JP2016048730A - Thermoelectric conversion material - Google Patents
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- JP2016048730A JP2016048730A JP2014173148A JP2014173148A JP2016048730A JP 2016048730 A JP2016048730 A JP 2016048730A JP 2014173148 A JP2014173148 A JP 2014173148A JP 2014173148 A JP2014173148 A JP 2014173148A JP 2016048730 A JP2016048730 A JP 2016048730A
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- 239000000463 material Substances 0.000 title claims abstract description 119
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 113
- 239000010949 copper Substances 0.000 claims abstract description 64
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 230000007704 transition Effects 0.000 claims abstract description 9
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 53
- 238000002441 X-ray diffraction Methods 0.000 claims description 11
- 238000001228 spectrum Methods 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 abstract description 24
- 239000011593 sulfur Substances 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 239000000306 component Substances 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 33
- 239000010936 titanium Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 16
- 239000011135 tin Substances 0.000 description 14
- 229910052719 titanium Inorganic materials 0.000 description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000005485 electric heating Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 229910052718 tin Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- YTYSNXOWNOTGMY-UHFFFAOYSA-N lanthanum(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[La+3].[La+3] YTYSNXOWNOTGMY-UHFFFAOYSA-N 0.000 description 6
- -1 rare earth sulfide Chemical class 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- 229910052714 tellurium Inorganic materials 0.000 description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 4
- 239000002918 waste heat Substances 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical group [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、熱電変換材料に関する。 The present invention relates to a thermoelectric conversion material.
従来、ゼーベック効果により材料両端の温度差によって電流を生じさせ熱エネルギーを電気エネルギーに変換する、又は、ペルチェ効果により電気エネルギーによって温度差を生じさせる熱電変換材料が知られている。熱電変換材料としては、熱エネルギーの高い方から低い方へ電子の移動により電流が生じるｎ型熱電変換材料と、正孔の移動により電流が生じるｐ型熱電変換材料とが存在する。 Conventionally, thermoelectric conversion materials are known in which a current is generated by a temperature difference between both ends of a material by the Seebeck effect and heat energy is converted into electric energy, or a temperature difference is generated by electric energy by a Peltier effect. As the thermoelectric conversion material, there are an n-type thermoelectric conversion material in which an electric current is generated by movement of electrons from a higher heat energy to a lower one, and a p-type thermoelectric conversion material in which an electric current is generated by movement of holes.
近年では、未利用エネルギーを有効利用するために、熱電変換材料を用いて廃熱を電気エネルギーに変換する技術の開発が進められている。未利用の廃熱の多くは、２００℃以下の比較的低温の廃熱である。このため、３００℃以下、好ましくは２００℃以下の比較的低温の温度領域において高い活性を有する熱電変換材料が望まれている。比較的低温の温度領域で高い活性を示す熱電変換材料としては、テルル（Ｔｅ）とビスマス（Ｂｉ）との化合物又はテルルとアンチモン（Ｓｂ）との化合物等が知られている。しかし、テルル及びアンチモンは、毒性が高いという問題を有している。そこで、テルル及びアンチモン等の毒性が疑われる元素を用いない熱電変換材料として、例えば、金属硫化物に関する検討が行われている。 In recent years, in order to effectively use unused energy, development of technology for converting waste heat into electrical energy using a thermoelectric conversion material has been advanced. Most of the unused waste heat is relatively low-temperature waste heat of 200 ° C. or lower. For this reason, a thermoelectric conversion material having high activity in a relatively low temperature range of 300 ° C. or lower, preferably 200 ° C. or lower is desired. Known thermoelectric conversion materials exhibiting high activity in a relatively low temperature range include a compound of tellurium (Te) and bismuth (Bi) or a compound of tellurium and antimony (Sb). However, tellurium and antimony have a problem of high toxicity. Thus, for example, metal sulfides have been studied as thermoelectric conversion materials that do not use elements that are suspected of toxicity such as tellurium and antimony.
特許文献１には、熱電変換材料用硫化ランタン焼結体が記載されている。この熱電変換材料用硫化ランタン焼結体は、β型硫化ランタン粉末と金属パラジウム粒を混合して焼結した、結晶構造がβ型を主成分とし、微量のγ型成分を有する硫化ランタン焼結体である。また、この熱電変換材料用硫化ランタン焼結体は、１〜５質量％の金属パラジウムを含有している。さらに、この熱電変換材料用硫化ランタン焼結体の比抵抗は１００ｋΩ・ｃｍ以下である。 Patent Document 1 describes a lanthanum sulfide sintered body for a thermoelectric conversion material. This lanthanum sulfide sintered compact for thermoelectric conversion materials is a sintered lanthanum sulfide having a β-type lanthanum sulfide powder and metallic palladium particles mixed and sintered, the crystal structure of which is β-type as a main component and a small amount of γ-type components Is the body. Moreover, this lanthanum sulfide sintered compact for thermoelectric conversion materials contains 1-5 mass% metallic palladium. Furthermore, the specific resistance of the lanthanum sulfide sintered body for thermoelectric conversion material is 100 kΩ · cm or less.
特許文献２には、熱電変換材料として利用可能な希土類硫化物焼結体が記載されている。この希土類硫化物焼結体は、正方晶の希土類三二硫化物にチタンを０．１ｗｔ％から２０ｗｔ％の範囲で添加して焼結して得られる。また、この希土類硫化物焼結体は、正方晶から変態した相を有する。 Patent Document 2 describes a rare earth sulfide sintered body that can be used as a thermoelectric conversion material. This rare earth sulfide sintered body is obtained by adding titanium to tetragonal rare earth tridisulfide in the range of 0.1 wt% to 20 wt% and sintering. The rare earth sulfide sintered body has a phase transformed from tetragonal crystal.
特許文献３には、パイライト構造を有するｐ型の熱電変換材料が記載されている。この熱電変換材料の組成は、Ｆｅ1-xＭxＳ2-yＴyで表わされる。元素ＭはＶ、Ｃｒ、Ｍｎ、Ｚｒ、Ｎｂ、Ｍｏ、Ｈｆ、Ｔａ、Ｗから選ばれる少なくとも一種類の元素であり、元素ＴはＢ、Ｃ、Ａｌ、Ｓｉ、Ｇｅ、Ｓｎ、Ｎ、Ｏ、Ｐ、Ｂｉから選ばれる少なくとも１種類の元素である。また、ｘ及びｙは、０＜ｘ＜０．５、０＜ｙ＜１の条件を満たす。 Patent Document 3 describes a p-type thermoelectric conversion material having a pyrite structure. The composition of this thermoelectric conversion material is represented by Fe 1-x M x S 2-y T y . The element M is at least one element selected from V, Cr, Mn, Zr, Nb, Mo, Hf, Ta, and W, and the element T is B, C, Al, Si, Ge, Sn, N, O, At least one element selected from P and Bi. X and y satisfy the conditions of 0 <x <0.5 and 0 <y <1.
