JP2018142639A - Thermoelectric conversion layer, thermoelectric conversion element, and thermoelectric conversion module - Google Patents
Thermoelectric conversion layer, thermoelectric conversion element, and thermoelectric conversion module Download PDFInfo
- Publication number
- JP2018142639A JP2018142639A JP2017036457A JP2017036457A JP2018142639A JP 2018142639 A JP2018142639 A JP 2018142639A JP 2017036457 A JP2017036457 A JP 2017036457A JP 2017036457 A JP2017036457 A JP 2017036457A JP 2018142639 A JP2018142639 A JP 2018142639A
- Authority
- JP
- Japan
- Prior art keywords
- thermoelectric conversion
- conversion layer
- dispersion
- inorganic nanoparticles
- nanocarbon material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 382
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 127
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 94
- 239000002105 nanoparticle Substances 0.000 claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims description 125
- 239000002041 carbon nanotube Substances 0.000 claims description 82
- 239000002245 particle Substances 0.000 claims description 77
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 74
- 239000010949 copper Substances 0.000 claims description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 239000011135 tin Substances 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 17
- 239000011133 lead Substances 0.000 claims description 15
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 238000012935 Averaging Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 100
- 239000003575 carbonaceous material Substances 0.000 abstract description 7
- 238000002441 X-ray diffraction Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 251
- 230000000052 comparative effect Effects 0.000 description 77
- 238000000034 method Methods 0.000 description 69
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 66
- 239000000243 solution Substances 0.000 description 50
- 238000002360 preparation method Methods 0.000 description 49
- 239000000203 mixture Substances 0.000 description 46
- 239000000126 substance Substances 0.000 description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 35
- 239000000758 substrate Substances 0.000 description 31
- 239000002585 base Substances 0.000 description 29
- GZTBKEOTCAVWNJ-UHFFFAOYSA-L C(C)O.C(C)(=O)[O-].[Cu+2].C(C)(=O)[O-] Chemical compound C(C)O.C(C)(=O)[O-].[Cu+2].C(C)(=O)[O-] GZTBKEOTCAVWNJ-UHFFFAOYSA-L 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 24
- 239000010408 film Substances 0.000 description 20
- 238000005259 measurement Methods 0.000 description 20
- 239000002612 dispersion medium Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 18
- -1 acrylate compound Chemical class 0.000 description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 15
- 229910021389 graphene Inorganic materials 0.000 description 15
- 239000011254 layer-forming composition Substances 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 239000002134 carbon nanofiber Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 7
- 229940071536 silver acetate Drugs 0.000 description 7
- SIGUVTURIMRFDD-UHFFFAOYSA-M sodium dioxidophosphanium Chemical compound [Na+].[O-][PH2]=O SIGUVTURIMRFDD-UHFFFAOYSA-M 0.000 description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 229920000547 conjugated polymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 6
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000011246 composite particle Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 229910003472 fullerene Inorganic materials 0.000 description 5
- 229940046892 lead acetate Drugs 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920002907 Guar gum Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001241 arc-discharge method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 229960003964 deoxycholic acid Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 235000010417 guar gum Nutrition 0.000 description 3
- 239000000665 guar gum Substances 0.000 description 3
- 229960002154 guar gum Drugs 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- FHHPUSMSKHSNKW-SMOYURAASA-M sodium deoxycholate Chemical compound [Na+].C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 FHHPUSMSKHSNKW-SMOYURAASA-M 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 3
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920002558 Curdlan Polymers 0.000 description 2
- 239000001879 Curdlan Substances 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- MRJXTUJZRLNIRB-UHFFFAOYSA-J [Cl-].[Cl-].[Cl-].[Cl-].[Sn+4].CCO Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Sn+4].CCO MRJXTUJZRLNIRB-UHFFFAOYSA-J 0.000 description 2
- CDXSJGDDABYYJV-UHFFFAOYSA-N acetic acid;ethanol Chemical compound CCO.CC(O)=O CDXSJGDDABYYJV-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 2
- VTDPERKJPOAPEQ-UHFFFAOYSA-K bismuth ethanol trichloride Chemical compound C(C)O.[Bi+3].[Cl-].[Cl-].[Cl-] VTDPERKJPOAPEQ-UHFFFAOYSA-K 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011852 carbon nanoparticle Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000010418 carrageenan Nutrition 0.000 description 2
- 229920001525 carrageenan Polymers 0.000 description 2
- 239000000679 carrageenan Substances 0.000 description 2
- 229940113118 carrageenan Drugs 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- CRCKGIUJMFFISH-UHFFFAOYSA-N copper;ethanolate Chemical compound [Cu+2].CC[O-].CC[O-] CRCKGIUJMFFISH-UHFFFAOYSA-N 0.000 description 2
- 235000019316 curdlan Nutrition 0.000 description 2
- 229940078035 curdlan Drugs 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920002674 hyaluronan Polymers 0.000 description 2
- 229960003160 hyaluronic acid Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- KXCLCNHUUKTANI-RBIYJLQWSA-N keratan Chemical compound CC(=O)N[C@@H]1[C@@H](O)C[C@@H](COS(O)(=O)=O)O[C@H]1O[C@@H]1[C@@H](O)[C@H](O[C@@H]2[C@H](O[C@@H](O[C@H]3[C@H]([C@@H](COS(O)(=O)=O)O[C@@H](O)[C@@H]3O)O)[C@H](NC(C)=O)[C@H]2O)COS(O)(=O)=O)O[C@H](COS(O)(=O)=O)[C@@H]1O KXCLCNHUUKTANI-RBIYJLQWSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002116 nanohorn Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920006289 polycarbonate film Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- GZNAASVAJNXPPW-UHFFFAOYSA-M tin(4+) chloride dihydrate Chemical compound O.O.[Cl-].[Sn+4] GZNAASVAJNXPPW-UHFFFAOYSA-M 0.000 description 2
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Substances O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XKKVXDJVQGBBFQ-UHFFFAOYSA-L zinc ethanol diacetate Chemical compound C(C)O.C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-] XKKVXDJVQGBBFQ-UHFFFAOYSA-L 0.000 description 2
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- HPGNGICCHXRMIP-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dithiine Chemical compound S1CCSC2=CSC=C21 HPGNGICCHXRMIP-UHFFFAOYSA-N 0.000 description 1
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002567 Chondroitin Polymers 0.000 description 1
- 229920001287 Chondroitin sulfate Polymers 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 235000017788 Cydonia oblonga Nutrition 0.000 description 1
- 229920000045 Dermatan sulfate Polymers 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920002971 Heparan sulfate Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 229920000288 Keratan sulfate Polymers 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- 229920000057 Mannan Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 244000090599 Plantago psyllium Species 0.000 description 1
- 235000010451 Plantago psyllium Nutrition 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 240000004584 Tamarindus indica Species 0.000 description 1
- 235000004298 Tamarindus indica Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920013629 Torelina Polymers 0.000 description 1
- 239000004742 Torelina™ Substances 0.000 description 1
- 229920001615 Tragacanth Polymers 0.000 description 1
- 229920001646 UPILEX Polymers 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- KGLAXXUXWSFQMO-UHFFFAOYSA-N [Na].C(C=C)(=O)C(N(C)C)CS(=O)(=O)O Chemical compound [Na].C(C=C)(=O)C(N(C)C)CS(=O)(=O)O KGLAXXUXWSFQMO-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000305 astragalus gummifer gum Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WSWYZRBSUBMICN-UHFFFAOYSA-N azanium;2-(dimethylamino)-3-oxopent-4-ene-1-sulfonate Chemical compound [NH4+].[O-]S(=O)(=O)CC(N(C)C)C(=O)C=C WSWYZRBSUBMICN-UHFFFAOYSA-N 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- DLGJWSVWTWEWBJ-HGGSSLSASA-N chondroitin Chemical compound CC(O)=N[C@@H]1[C@H](O)O[C@H](CO)[C@H](O)[C@@H]1OC1[C@H](O)[C@H](O)C=C(C(O)=O)O1 DLGJWSVWTWEWBJ-HGGSSLSASA-N 0.000 description 1
- 229940059329 chondroitin sulfate Drugs 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- AVJBPWGFOQAPRH-FWMKGIEWSA-L dermatan sulfate Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@H](OS([O-])(=O)=O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](C([O-])=O)O1 AVJBPWGFOQAPRH-FWMKGIEWSA-L 0.000 description 1
- 229940051593 dermatan sulfate Drugs 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FZWBNHMXJMCXLU-BLAUPYHCSA-N isomaltotriose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)O1 FZWBNHMXJMCXLU-BLAUPYHCSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 1
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
- 235000019423 pullulan Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940032147 starch Drugs 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は、熱電変換層、熱電変換素子、及び、熱電変換モジュールに関する。 The present invention relates to a thermoelectric conversion layer, a thermoelectric conversion element, and a thermoelectric conversion module.
熱エネルギーと電気エネルギーを相互に変換することができる熱電変換材料が、熱によって発電する発電素子やペルチェ素子のような熱電変換素子に用いられている。熱電変換素子は、熱エネルギーを直接電力に変換することができ、可動部を必要とせず、例えば、体温で作動する腕時計、僻地用電源、及び、宇宙用電源等に用いられている。 Thermoelectric conversion materials that can mutually convert thermal energy and electrical energy are used in thermoelectric conversion elements such as power generation elements and Peltier elements that generate electricity by heat. The thermoelectric conversion element can directly convert heat energy into electric power, does not require a movable part, and is used for, for example, a wristwatch operating at body temperature, a power source for remote areas, a power source for space, and the like.
熱電変換材料としては、カーボンナノチューブ（以下、「ＣＮＴ」ともいう。）に代表されるナノ炭素材料が提案されている。
例えば、特許文献１では、「半導体ナノワイヤー及び半導体ナノチューブからなる群より選択される少なくとも１種を含有する熱電変換材料であって、低熱伝導粒子を含む不織布状の熱電変換材料」を開示している。つまり、特許文献１では、ナノ炭素材料である半導体ナノワイヤー及び半導体ナノチューブと低熱伝導粒子とを含有する不織布状の熱電変換層を形成している。
特許文献１では、ナノ炭素材料と低熱伝導粒子とを混合することで熱電変換層を形成している。
As thermoelectric conversion materials, nanocarbon materials represented by carbon nanotubes (hereinafter also referred to as “CNT”) have been proposed.
For example, Patent Document 1 discloses "a non-woven thermoelectric conversion material that includes at least one selected from the group consisting of semiconductor nanowires and semiconductor nanotubes and includes low thermal conductive particles". Yes. That is, in Patent Document 1, a non-woven thermoelectric conversion layer containing semiconductor nanowires and semiconductor nanotubes, which are nanocarbon materials, and low thermal conductive particles is formed.
In Patent Document 1, a thermoelectric conversion layer is formed by mixing a nanocarbon material and low thermal conductive particles.
また、特許文献２では、「溶媒中で、（ｉ）金属酸塩、又は（ｉｉ）金属塩とカルコゲンとの混合物、を加熱分解させることにより得られる、半導体ナノ構造体」、及び「半導体ナノ構造体とカーボンナノチューブとを含有する熱電変換材料である複合材料」を開示している。つまり、特許文献２では、ナノ炭素材料であるカーボンナノチューブと、無機ナノ粒子である半導体ナノ粒子とを含有する熱電変換層を形成している。特許文献２では、ナノ炭素材料であるカーボンナノチューブに別途合成した半導体ナノ粒子を混合することで熱電変換層を形成している。 In Patent Document 2, “a semiconductor nanostructure obtained by thermally decomposing (i) a metal salt or (ii) a mixture of a metal salt and a chalcogen in a solvent” and “semiconductor nanostructure” A composite material that is a thermoelectric conversion material containing a structure and carbon nanotubes is disclosed. That is, in patent document 2, the thermoelectric conversion layer containing the carbon nanotube which is a nanocarbon material, and the semiconductor nanoparticle which is inorganic nanoparticle is formed. In patent document 2, the thermoelectric conversion layer is formed by mixing the semiconductor nanoparticle separately synthesize | combined with the carbon nanotube which is a nanocarbon material.
一方、昨今においては、熱電変換素子の耐久性等の観点から、熱電変換層と、熱電変換層と層の厚み方向に接する隣接層（例えば、基材）との密着性の向上も求められている。
本発明者らは、特許文献１及び２に記載された熱電変換層について検討したところ、昨今要求されている熱電変換性能（特に、性能指数Ｚ）を必ずしも満たさないことを明らかとした。さらに、上記熱電変換層を用いて熱電変換素子を作製したところ、熱電変換層と、熱電変換層と層の厚み方向に接する隣接層との密着性が低く、さらなる改善が必要であることを知見した。
On the other hand, in recent years, from the viewpoint of durability of the thermoelectric conversion element, improvement in adhesion between the thermoelectric conversion layer and the adjacent layer (for example, a base material) in contact with the thermoelectric conversion layer in the thickness direction of the layer is also required. Yes.
The inventors of the present invention have studied the thermoelectric conversion layers described in Patent Documents 1 and 2, and have clarified that the thermoelectric conversion performance (particularly, the figure of merit Z) required recently is not always satisfied. Furthermore, when a thermoelectric conversion element was produced using the thermoelectric conversion layer, it was found that the adhesion between the thermoelectric conversion layer and the thermoelectric conversion layer and the adjacent layer in the thickness direction of the layer is low, and further improvement is necessary. did.
そこで、本発明は、上記実情を鑑みて、熱電変換性能（特に、性能指数Ｚ）に優れ、かつ、熱電変換素子に適用した際に隣接層との密着性に優れた熱電変換層を提供することを課題とする。
また、本発明は、上記熱電変換層を備えた熱電変換素子及び熱電変換モジュールを提供することを課題とする。
Therefore, in view of the above circumstances, the present invention provides a thermoelectric conversion layer that is excellent in thermoelectric conversion performance (particularly, figure of merit Z) and that has excellent adhesion to an adjacent layer when applied to a thermoelectric conversion element. This is the issue.
Moreover, this invention makes it a subject to provide the thermoelectric conversion element and thermoelectric conversion module provided with the said thermoelectric conversion layer.
本発明者らは、上記課題を達成すべく鋭意検討した結果、所定の構成の熱電変換層によれば、上記課題を解決できることを見出し、本発明を完成させた。
すなわち、以下の構成により上記目的を達成することができることを見出した。
As a result of intensive studies to achieve the above-described problems, the present inventors have found that the above-described problems can be solved by a thermoelectric conversion layer having a predetermined configuration, and have completed the present invention.
That is, it has been found that the above object can be achieved by the following configuration.
〔１〕ナノ炭素材料と、金属元素を含有する無機ナノ粒子と、を含有する熱電変換層であって、
上記熱電変換層を走査型電子顕微鏡にて観察し、エネルギー分散型Ｘ線分析により得られる上記ナノ炭素材料由来の炭素元素に対する上記金属元素の含有比率を用いて、下記式（１）により算出される面内ばらつきの最大値Ｔが、０〜３０％である熱電変換層。
式（１）Ｔ＝｜最大偏差｜／｜平均値｜×１００
上記平均値とは、走査型電子顕微鏡にて観察した上記熱電変換層の１０か所の領域における上記ナノ炭素材料由来の炭素元素に対する上記金属元素の含有比率をそれぞれ算出し、それらを算術平均して得られる平均値である。
上記最大偏差とは、走査型電子顕微鏡にて観察した上記熱電変換層の１０か所の領域における上記ナノ炭素材料由来の炭素元素に対する上記金属元素の含有比率のうち上記平均値から最も離された測定値と、上記平均値との偏差である。
〔２〕 上記無機ナノ粒子の含有量が、上記ナノ炭素材料に対して、０．０１〜３００質量％である、〔１〕に記載の熱電変換層。
〔３〕 上記ナノ炭素材料が、カーボンナノチューブである〔１〕又は〔２〕に記載の熱電変換層。
〔４〕 上記無機ナノ粒子が、金属硫化物粒子又は金属酸化物粒子である、〔１〕〜〔３〕のいずれか１項に記載の熱電変換層。
〔５〕 上記無機ナノ粒子が、金属硫化物粒子である、〔４〕に記載の熱電変換層。
〔６〕 上記無機ナノ粒子が、銅、銀、鉛、亜鉛、及び錫からなる群より選ばれる少なくとも１種の金属元素を含有する、〔４〕又は〔５〕に記載の熱電変換層。
〔７〕 〔１〕〜〔６〕のいずれかに記載の熱電変換層を備えた、熱電変換素子。
〔８〕 〔７〕に記載の熱電変換素子を複数個備えた、熱電変換モジュール。
[1] A thermoelectric conversion layer containing a nanocarbon material and inorganic nanoparticles containing a metal element,
The thermoelectric conversion layer is observed with a scanning electron microscope, and is calculated by the following formula (1) using the content ratio of the metal element to the carbon element derived from the nanocarbon material obtained by energy dispersive X-ray analysis. A thermoelectric conversion layer having a maximum in-plane variation T of 0 to 30%.
Formula (1) T = | maximum deviation | / | average value | × 100
The average value is to calculate the content ratio of the metal element to the carbon element derived from the nanocarbon material in 10 regions of the thermoelectric conversion layer observed with a scanning electron microscope, respectively, and to arithmetically average them. Is the average value obtained.
The maximum deviation is the most distant from the average value among the content ratio of the metal element to the carbon element derived from the nanocarbon material in the 10 regions of the thermoelectric conversion layer observed with a scanning electron microscope. It is a deviation between the measured value and the average value.
[2] The thermoelectric conversion layer according to [1], wherein the content of the inorganic nanoparticles is 0.01 to 300% by mass with respect to the nanocarbon material.
[3] The thermoelectric conversion layer according to [1] or [2], wherein the nanocarbon material is a carbon nanotube.
[4] The thermoelectric conversion layer according to any one of [1] to [3], wherein the inorganic nanoparticles are metal sulfide particles or metal oxide particles.
[5] The thermoelectric conversion layer according to [4], wherein the inorganic nanoparticles are metal sulfide particles.
[6] The thermoelectric conversion layer according to [4] or [5], wherein the inorganic nanoparticles contain at least one metal element selected from the group consisting of copper, silver, lead, zinc, and tin.
[7] A thermoelectric conversion element comprising the thermoelectric conversion layer according to any one of [1] to [6].
