO)5核-壳大块样品。调节Ni包覆的In2O3(ZnO)5核-壳体材料的费米能级而引起σ的显着提高,从而使得ZT值从纯In2O3(ZnO)5的0.12增加到Ni包覆的In2O3(ZnO)5核-壳体材料的0.39。该发明为增强ZnO-In2O3陶瓷的热电性能提供了一种新的制备方法协同掺杂策略,本方法也适用于提高任何其他热电系统的性能。
下面以过渡金属Ni包覆In2O3(ZnO)5核-壳结构热电材料的具体制备过程为例操作如下:
以固相法合成In2O3(ZnO)5粉末。由1-甲基咪唑鎓和氯代丁烷在干燥的氩气氛下合成1-丁基-3-甲基咪唑鎓氯化物([bmim]Cl),将NH4BF4加入[bmim]Cl(摩尔比为1:1)中,303K下经过48小时合成3-甲基咪唑四氟硼酸盐[bmim]BF4离子液体。加入乙腈作为溶剂,然后过滤[bmim]BF4-氯化铵-丙酮混合物以除去氯化铵,并在减压下在353K下蒸发以除去残余溶剂直至形成均匀无色。通过预处理工艺和化学沉积两步制备Ni包覆的In2O3(ZnO)5粉体,在In2O3(ZnO)5粉体上镀Ni的无电沉积在无电镀镍浴中进行,加入离子液体[bmim]BF4添加剂进行Ni涂层In2O3(ZnO)5粉体制备。采用放电等离子(SPS)烧结法将In2O3(ZnO)5粉体和Ni包覆的In2O3(ZnO)5粉体烧结成块体样品。
上述的固相合成In2O3(ZnO)5粉末,其特征在于:经过固相合成的块体经研磨、过筛得到的颗粒尺寸在5~200 的粉体。
上述的溶液镀镍法合成的Ni包覆In2O3(ZnO)5粉末,其特征在于:NiSO4作为Ni源,NaH2PO2·H2O为还原剂,H3BO3为缓冲物质,镀镍溶液pH为9。
附图说明
图1为用[bmim] BF4离子液体作为添加剂的Ni-包覆的In2O3(ZnO)5粉体的无电沉积工艺的示意图;
图2为本体In2O3(ZnO)5样品和块体 Ni / In2O3(ZnO)5样品的XRD图谱;
图3为纯In2O3(ZnO)5, Ni/In2O3(ZnO)5随温度变化的电学性质;
其中(a)总热导率,(b)晶格热导率,(c)热电优值ZT,(d)本工作与其他In2O3-ZnO系统的ZT值比较图,计算ZT所涉及的所有测量的组合误差度小于15%。
具体实施方式
下面结合实施例和附图对本发明作进一步的说明,但不以任何方式对本发明加以限制,基于本发明教导所作的任何变换或替换,均属于本发明的保护范围。
本发明所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法是以固相法合成In2O3(ZnO)5粉末,研磨过筛,然后采用溶液法,以过渡金属盐作为过渡金属源制备得到核壳结构粉体,再通过放电等离子烧结制备得到目标物过渡金属包覆In2O3(ZnO)5核-壳结构热电材料。
所述的过渡金属为Ni、Pb、Cu、Fe、Co、 Mn等。
所述的过渡金属盐为过渡金属硫酸盐。
所述的研磨过筛后的In2O3(ZnO)5粉末粒径为5~200 。
所述的过渡金属为Ni时,具体的制备过程是以固相法合成In2O3(ZnO)5粉末,由1-甲基咪唑鎓和氯代丁烷在干燥的氩气氛下合成1-丁基-3-甲基咪唑鎓氯化物([bmim]Cl),将NH4BF4加入[bmim]Cl中,303K下经过48小时合成3-甲基咪唑四氟硼酸盐[bmim]BF4离子液体,加入乙腈作为溶剂,然后过滤[bmim]BF4-氯化铵-丙酮混合物以除去氯化铵,并在减压下在353K下蒸发以除去残余溶剂直至形成均匀无色,通过预处理工艺和化学沉积两步制备Ni包覆的In2O3(ZnO)5粉体,在In2O3(ZnO)5粉体上镀Ni的无电沉积在无电镀镍浴中进行,加入离子液体[bmim]BF4添加剂进行Ni涂层In2O3(ZnO)5粉体制备,采用放电等离子(SPS)烧结法将In2O3(ZnO)5粉体和Ni包覆的In2O3(ZnO)5粉体烧结成块体样品。
所述的NH4BF4和[bmim]Cl的摩尔比为1:1。
所述的烧结的温度为800~1000℃。
所述的烧结的时间为1~15min。
所述的烧结后还包括退火步骤。
所述的退火步骤是将烧结后的目标物在空气中退火1~3h以恢复氧的化学计量。
具体操作如下:
以固相法合成In2O3(ZnO)5粉末为前驱粉体,采用溶液法,以NiSO4作为Ni源,NaH2PO2·H2O为还原剂,H3BO3为缓冲物质,加入离子液体[bmim]BF4添加剂进行Ni涂层In2O3(ZnO)5粉体制备,镀镍溶液pH为9。将In2O3(ZnO)5核壳结构粉体置于石墨模具中,采用放电等离子烧结工艺制备出In2O3(ZnO)5粉体和Ni包覆的In2O3(ZnO)5的块体样品。