特許文献４には、ＣｄＩ2類縁型層状構造を有する熱電変換材料が記載されている。この熱電変換材料は、一般式ＡXＢＣ2-y（０≦ｘ≦２、０≦ｙ＜１）で表される。実施例としては、Ｂサイトがチタン（Ｔｉ）によって占有され、Ｃサイトが硫黄（Ｓ）によって占有された材料が記載されている。また、実施例として、Ａサイトが銅（Ｃｕ）によって占有されている材料が記載されている。 Patent Document 4 describes a thermoelectric conversion material having a CdI 2 -related layered structure. This thermoelectric conversion material is represented by the general formula A X BC 2-y (0 ≦ x ≦ 2, 0 ≦ y <1). As an example, a material in which the B site is occupied by titanium (Ti) and the C site is occupied by sulfur (S) is described. Further, as an example, a material in which the A site is occupied by copper (Cu) is described.
特許文献５には、一般式（ＡＣ）m（ＢＣ2）nで表され、ＮａＣｌ類縁型のＡＣ層とＣｄＩ2類縁型のＢＣ2層が格子不整合で積層したミスフィット構造を持つ熱電変換材料が記載されている。Ａはスズ（Ｓｎ）を、Ｂはチタン（Ｔｉ）を、Ｃは硫黄（Ｓ）を表し、０．５≦ｍ≦１．５、ｎ＝１、２、３、４又は５である。実施例として、Ｂサイトの一部が銅（Ｃｕ）に置換された材料及びＢＣ2層同士が積層した層間のインターカレーション可能なサイトであるＤサイトに銅（Ｃｕ）が配置された材料が記載されている。 Patent Document 5 discloses a thermoelectric conversion represented by the general formula (AC) m (BC 2 ) n and having a misfit structure in which an NaCl-like AC layer and a CdI 2 -like BC 2 layer are laminated in a lattice mismatch. The materials are listed. A represents tin (Sn), B represents titanium (Ti), C represents sulfur (S), and 0.5 ≦ m ≦ 1.5 and n = 1, 2, 3, 4, or 5. As an example, there is a material in which a part of the B site is replaced with copper (Cu) and a material in which copper (Cu) is disposed at the D site, which is an intercalable site between the layers in which the BC 2 layers are laminated. Have been described.
特許文献６には、熱電変換材料として有用な複合金属硫化物の製造方法が記載されている。実施例として、複合金属硫化物であるＮｄＣｕＳ2の単相を生成する方法及びＮｄＣｕＳ2の結晶構造を保っている非化学量論比のＮｄ0.5ＣｕＳ2を生成する方法が記載されている。 Patent Document 6 describes a method for producing a composite metal sulfide useful as a thermoelectric conversion material. As an example, a method for producing a single phase of NdCuS 2 which is a composite metal sulfide and a method for producing a non-stoichiometric ratio of Nd 0.5 CuS 2 while maintaining the crystal structure of NdCuS 2 are described.
非特許文献１には、Ｃｕ2Ｓ、Ｃｕ1.98Ｓ、及びＣｕ1.97Ｓに関し、電気伝導度及びゼーベック係数と、温度との関係が記載されている。 Non-Patent Document 1 describes the relationship between electrical conductivity, Seebeck coefficient, and temperature for Cu 2 S, Cu 1.98 S, and Cu 1.97 S.
特許文献４〜６及び非特許文献１に記載されているように、熱電変換材料として、銅（Ｃｕ）を含む金属硫化物を用いることが考えられる。特許文献４に記載の熱電変換材料は、ＣｄＩ2類縁型層状構造を有するので、層同士の間で剥離などが起こりやすく、機械的強度が十分でない可能性がある。また、層状構造は異方性が高いので単結晶を用いて材料を構成する必要があり、特許文献４に記載の熱電変換材料の量産には困難が伴う可能性が有る。さらに、特許文献４に記載の熱電変換材料は、その構造に起因して、熱電変換材料の特性の異方性が高い可能性がある。特許文献５に記載の熱電変換材料は、ＮａＣｌ類縁型の層とＣｄＩ2類縁型の層が格子不整合で積層したミスフィット構造を持つので、層同士の間で剥離などが起こりやすく、機械的強度が十分でない可能性がある。また、特許文献５に記載の熱電変換材料は、その構造に起因して、熱電変換材料の特性の異方性が高い可能性がある。 As described in Patent Documents 4 to 6 and Non-Patent Document 1, it is conceivable to use a metal sulfide containing copper (Cu) as the thermoelectric conversion material. Since the thermoelectric conversion material described in Patent Document 4 has a CdI 2 -related layered structure, peeling or the like is likely to occur between layers, and mechanical strength may not be sufficient. In addition, since the layered structure has high anisotropy, it is necessary to form the material using a single crystal, and mass production of the thermoelectric conversion material described in Patent Document 4 may be difficult. Furthermore, the thermoelectric conversion material described in Patent Document 4 may have high anisotropy in characteristics of the thermoelectric conversion material due to its structure. The thermoelectric conversion material described in Patent Document 5 has a misfit structure in which a NaCl-related layer and a CdI 2 -related layer are laminated in a lattice mismatch, so that peeling or the like easily occurs between the layers. The strength may not be sufficient. In addition, the thermoelectric conversion material described in Patent Document 5 may have high anisotropy in characteristics of the thermoelectric conversion material due to its structure.
特許文献６に記載の方法で、複合金属硫化物であるＮｄＣｕＳ2の単相を生成する場合、希少元素であるネオジム（Ｎｄ）を使用するので、熱電変換材料の製造コストが高くなってしまう可能性がある。 When a single phase of NdCuS 2 that is a composite metal sulfide is generated by the method described in Patent Document 6, neodymium (Nd) that is a rare element is used, which may increase the manufacturing cost of the thermoelectric conversion material. There is sex.
非特許文献１に記載された硫化銅は、銅（Ｃｕ）と硫黄（Ｓ）との２つの元素による化合物であるので、この硫化銅で熱電変換材料を量産する場合、銅（Ｃｕ）と硫黄（Ｓ）との量論比を一定に制御することが難しい。このため、非特許文献１に記載された硫化銅は、熱電変換材料としては、量産性の観点から改良の余地を有する。 Since the copper sulfide described in Non-Patent Document 1 is a compound of two elements of copper (Cu) and sulfur (S), when mass-producing a thermoelectric conversion material with this copper sulfide, copper (Cu) and sulfur It is difficult to keep the stoichiometric ratio with (S) constant. For this reason, the copper sulfide described in Non-Patent Document 1 has room for improvement as a thermoelectric conversion material from the viewpoint of mass productivity.
そこで、本発明は、銅（Ｃｕ）を含む金属硫化物でできており、高い機械的強度、低い製造コスト、及び優れた量産性を有する熱電変換材料を提供することを目的とする。 Therefore, an object of the present invention is to provide a thermoelectric conversion material that is made of a metal sulfide containing copper (Cu) and has high mechanical strength, low manufacturing cost, and excellent mass productivity.
