CN107488028A - 一种铑基氧化物热电材料及其制备方法 - Google Patents
一种铑基氧化物热电材料及其制备方法 Download PDFInfo
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- 239000010948 rhodium Substances 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 50
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 47
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 30
- 239000011812 mixed powder Substances 0.000 claims description 28
- 150000002739 metals Chemical class 0.000 claims description 18
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 17
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 210000002381 plasma Anatomy 0.000 claims description 8
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 7
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 3
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 2
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 16
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000010248 power generation Methods 0.000 abstract description 2
- 239000002918 waste heat Substances 0.000 abstract description 2
- 238000004378 air conditioning Methods 0.000 abstract 1
- 238000004891 communication Methods 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000002994 raw material Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 229910019603 Rh2O3 Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- HNWNJTQIXVJQEH-UHFFFAOYSA-N copper rhodium Chemical compound [Cu].[Rh] HNWNJTQIXVJQEH-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
本发明涉及一种铑基氧化物热电材料及其制备方法,属于新能源材料及其制备技术领域。本发明铑基氧化物热电材料的化学通式为ABxRh2‑2xO4;其中x=0.1~0.5,A为元素Cu、Li、Bi、Ca、Zn、Sr、Na或La,B为元素Fe、Co、Ni、Mn、Cr、Mg。该铑基氧化物热电材料粉体混合、预烧结、放电等离子体烧结等步骤制备而成。本发明所述的铑基氧化物热电材料具有耐高温、耐腐蚀、耐氧化性高等特点,可应用在废热发电、空调系统、冷热两用箱、干洗机、医疗保健、生物工程、通讯、航空航天领域等领域。
Description
技术领域
本发明涉及一种铑基氧化物热电材料及其制备方法,属于新能源材料及其制备技术领域。
背景技术
近年来,人口飞速增长及工业迅猛发展,化石燃料过度开采,能源和环境问题越发凸显,能源危机和环境危机已引起各国关注。然而,全球每年消耗的能源中约有70%以废热的形式被浪费掉,如果能将这些废热进行有效的回收利用,将极大的缓解能源短缺的问题。热电材料能直接将热能转换成电能,具有无传动部件、体积小、无噪音、无污染及可靠性好等优点,在汽车废热回收利用,工业余热发电方面有着巨大的应用前景。