[8] A thermoelectric conversion module comprising a plurality of thermoelectric conversion elements according to [7].
本発明によれば、熱電変換性能（特に、性能指数Ｚ）に優れ、かつ、熱電変換素子に適用した際に隣接層との密着性に優れた熱電変換層を提供することができる。
また、本発明によれば、上記熱電変換層を備えた熱電変換素子及び熱電変換モジュールを提供することができる。
According to the present invention, it is possible to provide a thermoelectric conversion layer excellent in thermoelectric conversion performance (particularly, figure of merit Z) and excellent in adhesion to an adjacent layer when applied to a thermoelectric conversion element.
Moreover, according to this invention, the thermoelectric conversion element and thermoelectric conversion module provided with the said thermoelectric conversion layer can be provided.
以下、本発明の熱電変換層、熱電変換素子、及び、熱電変換モジュールについて詳細に説明する。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に制限されるものではない。
なお、本明細書において、「〜」を用いて表される数値範囲は、「〜」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
本明細書において、「（メタ）アクリレート化合物」との記載は、「アクリレート化合物及びメタアクリレート化合物のいずれか一方又は双方」の意味を表す。
Hereinafter, the thermoelectric conversion layer, the thermoelectric conversion element, and the thermoelectric conversion module of the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, the description “(meth) acrylate compound” represents the meaning of “one or both of an acrylate compound and a methacrylate compound”.
〔熱電変換層〕
まず、本発明の熱電変換層の特徴点について説明する。
本発明の熱電変換層は、ナノ炭素材料と、金属元素を含有する無機ナノ粒子（以後、単に「無機ナノ粒子」とも称する）と、を含有する熱電変換層であり、熱電変換層を走査型電子顕微鏡（ＳＥＭ：Scanning Electron Microscope）にて観察し、エネルギー分散型Ｘ線分析（ＥＤＸ：Energy dispersive X-ray spectrometry）により得られるナノ炭素材料由来の炭素元素に対する金属元素の含有比率を用いて、下記式（１）により算出される面内ばらつきの最大値Ｔが、０〜３０％である。下記式（１）により算出される面内ばらつきの最大値Ｔは、性能指数Ｚにより優れる点で、０〜２５％であることがより好ましく、０〜２０％であることが更に好ましい。
式（１） Ｔ＝｜最大偏差｜／｜平均値｜×１００
[Thermoelectric conversion layer]
First, the features of the thermoelectric conversion layer of the present invention will be described.
The thermoelectric conversion layer of the present invention is a thermoelectric conversion layer containing a nanocarbon material and inorganic nanoparticles containing a metal element (hereinafter also simply referred to as “inorganic nanoparticles”), and the thermoelectric conversion layer is scanned. Using the content ratio of the metal element with respect to the carbon element derived from the nano carbon material obtained by observation with an electron microscope (SEM: Scanning Electron Microscope) and obtained by energy dispersive X-ray analysis (EDX), The maximum value T of in-plane variation calculated by the following formula (1) is 0 to 30%. The maximum value T of the in-plane variation calculated by the following formula (1) is more preferably 0 to 25%, and still more preferably 0 to 20% in that the figure of merit Z is more excellent.
Formula (1) T = | maximum deviation | / | average value | × 100
ここで、平均値とは、走査型電子顕微鏡にて観察した熱電変換層の１０か所の領域におけるナノ炭素材料由来の炭素元素に対する金属元素の含有比率をそれぞれ算出し、それらを算術平均して得られる平均値である。
最大偏差とは、走査型電子顕微鏡にて観察した熱電変換層の１０か所の領域におけるナノ炭素材料由来の炭素元素に対する金属元素の含有比率のうち平均値から最も離された測定値と、平均値との偏差である。
Here, the average value is to calculate the content ratio of the metal element to the carbon element derived from the nanocarbon material in 10 regions of the thermoelectric conversion layer observed with a scanning electron microscope, and arithmetically average them. The average value obtained.
The maximum deviation is a measured value farthest from the average value among the content ratio of the metal element to the carbon element derived from the nanocarbon material in 10 regions of the thermoelectric conversion layer observed with a scanning electron microscope, and the average Deviation from value.
なお、上記ＳＥＭにより観察される熱電変換層の任意の１０か所の抽出方法は特に限定されないが、各領域間の距離が少なくとも５００μｍ離れていることが好ましい。
また、ＳＥＭにより観察される各領域の大きさは、いずれも縦２５０μｍ×横２００μｍである。
また、ＳＥＭにより観察される熱電変換層としては、表面の大きさが縦５ｃｍ×横５ｃｍの熱電変換層を用いる。
In addition, although the extraction method of arbitrary 10 places of the thermoelectric conversion layer observed with the said SEM is not specifically limited, It is preferable that the distance between each area | region is separated at least 500 micrometers.
The size of each region observed by SEM is 250 μm long × 200 μm wide.
Moreover, as a thermoelectric conversion layer observed by SEM, the thermoelectric conversion layer whose surface size is 5 cm in length x 5 cm in width is used.
以下に、ナノ炭素材料としてカーボンナノチューブ、及び、無機ナノ粒子として酸化銅を含有する熱電変換層を例に挙げて、上記面内ばらつきの最大値Ｔの算出方法を説明する。
上記熱電変換層とする場合、上記ナノ炭素材料に対する上記無機ナノ粒子の存在比率は、ＳＥＭ−ＥＤＸにより、炭素元素に対する銅元素の含有比率として測定する。
具体的には、ＳＥＭにより熱電変換層表面の任意の１０か所の領域（Ｎ１〜Ｎ１０）を抽出し、ＥＤＸにより各領域における銅元素の存在量（Ｃｕ１〜Ｃｕ１０（質量％））及び炭素元素の存在量（Ｃ１〜Ｃ１０（質量％））を測定した後、各領域毎に炭素元素に対する銅元素の含有比率を算出する（Ａ１〜Ａ１０（質量％））。次いで、各領域毎に、炭素元素に対する銅元素の含有比率から平均値Ａｎを差し引いた値の絶対値をとり、偏差を求める。なお、上記平均値ＡｎはＡ１〜Ａ１０の平均として求められる。上記式（１）における最大偏差とは、上記偏差のうちの最大値を意味する。熱電変換層の面内ばらつきの最大値Ｔは、式（１）に基づき、上記最大偏差を平均値で除することにより得られる。
Below, the calculation method of the maximum value T of the in-plane variation will be described by taking a thermoelectric conversion layer containing carbon nanotubes as the nanocarbon material and copper oxide as the inorganic nanoparticles as an example.
When setting it as the said thermoelectric conversion layer, the abundance ratio of the said inorganic nanoparticle with respect to the said nanocarbon material is measured as a content ratio of the copper element with respect to a carbon element by SEM-EDX.
Specifically, arbitrary 10 regions (N 1 to N 10 ) on the surface of the thermoelectric conversion layer are extracted by SEM, and the abundance (Cu 1 to Cu 10 (mass%) of copper element in each region is extracted by EDX. ) And the abundance of carbon element (C 1 to C 10 (mass%)), the content ratio of copper element to carbon element is calculated for each region (A 1 to A 10 (mass%)). Then, for each of the regions, taking the absolute value of the value obtained by subtracting the average value A n from the content ratio of the copper element relative to carbon element, a deviation. Incidentally, the average value A n is determined as an average of A 1 to A 10. The maximum deviation in the above formula (1) means the maximum value among the deviations. The maximum value T of the in-plane variation of the thermoelectric conversion layer is obtained by dividing the maximum deviation by the average value based on the formula (1).
以下、特許文献１及び２に記載される熱電変換層と本発明の熱電変換層との構成上の差異を比較しながら、本発明の熱電変換層が本発明の効果を奏する上で推測される機序について説明する。
本発明の熱電変換層の特徴点は、熱電変換層中に含まれる無機ナノ粒子が凝集せず、面内に均一に存在している点にある。つまり、炭素ナノ材料に対する上記無機ナノ粒子の存在比率の面内におけるばらつき（面内ばらつき）が小さい点にある。
Hereinafter, it is speculated that the thermoelectric conversion layer of the present invention exhibits the effects of the present invention while comparing structural differences between the thermoelectric conversion layer described in Patent Documents 1 and 2 and the thermoelectric conversion layer of the present invention. The mechanism will be described.
The feature of the thermoelectric conversion layer of the present invention is that the inorganic nanoparticles contained in the thermoelectric conversion layer do not aggregate and exist uniformly in the plane. That is, the in-plane variation (in-plane variation) of the abundance ratio of the inorganic nanoparticles to the carbon nanomaterial is small.
本発明者らは、特許文献１及び２に記載される熱電変換層について検討したところ、特許文献１及び２に記載される熱電変換層は、ナノ炭素材料と低熱伝導粒子（特許文献１）又は半導体ナノ構造体（特許文献２）とを単に混合することで形成されているため、この結果として、熱電変換性能及び密着性の低下を引き起こしていることを知見した。具体的には、特許文献１及び２に記載される熱電変換層は、熱電変換層中に含まれる低熱伝導粒子又は半導体ナノ構造体が凝集し、ナノ炭素材料と不均一に存在することで、熱電変換性能及び密着性の低下を引き起こしていることを知見した。
本発明者らは、上記知見に基づき鋭意検討した結果、ナノ炭素材料上に無機ナノ粒子を凝集することなく均一に担持させることにより（つまり、面内ばらつきを小さくすることにより）、上記課題が解決できることを見出した。
なお、本発明者らは、熱電変換層中におけるナノ炭素材料上に無機ナノ粒子を均一に担持させる方法の一つとして、後述する実施例欄に示されるように、特定の製造方法により得られるナノ炭素材料と無機ナノ粒子とが複合化された複合粒子を用いて熱電変換層を形成する方法を見出している。
When the present inventors examined the thermoelectric conversion layer described in patent document 1 and 2, the thermoelectric conversion layer described in patent document 1 and 2 is nanocarbon material and low thermal conductive particle (patent document 1) or Since it was formed by simply mixing the semiconductor nanostructure (Patent Document 2), it was found that this resulted in a decrease in thermoelectric conversion performance and adhesion. Specifically, in the thermoelectric conversion layer described in Patent Documents 1 and 2, the low thermal conductive particles or semiconductor nanostructures contained in the thermoelectric conversion layer are aggregated and non-uniformly present with the nanocarbon material. It was found that the thermoelectric conversion performance and adhesiveness were reduced.
As a result of intensive studies based on the above findings, the present inventors have found that the above-mentioned problem is achieved by uniformly supporting inorganic nanoparticles on the nanocarbon material without agglomeration (that is, by reducing in-plane variation). I found that it can be solved.
In addition, as shown in the Example column mentioned later as one of the methods of carrying | supporting an inorganic nanoparticle uniformly on the nanocarbon material in a thermoelectric conversion layer, the present inventors are obtained by a specific manufacturing method. A method for forming a thermoelectric conversion layer using composite particles in which a nanocarbon material and inorganic nanoparticles are combined has been found.
上記無機ナノ粒子は、熱電変換層内において、主として、ナノ炭素材料に対するドーパントとしての機能と、ナノ炭素材料同士の熱伝導を抑制する機能とを有する。本発明の熱電変換層は、特許文献１及び２の熱電変換層と比較すると、熱電変換層中において上記無機ナノ粒子がより均一に存在する（なお、特許文献１及び２の熱電変換層は、上述のとおり、熱電変換層中に含まれる低熱伝導粒子又は半導体ナノ構造体が凝集し、ナノ炭素材料と不均一に存在していると推測される）。この結果、ナノ炭素材料に対するドーピング効果が向上する（導電率σ、ゼーベック係数Ｓが大きくなる）、及び／又は、ナノ炭素材料同士の熱伝導がより抑制される（熱伝導性κが小さくなる）ため、結果として、熱電変換層の性能指数Ｚが優れると推測される。
また、上記熱電変換層におけるナノ炭素材料の表面は、無機ナノ粒子が均一に存在するため、微細な凹凸を有すると推測される。この微細な凹凸が、隣接層表面の微細な凹凸に対し入り込むことで、熱電変換層を熱電変換素子又は熱電変換モジュールに適用した際に、熱電変換層と隣接層との密着性にも優れるものと推測される。
The inorganic nanoparticles mainly have a function as a dopant for the nanocarbon material and a function of suppressing heat conduction between the nanocarbon materials in the thermoelectric conversion layer. Compared with the thermoelectric conversion layers of Patent Documents 1 and 2, the thermoelectric conversion layer of the present invention has the inorganic nanoparticles more uniformly in the thermoelectric conversion layer (note that the thermoelectric conversion layers of Patent Documents 1 and 2 are As described above, it is estimated that the low thermal conductive particles or semiconductor nanostructures contained in the thermoelectric conversion layer are aggregated and non-uniformly exist with the nanocarbon material). As a result, the doping effect on the nanocarbon material is improved (the conductivity σ and the Seebeck coefficient S are increased) and / or the heat conduction between the nanocarbon materials is further suppressed (the thermal conductivity κ is decreased). Therefore, as a result, it is estimated that the figure of merit Z of the thermoelectric conversion layer is excellent.
Further, the surface of the nanocarbon material in the thermoelectric conversion layer is presumed to have fine irregularities because inorganic nanoparticles are present uniformly. This fine unevenness penetrates into the fine unevenness on the surface of the adjacent layer, so that when the thermoelectric conversion layer is applied to a thermoelectric conversion element or a thermoelectric conversion module, the adhesion between the thermoelectric conversion layer and the adjacent layer is excellent. It is guessed.
また、上記無機ナノ粒子が、金属硫化物粒子又は金属酸化物粒子である場合（好ましくは、無機ナノ粒子が、銅、銀、鉛、及び錫からなる群より選ばれる少なくとも１種の金属元素を含有する場合）には、上記無機ナノ粒子のナノ炭素材料に対するドーピング効果により優れ、結果として、上記熱電変換層は、性能指数Ｚにより一層優れる。 When the inorganic nanoparticles are metal sulfide particles or metal oxide particles (preferably, the inorganic nanoparticles include at least one metal element selected from the group consisting of copper, silver, lead, and tin). In the case of containing), the doping effect of the inorganic nanoparticles on the nanocarbon material is excellent, and as a result, the thermoelectric conversion layer is more excellent in the figure of merit Z.
以下に、熱電変換層を形成する各種成分について説明する。 Below, the various components which form a thermoelectric conversion layer are demonstrated.
本発明の熱電変換層は、ナノ炭素材料と無機ナノ粒子とを含有する。
以下、まず、熱電変換層を構成する各成分について説明し、次いで、熱電変換層の製造方法について説明する。
The thermoelectric conversion layer of the present invention contains a nanocarbon material and inorganic nanoparticles.
Hereinafter, each component constituting the thermoelectric conversion layer will be described first, and then a method for manufacturing the thermoelectric conversion layer will be described.
＜ナノ炭素材料＞
本発明において、ナノ炭素材料とは、ナノサイズ（１０００ｎｍ未満）であれば特に限定されない。なお、例えば、カーボンナノチューブ、カーボンナノホーン、カーボンナノファイバー、カーボンナノフィラメント、カーボンナノコイル、気相成長カーボン（ＶＧＣＦ）、及びコップ型のナノカーボン物質等の場合には、一次粒子の最も短い径の長さが１０００ｎｍ未満を満たしていれば、上記一次粒子が凝集した二次粒子もナノ炭素材料に含まれる。つまり、例えば、カーボンナノチューブ（以下「ＣＮＴ」ともいう。）は、強い分子間力で帯状または粒状に凝集するが、その凝集物の最も短い径の長さが１０００ｎｍを超えても、構成するカーボンナノチューブ一本の直径が１０００ｎｍ未満であれば、ナノ炭素材料に含まれる。また、例えば、グラフェン等の場合には、その厚みが１０００ｎｍ未満であればナノ炭素材料に含まれる。
<Nanocarbon materials>
In the present invention, the nanocarbon material is not particularly limited as long as it is nano-sized (less than 1000 nm). For example, in the case of carbon nanotubes, carbon nanohorns, carbon nanofibers, carbon nanofilaments, carbon nanocoils, vapor grown carbon (VGCF), cup-shaped nanocarbon materials, etc. If the length is less than 1000 nm, secondary particles in which the primary particles are aggregated are also included in the nanocarbon material. In other words, for example, carbon nanotubes (hereinafter also referred to as “CNT”) aggregate in a band shape or granular shape with a strong intermolecular force. Even if the length of the shortest diameter of the aggregate exceeds 1000 nm, the carbon that constitutes the carbon nanotube is formed. If the diameter of one nanotube is less than 1000 nm, it is included in the nanocarbon material. For example, in the case of graphene or the like, if the thickness is less than 1000 nm, it is included in the nanocarbon material.
ナノ炭素材料としては、上記要件を満たし、導電性を有する炭素材料であれば特に限定されない。
ナノ炭素材料としては、炭素原子のｓｐ２混成軌道で構成される炭素−炭素結合によって炭素原子同士が化学結合してなるナノメートルサイズの導電性材料等が挙げられ、具体的には、フラーレン、カーボンナノチューブ（以下「ＣＮＴ」ともいう。）、カーボンナノチューブの片側が閉じた形をしたカーボンナノホーン、カーボンナノファイバー、カーボンナノウォール、カーボンナノフィラメント、カーボンナノコイル、気相成長カーボン（ＶＧＣＦ）、グラファイト、グラフェン、カーボンナノ粒子、及び、カーボンナノチューブの頭部に穴があいたコップ型のナノカーボン物質等が挙げられる。また、ナノ炭素材料として、結晶構造がグラファイト型であり導電性を示す各種カーボンブラックも用いることができ、例えば、ケッチェンブラック、及びアセチレンブラック等が挙げられる。
The nanocarbon material is not particularly limited as long as it satisfies the above requirements and has conductivity.
Examples of the nanocarbon material include a nanometer-size conductive material in which carbon atoms are chemically bonded by a carbon-carbon bond composed of sp 2 hybrid orbitals of carbon atoms, specifically, fullerene, Carbon nanotube (hereinafter also referred to as “CNT”), carbon nanohorn with carbon nanotubes closed on one side, carbon nanofiber, carbon nanowall, carbon nanofilament, carbon nanocoil, vapor grown carbon (VGCF), graphite , Graphene, carbon nanoparticles, and cup-shaped nanocarbon materials having holes in the heads of carbon nanotubes. In addition, as the nanocarbon material, various carbon blacks having a crystalline structure and exhibiting conductivity can be used, and examples thereof include ketjen black and acetylene black.