本発明は、
立方晶、六方晶、正方晶、斜方晶、又は三方晶の結晶構造を有し、銅と、第１遷移元素又はｐブロック元素である、銅以外の少なくとも一つの金属とを主成分として含む複合金属硫化物でできた、熱電変換材料を提供する。
The present invention
It has a cubic, hexagonal, tetragonal, orthorhombic, or trigonal crystal structure, and contains copper and at least one metal other than copper, which is a first transition element or p-block element, as main components. A thermoelectric conversion material made of a composite metal sulfide is provided.
本発明によれば、熱電変換材料が、立方晶、六方晶、正方晶、斜方晶、又は三方晶の結晶構造を有する複合金属硫化物でできているので、熱電変換材料が高い機械的強度を有する。また、本発明の熱電変換材料は、異方性の低い構造を有するので、単結晶の状態で熱電変換材料を製造せずとも高い出力因子を示すことができる。さらに、熱電変換材料が、銅と、第１遷移元素又はｐブロック元素である、銅以外の少なくとも一つの金属とを主成分として含む複合金属硫化物でできているので、製造コストが低く、かつ、量産性に優れる。 According to the present invention, since the thermoelectric conversion material is made of a composite metal sulfide having a cubic, hexagonal, tetragonal, orthorhombic, or trigonal crystal structure, the thermoelectric conversion material has high mechanical strength. Have Moreover, since the thermoelectric conversion material of this invention has a structure with low anisotropy, it can show a high output factor, without manufacturing a thermoelectric conversion material in the state of a single crystal. Furthermore, since the thermoelectric conversion material is made of a composite metal sulfide containing, as a main component, copper and at least one metal other than copper, which is the first transition element or p-block element, the manufacturing cost is low, and Excellent in mass productivity.
以下、本発明の実施形態について説明する。なお、以下の説明は本発明の一例に関するものであり、本発明はこれらによって限定されるものではない。 Hereinafter, embodiments of the present invention will be described. The following description relates to an example of the present invention, and the present invention is not limited to these.
本発明に係る熱電変換材料は、複合金属硫化物でできている。この複合金属硫化物は、立方晶、六方晶、正方晶、斜方晶、又は三方晶の結晶構造を有する。これにより、熱電変換材料が高い機械的強度を有する。なぜなら、層状構造を有する構造などと異なり、剥離が生じにくいと考えられるからである。また、熱電変換材料が立体的に対称性の高い結晶構造を有するので、熱電変換材料の特性の異方性が小さい。そのため、熱電変換材料の特性の異方性を調整するために単結晶の状態で熱電変換材料を製造する必要がなく、熱電変換材料の量産が容易である。また、熱電変換材料を単結晶の状態で製造する必要がないので、ナノ粒子の焼結体として熱電変換材料を製造した場合でも、熱電変換材料の出力因子は、単結晶で構成された熱電変換材料の出力因子よりわずかに低いにすぎない。また、ナノ粒子の焼結体として製造された熱電変換材料は、単結晶で構成された熱電変換材料に比べて、フォノンを効果的に散乱させることができる。換言すると、ナノ粒子の焼結体として製造された熱電変換材料は、低い熱伝導率を示しやすい。このため、ナノ粒子の焼結体として製造された熱電変換材料は、高い性能指数を示しやすい。このように、本発明に係る熱電変換材料の特性の異方性が低いことにより、熱電変換材料を構成する粒子のサイズ又は形状を自由に調整することができることで、熱電変換材料素子を作製する際の形状などの制約が少なくなり、高い性能指数を確保しつつ多様な素子を作ることができる。 The thermoelectric conversion material according to the present invention is made of a composite metal sulfide. The composite metal sulfide has a cubic, hexagonal, tetragonal, orthorhombic, or trigonal crystal structure. Thereby, the thermoelectric conversion material has high mechanical strength. This is because, unlike a structure having a layered structure, it is considered that peeling is unlikely to occur. In addition, since the thermoelectric conversion material has a three-dimensionally symmetric crystal structure, the anisotropy of the characteristics of the thermoelectric conversion material is small. Therefore, it is not necessary to manufacture the thermoelectric conversion material in a single crystal state in order to adjust the anisotropy of the characteristics of the thermoelectric conversion material, and mass production of the thermoelectric conversion material is easy. In addition, since it is not necessary to manufacture the thermoelectric conversion material in a single crystal state, even when the thermoelectric conversion material is manufactured as a nanoparticle sintered body, the output factor of the thermoelectric conversion material is a thermoelectric conversion composed of a single crystal. It is only slightly lower than the power factor of the material. Moreover, the thermoelectric conversion material manufactured as a nanoparticle sintered body can scatter phonons more effectively than a thermoelectric conversion material composed of a single crystal. In other words, the thermoelectric conversion material manufactured as a nanoparticle sintered body tends to exhibit low thermal conductivity. For this reason, the thermoelectric conversion material manufactured as a nanoparticle sintered compact tends to show a high figure of merit. Thus, the thermoelectric conversion material element is produced by having the low anisotropy of the characteristics of the thermoelectric conversion material according to the present invention, so that the size or shape of the particles constituting the thermoelectric conversion material can be freely adjusted. There are fewer restrictions on the shape of the pattern, and various elements can be made while ensuring a high figure of merit.
複合金属硫化物は、銅（Ｃｕ）と、第１遷移元素又はｐブロック元素である、銅（Ｃｕ）以外の少なくとも一つの金属と、硫黄とを主成分として含む。ここで、「主成分」とは、複合金属硫化物において、少なくとも５重量％以上、好ましくは１０重量％以上含まれる元素を意味する。複合金属硫化物に主成分として含まれる銅（Ｃｕ）以外の第１遷移元素としては、スカンジウム（Ｓｃ）、チタン（Ｔｉ）、バナジウム（Ｖ）、クロム（Ｃｒ）、マンガン（Ｍｎ）、鉄（Ｆｅ）、コバルト（Ｃｏ）、又はニッケル（Ｎｉ）を挙げることができる。複合金属硫化物に主成分として含まれる銅（Ｃｕ）以外の第１遷移元素は、好ましくは、チタン、バナジウム、クロム、マンガン、鉄、コバルト、又はニッケルである。複合金属硫化物に主成分として含まれるｐブロック元素である、銅（Ｃｕ）以外の金属としては、アルミニウム（Ａｌ）、ガリウム（Ｇａ）、インジウム（Ｉｎ）、スズ（Ｓｎ）、タリウム（Ｔｌ）、鉛（Ｐｂ）、又はビスマス（Ｂｉ）を挙げることができる。複合金属硫化物に主成分として含まれるｐブロック元素は、好ましくは、アルミニウム、ガリウム、インジウム、又はスズである。複合金属硫化物に、銅と、銅以外の金属とが主成分として含まれていることにより、熱電変換材料を量産する際に、複合金属硫化物における各元素の量論比を一定に制御しやすい。このため、本発明の熱電変換材料が量産性に優れる。また、複合金属硫化物に主成分として含まれる銅以外の金属が第１遷移元素又はｐブロック元素であると、第１遷移元素及びｐブロック元素の多くは比較的入手しやすいので、熱電変換材料の製造コストを低減できる。複合金属硫化物に主成分として含まれる銅以外の金属は、望ましくは、４価の金属である。４価の金属としては、チタン又はスズを挙げることができる。 The composite metal sulfide contains copper (Cu), at least one metal other than copper (Cu), which is the first transition element or p-block element, and sulfur as main components. Here, the “main component” means an element contained in the composite metal sulfide at least 5 wt% or more, preferably 10 wt% or more. As the first transition element other than copper (Cu) contained as a main component in the composite metal sulfide, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron ( Fe), cobalt (Co), or nickel (Ni). The first transition element other than copper (Cu) contained as a main component in the composite metal sulfide is preferably titanium, vanadium, chromium, manganese, iron, cobalt, or nickel. Examples of metals other than copper (Cu), which are p-block elements contained as a main component in the composite metal sulfide, include aluminum (Al), gallium (Ga), indium (In), tin (Sn), and thallium (Tl). , Lead (Pb), or bismuth (Bi). The p block element contained as a main component in the composite metal sulfide is preferably aluminum, gallium, indium, or tin. Because the composite metal sulfide contains copper and metals other than copper as the main components, the stoichiometric ratio of each element in the composite metal sulfide is controlled to be constant when mass-producing thermoelectric conversion materials. Cheap. For this reason, the thermoelectric conversion material of this invention is excellent in mass-productivity. In addition, when the metal other than copper contained as a main component in the composite metal sulfide is the first transition element or the p block element, most of the first transition element and the p block element are relatively easily available. The manufacturing cost can be reduced. The metal other than copper contained as a main component in the composite metal sulfide is desirably a tetravalent metal. Examples of the tetravalent metal include titanium and tin.