实验条件如下:固相法合成In2O3(ZnO)5粉末的温度为1523K,溶液法的水浴温度为60℃,搅拌速度为300rpm,镀镍溶液的pH为9。放电等离子烧结技术的温度为1173K,压力为125MPa,致密后退火温度为1173K,时间为1~3小时。
下面以具体实施案例对发明做进一步说明:
实施例1
1.按照In2O3(ZnO)5的化学计量比称取氧化铟和氧化锌,在无水乙醇中混合后,置于球磨机中球磨(球磨机的转速为300r/min,球磨时间为300mim);
2.将步骤1球磨好的溶液置于干燥箱中,温度为70℃,干燥时间为12h;
3. 将步骤2所得的干燥In2O3(ZnO)5粉末研磨并300目过筛备用。
4.将步骤3制得的粉末样品在无电镀镍液中,加入离子液体[bmim]BF4添加剂进行Ni涂层In2O3(ZnO)5粉体制备。
5.将步骤4所得的Ni涂层In2O3(ZnO)5粉体采用放电等离子(SPS)烧结技术在800~1000℃下烧结1~15min得最终样品。
本实施例制备Ni涂层In2O3(ZnO)5样品的示意图如图1所示。
本实施例制备的In2O3(ZnO)5和Ni涂层In2O3(ZnO)5样品的XRD图如图2所示,且从图中可知,试样中无杂相存在。
本实施例制备的Ni涂层In2O3(ZnO)5样品的总热导率,晶格热导率,热电优值ZT以及参考文献对比的ZT图如图3所示。
Claims (10)
1.一种过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法,其特征在于所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法是以固相法合成In2O3(ZnO)5粉末,研磨过筛,然后采用溶液法,以过渡金属盐作为过渡金属源制备得到核壳结构粉体,再通过放电等离子烧结制备得到目标物过渡金属包覆In2O3(ZnO)5核-壳结构热电材料。
2.根据权利要求1所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法,其特征在于所述的过渡金属为Ni、Pb、Cu、Fe、Co、 Mn等。
3.根据权利要求1所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法,其特征在于所述的过渡金属盐为过渡金属硫酸盐。
4.根据权利要求1所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法,其特征在于所述的研磨过筛后的In2O3(ZnO)5粉末粒径为5~200 。
5.根据权利要求1~4任一所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法,其特征在于所述的过渡金属为Ni时,具体的制备过程是以固相法合成In2O3(ZnO)5粉末,由1-甲基咪唑鎓和氯代丁烷在干燥的氩气氛下合成1-丁基-3-甲基咪唑鎓氯化物([bmim]Cl),将NH4BF4加入[bmim]Cl中,303K下经过48小时合成3-甲基咪唑四氟硼酸盐[bmim]BF4离子液体,加入乙腈作为溶剂,然后过滤[bmim]BF4-氯化铵-丙酮混合物以除去氯化铵,并在减压下在353K下蒸发以除去残余溶剂直至形成均匀无色,通过预处理工艺和化学沉积两步制备Ni包覆的In2O3(ZnO)5粉体,在In2O3(ZnO)5粉体上镀Ni的无电沉积在无电镀镍浴中进行,加入离子液体[bmim]BF4添加剂进行Ni涂层In2O3(ZnO)5粉体制备,采用放电等离子(SPS)烧结法将In2O3(ZnO)5粉体和Ni包覆的In2O3(ZnO)5粉体烧结成块体样品。
6.根据权利要求5所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法,其特征在于所述的NH4BF4和[bmim]Cl的摩尔比为1:1。
7.根据权利要求5所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法,其特征在于所述的烧结的温度为800~1000℃。
8.根据权利要求5所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法,其特征在于所述的烧结的时间为1~15min。
9.根据权利要求5所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法,其特征在于所述的烧结后还包括退火步骤。
10.根据权利要求9所述的过渡金属包覆In2O3(ZnO)5核-壳结构热电材料的制备方法,其特征在于所述的退火步骤是将烧结后的目标物在空气中退火1~3h以恢复氧的化学计量。
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