これらのナノ炭素材料は、従来の製造方法によって製造できる。具体的には、二酸化炭素の接触水素還元、アーク放電法、レーザー蒸発法、ＣＶＤ（Chemical Vapor Deposition）法、気相成長法、気相流動法、一酸化炭素を高温高圧化で鉄触媒と共に反応させて気相で成長させるＨｉＰｃｏ（High Pressure CO）法、及びオイルファーネス法等が挙げられる。このようにして製造されたナノ炭素材料は、そのまま用いることもでき、また、洗浄、遠心分離、ろ過、酸化、及び、クロマトグラフ等によって精製されたものを用いることもできる。さらに、ナノ炭素材料は、必要に応じて、ボールミル、振動ミル、サンドミル、及びロールミル等のボール型混練装置等を用いて粉砕したもの、及び、化学的又は物理的処理によって短く切断されたもの等を用いることもできる。 These nanocarbon materials can be manufactured by a conventional manufacturing method. Specifically, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD (Chemical Vapor Deposition) method, vapor phase growth method, vapor phase flow method, carbon monoxide is reacted with iron catalyst at high temperature and high pressure Examples thereof include a HiPco (High Pressure CO) method, which is grown in a gas phase, and an oil furnace method. The nanocarbon material produced in this manner can be used as it is, or a material purified by washing, centrifugation, filtration, oxidation, chromatography, etc. can be used. Further, the nanocarbon material is pulverized using a ball-type kneading device such as a ball mill, a vibration mill, a sand mill, and a roll mill, as necessary, and a material cut short by chemical or physical treatment, etc. Can also be used.
ナノ炭素材料のサイズはナノメートルサイズであれば特に限定されない。ナノ炭素材料が、カーボンナノチューブ、カーボンナノホーン、カーボンナノファイバー、カーボンナノフィラメント、カーボンナノコイル、気相成長カーボン（ＶＧＣＦ）、又はコップ型のナノカーボン物質等である場合、製造容易性、成膜性、及び導電性等の観点から、平均長さは０．０１〜１０００μｍが好ましく、０．１〜１００μｍがより好ましい。また、それらの平均直径は、耐久性、透明性、成膜性、及び導電性等の観点から、０．４〜１００ｎｍが好ましく、０．４〜５０ｎｍがより好ましく、０．４〜１５ｎｍが更に好ましい。 The size of the nanocarbon material is not particularly limited as long as it is a nanometer size. When the nanocarbon material is a carbon nanotube, a carbon nanohorn, a carbon nanofiber, a carbon nanofilament, a carbon nanocoil, a vapor growth carbon (VGCF), a cup-shaped nanocarbon material, etc., ease of production, film formability From the viewpoints of conductivity and the like, the average length is preferably 0.01 to 1000 μm, more preferably 0.1 to 100 μm. In addition, the average diameter thereof is preferably 0.4 to 100 nm, more preferably 0.4 to 50 nm, and further preferably 0.4 to 15 nm from the viewpoints of durability, transparency, film formability, and conductivity. preferable.
ナノ炭素材料としては、導電性により優れる、及び／又は、溶媒中での分散性に優れる点で、カーボンナノチューブ、カーボンナノファイバー、フラーレン、グラファイト、グラフェン、又はカーボンナノ粒子が好ましく、カーボンナノチューブがより好ましい。 As the nanocarbon material, carbon nanotubes, carbon nanofibers, fullerenes, graphite, graphene, or carbon nanoparticles are preferable, and carbon nanotubes are more preferable because they are more excellent in conductivity and / or excellent in dispersibility in a solvent. preferable.
（カーボンナノチューブ）
以下、カーボンナノチューブ（ＣＮＴ）について説明する。
カーボンナノチューブ（ＣＮＴ）は、１枚の炭素膜（グラフェンシート）が円筒状に巻かれた単層ＣＮＴ、２枚のグラフェンシートが同心円状に巻かれた２層ＣＮＴ、及び、複数のグラフェンシートが同心円状に巻かれた多層ＣＮＴがある。なお、単層ＣＮＴ、２層ＣＮＴ、及び多層ＣＮＴを各々単独で用いても、２種以上を併用してもよい。特に、導電性及び半導体特性において優れた性質を持つ単層ＣＮＴ又は２層ＣＮＴを用いることが好ましく、単層ＣＮＴを用いることがより好ましい。
上記単層ＣＮＴは、半導体性のものであっても、金属性のものであってもよく、両者が併せて含有されていてもよい。また、ＣＮＴには金属等が内包されていてもよく、フラーレン等の分子が内包されたもの（特にフラーレンを内包したものをピーポッドという）が含有されていてもよい。
(carbon nanotube)
Hereinafter, the carbon nanotube (CNT) will be described.
A carbon nanotube (CNT) is a single-walled CNT in which a single carbon film (graphene sheet) is wound in a cylindrical shape, a double-walled CNT in which two graphene sheets are wound in a concentric shape, and a plurality of graphene sheets There are multi-walled CNTs wound concentrically. In addition, single-walled CNT, double-walled CNT, and multilayered CNT may be used alone or in combination of two or more. In particular, single-walled CNTs or double-walled CNTs having excellent properties in terms of conductivity and semiconductor properties are preferably used, and single-walled CNTs are more preferably used.
The single-walled CNT may be semiconducting or metallic, and both may be contained together. Further, the CNT may contain a metal or the like, or may contain a substance containing molecules such as fullerene (in particular, a substance containing fullerene is called a peapod).
ＣＮＴはアーク放電法、化学気相成長法（以下、ＣＶＤ法という）、及びレーザーアブレーション法等によって製造できる。ＣＮＴは、いずれの方法によって得られたものであってもよいが、アーク放電法又はＣＶＤ法により得られたものであることが好ましい。
ＣＮＴを製造する際には、同時にフラーレン、グラファイト、又は非晶性炭素が副生成物として生じることがある。これら副生成物を除去するために精製してもよい。ＣＮＴの精製方法は特に限定されないが、洗浄、遠心分離、ろ過、酸化、及びクロマトグラフ等の方法が挙げられる。その他に、硝酸、硫酸等による酸処理、又は超音波処理も不純物の除去には有効である。併せて、フィルターによる分離除去を行うことも、純度を向上させる観点からより好ましい。
CNT can be produced by an arc discharge method, a chemical vapor deposition method (hereinafter referred to as a CVD method), a laser ablation method, or the like. The CNT may be obtained by any method, but is preferably obtained by an arc discharge method or a CVD method.
When manufacturing CNT, fullerene, graphite, or amorphous carbon may be produced as a by-product at the same time. You may refine | purify in order to remove these by-products. Although the purification method of CNT is not specifically limited, Methods, such as washing | cleaning, centrifugation, filtration, oxidation, and a chromatograph, are mentioned. In addition, acid treatment with nitric acid, sulfuric acid or the like, or ultrasonic treatment is also effective for removing impurities. In addition, it is more preferable to perform separation and removal using a filter from the viewpoint of improving purity.
ＣＮＴを製造して使用する場合、精製の後、得られたＣＮＴをそのまま用いることもできる。また、ＣＮＴは一般に紐状で生成されるため、用途に応じて所望の長さにカットして用いてもよい。ＣＮＴは、硝酸及び硫酸等による酸処理、超音波処理、並びに、凍結粉砕法等により短繊維状にカットすることができる。また、併せてフィルターによる分離を行うことも、純度を向上させる観点から好ましい。
なお、カットしたＣＮＴだけではなく、あらかじめ短繊維状に作製したＣＮＴも同様に使用できる。
When producing and using CNT, the obtained CNT can also be used as it is after refinement | purification. Moreover, since CNT is generally produced in a string shape, it may be cut into a desired length depending on the application. CNT can be cut into short fibers by acid treatment with nitric acid, sulfuric acid or the like, ultrasonic treatment, freeze pulverization method, or the like. In addition, it is also preferable to perform separation using a filter from the viewpoint of improving purity.
In addition, not only the cut CNT but also a CNT prepared in a short fiber shape in advance can be used similarly.
単層ＣＮＴの平均長さは特に制限されないが、製造容易性、成膜性、及び導電性等の観点から、０．０１〜１０００μｍであることが好ましく、０．１〜１００μｍであることがより好ましい。
単層ＣＮＴの直径は、特に制限されないが、耐久性、成膜性、導電性、及び熱電性能等により優れる点で、０．５〜４．０ｎｍが好ましく、０．６〜３．０ｎｍがより好ましく、０．７〜２．０ｎｍが更に好ましい。
The average length of the single-walled CNT is not particularly limited, but is preferably 0.01 to 1000 μm and more preferably 0.1 to 100 μm from the viewpoints of manufacturability, film formability, and conductivity. preferable.
The diameter of the single-walled CNT is not particularly limited, but is preferably 0.5 to 4.0 nm, more preferably 0.6 to 3.0 nm in terms of durability, film formability, conductivity, thermoelectric performance, and the like. Preferably, 0.7 to 2.0 nm is more preferable.
・単層ＣＮＴの直径の算出
本明細書で記載する単層ＣＮＴの直径は、下記の方法により評価したものである。すなわち、単層ＣＮＴの５３２ｎｍ励起光でのラマンスペクトルを測定し（励起波長５３２ｎｍ）、ラジアルブリージング（ＲＢＭ）モードのシフトω（ＲＢＭ）（ｃｍ−１）より、下記算出式を用いて算出する。なお、上記ωは、ＲＢＭモード中の最大ピークの値を採用する。算出式：直径（ｎｍ）＝２４８／ω（ＲＢＭ）
-Calculation of diameter of single-walled CNT The diameter of the single-walled CNT described in this specification is evaluated by the following method. That is, the Raman spectrum of single-walled CNT with 532 nm excitation light is measured (excitation wavelength: 532 nm), and is calculated from the radial breathing (RBM) mode shift ω (RBM) (cm −1 ) using the following calculation formula. Note that the value of the maximum peak in the RBM mode is used as ω. Calculation formula: Diameter (nm) = 248 / ω (RBM)
ナノ炭素材料の含有量は、熱電変換層中、熱電変換層の全質量に対して、１〜９９質量％が好ましく、５〜９５質量％がより好ましく、１０〜９５質量％が更に好ましい。
ナノ炭素材料は、熱電変換層中、１種を単独で用いても、２種以上を併用してもよい。２種以上のナノ炭素材料を併用する場合には、合計含有量が上記範囲内であることが好ましい。
The content of the nanocarbon material is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, and still more preferably 10 to 95% by mass with respect to the total mass of the thermoelectric conversion layer in the thermoelectric conversion layer.
A nanocarbon material may be used individually by 1 type in a thermoelectric conversion layer, or may use 2 or more types together. When using 2 or more types of nano carbon materials together, it is preferable that total content is in the said range.
＜無機ナノ粒子＞
本発明において、無機ナノ粒子とは、ナノサイズ（１０００ｎｍ未満）であれば特に限定されない。なお、一次粒子の最も短い径（短径）の長さが１０００ｎｍ未満であれば、上記一次粒子が凝集した二次粒子も無機ナノ粒子に含まれる。なお、一次粒子の短径は、投影面積円相当径から求めることができる。
無機ナノ粒子としては、上記要件を満たし、且つ、金属元素を含有する無機材料であれば特に限定されず、金属粒子（例えば、銅粒子、銀粒子、鉛粒子、亜鉛粒子、及び錫粒子等）、金属酸化物粒子、及び金属硫化物粒子等が挙げられるが、なかでも、熱電変換性能により優れる点で、金属硫化物粒子又は金属酸化物粒子が好ましく、金属硫化物粒子がより好ましい。
また、上記金属硫化物粒子及び金属酸化物粒子は、熱電変換性能により優れる点で、銅、銀、鉛、亜鉛、及び錫からなる群より選ばれる少なくとも１種の金属元素を含有することが好ましく、銅、銀、鉛、及び錫からなる群より選ばれる少なくとも１種の金属元素を含有することがより好ましい。
無機ナノ粒子としては、なかでも、熱電変換性能により優れる点で、銅、銀、鉛、及び錫からなる群より選ばれる少なくとも１種の金属を含む硫化物であることがより好ましい。
なお、無機ナノ粒子は、上記金属元素のほかに、目的に応じ他の金属元素を含有してもよい。つまり、無機ナノ粒子は、銅、銀、鉛、亜鉛、及び錫からなる群より選ばれる少なくとも１種の金属元素と、銅、銀、鉛、亜鉛、及び錫以外の少なくとも１種の金属元素とを含有していてもよい。
２種以上の金属元素を含む酸化物及び硫化物としては、例えば、ＣｕＡｌＯ２、ＣｕＧａＯ２、ＣｕＩｎＯ２、ＡｇＡｌＯ２、ＡｇＧａＯ２、ＡｇＩｎＯ２、ＰｂＴｉＯ３、Ｓｎ２Ｎｂ２Ｏ７、Ｓｎ２Ｔａ２Ｏ７、ＳｎＮｂ２Ｏ６、ＳｎＴａ２Ｏ６、ＣｕＡｌＳ２、ＣｕＧａＳ２、ＣｕＩｎＳ２、Ｃｕ２ＺｎＧｅＳ４、Ｃｕ２ＺｎＳｎＳ４、Ｃｕ１２（１−ｘ−ｙ）Ｎｉ１２ｘＺｎ１２ｙＳｂ４Ｓ１３、Ｃｕ２６Ｖ２Ｓｉ６Ｓ３２、Ｃｕ２６Ｖ２Ｇｅ６Ｓ３２、Ｃｕ２６Ｖ２Ｓｎ６Ｓ３２、Ｃｕ２６Ｎｂ２Ｓｉ６Ｓ３２、Ｃｕ２６Ｎｂ２Ｇｅ６Ｓ３２、Ｃｕ２６Ｎｂ２Ｓｎ６Ｓ３２、Ｃｕ２６Ｔａ２Ｓｉ６Ｓ３２、Ｃｕ２６Ｔａ２Ｇｅ６Ｓ３２、Ｃｕ２６Ｔａ２Ｓｎ６Ｓ３２、ＡｇＡｌＳ２、ＡｇＧａＳ２、ＡｇＩｎＳ２、Ａｇ２ＺｎＧｅＳ４、Ａｇ２ＺｎＳｎＳ４、Ｓｎ１−ｘＮａｘＳ、Ｓｎ１−ｘＡｇｘＳ、Ｐｂ１−ｘＮａｘＳ、及びＰｂ１−ｘＡｇｘＳ等が挙げられる。なお、ｘは、０〜０．３であり、ｙは、０〜０．３である。
<Inorganic nanoparticles>
In the present invention, the inorganic nanoparticles are not particularly limited as long as they are nano-sized (less than 1000 nm). In addition, if the length of the shortest diameter (short diameter) of a primary particle is less than 1000 nm, the secondary particle which the said primary particle aggregated is also contained in an inorganic nanoparticle. The minor axis of the primary particles can be obtained from the projected area equivalent circle diameter.
The inorganic nanoparticles are not particularly limited as long as they satisfy the above requirements and contain a metal element. Metal particles (for example, copper particles, silver particles, lead particles, zinc particles, and tin particles) , Metal oxide particles, metal sulfide particles, and the like. Among them, metal sulfide particles or metal oxide particles are preferable, and metal sulfide particles are more preferable in terms of excellent thermoelectric conversion performance.
The metal sulfide particles and the metal oxide particles preferably contain at least one metal element selected from the group consisting of copper, silver, lead, zinc, and tin in that the thermoelectric conversion performance is superior. It is more preferable to contain at least one metal element selected from the group consisting of copper, silver, lead, and tin.
In particular, the inorganic nanoparticles are more preferably sulfides containing at least one metal selected from the group consisting of copper, silver, lead, and tin from the viewpoint of superior thermoelectric conversion performance.
In addition to the above metal elements, the inorganic nanoparticles may contain other metal elements depending on the purpose. That is, the inorganic nanoparticles include at least one metal element selected from the group consisting of copper, silver, lead, zinc, and tin, and at least one metal element other than copper, silver, lead, zinc, and tin. May be contained.
The oxides and sulfides containing two or more metal elements, for example, CuAlO 2, CuGaO 2, CuInO 2, AgAlO 2, AgGaO 2, AgInO 2, PbTiO 3, Sn 2 Nb 2 O 7, Sn 2 Ta 2 O 7 , SnNb 2 O 6 , SnTa 2 O 6 , CuAlS 2 , CuGaS 2 , CuInS 2 , Cu 2 ZnGeS 4 , Cu 2 ZnSnS 4 , Cu 12 (1-xy) Ni 12x Zn 12y Sb 4 S 13 , Cu 26 V 2 Si 6 S 32 , Cu 26 V 2 Ge 6 S 32, Cu 26 V 2 Sn 6 S 32, Cu 26 Nb 2 Si 6 S 32, Cu 26 Nb 2 Ge 6 S 32, Cu 26 Nb 2 Sn 6 S 32, Cu 26 Ta 2 Si 6 S 32, Cu 26 Ta 2 Ge 6 S 32, Cu 6 Ta 2 Sn 6 S 32, AgAlS 2, AgGaS 2, AgInS 2, Ag 2 ZnGeS 4, Ag 2 ZnSnS 4, Sn 1-x Na x S, Sn 1-x Ag x S, Pb 1-x Na x S , And Pb 1-x Ag x S. Note that x is 0 to 0.3, and y is 0 to 0.3.
無機ナノ粒子の含有量は、熱電変換層中、熱電変換層の全質量に対して、０．０１〜９０質量％が好ましく、０．０１〜８５質量％がより好ましく、０．０１〜８０質量％が更に好ましい。
無機ナノ粒子は、熱電変換層中、１種を単独で用いても、２種以上を併用してもよい。２種以上の無機ナノ粒子を併用する場合には、合計含有量が上記範囲内であることが好ましい。
The content of the inorganic nanoparticles is preferably 0.01 to 90% by mass, more preferably 0.01 to 85% by mass, and 0.01 to 80% by mass with respect to the total mass of the thermoelectric conversion layer in the thermoelectric conversion layer. % Is more preferable.