複合金属硫化物に主成分として含まれる銅以外の金属は、望ましくは、コバルト（Ｃｏ）、チタン（Ｔｉ）、鉄（Ｆｅ）、亜鉛（Ｚｎ）、スズ（Ｓｎ）、アルミニウム（Ａｌ）、及びインジウム（Ｉｎ）からなる群から選ばれる少なくとも１つの金属である。 The metals other than copper contained as a main component in the composite metal sulfide are desirably cobalt (Co), titanium (Ti), iron (Fe), zinc (Zn), tin (Sn), aluminum (Al), and It is at least one metal selected from the group consisting of indium (In).
複合金属硫化物は、上記の金属のうち２種類以上の金属を、銅以外の金属の主成分として含んでいてもよい。複合金属硫化物に主成分として含まれる銅以外の２種類の金属の組み合わせとしては、例えば、コバルト（Ｃｏ）とチタン（Ｔｉ）との組み合わせ、鉄（Ｆｅ）とスズ（Ｓｎ）との組み合わせ、鉄（Ｆｅ）とチタン（Ｔｉ）との組み合わせ、又は亜鉛（Ｚｎ）とチタン（Ｔｉ）との組み合わせを挙げることができる。 The composite metal sulfide may contain two or more kinds of metals among the above metals as main components of metals other than copper. As a combination of two kinds of metals other than copper contained as a main component in the composite metal sulfide, for example, a combination of cobalt (Co) and titanium (Ti), a combination of iron (Fe) and tin (Sn), A combination of iron (Fe) and titanium (Ti) or a combination of zinc (Zn) and titanium (Ti) can be given.
複合金属硫化物において、銅（Ｃｕ）の含有量は、例えば、５重量％以上９０重量％以下であり、好ましくは、１０重量％以上８０重量％以下であり、より好ましくは１５重量％以上７０重量％以下である。 In the composite metal sulfide, the content of copper (Cu) is, for example, 5 wt% or more and 90 wt% or less, preferably 10 wt% or more and 80 wt% or less, more preferably 15 wt% or more and 70 wt% or less. % By weight or less.
熱電変換材料の性能を示す指標の一つとして無次元性能指数ＺＴが知られている。ここで、Ｚは性能指数を意味し、Ｋ-1の次元を有する。また、Ｔは絶対温度を意味する。無次元性能指数ＺＴの値が大きいほど、熱電変換材料が高い性能を示す。熱電変換材料の無次元性能指数ＺＴは、以下の式（１）で定義される。α、σ、及びκは、それぞれ、熱電変換材料の、ゼーベック係数、電気伝導率、及び熱伝導率を意味する。
ＺＴ＝α2σＴ／κ （１）
また、熱電変換材料の性能を示す別の指標として、出力因子（パワーファクター）Ｐが知られている。熱電変換材料の出力因子Ｐは、以下の式（２）で定義される。
Ｐ＝α2σ （２）
A dimensionless figure of merit ZT is known as one of the indexes indicating the performance of thermoelectric conversion materials. Here, Z means a figure of merit and has a dimension of K- 1 . T means absolute temperature. The larger the dimensionless figure of merit ZT, the higher the performance of the thermoelectric conversion material. The dimensionless figure of merit ZT of the thermoelectric conversion material is defined by the following formula (1). α, σ, and κ mean the Seebeck coefficient, electrical conductivity, and thermal conductivity of the thermoelectric conversion material, respectively.
ZT = α 2 σT / κ (1)
Further, as another index indicating the performance of the thermoelectric conversion material, an output factor (power factor) P is known. The output factor P of the thermoelectric conversion material is defined by the following formula (2).
P = α 2 σ (2)
式（１）から分かるように、無次元性能指数ＺＴを向上させるためには、熱伝導率κを低減させることが望ましい。熱伝導率κを低減させる方法の一つとして、熱電変換材料の結晶子サイズを所定の範囲とすることが考えられる。この観点から、焼結体のＸ線回折スペクトルのメインピークからScherrerの式を用いて求まる熱電変換材料の結晶子サイズは、１０００ｎｍ以下であることが望ましい。また、熱電変換材料の結晶子サイズは、１ｎｍ〜５００ｎｍであることが望ましく、２ｎｍ〜２００ｎｍであることがより望ましく、５ｎｍ〜１００ｎｍであることがさらに望ましい。これにより、熱電変換材料の熱伝導率κを低減して、熱電変換材料の性能を高めることができる。 As can be seen from Equation (1), in order to improve the dimensionless figure of merit ZT, it is desirable to reduce the thermal conductivity κ. As one method for reducing the thermal conductivity κ, it can be considered that the crystallite size of the thermoelectric conversion material is set within a predetermined range. From this viewpoint, it is desirable that the crystallite size of the thermoelectric conversion material obtained from the main peak of the X-ray diffraction spectrum of the sintered body using the Scherrer equation is 1000 nm or less. Further, the crystallite size of the thermoelectric conversion material is preferably 1 nm to 500 nm, more preferably 2 nm to 200 nm, and further preferably 5 nm to 100 nm. Thereby, the thermal conductivity (kappa) of a thermoelectric conversion material can be reduced, and the performance of a thermoelectric conversion material can be improved.