热电材料的转换效率由无量纲热电优值ZT(ZT=s2σT/κ,其中s为Seebeck系数、σ为电导率、κ为导热系数、T为绝对温度,s2σ称为功率因子) 决定。ZT越大,材料的热电转换效率越高。由上述方程式所显见;为了改善热电转换材料的性能,需要提高塞贝克系数s和电导率或需要降低导热系数κ。
Martinez H等通过固相反应法,用Mg对CuRhO2的Rh位掺杂,得到一种在1000 K温度下ZT为0.15的热电结构的CuMgxRh1-xO2热电材料,在x=0.05附近,室温下显示出金属-绝缘体的转变,x=0.2时,样品显示低电阻率(4mΩ•cm),高赛贝克系数(130μV/K),功率因子为4225μW/cm.K2,是一种很好的热电材料。
目前对铑基氧化物热电材料研究较少,尚未有简单易行的制备铑基氧化物热电材料的方法。
发明内容
本发明的目的是公开一种铑基氧化物热电材料,其化学通式为ABxRh2-2xO4;其中x=0.1~0.5,A为元素Cu、Li、Bi、Ca、Zn、Sr、Na或La,B为元素Fe、Co、Ni、Mn、Cr、或Mg。
进一步地,A金属元素与铑金属元素的摩尔比为1:(0.5~1),铑金属元素与B金属元素的摩尔比为1:(0.05~0.5)。
本发明的另一目的是提供该铑基氧化物热电材料的制备方法,具体步骤如下:
(1)将氧化铑、A金属的氧化物和B金属的氧化物混合均匀、过筛得到混合粉体A;
(2)将步骤(1)所得混合粉体A进行预烧结、磨碎、过筛得到混合粉体B;
(3)在真空条件下,将步骤(2)所得混合粉体B进行放电等离子体烧结即得铑基氧化物热电材料;
所述过筛的筛网为200~300目筛网;
所述步骤(1)中A金属的氧化物与铑金属的氧化物摩尔比为1:(0.5~1),A金属的氧化物为CuO、Cu2O、Li2O、Bi2O3、CaO、ZnO、SrO、Na2O或La2O3;铑金属的氧化物与B金属的氧化物的摩尔比为1:(0.1~1),B金属的氧化物为Fe2O3、Co2O3、Ni2O3、MnO2、Cr2O3、或MgO;
所述步骤(2)中预烧结的温度为800~1000℃,时间为24~48h;
进一步地,所述步骤(2)中磨碎为球磨,磨球直径为10~20mm,球磨介质为无水乙醇,球磨球、原料和无水乙醇的质量比为6~8:1:1.5~2;球磨机转速为300~500r/min,球磨时间为6~12h;
所述步骤(3)中放电等离子体烧结温度为700~1100℃,时间为10~30min,压力为15-30kN;
进一步地,所述步骤(3)中真空条件的真空度为5x10-3~1x10-2Pa。
本发明的有益效果是:
(1)本发明所述铑基氧化物热电材料具有耐高温、耐腐蚀、耐氧化性高等特点;
(2)本发明方法可制备出质量好的铑基氧化物热电材料;
(3)本发明方法具有工艺流程简单、效率高、生产成本低、对环境无污染的特点。
附图说明
图1为铜铑基氧化物热电材料的结构示意图;
图2为实施例1铑基氧化物热电材料CuMg0.1Rh1.8O4的XRD图;
图3为实施例1~5的铑基氧化物热电材料的ZT值。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1:一种铑基氧化物热电材料CuMg0.1Rh1.8O4的制备方法,具体步骤如下:
(1)称取0.8g氧化铜(CuO)、0.04g氧化镁(MgO)、2.54g氧化铑(Rh2O3),即A金属的氧化物(氧化铜)与氧化铑的摩尔比为1:1,氧化铑与B金属的氧化物(氧化镁)的摩尔比为1:0.1;然后将粉体置于玛瑙球磨罐中,按照球磨球、原料和无水乙醇的质量比为6:1:1.5的比例,加入玛瑙磨球和无水乙醇,在转速300r/min磨球机上进行球磨12h将其粉体混合均匀,过200目筛网得到混合粉体A;
(2)将步骤(1)所得混合粉体A置于箱式电阻炉中,设定升温速率为5℃/min,加热至温度为940℃,并进行恒温预烧结36h,随炉冷却至室温,将预烧结产物置于玛瑙球磨罐中,按照球磨球、原料和无水乙醇的质量比为6:1:1.5的比例,加入玛瑙球磨球和无水乙醇,在磨球机上,转速300r/min进行球磨6h将其粉体混合均匀,在过200目筛网得到混合粉体B;