Inorganic nano particles may be used individually by 1 type in a thermoelectric conversion layer, or may use 2 or more types together. When using 2 or more types of inorganic nanoparticles together, it is preferable that total content is in the said range.
また、ナノ炭素材料に対する無機ナノ粒子の含有量は特に制限されず、通常、０．００１〜４００質量％の場合が多い。なかでも、性能指数Ｚにより優れる点で、ナノ炭素材料に対する無機ナノ粒子の含有量は、０．０１〜３００質量％であることが好ましい。なかでも、性能指数Ｚにより一層優れる点で、無機ナノ粒子の含有量は、ナノ炭素材料に対して、０．０５質量％以上が好ましく、２５０質量％以下が好ましく、１００質量％以下がより好ましく、５０質量％以下が更に好ましく、８質量％以下が特に好ましく、３質量％以下が最も好ましい。 Moreover, the content of the inorganic nanoparticles with respect to the nanocarbon material is not particularly limited, and is usually 0.001 to 400% by mass in many cases. Especially, it is preferable that content of the inorganic nanoparticle with respect to a nanocarbon material is 0.01-300 mass% by the point which is excellent with the figure of merit Z. Among them, the content of the inorganic nanoparticles is preferably 0.05% by mass or more, preferably 250% by mass or less, and more preferably 100% by mass or less with respect to the nanocarbon material in that the performance index Z is more excellent. 50 mass% or less is further more preferable, 8 mass% or less is especially preferable, and 3 mass% or less is the most preferable.
［任意成分］
本発明の熱電変換層は、上述した成分以外の他の成分（バインダー、界面活性剤、酸化防止剤、耐光安定剤、耐熱安定剤、及び可塑剤等）を含有してもよい。各成分の定義、具体例及び好適な態様は、それぞれ、後述する熱電変換層形成用組成物に含有される各成分と同じである。
[Optional ingredients]
The thermoelectric conversion layer of the present invention may contain other components (binder, surfactant, antioxidant, light-resistant stabilizer, heat-resistant stabilizer, plasticizer, etc.) other than the components described above. Definitions, specific examples, and preferred embodiments of the respective components are the same as the respective components contained in the thermoelectric conversion layer forming composition described later.
〔熱電変換層の製造方法〕
熱電変換層を製造する方法は特に制限されないが、例えば、以下に示す態様等が挙げられる。具体的には、所定の成分を含有する熱電変換層形成用組成物を予め調製し、この熱電変換層形成用組成物を用いて熱電変換層を形成する方法である。
まず、熱電変換層形成用組成物について述べ、その後、製造方法について述べる。
[Method for producing thermoelectric conversion layer]
Although the method in particular of manufacturing a thermoelectric conversion layer is not restrict | limited, For example, the aspect shown below etc. are mentioned. Specifically, a thermoelectric conversion layer forming composition containing a predetermined component is prepared in advance, and a thermoelectric conversion layer is formed using this thermoelectric conversion layer forming composition.
First, a composition for forming a thermoelectric conversion layer is described, and then a manufacturing method is described.
（熱電変換層形成用組成物）
上述のとおり、熱電変換層形成用組成物は、ナノ炭素材料及び無機ナノ粒子を含有する。
まず、組成物中に含有される各成分について述べ、その後、組成物の調製方法について述べる。
(Composition for forming thermoelectric conversion layer)
As described above, the composition for forming a thermoelectric conversion layer contains a nanocarbon material and inorganic nanoparticles.
First, each component contained in the composition is described, and then a method for preparing the composition is described.
（１）ナノ炭素材料及び無機ナノ粒子
上記ナノ炭素材料及び無機ナノ粒子の定義、具体例及び好適な態様については上述のとおりである。熱電変換層形成用組成物中の上記ナノ炭素材料及び無機ナノ粒子の合計含有量は特に制限されないが、組成物全量に対して、０．１〜２０質量％が好ましく、１〜１０質量％がより好ましい。また、固形分中の上記ナノ炭素材料及び無機ナノ粒子の合計含有量は、５〜９９．５質量％が好ましく、１０〜９０質量％がより好ましく、１０〜８０質量％が更に好ましい。なお、上記固形分とは、熱電変換層を形成する成分を意図し、溶媒は含まれない。
(1) Nanocarbon materials and inorganic nanoparticles The definitions, specific examples, and preferred embodiments of the nanocarbon materials and inorganic nanoparticles are as described above. The total content of the nanocarbon material and inorganic nanoparticles in the composition for forming a thermoelectric conversion layer is not particularly limited, but is preferably 0.1 to 20% by mass, and preferably 1 to 10% by mass with respect to the total amount of the composition. More preferred. Moreover, 5-99.5 mass% is preferable, as for the total content of the said nano carbon material and inorganic nanoparticle in solid content, 10-90 mass% is more preferable, and 10-80 mass% is still more preferable. In addition, the said solid content intends the component which forms a thermoelectric conversion layer, and a solvent is not contained.
（２）分散媒
熱電変換層形成用組成物は、上記ナノ炭素材料及び無機ナノ粒子の他に分散媒を含有するのが好ましい。
分散媒（溶媒）は、上記成分を分散できればよく、水、有機溶媒及びこれらの混合溶媒を用いることができる。有機溶媒としては、例えば、アルコール系溶媒、クロロホルム等の脂肪族ハロゲン系溶媒、ＤＭＦ（ジメチルホルムアミド）、ＮＭＰ（Ｎ−メチルピロリドン）、及びＤＭＳＯ（ジメチルスルホキシド）等の非プロトン性の極性溶媒、クロロベンゼン、ジクロロベンゼン、ベンゼン、トルエン、キシレン、メシチレン、テトラリン、テトラメチルベンゼン、及びピリジン等の芳香族系溶媒、シクロヘキサノン、アセトン、及びメチルエチルケトン等のケトン系溶媒、ジエチルエーテル、ＴＨＦ（テトラヒドロフラン）、ｔ−ブチルメチルエーテル、ジメトキシエタン、及びジグライム等のエーテル系溶媒等が挙げられる。
分散媒は、１種単独で又は２種以上組み合わせて使用することができる。
(2) Dispersion medium It is preferable that the composition for thermoelectric conversion layer formation contains a dispersion medium other than the said nano carbon material and an inorganic nanoparticle.
The dispersion medium (solvent) only needs to be able to disperse the above components, and water, organic solvents, and mixed solvents thereof can be used. Examples of the organic solvent include alcohol solvents, aliphatic halogen solvents such as chloroform, aprotic polar solvents such as DMF (dimethylformamide), NMP (N-methylpyrrolidone), and DMSO (dimethylsulfoxide), and chlorobenzene. Aromatic solvents such as dichlorobenzene, benzene, toluene, xylene, mesitylene, tetralin, tetramethylbenzene, and pyridine, ketone solvents such as cyclohexanone, acetone, and methyl ethyl ketone, diethyl ether, THF (tetrahydrofuran), t-butyl Examples thereof include ether solvents such as methyl ether, dimethoxyethane, and diglyme.
A dispersion medium can be used individually by 1 type or in combination of 2 or more types.
また、分散媒は、あらかじめ脱気しておくことが好ましい。分散媒中における溶存酸素濃度を、１０ｐｐｍ以下とすることが好ましい。脱気の方法としては、減圧下超音波を照射する方法、及び、アルゴン等の不活性ガスをバブリングする方法等が挙げられる。
更に、分散媒として水以外を使用する場合は、あらかじめ脱水しておくことが好ましい。分散媒中における水分量を、１０００ｐｐｍ以下とすることが好ましく、１００ｐｐｍ以下とすることがより好ましい。分散媒の脱水方法としては、モレキュラーシーブを用いる方法及び蒸留等の公知の方法を用いることができる。
The dispersion medium is preferably deaerated beforehand. The dissolved oxygen concentration in the dispersion medium is preferably 10 ppm or less. Examples of the degassing method include a method of irradiating ultrasonic waves under reduced pressure, a method of bubbling an inert gas such as argon, and the like.
Furthermore, when using other than water as the dispersion medium, it is preferable to dehydrate in advance. The amount of water in the dispersion medium is preferably 1000 ppm or less, and more preferably 100 ppm or less. As a method for dehydrating the dispersion medium, a method using a molecular sieve and a known method such as distillation can be used.
熱電変換層形成用組成物中の分散媒の含有量は、組成物全量に対して、２５〜９９．９質量％であることが好ましい。 It is preferable that content of the dispersion medium in the composition for thermoelectric conversion layer formation is 25-99.9 mass% with respect to the composition whole quantity.
（３）その他の成分
上述した成分の他、バインダー、界面活性剤、酸化防止剤、耐光安定剤、耐熱安定剤、及び可塑剤等が含まれていてもよい。
バインダーとしては、共役高分子及び非共役高分子が挙げられる。バインダーはナノ炭素材料の距離を調整することにより熱伝導率を低下させる効果を示す。
共役高分子としては、例えば、ポリチオフェン、ポリフルオレン、ＰＥＤＯＴ−ＰＳＳ（ポリエチレンジオキシチオフェン／ポリスチレンスルホン酸）、ポリアニリン、及び、ポリピロール等が挙げられる。非共役高分子としては、例えば、ポリスチレン、ポリ（メタ）アクリレート、ポリカーボネート、ポリエステル、エポキシ化合物、ポリシロキサン、及び、ゼラチン等が挙げられる。
なかでも、熱電変換層の熱電変換性能（特に、性能指数Ｚ）により優れる点で、上記バインダーは、非共役高分子が好ましく、水素結合性官能基を有する樹脂（水素結合性樹脂）がより好ましい。
水素結合性官能基としては、水素結合性を有する官能基であればよく、例えば、ＯＨ基、ＮＨ２基、ＮＨＲ基（Ｒは、芳香族基又は脂肪族炭化水素基を表す）、ＣＯＯＨ基、ＣＯＮＨ２基、ＮＨＯＨ基、ＳＯ３Ｈ基（スルホン酸基）、及び−ＯＰ（＝Ｏ）ＯＨ２基（リン酸基）等のほか、−ＮＨＣＯ−基、−ＮＨ−基、−ＣＯＮＨＣＯ−結合、−ＮＨ−ＮＨ−結合、−Ｃ（＝Ｏ）−基（カルボニル基）、及び−ＲＯＲ−基（エーテル基：Ｒは、それぞれ独立に、２価の芳香族炭化水素基又は２価の脂肪族炭化水素基を表す。ただし、２つのＲは同一であっても異なっていてもよい。）等を有する基が挙げられる。
水素結合性樹脂としては、カルボキシメチルセルロース、カルボキシエチルセルロース、メチルセルロース、エチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、メチルヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、結晶セルロース、キサンタンガム、グァーガム、ヒドロキシエチルグァーガム、カルボキシメチルグァーガム、トラガントガム、ローカストビーンガム、タマリンドシードガム、サイリウムシードガム、クインスシード、カラギーナン、ガラクタン、アラビアガム、ペクチン、プルラン、マンナン、グルコマンナン、デンプン、カードラン、カラギーナン、コンドロイチン硫酸、デルマタン硫酸、グリコーゲン、ヘパラン硫酸、ヒアルロン酸、ヒアルロン酸、ケラタン硫酸、コンドロイチン、ムコイチン硫酸、デキストラン、ケラト硫酸、サクシノグルカン、カロニン酸、アルギン酸、アルギン酸プロピレングリコール、マクロゴール、キチン、キトサン、カルボキシメチルキチン、ゼラチン、寒天、カードラン、ポリビニルアルコール、ポリビニルピロリドン、カルボキシビニルポリマー、アルキル変性カルボキシビニルポリマー、ポリアクリル酸、アクリル酸／メタクリル酸アルキル共重合体、ポリエチレングリコール、（アクリル酸ヒドロキシエチル／アクリロイルジメチルタウリンナトリウム）コポリマー、（アクリロイルジメチルタウリンアンモニウム／ビニルピロリドン）コポリマー、澱粉、化工澱粉、及び、ベントナイト等が挙げられる。なお、カルボキシ基等の酸性基を有するものは、一部もしくはすべてがナトリウム塩、カリウム塩、及びアンモニウム塩等の塩になっていてもよい。
(3) Other components In addition to the components described above, a binder, a surfactant, an antioxidant, a light-resistant stabilizer, a heat-resistant stabilizer, a plasticizer, and the like may be included.
Examples of the binder include conjugated polymers and non-conjugated polymers. The binder exhibits the effect of reducing the thermal conductivity by adjusting the distance of the nanocarbon material.
Examples of the conjugated polymer include polythiophene, polyfluorene, PEDOT-PSS (polyethylenedioxythiophene / polystyrene sulfonic acid), polyaniline, and polypyrrole. Examples of the non-conjugated polymer include polystyrene, poly (meth) acrylate, polycarbonate, polyester, epoxy compound, polysiloxane, and gelatin.
Among these, the binder is preferably a non-conjugated polymer, and more preferably a resin having a hydrogen-bonding functional group (hydrogen-bonding resin) from the viewpoint of superior thermoelectric conversion performance (particularly, figure of merit Z) of the thermoelectric conversion layer. .
The hydrogen bonding functional group may be any functional group having hydrogen bonding properties, for example, OH group, NH 2 group, NHR group (R represents an aromatic group or an aliphatic hydrocarbon group), COOH group. , CONH 2 group, NHOH group, SO 3 H group (sulfonic acid group), —OP (═O) OH 2 group (phosphoric acid group), etc., —NHCO— group, —NH— group, —CONHCO— Bond, —NH—NH— bond, —C (═O) — group (carbonyl group), and —ROR— group (ether group: R each independently represents a divalent aromatic hydrocarbon group or a divalent Represents an aliphatic hydrocarbon group, provided that two Rs may be the same or different, and the like.
Examples of hydrogen bonding resins include carboxymethyl cellulose, carboxyethyl cellulose, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose, hydroxypropyl methyl cellulose, crystalline cellulose, xanthan gum, guar gum, hydroxyethyl guar gum, carboxymethyl guar gum, tragacanth gum, locust Bean gum, tamarind seed gum, psyllium seed gum, quince seed, carrageenan, galactan, gum arabic, pectin, pullulan, mannan, glucomannan, starch, curdlan, carrageenan, chondroitin sulfate, dermatan sulfate, glycogen, heparan sulfate, hyaluronic acid , Hyaluronic acid, keratan sulfate , Chondroitin, mucoitin sulfate, dextran, keratosulfate, succinoglucan, carolinic acid, alginic acid, propylene glycol alginate, macrogol, chitin, chitosan, carboxymethylchitin, gelatin, agar, curdlan, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl Polymer, alkyl-modified carboxyvinyl polymer, polyacrylic acid, acrylic acid / alkyl methacrylate copolymer, polyethylene glycol, (hydroxyethyl acrylate / acryloyldimethyltaurine sodium) copolymer, (acryloyldimethyltaurine ammonium / vinylpyrrolidone) copolymer, starch , Modified starch, bentonite and the like. In addition, what has acidic groups, such as a carboxy group, may partly or entirely become salts, such as sodium salt, potassium salt, and ammonium salt.
上述した共役高分子又は非共役高分子の重量平均分子量は特に制限されず、例えば１０００以上であり、５０００以上が好ましく、７０００〜３００，０００がより好ましい。重量平均分子量は、ゲル浸透クロマトグラフィ法（ＧＰＣ（Gel Permeation Chromatography））法にて測定され、標準ポリスチレンで換算して求められる。 The weight average molecular weight of the conjugated polymer or nonconjugated polymer described above is not particularly limited, and is, for example, 1000 or more, preferably 5000 or more, and more preferably 7000 to 300,000. The weight average molecular weight is measured by a gel permeation chromatography (GPC (Gel Permeation Chromatography)) method and is determined by conversion with standard polystyrene.
上記ナノ炭素材料及び無機ナノ粒子の合計含有量に対するバインダーの含有量は、特に限定されず、０．１〜１００質量％が好ましい。 The content of the binder with respect to the total content of the nanocarbon material and inorganic nanoparticles is not particularly limited, and is preferably 0.1 to 100% by mass.
界面活性剤としては、公知の界面活性剤（カチオン性界面活性剤、及びアニオン性界面活性剤等）が挙げられる。なかでも、アニオン性界面活性剤が好ましく、デオキシコール酸ナトリウムがより好ましい。なお、界面活性剤は分散剤としての機能を有する。
界面活性剤の含有量は、組成物全量に対して、０．１〜２０質量％が好ましく、１〜１０質量％がより好ましい。
また、熱電変換層は、酸化防止剤、耐光安定剤、耐熱安定剤、及び可塑剤等も含有してもよい。
酸化防止剤としては、イルガノックス１０１０（日本チバガイギー製）、スミライザーＧＡ−８０（住友化学工業（株）製）、スミライザーＧＳ（住友化学工業（株）製）、及びスミライザーＧＭ（住友化学工業（株）製）等が挙げられる。
耐光安定剤としては、ＴＩＮＵＶＩＮ ２３４（ＢＡＳＦ製）、ＣＨＩＭＡＳＳＯＲＢ ８１（ＢＡＳＦ製）、及びサイアソーブＵＶ−３８５３（サンケミカル製）等が挙げられる。
耐熱安定剤としては、ＩＲＧＡＮＯＸ １７２６（ＢＡＳＦ製）が挙げられる。
可塑剤としては、アデカサイザーＲＳ（アデカ製）等が挙げられる。
Examples of the surfactant include known surfactants (such as a cationic surfactant and an anionic surfactant). Among these, an anionic surfactant is preferable, and sodium deoxycholate is more preferable. The surfactant has a function as a dispersant.
0.1-20 mass% is preferable with respect to the composition whole quantity, and, as for content of surfactant, 1-10 mass% is more preferable.
The thermoelectric conversion layer may also contain an antioxidant, a light-resistant stabilizer, a heat-resistant stabilizer, a plasticizer, and the like.
As antioxidants, Irganox 1010 (manufactured by Ciba Geigy Japan), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), and Sumilizer GM (Sumitomo Chemical Industries, Ltd.) )) And the like.