熱電変換材料において、比較的低温の廃熱（例えば３００℃以下、好ましくは２００℃以下）によって電子の熱励起を生じさせて熱電変換材料の性能を向上させるためには、熱電変換材料が所定のバンドギャップを有していることが望ましい。この観点から、熱電変換材料が、０．３ｅＶ〜２．５ｅＶのバンドギャップを有していることが好ましく、０．５ｅＶ〜２．０ｅＶのバンドギャップを有していることがより好ましい。 In thermoelectric conversion materials, in order to improve the performance of thermoelectric conversion materials by causing thermal excitation of electrons by relatively low-temperature waste heat (for example, 300 ° C. or less, preferably 200 ° C. or less), It is desirable to have a band gap. From this viewpoint, the thermoelectric conversion material preferably has a band gap of 0.3 eV to 2.5 eV, and more preferably has a band gap of 0.5 eV to 2.0 eV.
次に、本発明に係る熱電変換材料の製造方法の一例を説明する。本発明の熱電変換材料は、複合金属硫化物の原料を混合する混合工程と、その混合工程により得られた混合物を所定の圧力で加圧しながら焼結する焼結工程と、を備える。混合工程において、硫黄、銅、及び銅以外の上記の金属を含む、複合金属硫化物の原料となる単体又は化合物が所定のモル比で混合される。複合金属硫化物の原料となる化合物としては、例えば、金属硫化物を用いることができる。原料の形状及び大きさは、特に制限されず、ある程度の大きさを有する塊であってもよいし、粒体又は粉体であってもよい。原料を混合する方法は、特に制限されず、例えば、遊星ボールミル、ビーズミル、又は粉体ミキサーなどを用いて粉砕混合を行う方法などが考えられる。これにより、原料を粉砕しつつ、均一に混合することができる。原料を混合する方法としては、粉砕混合による方法以外に、乾式混合又は湿式混合として知られている公知の方法を用いることもできる。 Next, an example of a method for producing a thermoelectric conversion material according to the present invention will be described. The thermoelectric conversion material of the present invention includes a mixing step of mixing the raw materials of the composite metal sulfide, and a sintering step of sintering the mixture obtained by the mixing step while pressing the mixture at a predetermined pressure. In the mixing step, a simple substance or a compound that is a raw material of the composite metal sulfide containing sulfur, copper, and the above-described metal other than copper is mixed at a predetermined molar ratio. For example, a metal sulfide can be used as a compound that is a raw material for the composite metal sulfide. The shape and size of the raw material are not particularly limited, and may be a lump having a certain size, or a granule or powder. The method for mixing the raw materials is not particularly limited, and for example, a method of performing pulverization and mixing using a planetary ball mill, a bead mill, a powder mixer, or the like can be considered. Thereby, it can mix uniformly, grind | pulverizing a raw material. As a method of mixing the raw materials, a known method known as dry mixing or wet mixing can be used in addition to the method by pulverization mixing.
また、複合金属硫化物は、溶液中で合成されてもよい。例えば、金属の硝酸塩、金属塩化物、若しくは金属酢酸塩などの金属塩の水溶液又は金属アセチルアセトナートなどの金属錯体の水溶液に硫化剤を加えることによって、複合金属硫化物を合成できる。この場合、硫化剤としては、例えば、硫化ナトリウム若しくは硫化カリウムなどのアルカリ金属の硫化物、アルカリ土類金属の硫化物、又は硫化アンモニウムなどのアンモニウムイオンの硫化物などの硫化物が挙げられる。また、複合金属硫化物は、金属イオンが溶解している水溶液に適切な水素イオン濃度のもとで硫化水素ガスを吹き込んで複合金属硫化物の沈殿物を生じさせることによっても得ることができる。 The composite metal sulfide may be synthesized in a solution. For example, a composite metal sulfide can be synthesized by adding a sulfiding agent to an aqueous solution of a metal salt such as metal nitrate, metal chloride, or metal acetate or an aqueous solution of a metal complex such as metal acetylacetonate. In this case, examples of the sulfiding agent include sulfides such as sulfides of alkali metals such as sodium sulfide or potassium sulfide, sulfides of alkaline earth metals, and sulfides of ammonium ions such as ammonium sulfide. The composite metal sulfide can also be obtained by blowing hydrogen sulfide gas into an aqueous solution in which metal ions are dissolved under an appropriate hydrogen ion concentration to generate a precipitate of the composite metal sulfide.
複合金属硫化物は、有機溶媒中で合成されてもよい。この場合、複合金属硫化物の一次粒子の粒径を数ナノメールまで小さくすることができる。例えば、トリエチレンテトラミン若しくはオクチルアミンなどのアミン系溶媒、又は、オクタンチオール若しくはデカンチオールなどのチオール系溶媒中に、金属の硝酸塩、金属塩化物、若しくは金属酢酸塩などの金属塩又は金属アセチルアセトナートなどの金属錯体と、チオ尿素、チオアセトアミド、若しくはジチオカルバミン酸などの含硫黄有機化合物又は硫黄粉末とを所定量混合し還流することによって、複合金属硫化物を得ることができる。 The composite metal sulfide may be synthesized in an organic solvent. In this case, the particle size of the primary particles of the composite metal sulfide can be reduced to several nanomails. For example, a metal salt such as a metal nitrate, metal chloride, or metal acetate or a metal acetylacetonate in an amine solvent such as triethylenetetramine or octylamine, or a thiol solvent such as octanethiol or decanethiol. A composite metal sulfide can be obtained by mixing and refluxing a predetermined amount of a metal complex such as thiourea, thioacetamide, or a sulfur-containing organic compound such as dithiocarbamic acid or sulfur powder.
水溶液中又は有機溶媒中で得られた複合金属硫化物は、ろ過又は遠心分離などの固液分離方法によって水溶液中又は有機溶媒中から分離される。この場合、複合金属硫化物の粒子の表面には、水溶液、有機溶媒、又は原料に由来する不純物である分子が付着しているので、以下に述べる焼結工程の前に、洗浄又は仮焼成などの公知の方法で不純物を複合金属硫化物の粒子から取り除いておくことが好ましい。水溶液中又は有機溶媒中で得られた複合金属硫化物に、以下に述べる焼結工程を施して熱電変換材料を製造することができる。 The composite metal sulfide obtained in an aqueous solution or an organic solvent is separated from the aqueous solution or the organic solvent by a solid-liquid separation method such as filtration or centrifugation. In this case, the surface of the particles of the composite metal sulfide is attached with molecules that are impurities derived from an aqueous solution, an organic solvent, or a raw material. It is preferable to remove impurities from the composite metal sulfide particles by the known method. A thermoelectric conversion material can be produced by subjecting the composite metal sulfide obtained in an aqueous solution or an organic solvent to a sintering step described below.