(3)将步骤(2)所得混合粉体B置于石墨模具中,然后再置于放电等离子(SPS)烧结炉中,抽真空至真空度为5x10-3pa,设定升温速率为60℃/min,加热至温度为720℃,压力为15kN,恒温烧结10min,随炉冷却至室温即得铑基氧化物热电材料CuMg0.1Rh1.8O4;
本实施例铜铑基氧化物热电材料的结构示意图如图1所示,从图1可知,铜铑基氧化物热电材料由Cu2+和RhO单元沿c轴交替叠加组成,具有热电材料层状分布的结构特点;
本实施例铑基氧化物热电材料CuMg0.1Rh1.8O4的XRD图如图2所示,从图2可知, Mg的掺杂量摩尔比为0.1时,与标准CuRh2O4的标准PDF卡片衍射峰位置相吻合,并无明显杂相峰,说明通过SPS烧结工艺,掺杂效果较好,已完成单一物相的制备;
本实施例铑基氧化物热电材料CuMg0.1Rh1.8O4的ZT值如图3所示,从图3可知,CuMg0.1Rh1.8O4的ZT值随着温度的上升而增大,在温度900℃时可达到0.31。
实施例2:一种铑基氧化物热电材料CaMn0.2Rh1.6O4的制备方法,具体步骤如下:
(1)称取0.56g氧化钙(CaO)、0.087g二氧化锰(MnO2)、2.413g氧化铑(Rh2O3),即A金属的氧化物(氧化钙)与氧化铑的摩尔比为1:0.8,B金属的氧化物(二氧化锰)与氧化铑的摩尔比为1: 0.125;然后将粉体置于玛瑙球磨罐中,按照球磨球、原料和无水乙醇的质量比为6:1:1.5的比例,加入玛瑙球磨球和无水乙醇,在转速400r/min磨球机上进行球磨12h将其粉体混合均匀,过200目筛网得到混合粉体A;
(2)将步骤(1)所得混合粉体A置于箱式电阻炉中,设定升温速率为5℃/min,加热至温度为930℃,并进行恒温预烧结48h,随炉冷却至室温,将预烧结产物置于玛瑙球磨罐中,按照球磨球、原料和无水乙醇的质量比为6:1:1.5的比例,加入玛瑙球磨球和无水乙醇,在磨球机上,转速300r/min进行球磨12h将其粉体混合均匀,过200目筛网得到混合粉体B;
(3)将步骤(2)所得混合粉体B置于石墨模具中,然后再置于放电等离子(SPS)烧结炉中,抽真空至真空度为6x10-3pa,设定升温速率为50℃/min,加热至温度为850℃,压力为20kN,恒温烧结30min,随炉冷却至室温即得铑基氧化物热电材料CaMn0.2Rh1.6O4;
本实施例铑基氧化物热电材料CaMn0.2Rh1.6O4的ZT值如图3所示,从图3可知,CaMn0.2Rh1.6O4的ZT值也是随着温度的上升而增大,在温度900℃时达到0.40。
实施例3:一种铑基氧化物热电材料ZnCo0.2Rh1.6O4的制备方法,具体步骤如下:
(1)称取0.83g氧化锌(ZnO)、0.164g氧化钴(Co2O3)、2.413g氧化铑(Rh2O3),即A金属的氧化物(氧化锌)与氧化铑的摩尔比为1:0.8,B金属的氧化物(氧化钴)与氧化铑的摩尔比为1:0.125;然后将粉体置于玛瑙球磨罐中,按照球磨球、原料和无水乙醇的质量比为6:1:1.5的比例,加入玛瑙球磨球和无水乙醇,在转速300r/min磨球机上进行球磨10h将其粉体混合均匀,过200目筛网得到混合粉体A;
(2)将步骤(1)所得混合粉体A置于箱式电阻炉中,设定升温速率为5℃/min,加热至温度为900℃,并进行恒温预烧结36h,随炉冷却至室温,将预烧结产物置于玛瑙球磨罐中,按照球磨球、原料和无水乙醇的质量比为6:1:1.5的比例,加入玛瑙球磨球和无水乙醇,在磨球机上,转速300r/min进行球磨12h将其粉体混合均匀,过300目筛网得到混合粉体B;
(3)将步骤(2)所得混合粉体B置于石墨模具中,然后再置于放电等离子(SPS)烧结炉中,抽真空至真空度为1x10-2pa,设定升温速率为100℃/min,加热至温度为1000℃,压力为25kN,恒温烧结20min,随炉冷却至室温即得铑基氧化物热电材料ZnCo0.3Rh1.4O4;
本实施例铑基氧化物热电材料ZnCo0.2Rh1.6O4的ZT值如图3所示,从图3可知,ZnCo0.2Rh1.6O4的ZT值随着温度的上升而增大,在温度900℃时达到0.43。
实施例4:一种铑基氧化物热电材料CuCr0.4Rh1.2O4的制备方法,具体步骤如下:
(1)称取1.44g氧化亚铜(Cu2O)、0.152g氧化铬(Cr2O3)、2.413g氧化铑(Rh2O3),即A金属的氧化物(氧化亚铜)与氧化铑的摩尔比为1:0.6,B金属的氧化物(氧化铬)与氧化铑的摩尔比为1:0.35;然后将粉体置于玛瑙球磨罐中,按照球磨球、原料和无水乙醇的质量比为6:1:1.5的比例,加入玛瑙球磨球和无水乙醇,在转速300r/min磨球机上进行球磨12h将其粉体混合均匀,过200目筛网得到混合粉体A;