Examples of the light-resistant stabilizer include TINUVIN 234 (manufactured by BASF), CHIMASSORB 81 (manufactured by BASF), and Siasorb UV-3853 (manufactured by Sun Chemical).
IRGANOX 1726 (made by BASF) is mentioned as a heat-resistant stabilizer.
Examples of the plasticizer include Adeka Sizer RS (manufactured by Adeka).
（熱電変換層形成用組成物の製造方法）
熱電変換層形成用組成物の製造方法は特に制限されないが、以下の工程１及び工程２を含む製造方法が好ましく挙げられる。この製造方法にて得られる熱電変換層形成用組成物中には、ナノ炭素材料と無機ナノ粒子とが複合化された複合材料（複合粒子）が含まれる。
（工程１）ナノ炭素材料の分散液を調製する工程
（工程２）上記分散液中で無機ナノ粒子を形成し、ナノ炭素材料及び無機ナノ粒子を含有する熱電変換層形成用組成物を得る工程
(Method for producing composition for forming thermoelectric conversion layer)
Although the manufacturing method in particular of the composition for thermoelectric conversion layer formation is not restrict | limited, The manufacturing method containing the following process 1 and process 2 is mentioned preferably. The composition for forming a thermoelectric conversion layer obtained by this production method includes a composite material (composite particles) in which a nanocarbon material and inorganic nanoparticles are combined.
(Step 1) Step of preparing a dispersion of nanocarbon material (Step 2) Step of forming inorganic nanoparticles in the dispersion to obtain a composition for forming a thermoelectric conversion layer containing the nanocarbon material and inorganic nanoparticles
（工程１）
工程１は、ナノ炭素材料の分散液を調製する工程である。
分散媒（溶媒）は、ナノ炭素材料を分散できればよく、水、有機溶媒及びこれらの混合溶媒を用いることができる。有機溶媒としては、例えば、メタノール、エタノール及びイソプピルアルコール等のアルコール類等が挙げられる。
分散媒は、１種単独で又は２種以上組み合わせて使用することができる。
(Process 1)
Step 1 is a step of preparing a dispersion of nanocarbon material.
The dispersion medium (solvent) only needs to be able to disperse the nanocarbon material, and water, an organic solvent, and a mixed solvent thereof can be used. Examples of the organic solvent include alcohols such as methanol, ethanol and isopropyl alcohol.
A dispersion medium can be used individually by 1 type or in combination of 2 or more types.
また、分散媒は、あらかじめ脱気しておくことが好ましい。分散媒中における溶存酸素濃度を、１０ｐｐｍ以下とすることが好ましい。脱気の方法としては、減圧下超音波を照射する方法、及び、アルゴン等の不活性ガスをバブリングする方法等が挙げられる。
さらに、分散媒として水以外を使用する場合は、あらかじめ脱水しておくことが好ましい。分散媒中における水分量を、１０００ｐｐｍ以下とすることが好ましく、１００ｐｐｍ以下とすることがより好ましい。分散媒の脱水方法としては、モレキュラーシーブを用いる方法及び蒸留等の公知の方法を用いることができる。
分散液中の分散媒の含有量は、組成物全量に対して、２５〜９９．９９質量％が好ましく、３０〜９９．９５質量％がより好ましく、３０〜９９．９質量％が更に好ましい。
なお、分散液は、ナノ炭素材料のほか、所望により他の成分を混合して調製することができる。好ましくは、分散媒にナノ炭素材料、及び所望により他の成分を混合して、ナノ炭素材料を分散させて調製する。
分散液の調製方法に特に制限はなく、通常の混合装置等を用いて常温常圧下で行うことができる。例えば、各成分を溶媒中で撹拌、振とう、又は、混練して、溶解又は分散させて調製すればよい。溶解又は分散を促進するため超音波処理を行ってもよい。
また、上記分散工程において溶媒を室温以上沸点以下の温度まで加熱する、分散時間を延ばす、又は、撹拌、振とう、混練、及び超音波等の印加強度を上げる等によって、ナノ炭素材料の分散性を高めることができる。
The dispersion medium is preferably deaerated beforehand. The dissolved oxygen concentration in the dispersion medium is preferably 10 ppm or less. Examples of the degassing method include a method of irradiating ultrasonic waves under reduced pressure, a method of bubbling an inert gas such as argon, and the like.
Furthermore, when using other than water as the dispersion medium, it is preferable to dehydrate in advance. The amount of water in the dispersion medium is preferably 1000 ppm or less, and more preferably 100 ppm or less. As a method for dehydrating the dispersion medium, a method using a molecular sieve and a known method such as distillation can be used.
The content of the dispersion medium in the dispersion is preferably 25 to 99.99% by mass, more preferably 30 to 99.95% by mass, and still more preferably 30 to 99.9% by mass with respect to the total amount of the composition.
In addition to the nanocarbon material, the dispersion can be prepared by mixing other components as desired. Preferably, the nanocarbon material is mixed with the dispersion medium and optionally other components, and the nanocarbon material is dispersed to prepare.
There is no restriction | limiting in particular in the preparation method of a dispersion liquid, It can carry out under normal temperature normal pressure using a normal mixing apparatus etc. For example, each component may be prepared by stirring, shaking or kneading in a solvent and dissolving or dispersing. Sonication may be performed to promote dissolution or dispersion.
Further, in the above dispersion step, the dispersibility of the nanocarbon material is increased by heating the solvent to a temperature not lower than the room temperature and not higher than the boiling point, extending the dispersion time, or increasing the application strength such as stirring, shaking, kneading, and ultrasonic waves. Can be increased.
（工程２）
工程２は、上記分散液中で無機ナノ粒子を形成する工程である。一般的に、溶液中での無機ナノ粒子の形成では、溶液中に目的物が析出する反応（均一核生成）と、溶液中に予め存在する核上又は反応容器の壁上に目的物が析出する反応（不均一核生成）とが同時に進行する。一般に、均一核生成と不均一核生成とでは、後者の方がより低いエネルギーで進行する。上記分散液中で無機ナノ粒子を形成することで、ナノ炭素材料を核とし、ナノ炭素材料上への目的物の析出が支配的に進行し、無機ナノ粒子が凝集することなく、ナノ炭素材料上に無機ナノ粒子が均一に担持された複合粒子を得ることができる。
上記分散液中で無機ナノ粒子を形成する工程は特に限定されないが、例えば、無機ナノ材料の前駆体となる金属塩をナノ炭素材料の存在下で金属元素を含有する無機ナノ粒子とする方法等が挙げられる。
無機ナノ粒子が金属酸化物粒子である場合には、例えば、上記分散液中、ナノ炭素材料の存在下でアルカリにより金属塩を金属水酸化物としたのち、熱処理により金属酸化物粒子とする方法が挙げられる。
また、無機ナノ粒子が金属硫化物粒子である場合には、例えば、上記分散液中、硫黄源（例えば、チオアセトアミド等）と、金属塩とを反応させることにより金属硫化物粒子を得る方法が挙げられる。
上記金属塩としては、適切な溶剤に溶解して金属イオンと塩基（陰イオン）とに解離されるものであれば特に制限はなく、Ｍ（ＣＨ３ＣＯＯ）ｎ、Ｍ（ＮＯ３）ｎ、ＭＣｌｎ、Ｍ２/ｎ（ＳＯ４）、及び、Ｍ３/ｎ（ＰＯ４）（Ｍは、ｎ価の金属原子を表す）等が挙げられる。上記金属イオンとしては、上記の金属塩が解離したものを好適に用いることができる。具体例としては、例えば、Ｃｕ（Ｉ）イオン、Ｃｕ（ＩＩ）イオン、Ａｇ（Ｉ）イオン、Ｐｂ（ＩＩ）イオン、Ｚｎ（ＩＩ）イオン、及び、Ｓｎ（ＩＩ）イオンが挙げられ、なかでも、Ｃｕ（Ｉ）イオン、Ｃｕ（ＩＩ）イオン、Ａｇ（Ｉ）イオン、Ｐｂ（ＩＩ）イオン、Ｚｎ（ＩＩ）イオン、又は、Ｓｎ（ＩＩ）イオンが好ましい。
(Process 2)
Step 2 is a step of forming inorganic nanoparticles in the dispersion. In general, in the formation of inorganic nanoparticles in a solution, a reaction in which the target product precipitates in the solution (homogeneous nucleation), and the target product precipitates on the nucleus pre-existing in the solution or on the wall of the reaction vessel. Reaction (heterogeneous nucleation) proceeds simultaneously. In general, in homogeneous nucleation and heterogeneous nucleation, the latter proceeds with lower energy. By forming inorganic nanoparticles in the above dispersion, the nanocarbon material is used as a nucleus, and the precipitation of the target substance on the nanocarbon material proceeds predominantly, and the inorganic nanoparticles are not aggregated. Composite particles having inorganic nanoparticles uniformly supported thereon can be obtained.
The step of forming inorganic nanoparticles in the dispersion is not particularly limited. For example, a method in which a metal salt that is a precursor of an inorganic nanomaterial is converted to inorganic nanoparticles containing a metal element in the presence of a nanocarbon material, etc. Is mentioned.
When the inorganic nanoparticles are metal oxide particles, for example, a method in which the metal salt is converted into a metal hydroxide with an alkali in the presence of the nanocarbon material in the dispersion and then converted into metal oxide particles by heat treatment. Is mentioned.
When the inorganic nanoparticles are metal sulfide particles, for example, there is a method for obtaining metal sulfide particles by reacting a sulfur source (for example, thioacetamide) with a metal salt in the dispersion. Can be mentioned.
The metal salt is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (CH 3 COO) n , M (NO 3 ) n , MCl n , M 2 / n (SO 4 ), M 3 / n (PO 4 ) (M represents an n-valent metal atom), and the like. As said metal ion, what dissociated said metal salt can be used suitably. Specific examples include Cu (I) ion, Cu (II) ion, Ag (I) ion, Pb (II) ion, Zn (II) ion, and Sn (II) ion, among others. Cu (I) ions, Cu (II) ions, Ag (I) ions, Pb (II) ions, Zn (II) ions, or Sn (II) ions are preferred.
ナノ炭素材料上に無機ナノ粒子を均一に形成するための好ましい条件について説明する。
上記分散液中で無機ナノ粒子を形成する際の金属塩の濃度としては、１×１０−１０〜１×１０−１Ｍが好ましく、１×１０−１０〜１×１０−３Ｍがより好ましく、１×１０−１０〜１×１０−５Ｍが更に好ましい。同様に、金属塩のナノ炭素材料に対する質量比としては、２０質量％以下が好ましく、１０％質量以下がより好ましく、１質量％以下が更に好ましい。
上記分散液中で無機ナノ粒子を形成する際の温度としては、溶媒にもよるが、３０〜２００℃が好ましく、５０〜１５０℃がより好ましく、５０〜１００℃が更に好ましく、５０〜８０℃が特に好ましい。同様に、上記分散液中で無機ナノ粒子を形成する際の時間としては、１５〜１８０分が好ましく、３０〜１８０分がより好ましく、６０〜１８０分が更に好ましい。
Preferred conditions for uniformly forming inorganic nanoparticles on the nanocarbon material will be described.
The concentration of the metal salt for forming the inorganic nanoparticles in the above dispersion, 1 × 10 -10 ~1 × 10 -1 M , more preferably 1 × 10 -10 ~1 × 10 -3 M 1 × 10 −10 to 1 × 10 −5 M is more preferable. Similarly, the mass ratio of the metal salt to the nanocarbon material is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 1% by mass or less.
As temperature at the time of forming an inorganic nanoparticle in the said dispersion liquid, although based also on a solvent, 30-200 degreeC is preferable, 50-150 degreeC is more preferable, 50-100 degreeC is still more preferable, 50-80 degreeC Is particularly preferred. Similarly, the time for forming the inorganic nanoparticles in the dispersion is preferably 15 to 180 minutes, more preferably 30 to 180 minutes, and still more preferably 60 to 180 minutes.
上記で得られた熱電変換層形成用組成物には、さらに必要に応じて、他の成分（例えば、溶媒、バインダー、界面活性剤、酸化防止剤、耐光安定剤、耐熱安定剤、及び可塑剤等）を混合してもよい。
混合方法は特に制限されず、通常の混合装置等を用いて常温常圧下で行うことができる。各成分の分散を促進するため超音波処理を行ってもよい。
The composition for forming a thermoelectric conversion layer obtained above may further contain other components (for example, a solvent, a binder, a surfactant, an antioxidant, a light stabilizer, a heat stabilizer, and a plasticizer as necessary. Etc.) may be mixed.
The mixing method is not particularly limited, and the mixing can be performed using a normal mixing apparatus or the like at normal temperature and pressure. Sonication may be performed to promote dispersion of each component.
（熱電変換層の製造方法）
熱電変換層形成用組成物を用いて熱電変換層を製造する方法は特に制限されないが、例えば、基材上に上記組成物を塗布し、成膜する方法等が挙げられる。
成膜方法は特に制限されず、例えば、スピンコート法、エクストルージョンダイコート法、ブレードコート法、バーコート法、スクリーン印刷法、ステンシル印刷法、メタルマスク印刷法、ロールコート法、カーテンコート法、スプレーコート法、ディップコート法、及びインクジェット法等の公知の塗布方法を用いることができる。
また、塗布後は、必要に応じて乾燥工程を行う。例えば、熱風を吹き付けることにより溶媒を揮発、及び乾燥させることができる。
(Method for producing thermoelectric conversion layer)
Although the method in particular of manufacturing a thermoelectric conversion layer using the composition for thermoelectric conversion layer formation is not restrict | limited, For example, the method of apply | coating the said composition on a base material, and forming into a film is mentioned.
The film forming method is not particularly limited. For example, spin coating method, extrusion die coating method, blade coating method, bar coating method, screen printing method, stencil printing method, metal mask printing method, roll coating method, curtain coating method, spraying Known coating methods such as a coating method, a dip coating method, and an ink jet method can be used.
Moreover, after application | coating, a drying process is performed as needed. For example, the solvent can be volatilized and dried by blowing hot air.
〔厚み〕
本発明の熱電変換層の平均厚みは、温度差を付与する観点等から、１〜５００μｍが好ましく、２〜３００μｍがより好ましく、３〜２００μｍが更に好ましく、５〜１００μｍが特に好ましい。
なお、熱電変換層の平均厚みは、任意の１０点における熱電変換層の厚みを測定し、それらを算術平均して求める。
[Thickness]
The average thickness of the thermoelectric conversion layer of the present invention is preferably 1 to 500 μm, more preferably 2 to 300 μm, still more preferably 3 to 200 μm, and particularly preferably 5 to 100 μm from the viewpoint of imparting a temperature difference.
In addition, the average thickness of a thermoelectric conversion layer measures the thickness of the thermoelectric conversion layer in arbitrary 10 points | pieces, and calculates | requires them by arithmetic average.
〔熱電変換素子、熱電変換モジュール〕
本発明の熱電変換素子は、上述した熱電変換層を備えていればよく、その構成は特に制限されないが、例えば、上述した熱電変換層と、熱電変換層と電気的に接続した電極対とを備える態様が挙げられる。本発明の熱電変換素子は、上述した熱電変換層をｐ型熱電変換層として備えていることが好ましい。
また、本発明の熱電変換モジュールは、上記熱電変換素子を複数個備えていれば、その構成は特に制限されない。
[Thermoelectric conversion element, thermoelectric conversion module]
The thermoelectric conversion element of the present invention may be provided with the thermoelectric conversion layer described above, and the configuration thereof is not particularly limited. For example, the thermoelectric conversion layer described above and an electrode pair electrically connected to the thermoelectric conversion layer are provided. The aspect provided is mentioned. The thermoelectric conversion element of the present invention preferably includes the above-described thermoelectric conversion layer as a p-type thermoelectric conversion layer.
Moreover, the thermoelectric conversion module of this invention will not be restrict | limited especially if the said thermoelectric conversion element is provided with two or more.
以下に、本発明の熱電変換層を備える熱電変換素子、及び上記熱電変換素子を複数個備えた熱電変換モジュールについて、その各好適態様を詳述する。 Below, each suitable aspect is explained in full detail about the thermoelectric conversion element provided with the thermoelectric conversion layer provided with the thermoelectric conversion layer of this invention, and the said thermoelectric conversion element.
本発明の熱電変換素子は、熱電変換層が本発明の熱電変換層のみからなるものでもよいし、更に、例えば、本発明の熱電変換層をｐ型熱電変換層として機能させることにより、このｐ型熱電変換層と、電気的に接続されたｎ型熱電変換層とを備えるものでもよい。ｎ型熱電変換層とｐ型熱電変換層とは両者が電気的に接続されていれば、直接両者が接していても、導体（例えば、電極）が間に配置されていてもよい。 In the thermoelectric conversion element of the present invention, the thermoelectric conversion layer may be composed only of the thermoelectric conversion layer of the present invention. Further, for example, by making the thermoelectric conversion layer of the present invention function as a p-type thermoelectric conversion layer, this p A type thermoelectric conversion layer and an electrically connected n-type thermoelectric conversion layer may be provided. As long as both the n-type thermoelectric conversion layer and the p-type thermoelectric conversion layer are electrically connected to each other, they may be in direct contact with each other, or a conductor (for example, an electrode) may be disposed therebetween.
＜第１実施態様＞
図１に、本発明の熱電変換素子の第１実施態様の断面図を示す。
図１に示す熱電変換素子１１０は、第１の基材１２上に、第１の電極１３及び第２の電極１５を含む一対の電極と、第１の電極１３及び第２の電極１５間に、上記熱電変換層１４を備えている。第２の電極１５の他方の表面には第２の基材１６が配設されており、第１の基材１２及び第２の基材１６の外側には互いに対向して金属板１１及び１７が配設されている。
<First Embodiment>
In FIG. 1, sectional drawing of the 1st embodiment of the thermoelectric conversion element of this invention is shown.
The thermoelectric conversion element 110 illustrated in FIG. 1 includes a pair of electrodes including a first electrode 13 and a second electrode 15 on a first base 12 and a gap between the first electrode 13 and the second electrode 15. The thermoelectric conversion layer 14 is provided. A second base material 16 is disposed on the other surface of the second electrode 15, and the metal plates 11 and 17 face each other outside the first base material 12 and the second base material 16. Is arranged.