焼結工程において、原料を混合することによって得られた混合物又は合成された複合金属硫化物が所定の形状の型に充填され、加圧されながら焼結される。このように、混合物又は合成された複合金属硫化物を加圧しながら焼結する方法としては、例えば、放電プラズマ焼結（Spark Plasma Sintering）を用いることができる。焼結温度は特に制限されないが、例えば、１５０℃〜１５００℃であり、好ましくは、２００℃〜１０００℃である。焼結時間は、例えば、０分〜１０分であり、好ましくは、０〜５分である。また、焼結工程の開始から焼結工程中の最高温度に到達するまでに必要な昇温時間は、例えば、２分〜１０分である。例えば、混合物又は合成された複合金属硫化物が充填された型の内部の温度を上記の昇温速度で最高温度まで昇温させ、型の内部の温度を最高温度で所定の時間（焼結時間）だけ維持し、その後加熱を停止して焼結体を自然冷却させる。このように、焼結時間を短くすることによって、一次粒子サイズを維持させたまま焼結することが可能となる。これにより、熱伝導率を下げ性能指数を向上させることができる。焼結工程中に混合物又は合成された複合金属硫化物を加圧する圧力は、例えば、０．５ＭＰａ〜１００ＭＰａであり、好ましくは、５ＭＰａ〜５０ＭＰａである。この焼結工程は、不活性ガス雰囲気又は真空雰囲気において行うことができる。この焼結工程は、好ましくは、真空雰囲気で行われる。このようにして、上記の複合金属硫化物でできた熱電変換材料を得ることができる。このように、原料の混合物又は合成された複合金属硫化物が加圧しながら焼結されることによって、高い機械的強度を有する熱電変換材料を製造できる。 In the sintering step, a mixture obtained by mixing raw materials or a synthesized composite metal sulfide is filled in a mold having a predetermined shape and sintered while being pressed. As described above, for example, spark plasma sintering can be used as a method of sintering the mixture or the synthesized composite metal sulfide while applying pressure. The sintering temperature is not particularly limited, and is, for example, 150 ° C to 1500 ° C, and preferably 200 ° C to 1000 ° C. The sintering time is, for example, 0 minutes to 10 minutes, preferably 0 to 5 minutes. Moreover, the temperature increase time required from the start of a sintering process until it reaches the maximum temperature in a sintering process is 2 minutes-10 minutes, for example. For example, the temperature inside the mold filled with the mixture or the synthesized composite metal sulfide is raised to the maximum temperature at the above temperature increase rate, and the temperature inside the mold is kept at the maximum temperature for a predetermined time (sintering time). ), And then the heating is stopped and the sintered body is allowed to cool naturally. Thus, by shortening the sintering time, it becomes possible to sinter while maintaining the primary particle size. Thereby, a thermal conductivity can be lowered | hung and a performance index can be improved. The pressure which pressurizes the mixture or the synthesized composite metal sulfide during the sintering step is, for example, 0.5 MPa to 100 MPa, and preferably 5 MPa to 50 MPa. This sintering step can be performed in an inert gas atmosphere or a vacuum atmosphere. This sintering step is preferably performed in a vacuum atmosphere. In this way, a thermoelectric conversion material made of the above composite metal sulfide can be obtained. Thus, a thermoelectric conversion material having high mechanical strength can be produced by sintering a mixture of raw materials or a synthesized composite metal sulfide while applying pressure.
以下に、実施例を用いて本発明を詳細に説明する。なお、以下の実施例は本発明の一例であり、本発明は以下の実施例に限定されない。 Hereinafter, the present invention will be described in detail with reference to examples. The following examples are examples of the present invention, and the present invention is not limited to the following examples.
＜実施例１＞
銅と、コバルトと、チタンと、硫黄とのモル比が２：１：１：４になるように、単体の銅の粉末、単体のコバルトの粉末、単体のチタンの粉末、及び単体の硫黄の粉末を秤量して遊星ボールミルの容器の内部に入れ、遊星ボールミルによって乾式粉砕混合して混合サンプルを得た。この混合サンプルを型に充填し、放電プラズマ焼結装置（株式会社シンターランド製、型番：ＬＡＢＯＸ−１２５）を用いて、３０ＭＰａで加圧しながら真空中で焼結を行った。放電プラズマ焼結装置の通電加熱によって、約１００℃／分の昇温速度で型の内部の温度を６００℃まで上昇させた後、型の内部の温度を６００℃で５分間維持した。その後、放電プラズマ焼結装置の通電加熱を停止し、自然冷却により焼結体を室温まで冷却し、型から焼結体を取り出した。焼結体は、直径約１０ｍｍ及び厚さ約２ｍｍの円盤形状を有していた。このようにして、実施例１に係る、複合金属硫化物（Ｃｕ2ＣｏＴｉＳ4）でできた熱電変換材料を得た。
<Example 1>
A simple copper powder, a simple cobalt powder, a simple titanium powder, and a simple sulfur so that the molar ratio of copper, cobalt, titanium and sulfur is 2: 1: 1: 4. The powder was weighed and placed in a planetary ball mill container, and dry pulverized and mixed with the planetary ball mill to obtain a mixed sample. This mixed sample was filled into a mold and sintered in a vacuum while being pressurized at 30 MPa using a discharge plasma sintering apparatus (manufactured by Sinterland, model number: LABOX-125). The temperature inside the mold was increased to 600 ° C. at a rate of temperature increase of about 100 ° C./min by energization heating of the discharge plasma sintering apparatus, and then the temperature inside the mold was maintained at 600 ° C. for 5 minutes. Thereafter, the energization heating of the discharge plasma sintering apparatus was stopped, the sintered body was cooled to room temperature by natural cooling, and the sintered body was taken out from the mold. The sintered body had a disk shape with a diameter of about 10 mm and a thickness of about 2 mm. In this way, a thermoelectric conversion material made of composite metal sulfide (Cu 2 CoTiS 4 ) according to Example 1 was obtained.
＜実施例２＞
銅と、鉄と、スズと、硫黄とのモル比が２：１：１：４になるように、単体の銅の粉末、単体の鉄の粉末、単体のスズの粉末、及び単体の硫黄の粉末を秤量して遊星ボールミルの容器の内部に入れた以外は、実施例１と同様にして、実施例２に係る、複合金属硫化物（Ｃｕ2ＦｅＳｎＳ4）でできた熱電変換材料を得た。
<Example 2>
In order for the molar ratio of copper, iron, tin, and sulfur to be 2: 1: 1: 4, simple copper powder, simple iron powder, simple tin powder, and simple sulfur A thermoelectric conversion material made of a composite metal sulfide (Cu 2 FeSnS 4 ) according to Example 2 was obtained in the same manner as in Example 1 except that the powder was weighed and placed inside the planetary ball mill container. .
＜実施例３＞
銅と、鉄と、チタンと、硫黄とのモル比が２：１：１：４になるように、単体の銅の粉末、単体の鉄の粉末、単体のチタンの粉末、及び単体の硫黄の粉末を秤量して遊星ボールミルの容器の内部に入れ、放電プラズマ焼結装置による通電加熱の条件を以下のように変更した以外は、実施例１と同様にして、実施例３に係る、複合金属硫化物（Ｃｕ2ＦｅＴｉＳ4）でできた熱電変換材料を得た。約１００℃／分の昇温速度で型の内部の温度を４００℃まで上昇させた後、型の内部の温度を４００℃で５分間維持して、放電プラズマ焼結装置の通電加熱を停止した。
<Example 3>
In order for the molar ratio of copper, iron, titanium, and sulfur to be 2: 1: 1: 4, simple copper powder, simple iron powder, simple titanium powder, and simple sulfur The composite metal according to Example 3 in the same manner as in Example 1 except that the powder was weighed and put into the container of the planetary ball mill, and the conditions of current heating by the discharge plasma sintering apparatus were changed as follows. A thermoelectric conversion material made of sulfide (Cu 2 FeTiS 4 ) was obtained. After the temperature inside the mold was raised to 400 ° C. at a rate of temperature increase of about 100 ° C./min, the temperature inside the mold was maintained at 400 ° C. for 5 minutes to stop the electric heating of the discharge plasma sintering apparatus. .