(2)将步骤(1)所得混合粉体A置于箱式电阻炉中,设定升温速率为5℃/min,加热至温度为850℃,并进行恒温预烧结48h,随炉冷却至室温,将预烧结产物置于玛瑙球磨罐中,按照球磨球、原料和无水乙醇的质量比为6:1:1.5的比例,加入玛瑙球磨球和无水乙醇,在磨球机上,转速300r/min进行球磨12h将其粉体混合均匀,过250目筛网得到混合粉体B;
(3)将步骤(2)所得混合粉体B置于石墨模具中,然后再置于放电等离子(SPS)烧结炉中,抽真空至真空度为5x10-3pa,设定升温速率为50℃/min,加热至温度为950℃,压力为20kN,恒温烧结30min,随炉冷却至室温即得铑基氧化物热电材料CuCr0.4Rh1.2O4;
本实施例铑基氧化物热电材料CuCr0.4Rh1.2O4的ZT值图如图3所示,从图3可知,CuCr0.4Rh1.2O4的ZT值随着温度的上升而增大,在温度900℃时达到0.55。
实施例5:一种铑基氧化物热电材料SrNi0.5RhO4的制备方法,具体步骤如下:
(1)称取1.04g氧化锶(SrO)、0.164g氧化镍(Ni2O3)、2.413g氧化铑(Rh2O3),即A金属的氧化物(氧化锶)与氧化铑的摩尔比为1:0.5,B金属的氧化物(氧化镍)与氧化铑的摩尔比为1:1;然后将粉体置于玛瑙球磨罐中,按照球磨球、原料和无水乙醇的质量比为6:1:1.5的比例,加入玛瑙球磨球和无水乙醇,在磨球机上,转速500r/min进行球磨12h将其粉体混合均匀,过200目筛网得到混合粉体A;
(2)将步骤(1)所得混合粉体A置于箱式电阻炉中,设定升温速率为5℃/min,加热至温度为800℃,并进行恒温预烧结36h,随炉冷却至室温,将预烧结产物置于玛瑙球磨罐中,按照球磨球、原料和无水乙醇的质量比为6:1:1.5的比例,加入玛瑙球磨球和无水乙醇,在磨球机上,转速300r/min进行球磨12h将其粉体混合均匀,过200目筛网得到混合粉体B;
(3)将步骤(2)所得混合粉体B置于石墨模具中,然后再置于放电等离子(SPS)烧结炉中,抽真空至真空度为8x10-3pa,设定升温速率为100℃/min,加热至温度为900℃,压力为30kN,恒温烧结20min,随炉冷却至室温即得铑基氧化物热电材料SrNi0.5RhO4;
本实施例铑基氧化物热电材料SrNi0.5RhO4的ZT值如图3所示,从图3可知, SrNi0.5RhO4的ZT值随着温度的上升而增大,在温度900℃时达到0.46。
Claims (6)
1.一种铑基氧化物热电材料,其特征在于,其化学通式为ABxRh2-2xO4;其中x=0.1~0.5,A为元素Cu、Li、Bi、Ca、Zn、Sr、Na或La,B为元素Fe、Co、Ni、Mn、Cr、或Mg。
2.根据权利要求1所述的铑基氧化物热电材料,其特征在于:A金属元素与铑金属元素的摩尔比为1:(0.5~1),铑金属元素与B金属元素的摩尔比为1:(0.05~0.5)。
3.如权利要求1所述的铑基氧化物热电材料的制备方法,其特征在于,具体步骤如下:
(1)将氧化铑、A金属的氧化物和B金属的氧化物混合均匀、过筛得到混合粉体A;
(2)将步骤(1)所得混合粉体A进行预烧结、磨碎、过筛得到混合粉体B;
(3)在真空条件下,将步骤(2)所得混合粉体B进行放电等离子体烧结即得铑基氧化物热电材料。
4.根据权利要求3所述的铑基氧化物热电材料的制备方法,其特征在于:步骤(1)中A金属的氧化物与铑金属的氧化物的摩尔比为1:(0.5~1),A金属的氧化物为CuO、Cu2O、Li2O、Bi2O3、CaO、ZnO、SrO、Na2O或La2O3;铑金属的氧化物与B金属的氧化物的摩尔比为1:(0.1~1),B金属的氧化物为Fe2O3、Co2O3、Ni2O3、MnO2、Cr2O3、或MgO。
5.根据权利要求3或4所述的铑基氧化物热电材料的制备方法,其特征在于:步骤(2)中预烧结的温度为800~1000℃,时间为24~48h。
6.根据权利要求3所述的铑基氧化物热电材料的制备方法,其特征在于:步骤(3)中放电等离子体烧结温度为700~1100℃,时间为10~30min,压力为15~30kN。
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