＜第２実施態様＞
図２に、本発明の熱電変換素子の第２実施態様の断面図を示す。
図２に示す熱電変換素子１２０は、第１の基材２２上に、第１の電極２３及び第２の電極２５が配置され、その上に上記熱電変換層２４が設けられている。また、熱電変換層２４の他方の表面には第２の基材２６が設けられている。
<Second Embodiment>
In FIG. 2, sectional drawing of the 2nd embodiment of the thermoelectric conversion element of this invention is shown.
In the thermoelectric conversion element 120 shown in FIG. 2, a first electrode 23 and a second electrode 25 are disposed on a first base material 22, and the thermoelectric conversion layer 24 is provided thereon. In addition, a second substrate 26 is provided on the other surface of the thermoelectric conversion layer 24.
＜第３実施態様＞
図３Ａ〜図３Ｃに、本発明の熱電変換素子の第３実施態様を概念的に示す。なお、図３Ａは上面図（図３Ｂを紙面上方から見た図）、図３Ｂは正面図（後述する基板等の面方向から見た図）、図３Ｃは底面図（図３Ｂを紙面下方から見た図）である。
図３Ａ〜図３Ｃに示すように、熱電変換素子１３０は、基本的に、第１基板３２と、上記熱電変換層３４と、第２基板３０と、第１の電極３６及び第２の電極３８とを有して構成される。
具体的には、第１基板３２の表面には、熱電変換層３４が形成される。また、第１基板３２の表面には、熱電変換層３４を第１基板３２の基板面方向（以下、単に『面方向』とも言う。言い換えれば、第１基板３２及び第２基板３０を積層する方向とは直交する方向。）に挟むようにして、熱電変換層３４に接触して第１の電極３６及び第２の電極３８（電極対）が形成される。
また、図３Ａ〜図３Ｃにおいては図示しないが、第１基板３２と熱電変換層３４との間、又は、第２基板３０と熱電変換層３４との間において、粘着層が配置されていてもよい。
<Third embodiment>
3A to 3C conceptually show a third embodiment of the thermoelectric conversion element of the present invention. 3A is a top view (a view of FIG. 3B viewed from above), FIG. 3B is a front view (a view of a substrate or the like to be described later), and FIG. 3C is a bottom view (FIG. 3B is viewed from below the view). It is a view).
As shown in FIGS. 3A to 3C, the thermoelectric conversion element 130 basically includes a first substrate 32, the thermoelectric conversion layer 34, the second substrate 30, the first electrode 36, and the second electrode 38. And is configured.
Specifically, a thermoelectric conversion layer 34 is formed on the surface of the first substrate 32. Further, on the surface of the first substrate 32, the thermoelectric conversion layer 34 is also referred to as a substrate surface direction (hereinafter simply referred to as “surface direction”) of the first substrate 32. In other words, the first substrate 32 and the second substrate 30 are laminated. The first electrode 36 and the second electrode 38 (electrode pair) are formed in contact with the thermoelectric conversion layer 34 so as to be sandwiched in a direction perpendicular to the direction.
Although not shown in FIGS. 3A to 3C, an adhesive layer may be disposed between the first substrate 32 and the thermoelectric conversion layer 34 or between the second substrate 30 and the thermoelectric conversion layer 34. Good.
図３Ａ〜図３Ｃに示すように、第１基板３２は、低熱伝導部３２ａ、及び、低熱伝導部３２ａよりも熱伝導率が高い高熱伝導部３２ｂを有する。同様に、第２基板３０も、低熱伝導部３０ａ、及び、低熱伝導部３０ａよりも熱伝導率が高い高熱伝導部３０ｂを有する。 As shown in FIGS. 3A to 3C, the first substrate 32 includes a low thermal conductivity portion 32 a and a high thermal conductivity portion 32 b having a higher thermal conductivity than the low thermal conductivity portion 32 a. Similarly, the 2nd board | substrate 30 also has the high heat conductive part 30b whose heat conductivity is higher than the low heat conductive part 30a and the low heat conductive part 30a.
熱電変換素子１３０において、両基板は、互いの高熱伝導部が、第１の電極３６と第２の電極３８との離間方向（すなわち通電方向）に異なる位置となるように配置される。
熱電変換素子１３０は、好ましい態様として、粘着層で貼着される第２基板３０を有し、更に、第１基板３２及び第２基板３０が、共に、低熱伝導部及び高熱伝導部を有する。熱電変換素子１３０は、高熱伝導部及び低熱伝導部を有する基板を２枚用い、両基板の高熱伝導部を面方向に異なる位置として、この２枚の基板で熱電変換層を挟持してなる構成を有する。
In the thermoelectric conversion element 130, the two substrates are arranged such that their high thermal conductivity portions are at different positions in the separation direction (that is, the energization direction) between the first electrode 36 and the second electrode 38.
The thermoelectric conversion element 130 has the 2nd board | substrate 30 stuck by the adhesion layer as a preferable aspect, and also the 1st board | substrate 32 and the 2nd board | substrate 30 have both a low heat conduction part and a high heat conduction part. The thermoelectric conversion element 130 has a configuration in which two substrates having a high heat conduction portion and a low heat conduction portion are used, and the high heat conduction portions of the two substrates are located at different positions in the plane direction, and the thermoelectric conversion layer is sandwiched between the two substrates. Have
すなわち、熱電変換素子１３０は、熱電変換層の面方向に温度差を生じさせて熱エネルギーを電気エネルギーに変換する熱電変換素子（以下、ｉｎ ｐｌａｎｅ型の熱電変換素子とも言う）であって、図示例においては、低熱伝導部と低熱伝導部よりも熱伝導率が高い高熱伝導部とを有する基板を用いることにより、熱電変換層３４の面方向に温度差を生じさせて、熱エネルギーを電気エネルギーに変換することができる。 That is, the thermoelectric conversion element 130 is a thermoelectric conversion element (hereinafter also referred to as an in-plane type thermoelectric conversion element) that generates a temperature difference in the surface direction of the thermoelectric conversion layer and converts thermal energy into electric energy. In the example shown, by using a substrate having a low thermal conductivity portion and a high thermal conductivity portion having a higher thermal conductivity than the low thermal conductivity portion, a temperature difference is generated in the surface direction of the thermoelectric conversion layer 34, and the thermal energy is converted into electrical energy. Can be converted to
＜第４実施態様＞
図４に、熱電変換素子の第４実施態様を概念的に示す。なお、以下の態様では、上記熱電変換層をｐ型熱電変換層として用いた場合について詳述する。
図４に示す熱電変換素子１４０は、ｎ型熱電変換層（ｎ型熱電変換部）４１とｐ型熱電変換層（ｐ型熱電変換部）４２とを有しており、両者は並列に配置されている。ｐ型熱電変換層４２は、ナノ炭素材料と、金属元素を含有する無機ナノ粒子と、を含有するｐ型熱電変換層である。ｎ型熱電変換層４１の構成については、後段で詳述する。
ｎ型熱電変換層４１の上端部は第１の電極４５Ａに、また、ｐ型熱電変換層４２の上端部は第３の電極４５Ｂにそれぞれ電気的及び機械的に接続されている。第１の電極４５Ａ及び第３の電極４５Ｂの外側には、上側基材４６が配置されている。ｎ型熱電変換層４１及びｐ型熱電変換層４２の下端部は、それぞれ下側基材４３に支持された第２の電極４４に電気的及び機械的に接続されている。このように、ｎ型熱電変換層４１及びｐ型熱電変換層４２は第１の電極４５Ａ、第２の電極４４、及び第３の電極４５Ｂにより直列接続されている。つまり、ｎ型熱電変換層４１及びｐ型熱電変換層４２は、第２の電極４４を介して、電気的に接続されている。
熱電変換素子１４０は、上側基材４６及び下側基材４３間に温度差（図４中の矢印方向）を与え、例えば、上側基材４６側を低温部、下側基材４３側を高温部にする。このような温度差を与えた場合、ｎ型熱電変換層４１の内部においては負の電荷を持った電子４７が低温部側（上側基材４６側）に移動し、第２の電極４４は第１の電極４５Ａより高電位となる。一方、ｐ型熱電変換層４２の内部では、正の電荷を持ったホール４８が低温部側（上側基材４６側）に移動し、第３の電極４５Ｂは第２の電極４４より高電位となる。その結果、第１の電極４５Ａと第３の電極４５Ｂ間に電位差が生じ、例えば電極の終端に負荷を接続すると電力を取り出すことができる。この際、第１の電極４５Ａは負極、第３の電極４５Ｂは正極となる。
<Fourth embodiment>
FIG. 4 conceptually shows a fourth embodiment of the thermoelectric conversion element. In addition, in the following aspects, the case where the said thermoelectric conversion layer is used as a p-type thermoelectric conversion layer is explained in full detail.
The thermoelectric conversion element 140 shown in FIG. 4 has an n-type thermoelectric conversion layer (n-type thermoelectric conversion unit) 41 and a p-type thermoelectric conversion layer (p-type thermoelectric conversion unit) 42, both of which are arranged in parallel. ing. The p-type thermoelectric conversion layer 42 is a p-type thermoelectric conversion layer containing a nanocarbon material and inorganic nanoparticles containing a metal element. The configuration of the n-type thermoelectric conversion layer 41 will be described in detail later.
The upper end of the n-type thermoelectric conversion layer 41 is electrically and mechanically connected to the first electrode 45A, and the upper end of the p-type thermoelectric conversion layer 42 is electrically and mechanically connected to the third electrode 45B. An upper base material 46 is disposed outside the first electrode 45A and the third electrode 45B. The lower ends of the n-type thermoelectric conversion layer 41 and the p-type thermoelectric conversion layer 42 are electrically and mechanically connected to the second electrode 44 supported by the lower substrate 43, respectively. Thus, the n-type thermoelectric conversion layer 41 and the p-type thermoelectric conversion layer 42 are connected in series by the first electrode 45A, the second electrode 44, and the third electrode 45B. That is, the n-type thermoelectric conversion layer 41 and the p-type thermoelectric conversion layer 42 are electrically connected via the second electrode 44.
The thermoelectric conversion element 140 gives a temperature difference (in the direction of the arrow in FIG. 4) between the upper base material 46 and the lower base material 43. For example, the upper base material 46 side is a low temperature part and the lower base material 43 side is a high temperature. Part. When such a temperature difference is given, electrons 47 having a negative charge move to the low temperature part side (upper base material 46 side) inside the n-type thermoelectric conversion layer 41, and the second electrode 44 is The potential is higher than that of the first electrode 45A. On the other hand, inside the p-type thermoelectric conversion layer 42, the positively charged hole 48 moves to the low temperature part side (upper base material 46 side), and the third electrode 45B has a higher potential than the second electrode 44. Become. As a result, a potential difference is generated between the first electrode 45A and the third electrode 45B. For example, when a load is connected to the end of the electrode, electric power can be taken out. At this time, the first electrode 45A is a negative electrode, and the third electrode 45B is a positive electrode.
＜第５実施態様＞
なお、熱電変換素子１４０は、例えば、図５に示すように、複数のｎ型熱電変換層４１、４１・・・と複数のｐ型熱電変換層４２、４２・・・とを交互に配置し、これらを第１及び第３の電極４５と第２の電極４４とで直列接続することによって、より高い電圧を得ることができる。
図５に示すように、本発明においては、複数の熱電変換素子を電気的に接続させ、いわゆるモジュール（熱電変換モジュール）を構成してもよい。
<Fifth embodiment>
In addition, the thermoelectric conversion element 140 arrange | positions several n-type thermoelectric conversion layers 41, 41 ... and several p-type thermoelectric conversion layers 42, 42 ... alternately, for example, as shown in FIG. By connecting these in series with the first and third electrodes 45 and the second electrode 44, a higher voltage can be obtained.
As shown in FIG. 5, in the present invention, a plurality of thermoelectric conversion elements may be electrically connected to form a so-called module (thermoelectric conversion module).
以下、熱電変換素子を構成する各部材について詳述する。 Hereinafter, each member which comprises a thermoelectric conversion element is explained in full detail.
＜基材＞
熱電変換素子中の基材（第１実施態様の第１の基材１２及び第２の基材１６、第２実施態様の第１の基材２２及び第２の基材２６、第３実施態様の低熱伝導部３２ａ、３０ａ、第４実施態様の上側基材４６及び下側基材４３）は、ガラス、透明セラミックス、及びプラスチックフィルム等の基材を用いることができる。本発明の熱電変換素子において、基材はフレキシビリティーを有しているのが好ましく、具体的には、ＡＳＴＭ Ｄ２１７６に規定の測定法による耐屈曲回数ＭＩＴが１万サイクル以上であるフレキシビリティーを有しているのが好ましい。このようなフレキシビリティーを有する基材は、プラスチックフィルムが好ましく、具体的には、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリ（１，４−シクロヘキシレンジメチレンテレフタレート）、ポリエチレン−２，６−ナフタレンジカルボキシレート、及び、ビスフェノールＡとイソ及びテレフタル酸のポリエステルフィルム等のポリエステルフィルム；ゼオノアフィルム（商品名、日本ゼオン社製）、アートンフィルム（商品名、ＪＳＲ社製）、及びスミライトＦＳ１７００（商品名、住友ベークライト社製）等のポリシクロオレフィンフィルム；カプトン（商品名、東レ・デュポン社製）、アピカル（商品名、カネカ社製）、ユーピレックス（商品名、宇部興産社製）、及びポミラン（商品名、荒川化学社製）等のポリイミドフィルム；ピュアエース（商品名、帝人化成社製）、及びエルメック（商品名、カネカ社製）等のポリカーボネートフィルム；スミライトＦＳ１１００（商品名、住友ベークライト社製）等のポリエーテルエーテルケトンフィルム；トレリナ（商品名、東レ社製）等のポリフェニルスルフィドフィルム；等が挙げられる。入手の容易性、耐熱性（好ましくは１００℃以上）及び経済性の観点から、市販のポリエチレンテレフタレート、ポリエチレンナフタレート、各種ポリイミド、又はポリカーボネートフィルム等が好ましい。
<Base material>
Base material in thermoelectric conversion element (first base material 12 and second base material 16 of the first embodiment, first base material 22 and second base material 26 of the second embodiment, third embodiment The low heat conducting portions 32a, 30a, the upper base material 46 and the lower base material 43) of the fourth embodiment can use base materials such as glass, transparent ceramics, and plastic films. In the thermoelectric conversion element of the present invention, it is preferable that the base material has flexibility. Specifically, the flexibility in which the number of bending resistances MIT according to the measurement method specified in ASTM D2176 is 10,000 cycles or more. It is preferable to have. The substrate having such flexibility is preferably a plastic film, specifically, polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), Polyester films such as polyethylene-2,6-naphthalenedicarboxylate and polyester films of bisphenol A, iso and terephthalic acid; Zeonore film (trade name, manufactured by Nippon Zeon), Arton film (trade name, manufactured by JSR) , And Sumilite FS1700 (trade name, manufactured by Sumitomo Bakelite Co., Ltd.), etc .; Kapton (trade name, manufactured by Toray DuPont), Apical (trade name, manufactured by Kaneka), Upilex (trade) Polyimide films such as name, Ube Industries, Ltd., and Pomilan (trade name, manufactured by Arakawa Chemical Co., Ltd.); Polycarbonate films, such as Pure Ace (trade name, manufactured by Teijin Chemicals Ltd.), and Elmec (trade name, manufactured by Kaneka Corporation) A polyether ether ketone film such as Sumilite FS1100 (trade name, manufactured by Sumitomo Bakelite Co., Ltd.); a polyphenyl sulfide film such as Torelina (trade name, manufactured by Toray Industries, Inc.); Commercially available polyethylene terephthalate, polyethylene naphthalate, various polyimides, polycarbonate films, and the like are preferable from the viewpoints of availability, heat resistance (preferably 100 ° C. or higher) and economy.
基材の厚さは、取り扱い性、耐久性等の観点から、好ましくは５〜３０００μｍ、より好ましくは５〜５００μｍ、更に好ましくは５〜１００μｍ、特に好ましくは５〜５０μｍである。基材の厚みをこの範囲にすることで、熱電変換層に効率的に温度差を付与することができ、外部衝撃による熱電変換層の損傷も起こりにくい。 The thickness of the substrate is preferably 5 to 3000 μm, more preferably 5 to 500 μm, still more preferably 5 to 100 μm, and particularly preferably 5 to 50 μm from the viewpoints of handleability and durability. By setting the thickness of the base material within this range, a temperature difference can be efficiently applied to the thermoelectric conversion layer, and the thermoelectric conversion layer is hardly damaged by an external impact.
＜電極＞
熱電変換素子中の電極を形成する電極材料としては、ＩＴＯ（Ｉｎｄｉｕｍ−Ｔｉｎ−Ｏｘｉｄｅ）、及びＺｎＯ等の透明電極材料；銀、銅、金、及びアルミニウム等の金属電極材料；ＣＮＴ、及びグラフェン等の炭素材料；ＰＥＤＯＴ（ｐｏｌｙ（３，４−ｅｔｈｙｌｅｎｅｄｉｏｘｙｔｈｉｏｐｈｅｎｅ））／ＰＳＳ（ｐｏｌｙｓｔｙｒｅｎｅ ｓｕｌｆｏｎａｔｅ）、及びＰＥＤＯＴ／Ｔｏｓ（Ｔｏｓｙｌａｔｅ）等の有機材料；が挙げられる。なお、電極は、金、銀、銅、若しくはカーボン等の導電性微粒子を分散した導電性ペースト、はんだ、又は、金、銀、銅、若しくはアルミニウム等の金属ナノワイヤーを含有する導電性ペースト等を使用して形成することができる。
<Electrode>
As electrode materials for forming electrodes in thermoelectric conversion elements, transparent electrode materials such as ITO (Indium-Tin-Oxide) and ZnO; metal electrode materials such as silver, copper, gold, and aluminum; CNT, graphene, and the like Carbon materials; organic materials such as PEDOT (poly (3,4-ethylenedithiothiophene)) / PSS (polystyrene sulfate) and PEDOT / Tos (Tosylate). The electrode is a conductive paste in which conductive fine particles such as gold, silver, copper, or carbon are dispersed, solder, or a conductive paste containing metal nanowires such as gold, silver, copper, or aluminum. Can be formed using.