＜実施例４＞
銅と、スズと、硫黄とのモル比が２：１：３となるように、単体の銅の粉末、単体のスズの粉末、及び単体の硫黄の粉末を秤量して遊星ボールミルの容器の内部に入れ、放電プラズマ焼結装置による通電加熱の条件を以下のように変更した以外は、実施例１と同様にして、実施例４に係る、複合金属硫化物（Ｃｕ2ＳｎＳ3）でできた熱電変換材料を得た。約１００℃／分の昇温速度で型の内部の温度を４００℃まで上昇させた後、型の内部の温度を４００℃で５分間維持して、放電プラズマ焼結装置の通電加熱を停止した。
<Example 4>
Inside the planetary ball mill container, weigh the simple copper powder, simple tin powder, and simple sulfur powder so that the molar ratio of copper, tin, and sulfur is 2: 1: 3. The composite metal sulfide (Cu 2 SnS 3 ) according to Example 4 was made in the same manner as in Example 1 except that the conditions of the electric heating by the discharge plasma sintering apparatus were changed as follows. A thermoelectric conversion material was obtained. After the temperature inside the mold was raised to 400 ° C. at a rate of temperature increase of about 100 ° C./min, the temperature inside the mold was maintained at 400 ° C. for 5 minutes to stop the electric heating of the discharge plasma sintering apparatus. .
＜実施例５＞
銅と、亜鉛と、スズと、硫黄とのモル比が２：１：１：４になるように、単体の銅の粉末、単体の亜鉛の粉末、単体のスズの粉末、及び単体の硫黄の粉末を秤量して遊星ボールミルの容器の内部に入れ、放電プラズマ焼結装置による通電加熱の条件を以下のように変更した以外は、実施例１と同様にして、実施例５に係る、複合金属硫化物（Ｃｕ2ＺｎＳｎＳ4）でできた熱電変換材料を得た。約１００℃／分の昇温速度で型の内部の温度を５００℃まで上昇させ、型の内部の温度が５００℃に達した直後に放電プラズマ焼結装置による通電加熱を停止した。
<Example 5>
A simple copper powder, a simple zinc powder, a simple tin powder, and a simple sulfur so that the molar ratio of copper, zinc, tin and sulfur is 2: 1: 1: 4. The composite metal according to Example 5 is the same as Example 1, except that the powder is weighed and placed in the container of the planetary ball mill, and the conditions of the electric heating by the discharge plasma sintering apparatus are changed as follows. A thermoelectric conversion material made of sulfide (Cu 2 ZnSnS 4 ) was obtained. The temperature inside the mold was increased to 500 ° C. at a rate of temperature increase of about 100 ° C./min. Immediately after the temperature inside the mold reached 500 ° C., the energization heating by the discharge plasma sintering apparatus was stopped.
＜実施例６＞
銅と、鉄と、硫黄とのモル比が５：１：４になるように、単体の銅の粉末、単体の鉄の粉末、及び単体の硫黄の粉末を秤量して遊星ボールミルの容器の内部に入れ、放電プラズマ焼結装置による通電加熱の条件を以下のように変更した以外は、実施例１と同様にして実施例６に係る、複合金属硫化物（Ｃｕ5ＦｅＳ4）でできた熱電変換材料を得た。約１００℃／分の昇温速度で型の内部の温度を４００℃まで上昇させた後、型の内部の温度を４００℃で５分間維持して、放電プラズマ焼結装置の通電加熱を停止した。
<Example 6>
Inside the planetary ball mill container, weigh the simple copper powder, simple iron powder, and simple sulfur powder so that the molar ratio of copper, iron and sulfur is 5: 1: 4. In the same manner as in Example 1, except that the conditions for the electric heating by the discharge plasma sintering apparatus were changed as follows, the thermoelectric made of the composite metal sulfide (Cu 5 FeS 4 ) according to Example 6 was used. A conversion material was obtained. After the temperature inside the mold was raised to 400 ° C. at a rate of temperature increase of about 100 ° C./min, the temperature inside the mold was maintained at 400 ° C. for 5 minutes to stop the electric heating of the discharge plasma sintering apparatus. .
＜実施例７＞
銅と、アルミニウムと、硫黄とのモル比が１：１：２になるように、単体の銅の粉末、単体のアルミニウムの粉末、及び単体の硫黄の粉末を秤量して遊星ボールミルの容器の内部に入れ、放電プラズマ焼結装置による通電加熱の条件を以下のように変更した以外は、実施例１と同様にして、実施例７に係る、複合金属硫化物（ＣｕＡｌＳ2）でできた熱電変換材料を得た。約１００℃／分の昇温速度で型の内部の温度を４００℃まで上昇させた後、型の内部の温度を４００℃で５分間維持して、放電プラズマ焼結装置の通電加熱を停止した。
<Example 7>
Inside the planetary ball mill container, weigh the simple copper powder, simple aluminum powder, and simple sulfur powder so that the molar ratio of copper, aluminum, and sulfur is 1: 1: 2. The thermoelectric conversion made of the composite metal sulfide (CuAlS 2 ) according to Example 7 was performed in the same manner as in Example 1 except that the conditions of the electric current heating by the discharge plasma sintering apparatus were changed as follows. Obtained material. After the temperature inside the mold was raised to 400 ° C. at a rate of temperature increase of about 100 ° C./min, the temperature inside the mold was maintained at 400 ° C. for 5 minutes to stop the electric heating of the discharge plasma sintering apparatus. .
＜実施例８＞
銅と、鉄と、硫黄とのモル比が１：１：２になるように、単体の銅の粉末、単体の鉄の粉末、及び単体の硫黄の粉末を秤量して遊星ボールミルの容器の内部に入れ、放電プラズマ焼結装置による通電加熱の条件を以下のように変更した以外は、実施例１と同様にして実施例８に係る、複合金属硫化物（ＣｕＦｅＳ2）でできた熱電変換材料を得た。約１００℃／分の昇温速度で型の内部の温度を２００℃まで上昇させた後、型の内部の温度を５００℃で５分間維持して、放電プラズマ焼結装置の通電加熱を停止した。
<Example 8>
Inside the planetary ball mill container, weigh the simple copper powder, simple iron powder, and simple sulfur powder so that the molar ratio of copper, iron and sulfur is 1: 1: 2. And a thermoelectric conversion material made of a composite metal sulfide (CuFeS 2 ) according to Example 8 in the same manner as in Example 1 except that the conditions of current heating by the discharge plasma sintering apparatus were changed as follows. Got. The temperature inside the mold was raised to 200 ° C. at a rate of temperature increase of about 100 ° C./min, and then the temperature inside the mold was maintained at 500 ° C. for 5 minutes to stop the electric heating of the discharge plasma sintering apparatus. .