＜ｎ型熱電変換層＞
第４実施態様の熱電変換素子及び第５実施態様の熱電変換モジュールが有するｎ型熱電変換層としては、公知のｎ型熱電変換層が使用される。ｎ型熱電変換層に含まれる材料としては、公知の材料が適宜使用される。
<N-type thermoelectric conversion layer>
As the n-type thermoelectric conversion layer included in the thermoelectric conversion element of the fourth embodiment and the thermoelectric conversion module of the fifth embodiment, a known n-type thermoelectric conversion layer is used. As a material contained in the n-type thermoelectric conversion layer, a known material is appropriately used.
なお、ｎ型熱電変換層の形成方法（製造方法）は、上述した本発明の熱電変換層の製造方法と同様の方法により形成することができる。 In addition, the formation method (manufacturing method) of an n-type thermoelectric conversion layer can be formed by the method similar to the manufacturing method of the thermoelectric conversion layer of this invention mentioned above.
〔熱電発電用物品〕
本発明の熱電変換素子は、各種の熱電発電用物品に適用することができる。熱電発電用物品としては、具体的には、温泉熱発電機、太陽熱発電機、及び廃熱発電機等の発電機、並びに、腕時計用電源、半導体駆動電源、及び小型センサー用電源等の電源が挙げられる。また、本発明の熱電変換素子を適用した熱電発電用物品は、ペルチェ素子として冷却又は温度制御等に用いることもできる。
[Articles for thermoelectric generation]
The thermoelectric conversion element of the present invention can be applied to various articles for thermoelectric power generation. Specific examples of thermoelectric power generation products include power generators such as hot spring thermal power generators, solar thermal power generators, and waste heat power generators, and power supplies such as wristwatch power supplies, semiconductor drive power supplies, and small sensor power supplies. . The article for thermoelectric power generation to which the thermoelectric conversion element of the present invention is applied can also be used for cooling or temperature control as a Peltier element.
以下に実施例に基づいて本発明をさらに詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、及び処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す実施例により限定的に解釈されるべきものではない。 Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.
〔分散液の作製〕
（分散液１の調製）
単層ＣＮＴ０．４ｇ（ＯＣＳｉＡｌ社製ＴＵＢＡＬＬ １．５ｎｍ（直径））とエタノール４００ｍＬとをメカニカルホモジナイザー（エスエムテー社製、ＨＩＧＨ−ＦＬＥＸ ＨＯＭＯＧＥＮＩＺＥＲ ＨＦ９３）を用いて、１８０００ｒｐｍで５分間混合して、ＣＮＴ分散液を得た。
次に、エタノール２００ｍＬに酢酸銅一水和物（和光純薬工業社製）を溶解させ、０．１Ｍの酢酸銅エタノール溶液を調製した。同様に、純水２００ｍＬに水酸化ナトリウム（和光純薬工業社製）を溶解させ、１．２Ｍの水酸化ナトリウム水溶液を調製した。
上記ＣＮＴ分散液に、上記水酸化ナトリウム水溶液を加えた。その後、得られた分散液を水浴にて６０℃に昇温し、上記酢酸銅エタノール溶液を滴下しながら１２０分間反応させ、ＣＮＴ存在下でＣｕＯ粒子を形成し、分散液１を得た。
なお、酢酸銅エタノール溶液はＣｕＯ粒子がＣＮＴに対して３５０質量％となるよう、水酸化ナトリウム水溶液は、添加される水酸化ナトリウム水溶液中の水酸化ナトリウム量が、添加される酢酸銅エタノール溶液中のＣｕ量に対して４モル当量となるよう、それぞれ加えた。また、酢酸銅エタノール溶液は、滴下直後の全溶液に対する酢酸銅の濃度が１×１０−５Ｍ以下となるよう滴下量／間隔を調整した。
(Preparation of dispersion)
(Preparation of dispersion 1)
Single layer CNT 0.4g (TUBALL 1.5nm (diameter) manufactured by OCSiAl) and ethanol 400mL were mixed for 5 minutes at 18000rpm using mechanical homogenizer (manufactured by SMT Co., Ltd., HIGH-FLEX HOMOGENIZER HF93). Got.
Next, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 200 mL of ethanol to prepare a 0.1 M copper acetate ethanol solution. Similarly, sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 200 mL of pure water to prepare a 1.2 M sodium hydroxide aqueous solution.
The sodium hydroxide aqueous solution was added to the CNT dispersion. Thereafter, the obtained dispersion was heated to 60 ° C. in a water bath and reacted for 120 minutes while dropping the copper acetate ethanol solution to form CuO particles in the presence of CNTs, whereby Dispersion 1 was obtained.
In addition, in the copper acetate ethanol solution, the amount of sodium hydroxide in the sodium hydroxide aqueous solution added is within the copper acetate ethanol solution added so that the CuO particles are 350% by mass with respect to CNT. It added so that it might become 4 molar equivalent with respect to Cu amount of each. Moreover, the copper acetate ethanol solution adjusted the dripping amount / space | interval so that the density | concentration of the copper acetate with respect to all the solutions immediately after dripping might be 1 * 10 < -5 > M or less.
（分散液２の調製）
分散液１の調製において、ＣｕＯ粒子がＣＮＴに対して３００質量％となるよう、酢酸銅エタノール溶液の使用量を変更した以外は、同様の方法により分散液２を調製した。
(Preparation of dispersion 2)
Dispersion 2 was prepared in the same manner as in Dispersion 1, except that the amount of copper acetate ethanol solution was changed so that the CuO particles were 300% by mass with respect to CNTs.
（分散液３〜８の調製）
分散液１の調製において、酢酸銅エタノール溶液及び水酸化ナトリウム水溶液の濃度をそれぞれ０．００１Ｍ及び０．２Ｍとし、酢酸銅エタノール溶液をＣｕＯ粒子がＣＮＴに対して表２に記載の質量（単位：質量％）となるよう酢酸銅エタノール溶液の使用量を変更した以外は、同様の方法により分散液３〜８を調製した。
(Preparation of dispersions 3-8)
In the preparation of Dispersion 1, the concentrations of the copper acetate ethanol solution and the sodium hydroxide aqueous solution were 0.001 M and 0.2 M, respectively, and the mass of the copper acetate ethanol solution described in Table 2 with respect to CNT (unit: Dispersions 3 to 8 were prepared by the same method except that the amount of the copper acetate ethanol solution was changed so as to be (mass%).
（分散液９の調製）
分散液１の調製において、酢酸銅一水和物（和光純薬工業社製）を酢酸銀（和光純薬工業社製）に変えて０．００１Ｍの酢酸銀水溶液を調製し、水酸化ナトリウム水溶液の濃度を０．２Ｍとし、酢酸銀水溶液をＡｇ２Ｏ粒子がＣＮＴに対して１質量％になるように加えた以外は、同様の方法により分散液９を調製した。
(Preparation of dispersion 9)
In the preparation of Dispersion 1, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to silver acetate (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a 0.001M silver acetate aqueous solution, and sodium hydroxide aqueous solution Dispersion 9 was prepared in the same manner except that the concentration of A was 0.2 M and an aqueous silver acetate solution was added so that the Ag 2 O particles were 1% by mass with respect to CNT.
（分散液１０の調製）
分散液１の調製において、酢酸銅一水和物（和光純薬工業社製）を塩化スズ（ＩＩ）二水和物（関東化学社製）に変えて０．００１Ｍの塩化スズエタノール溶液を調製し、水酸化ナトリウム水溶液の濃度を０．２Ｍとし、塩化スズエタノール溶液をＳｎＯ粒子がＣＮＴに対して１質量％になるように加えた以外は、同様の方法により分散液１０を調製した。
(Preparation of dispersion 10)
In the preparation of Dispersion 1, copper acetate monohydrate (Wako Pure Chemical Industries, Ltd.) was changed to tin (II) chloride dihydrate (Kanto Chemical Co., Ltd.) to prepare a 0.001M tin chloride ethanol solution. Then, a dispersion 10 was prepared in the same manner except that the concentration of the sodium hydroxide aqueous solution was 0.2 M and the tin chloride ethanol solution was added so that the SnO particles were 1% by mass with respect to CNT.
（分散液１１の調製）
分散液１の調製において、酢酸銅一水和物（和光純薬工業社製）を酢酸鉛三水和物（関東化学社製）に変えて０．００１Ｍの酢酸鉛エタノール溶液を調製し、水酸化ナトリウム水溶液の濃度を０．２Ｍとし、酢酸鉛エタノール溶液をＰｂＯ粒子がＣＮＴに対して１質量％になるように加えた以外は、同様の方法により分散液１１を調製した。
(Preparation of dispersion 11)
In the preparation of Dispersion 1, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to lead acetate trihydrate (manufactured by Kanto Chemical Co., Ltd.) to prepare a 0.001M lead acetate ethanol solution, and water Dispersion 11 was prepared in the same manner except that the concentration of the aqueous sodium oxide solution was 0.2M and the lead acetate ethanol solution was added so that the PbO particles were 1% by mass with respect to CNT.
（分散液１２の調製）
分散液１の調製において、酢酸銅一水和物（和光純薬工業社製）を酢酸亜鉛二水和物（関東化学社製）に変えて０．００１Ｍの酢酸亜鉛エタノール溶液を調製し、水酸化ナトリウム水溶液の濃度を０．２Ｍとし、酢酸亜鉛エタノール溶液をＺｎＯ粒子がＣＮＴに対して１質量％になるように加えた以外は、同様の方法により分散液１２を調製した。
(Preparation of dispersion 12)
In the preparation of Dispersion 1, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to zinc acetate dihydrate (manufactured by Kanto Chemical Co., Ltd.) to prepare a 0.001M zinc acetate ethanol solution, and water Dispersion 12 was prepared by the same method except that the concentration of the aqueous sodium oxide solution was 0.2 M and the zinc acetate ethanol solution was added so that the ZnO particles were 1% by mass with respect to CNT.
（分散液１３の調製）
分散液１の調製において、酢酸銅一水和物（和光純薬工業社製）を塩化ビスマス（ＩＩＩ）（和光純薬工業社製）に変えて０．００１Ｍの塩化ビスマスエタノール溶液を調製し、水酸化ナトリウム水溶液の濃度を０．２Ｍとし、塩化ビスマスエタノール溶液をＢｉ２Ｏ３粒子がＣＮＴに対して１質量％になるように加えた以外は、同様の方法により分散液１３を調製した。
(Preparation of dispersion 13)
In the preparation of dispersion 1, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to bismuth chloride (III) (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a 0.001M bismuth chloride ethanol solution, Dispersion 13 was prepared in the same manner except that the concentration of the sodium hydroxide aqueous solution was 0.2 M and the bismuth chloride ethanol solution was added so that the Bi 2 O 3 particles were 1% by mass with respect to CNT.
（分散液１４の調製）
単層ＣＮＴ０．４ｇ（ＯＣＳｉＡｌ社製ＴＵＢＡＬＬ １．５ｎｍ（直径））とエタノール４００ｍＬとをメカニカルホモジナイザー（エスエムテー社製、ＨＩＧＨ−ＦＬＥＸ ＨＯＭＯＧＥＮＩＺＥＲ ＨＦ９３）を用いて、１８０００ｒｐｍで５分間混合して、ＣＮＴ分散液を得た。
次に、アセトン２００ｍＬに酢酸パラジウム（ＩＩ）（東京化成工業社製）を溶解させ、０．００１Ｍの酢酸パラジウムアセトン溶液を調製した。同様に、純水２００ｍＬにホスフィン酸ナトリウム（和光純薬工業社製）を溶解させ、０．１Ｍのホスフィン酸ナトリウム水溶液を調製した。
上記ＣＮＴ分散液に、ホスフィン酸ナトリウム水溶液を加えた。その後、得られた分散液を水浴にて６０℃に昇温し、上記酢酸パラジウムアセトン溶液を滴下しながら１２０分間反応させ、ＣＮＴ存在下でＰｄ粒子を形成し、分散液１４を得た。
なお、酢酸パラジウムアセトン溶液はＰｄ粒子がＣＮＴに対して１質量％となるよう、ホスフィン酸ナトリウム水溶液は、添加されるホスフィン酸ナトリウム水溶液中のホスフィン酸ナトリウム量が、添加される酢酸パラジウムアセトン溶液中のＰｄ量に対して１０モル当量となるよう、それぞれ加えた。また、酢酸パラジウムアセトン溶液は、滴下直後の全溶液に対する酢酸パラジウムの濃度が１×１０−５Ｍ以下となるよう滴下量／間隔を調整した。
(Preparation of dispersion 14)
Single layer CNT 0.4g (TUBALL 1.5nm (diameter) manufactured by OCSiAl) and ethanol 400mL were mixed for 5 minutes at 18000rpm using mechanical homogenizer (manufactured by SMT Co., Ltd., HIGH-FLEX HOMOGENIZER HF93). Got.
Next, palladium acetate (II) (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 mL of acetone to prepare a 0.001 M palladium acetate / acetone solution. Similarly, sodium phosphinate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 200 mL of pure water to prepare a 0.1 M sodium phosphinate aqueous solution.
A sodium phosphinate aqueous solution was added to the CNT dispersion. Thereafter, the obtained dispersion was heated to 60 ° C. in a water bath and reacted for 120 minutes while dropping the palladium acetate / acetone solution to form Pd particles in the presence of CNTs, whereby dispersion 14 was obtained.
In addition, the amount of sodium phosphinate in the aqueous solution of sodium phosphinate is the amount of sodium phosphinate in the aqueous solution of sodium phosphinate added so that the Pd particles are 1% by mass with respect to CNT in the palladium acetate acetone solution. It added so that it might become 10 molar equivalent with respect to the amount of Pd. Moreover, the palladium acetate acetone solution adjusted the dripping amount / interval so that the concentration of palladium acetate with respect to the entire solution immediately after the dropping would be 1 × 10 −5 M or less.
（分散液１５の調製）
単層ＣＮＴ０．４ｇ（ＯＣＳｉＡｌ社製ＴＵＢＡＬＬ １．５ｎｍ（直径））とエタノール４００ｍＬとをメカニカルホモジナイザー（エスエムテー社製、ＨＩＧＨ−ＦＬＥＸ ＨＯＭＯＧＥＮＩＺＥＲ ＨＦ９３）を用いて、１８０００ｒｐｍで５分間混合して、ＣＮＴ分散液を得た。
次に、エタノール２００ｍＬに酢酸銅一水和物（和光純薬工業社製）を溶解させ、０．００１Ｍの酢酸銅エタノール溶液を調製した。同様に、純水２００ｍＬにチオアセトアミド（東京化成工業社製）を溶解させ、０．０１Ｍのチオアセトアミド水溶液を調製した。
上記ＣＮＴ分散液に、チオアセトアミド水溶液を加えた。その後、得られた分散液を水浴にて６０℃に昇温し、上記酢酸銅エタノール溶液を滴下しながら１２０分間反応させ、ＣＮＴ存在下でＣｕＳ粒子を形成し、分散液１５を調製した。
なお、酢酸銅エタノール溶液はＣｕＳ粒子がＣＮＴに対して１質量％となるよう、チオアセトアミド水溶液は、添加されるチオアセトアミド水溶液中のチオアセトアミド量が、添加される酢酸銅エタノール溶液中のＣｕ量に対して４モル当量となるように、それぞれ加えた。また、酢酸銅エタノール溶液は、滴下直後の全溶液に対する酢酸銅の濃度が１×１０−５Ｍ以下となるよう滴下量／間隔を調整した。
(Preparation of dispersion 15)
Single layer CNT 0.4g (TUBALL 1.5nm (diameter) manufactured by OCSiAl) and ethanol 400mL were mixed for 5 minutes at 18000rpm using mechanical homogenizer (manufactured by SMT Co., Ltd., HIGH-FLEX HOMOGENIZER HF93). Got.
Next, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 200 mL of ethanol to prepare a 0.001 M copper acetate ethanol solution. Similarly, thioacetamide (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 mL of pure water to prepare a 0.01M thioacetamide aqueous solution.
A thioacetamide aqueous solution was added to the CNT dispersion. Thereafter, the obtained dispersion was heated to 60 ° C. in a water bath, reacted for 120 minutes while dropping the copper acetate ethanol solution, CuS particles were formed in the presence of CNTs, and dispersion 15 was prepared.
In addition, the amount of thioacetamide in the thioacetamide aqueous solution added is the amount of Cu in the copper acetate ethanol solution added so that the CuS particles in the copper acetate ethanol solution is 1% by mass with respect to CNT. Each was added so that it might be 4 molar equivalents. Moreover, the copper acetate ethanol solution adjusted the dripping amount / space | interval so that the density | concentration of the copper acetate with respect to all the solutions immediately after dripping might be 1 * 10 < -5 > M or less.
（分散液１６の調製）
分散液１５の調製において、酢酸銅一水和物（和光純薬工業社製）を酢酸銀（和光純薬工業社製）に変えて０．００１Ｍの酢酸銀水溶液を調製した以外は、同様の方法により分散液１６を調製した。
(Preparation of dispersion 16)
In the preparation of dispersion 15, the same procedure was performed except that a copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was changed to silver acetate (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a 0.001 M aqueous silver acetate solution. Dispersion 16 was prepared by the method.
（分散液１７〜２０の調製）
分散液１５の調製において、酢酸銅一水和物（和光純薬工業社製）を塩化スズ（ＩＩ）二水和物（関東化学社製）、酢酸鉛三水和物（関東化学社製）、酢酸亜鉛二水和物（関東化学社製）、及び塩化ビスマス（ＩＩＩ）（和光純薬工業社製）に変えた以外は、同様の方法により分散液１７〜２０をそれぞれ調製した。
(Preparation of dispersions 17-20)
In the preparation of the dispersion 15, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.), tin (II) chloride dihydrate (manufactured by Kanto Chemical Co., Ltd.), lead acetate trihydrate (manufactured by Kanto Chemical Co., Inc.) Dispersions 17 to 20 were prepared in the same manner except that they were changed to zinc acetate dihydrate (manufactured by Kanto Chemical Co., Inc.) and bismuth (III) chloride (manufactured by Wako Pure Chemical Industries, Ltd.).