＜実施例９＞
銅と、インジウムと、硫黄とのモル比が１：１：２になるように、単体の銅の粉末、単体のインジウムの粉末、及び単体の硫黄の粉末を秤量して遊星ボールミルの容器の内部に入れた以外は、実施例１と同様にして実施例９に係る、複合金属硫化物（ＣｕＩｎＳ2）でできた熱電変換材料を得た。
<Example 9>
Inside the planetary ball mill container, weigh the simple copper powder, simple indium powder, and simple sulfur powder so that the molar ratio of copper, indium, and sulfur is 1: 1: 2. A thermoelectric conversion material made of a composite metal sulfide (CuInS 2 ) according to Example 9 was obtained in the same manner as in Example 1 except that it was put in the process.
＜実施例１０＞
銅と、チタンと、硫黄とのモル比が１：２：４になるように、単体の銅の粉末、単体のチタンの粉末、及び単体の硫黄の粉末を秤量して遊星ボールミルの容器の内部に入れ、放電プラズマ焼結装置による通電加熱の条件を以下のように変更した以外は、実施例１と同様にして実施例１０に係る、複合金属硫化物（ＣｕＴｉ2Ｓ4）でできた熱電変換材料を得た。約１００℃／分の昇温速度で型の内部の温度を５００℃まで上昇させた後、型の内部の温度を５００℃で２分間維持して、放電プラズマ焼結装置の通電加熱を停止した。
<Example 10>
Inside the planetary ball mill container, weigh the single copper powder, single titanium powder, and single sulfur powder so that the molar ratio of copper, titanium and sulfur is 1: 2: 4. In the same manner as in Example 1 except that the conditions of the electric heating by the discharge plasma sintering apparatus were changed as follows, a thermoelectric made of a composite metal sulfide (CuTi 2 S 4 ) according to Example 10 was used. A conversion material was obtained. The temperature inside the mold was raised to 500 ° C. at a rate of temperature increase of about 100 ° C./min, and then the temperature inside the mold was maintained at 500 ° C. for 2 minutes to stop the electric heating of the discharge plasma sintering apparatus. .
＜熱電変換材料の特性評価＞
各実施例の熱電変換材料の円柱状の試料の二つの底面を研磨機によって湿式研磨し、各実施例の熱電変換材料について、四端子測定法によって室温（約２５℃）での電気抵抗率を測定した。また、各実施例の複数の熱電変換材料の試料の上面において、平均温度が約２５℃となるように一部を温め、別の一部を冷やすことによって、熱電変換材料の試料の上面に所定の温度差を生じさせ、この状態で起電力を測定した。それぞれの試料における温度差及び起電力の関係を示す、縦軸を起電力とし、横軸を温度差とするグラフを作成した。このグラフの傾きから、各実施例の熱電変換材料のゼーベック係数を算出した。また、各実施例の熱電変換材料の出力因子Ｐを、Ｐ＝（ゼーベック係数）2／電気抵抗率の関係に基づき算出した。表１に、各実施例の熱電変換材料の電気抵抗率、ゼーベック係数、及び出力因子Ｐを示す。
<Characteristic evaluation of thermoelectric conversion material>
Two bottom surfaces of the columnar sample of the thermoelectric conversion material of each example were wet-polished by a polishing machine, and the thermoelectric conversion material of each example was measured for electric resistivity at room temperature (about 25 ° C.) by a four-terminal measurement method. It was measured. Further, on the upper surface of the plurality of thermoelectric conversion material samples of each example, a predetermined temperature is applied to the upper surface of the thermoelectric conversion material sample by heating a part so that the average temperature is about 25 ° C. and cooling another part. The electromotive force was measured in this state. A graph showing the relationship between the temperature difference and the electromotive force in each sample and having the vertical axis as the electromotive force and the horizontal axis as the temperature difference was created. From the slope of this graph, the Seebeck coefficient of the thermoelectric conversion material of each example was calculated. Moreover, the output factor P of the thermoelectric conversion material of each Example was calculated based on the relationship of P = (Seebeck coefficient) 2 / electric resistivity. Table 1 shows the electrical resistivity, Seebeck coefficient, and output factor P of the thermoelectric conversion material of each example.
＜Ｘ線回折測定＞
Ｘ線回折装置（Rigaku社製、試料水平型Ｘ線回折装置 Ｓｍａｒｔ Ｌａｂ）を用いて各実施例の熱電変換材料についてＸ線回折スペクトルを測定した。Ｘ線回折スペクトルの測定結果から、各実施例の熱電変換材料が表１に記載されている結晶構造を主として有することが確認された。また、Ｘ線回折スペクトルのメインピークからScherrerの式を用いて各実施例の熱電変換材料の結晶子サイズを求めた。結果を表１に示す。また、実施例２、５、７、及び１０に係る熱電変換材料のＸ線回折スペクトルをそれぞれ図１、２、３、及び４に示す。
<X-ray diffraction measurement>
An X-ray diffraction spectrum was measured for the thermoelectric conversion material of each example using an X-ray diffractometer (manufactured by Rigaku, sample horizontal X-ray diffractometer Smart Lab). From the measurement result of the X-ray diffraction spectrum, it was confirmed that the thermoelectric conversion material of each Example mainly has the crystal structure described in Table 1. Moreover, the crystallite size of the thermoelectric conversion material of each Example was calculated | required using the Scherrer formula from the main peak of the X-ray diffraction spectrum. The results are shown in Table 1. Moreover, the X-ray-diffraction spectrum of the thermoelectric conversion material which concerns on Example 2, 5, 7, and 10 is shown to FIG. 1, 2, 3, and 4, respectively.
＜バンドギャップの測定＞
実施例４、５、及び９に係る熱電変換材料を硫酸バリウム白板に少量載せ、表面を平らにした。このようにして作製した測定用試料の拡散反射ＵＶ−ＶｉｓスペクトルをＵＶ−Ｖｉｓ−ＮＩＲ分光器（島津製作所社製、型番：ＵＶ３１００ＰＣ）を用いて測定した。得られた拡散反射ＵＶ−ＶｉｓスペクトルをKubelka-Munk変換して得られるTaucプロットの接線から、実施例４、５、及び９に係る熱電変換材料のバンドギャップを求めた。
<Measurement of band gap>
A small amount of the thermoelectric conversion material according to Examples 4, 5, and 9 was placed on a white barium sulfate plate to flatten the surface. The diffuse reflection UV-Vis spectrum of the measurement sample thus prepared was measured using a UV-Vis-NIR spectrometer (manufactured by Shimadzu Corporation, model number: UV3100PC). The band gap of the thermoelectric conversion materials according to Examples 4, 5, and 9 was determined from the tangent line of the Tauc plot obtained by Kubelka-Munk conversion of the obtained diffuse reflection UV-Vis spectrum.
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