（分散液２１の調製）
グラフェン（商品名「グラフェンナノプレートレット」東京化成社製 厚さ６〜８ｎｍ）４０ｍｇとアセトン３２ｍＬとをメカニカルホモジナイザー（エスエムテー社製、ＨＩＧＨ−ＦＬＥＸ ＨＯＭＯＧＥＮｉＺＥＲ ＨＦ９３）を用いて、１８０００ｒｐｍで５分間混合して、分散液を得た。
次に、エタノール２００ｍＬに酢酸銅一水和物（和光純薬工業社製）を溶解させ、０．００１Ｍの酢酸銅エタノール溶液を調製した。同様に、純水２００ｍＬに水酸化ナトリウム（和光純薬工業社製）を溶解させ、０．２Ｍの水酸化ナトリウム水溶液を調製した。
上記ＣＮＴ分散液に、水酸化ナトリウム水溶液を加えた。その後、得られた分散液を水浴にて６０℃に昇温し、上記酢酸銅エタノール溶液を滴下しながら１２０分間反応させ、グラフェン存在下でＣｕＯ粒子を形成し、分散液２１を得た。
なお、酢酸銅エタノール溶液はＣｕＯ粒子がグラフェンに対して１質量％となるよう、水酸化ナトリウム水溶液は、添加される水酸化ナトリウム水溶液中の水酸化ナトリウム量が、添加される酢酸銅エタノール溶液中のＣｕ量に対して４モル当量となるように、それぞれ加えた。また、酢酸銅エタノール溶液は、滴下直後の全溶液に対する酢酸銅の濃度が１×１０−５Ｍ以下となるよう滴下量／間隔を調整した。
(Preparation of dispersion 21)
Graphene (trade name “Graphene Nanoplatelet”, manufactured by Tokyo Chemical Industry Co., Ltd., thickness 6-8 nm) 40 mg and acetone 32 mL are mixed for 5 minutes at 18000 rpm using a mechanical homogenizer (manufactured by SMT Co., Ltd., HIGH-FLEX HOMOGENIZER HF93). A dispersion was obtained.
Next, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 200 mL of ethanol to prepare a 0.001 M copper acetate ethanol solution. Similarly, sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 200 mL of pure water to prepare a 0.2M sodium hydroxide aqueous solution.
A sodium hydroxide aqueous solution was added to the CNT dispersion. Thereafter, the obtained dispersion was heated to 60 ° C. in a water bath and reacted for 120 minutes while dropping the copper acetate ethanol solution to form CuO particles in the presence of graphene, thereby obtaining dispersion 21.
In addition, the amount of sodium hydroxide in the sodium hydroxide aqueous solution is the amount of sodium hydroxide in the sodium hydroxide aqueous solution added so that the CuO particles in the copper acetate ethanol solution is 1% by mass with respect to graphene. It added so that it might become 4 molar equivalent with respect to the amount of Cu of each. Moreover, the copper acetate ethanol solution adjusted the dripping amount / space | interval so that the density | concentration of the copper acetate with respect to all the solutions immediately after dripping might be 1 * 10 < -5 > M or less.
〔実施例１〕
＜熱電変換層形成用組成物の調製＞
上記で得られた分散液１を、濾紙（直径１２５ｍｍ）を設置したブフナー漏斗と吸引瓶とを用いて減圧濾過することにより、バッキーペーパー膜を得た。
分散剤としてデオキシコール酸ナトリウム（東京化成工業社製）１２００ｍｇを、分散溶媒である水１６ｍＬに溶解させて混合液とし、得られた混合液に３ｍｍ角程度のサイズにカットしたバッキーペーパー４００ｍｇを加えた。更に得られた組成物を、メカニカルホモジナイザー（エスエムテー社製、ＨＩＧＨ−ＦＬＥＸ ＨＯＭＯＧＥＮＩＺＥＲ ＨＦ９３）を用いて、１０００ｒｐｍで２分間、５０００ｒｐｍで５分間混合して、予備混合物を得た。得られた予備混合物を、薄膜旋回型高速ミキサー「フィルミックス４０−４０型」（プライミクス社製）を用いて、１０℃以下の恒温層中、周速１０ｍ／ｓｅｃで２分間、次いで周速４０ｍ／ｓｅｃで５分間、高速旋回薄膜分散法で分散処理した。得られた分散組成物を自転・公転ミキサー（シンキー社製、あわとり練太郎ＡＲＥ−３１０）にて、２０００ｒｐｍで３０秒間混合、２２００ｒｐｍで３０秒間脱泡して、熱電変換層形成用組成物を調製した。
[Example 1]
<Preparation of composition for forming thermoelectric conversion layer>
The dispersion liquid 1 obtained above was filtered under reduced pressure using a Buchner funnel equipped with filter paper (diameter 125 mm) and a suction bottle, to obtain a bucky paper film.
As a dispersant, 1200 mg of sodium deoxycholate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 16 mL of water as a dispersion solvent to form a mixed solution, and 400 mg of bucky paper cut to a size of about 3 mm square was added to the obtained mixed solution. It was. Furthermore, the obtained composition was mixed for 2 minutes at 1000 rpm for 5 minutes at 5000 rpm using a mechanical homogenizer (manufactured by SMT Co., Ltd., HIGH-FLEX HOMOGENIZER HF93) to obtain a preliminary mixture. Using the thin film swirl type high-speed mixer “Filmix 40-40” (manufactured by Primics), the obtained preliminary mixture was placed in a thermostatic layer at 10 ° C. or lower for 2 minutes at a peripheral speed of 10 m / sec, and then a peripheral speed of 40 m. Dispersion treatment was performed by a high-speed rotating thin film dispersion method for 5 minutes at / sec. The obtained dispersion composition was mixed at 2000 rpm for 30 seconds with a rotating / revolving mixer (Shinky Corp., Awatori Nertaro ARE-310) and defoamed at 2200 rpm for 30 seconds to obtain a thermoelectric conversion layer forming composition. Prepared.
＜熱電変換層の作製＞
厚さ１．１ｍｍ、サイズ４０ｍｍｘ５０ｍｍのポリイミド基板にテフロン（登録商標）製の枠１枚（厚さ０．２μｍ）を貼り付け、その枠内に得られた熱電変換層形成用組成物を塗布して塗膜を形成した。得られた塗膜を５０℃で３０分、１２０℃で３０分乾燥した後、乾燥後の塗膜をエタノールに１時間浸漬することにより分散剤を除去した。更に、分散剤を除去した塗膜を５０℃で３０分、１２０℃で１５０分乾燥することにより熱電変換層を得た。
得られた熱電変換層を５ｃｍ角程度のサイズ（面内ばらつき用測定試料）と、１ｃｍ角程度のサイズ（熱電変換性能測定用試料）にカットし、測定用の熱電変換層を作製した。
<Preparation of thermoelectric conversion layer>
A Teflon (registered trademark) frame (0.2 μm thick) is attached to a polyimide substrate having a thickness of 1.1 mm and a size of 40 mm × 50 mm, and the resulting composition for forming a thermoelectric conversion layer is applied to the frame. A coating film was formed. The obtained coating film was dried at 50 ° C. for 30 minutes and 120 ° C. for 30 minutes, and then the dried coating film was immersed in ethanol for 1 hour to remove the dispersant. Furthermore, the thermoelectric conversion layer was obtained by drying the coating film from which the dispersing agent was removed at 50 ° C. for 30 minutes and at 120 ° C. for 150 minutes.
The obtained thermoelectric conversion layer was cut into a size of about 5 cm square (measurement sample for in-plane variation) and a size of about 1 cm square (sample for measuring thermoelectric conversion performance) to prepare a thermoelectric conversion layer for measurement.
〔実施例２〜２０〕
上記実施例１の熱電変換層の作製において、分散液１を分散液２〜２０に変えた以外は同様の方法により、実施例２〜２０の熱電変換層を作製した。また、実施例１と同様に、得られた熱電変換層を５ｃｍ角程度のサイズ（面内ばらつき用測定試料）と、１ｃｍ角程度のサイズ（熱電変換性能測定用試料）にカットし、測定用の熱電変換層を作製した。
[Examples 2 to 20]
In the production of the thermoelectric conversion layer of Example 1, the thermoelectric conversion layers of Examples 2 to 20 were produced in the same manner except that the dispersion 1 was changed to the dispersions 2 to 20. Further, similarly to Example 1, the obtained thermoelectric conversion layer was cut into a size of about 5 cm square (in-plane variation measurement sample) and a size of about 1 cm square (thermoelectric conversion performance measurement sample) for measurement. A thermoelectric conversion layer was prepared.
〔実施例２１〕
＜熱電変換層形成用組成物の調製＞
分散液２１をＰＴＦＥ（ポリテトラフルオロエチレン）製のメンブレンフィルターを設置したグラスフィルターと吸引瓶を用いて減圧濾過することにより、グラフェン膜を得た。
分散剤としてデオキシコール酸ナトリウム（東京化成工業社製）１２００ｍｇを、分散溶媒である水１６ｍＬに溶解させて混合液とし、得られた混合液に３ｍｍ角程度のサイズにカットしたグラフェン膜４００ｍｇを加えた。更に得られた組成物を、メカニカルホモジナイザー（エスエムテー社製、ＨＩＧＨ−ＦＬＥＸ ＨＯＭＯＧＥＮＩＺＥＲ ＨＦ９３）を用いて、１０００ｒｐｍで２分間、５０００ｒｐｍで５分間混合して、予備混合物を得た。得られた予備混合物を、薄膜旋回型高速ミキサー「フィルミックス４０−４０型」（プライミクス社製）を用いて、１０℃以下の恒温層中、周速１０ｍ／ｓｅｃで２分間、次いで周速４０ｍ／ｓｅｃで５分間、高速旋回薄膜分散法で分散処理した。得られた分散組成物を自転・公転ミキサー（シンキー社製、あわとり練太郎ＡＲＥ−３１０）にて、２０００ｒｐｍで３０秒間混合、２２００ｒｐｍで３０秒間脱泡して、熱電変換層形成用組成物を調製した。
＜熱電変換層の作製＞
ついで、上記実施例１と同様の方法により、実施例２１の熱電変換層を作製し、さらに測定用の熱電変換層を作製した。
Example 21
<Preparation of composition for forming thermoelectric conversion layer>
A graphene film was obtained by filtering the dispersion 21 under reduced pressure using a glass filter and a suction bottle provided with a membrane filter made of PTFE (polytetrafluoroethylene).
As a dispersant, 1200 mg of sodium deoxycholate (manufactured by Tokyo Chemical Industry Co., Ltd.) is dissolved in 16 mL of water as a dispersion solvent to form a mixed solution, and 400 mg of a graphene film cut to a size of about 3 mm square is added to the obtained mixed solution. It was. Furthermore, the obtained composition was mixed for 2 minutes at 1000 rpm for 5 minutes at 5000 rpm using a mechanical homogenizer (manufactured by SMT Co., Ltd., HIGH-FLEX HOMOGENIZER HF93) to obtain a preliminary mixture. Using the thin film swirl type high-speed mixer “Filmix 40-40” (manufactured by Primics), the obtained preliminary mixture was placed in a thermostatic layer at 10 ° C. or lower for 2 minutes at a peripheral speed of 10 m / sec, and then a peripheral speed of 40 m. Dispersion treatment was performed by a high-speed rotating thin film dispersion method for 5 minutes at / sec. The obtained dispersion composition was mixed at 2000 rpm for 30 seconds with a rotating / revolving mixer (Shinky Corp., Awatori Nertaro ARE-310) and defoamed at 2200 rpm for 30 seconds to obtain a thermoelectric conversion layer forming composition. Prepared.
<Preparation of thermoelectric conversion layer>
Subsequently, the thermoelectric conversion layer of Example 21 was produced by the same method as in Example 1, and a thermoelectric conversion layer for measurement was further produced.
〔比較例１〕
単層ＣＮＴ０．４ｇ（ＯＣＳｉＡｌ社製ＴＵＢＡＬＬ １．５ｎｍ（直径））とエタノール４００ｍＬとをメカニカルホモジナイザー（エスエムテー社製、ＨＩＧＨ−ＦＬＥＸ ＨＯＭＯＧＥＮＩＺＥＲ ＨＦ９３）を用いて、１８０００ｒｐｍで５分間混合して、比較例１のＣＮＴ分散液を得た。
上記実施例１の熱電変換層の作製において、分散液１を上記比較例１のＣＮＴ分散液に変えた以外は同様の方法により、比較例１の熱電変換層を作製した。また、実施例１と同様に、得られた熱電変換層を５ｃｍ角程度のサイズ（面内ばらつき用測定試料）と、１ｃｍ角程度のサイズ（熱電変換性能測定用試料）にカットし、測定用の熱電変換層を作製した。
[Comparative Example 1]
Comparative Example 1 Single-walled CNT 0.4 g (TUBALL 1.5 nm (diameter) manufactured by OCSiAl) and ethanol 400 mL were mixed for 5 minutes at 18000 rpm using a mechanical homogenizer (manufactured by SMT Co., Ltd., HIGH-FLEX HOMOGENIZER HF93). A CNT dispersion was obtained.
A thermoelectric conversion layer of Comparative Example 1 was prepared in the same manner as in the preparation of the thermoelectric conversion layer of Example 1, except that the dispersion 1 was changed to the CNT dispersion of Comparative Example 1. Further, similarly to Example 1, the obtained thermoelectric conversion layer was cut into a size of about 5 cm square (in-plane variation measurement sample) and a size of about 1 cm square (thermoelectric conversion performance measurement sample) for measurement. A thermoelectric conversion layer was prepared.
〔比較例２〕
＜熱電変換層形成用組成物の調製＞
単層ＣＮＴ０．４ｇ（ＯＣＳｉＡｌ社製ＴＵＢＡＬＬ １．５ｎｍ（直径））とエタノール４００ｍＬとをメカニカルホモジナイザー（エスエムテー社製、ＨＩＧＨ−ＦＬＥＸ ＨＯＭＯＧＥＮＩＺＥＲ ＨＦ９３）を用いて、１８０００ｒｐｍで５分間混合して、ＣＮＴ分散液を得た。
次に、エタノール２００ｍＬに酢酸銅一水和物（和光純薬工業社製）を溶解させ、０．００１Ｍの酢酸銅エタノール溶液を調製した。同様に、純水２００ｍＬに水酸化ナトリウム（和光純薬工業社製）を溶解させ、０．２Ｍの水酸化ナトリウム水溶液を調製した。エタノール１００ｍＬ、上記酢酸銅エタノール溶液、及び水酸化ナトリウム水溶液を混合し、水浴にて６０℃に昇温し、更に１２０分間反応させてＣｕＯ粒子を形成することにより、ＣｕＯ粒子分散液を調製した。
このＣｕＯ粒子分散液に上記ＣＮＴ分散液を混合することにより、比較例２の熱電変換層形成用組成物を得た。
なお、酢酸銅エタノール溶液はＣｕＯ粒子がＣＮＴに対して１質量％となるよう、水酸化ナトリウム水溶液は、添加される水酸化ナトリウム水溶液中の水酸化ナトリウム量が、添加される酢酸銅エタノール溶液中のＣｕ量に対して４モル当量となるよう、それぞれ混合した。
[Comparative Example 2]
<Preparation of composition for forming thermoelectric conversion layer>
Single layer CNT 0.4g (TUBALL 1.5nm (diameter) manufactured by OCSiAl) and ethanol 400mL were mixed for 5 minutes at 18000rpm using mechanical homogenizer (manufactured by SMT Co., Ltd., HIGH-FLEX HOMOGENIZER HF93). Got.
Next, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 200 mL of ethanol to prepare a 0.001 M copper acetate ethanol solution. Similarly, sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 200 mL of pure water to prepare a 0.2M sodium hydroxide aqueous solution. 100 mL of ethanol, the above copper acetate ethanol solution, and an aqueous sodium hydroxide solution were mixed, heated to 60 ° C. in a water bath, and further reacted for 120 minutes to form CuO particles, thereby preparing a CuO particle dispersion.
The composition for forming a thermoelectric conversion layer of Comparative Example 2 was obtained by mixing the CNT dispersion with this CuO particle dispersion.
In addition, in the copper acetate ethanol solution, the amount of sodium hydroxide in the sodium hydroxide aqueous solution added is the amount of sodium hydroxide in the added copper acetate ethanol solution so that the CuO particles are 1% by mass with respect to CNT. Each was mixed so as to be 4 molar equivalents relative to the amount of Cu.
＜熱電変換層の作製＞
ついで、上記実施例１と同様の方法により、比較例２の熱電変換層を作製し、さらに測定用の熱電変換層を作製した。
<Preparation of thermoelectric conversion layer>
Next, a thermoelectric conversion layer of Comparative Example 2 was produced by the same method as in Example 1, and a thermoelectric conversion layer for measurement was further produced.
〔比較例３〕
＜熱電変換層形成用組成物の調製＞
比較例２の熱電変換層形成用組成物の調製において、ＣｕＯ粒子をＡｇ２Ｏ粒子に変えた以外は同様の方法により比較例３の熱電変換層形成用組成物を調製した。
なお、Ａｇ２Ｏ粒子は、比較例２のＣｕＯ粒子分散液の調整において、酢酸銅一水和物（和光純薬工業社製）を酢酸銀（和光純薬工業社製）に変え、溶媒をエタノールから純水に変えた以外は、同様の方法により調製したものである。
[Comparative Example 3]
<Preparation of composition for forming thermoelectric conversion layer>
In the preparation of the thermoelectric conversion layer forming composition of Comparative Example 2, the thermoelectric conversion layer forming composition of Comparative Example 3 was prepared in the same manner except that the CuO particles were changed to Ag 2 O particles.
Incidentally, Ag 2 O particles, in the adjustment of CuO particle dispersion of Comparative Example 2, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) instead of the silver acetate (produced by Wako Pure Chemical Industries, Ltd.), the solvent It was prepared by the same method except that ethanol was changed to pure water.
＜熱電変換層の作製＞
ついで、上記実施例１と同様の方法により、比較例３の熱電変換層を作製し、さらに測定用の熱電変換層を作製した。
<Preparation of thermoelectric conversion layer>
Subsequently, the thermoelectric conversion layer of Comparative Example 3 was produced by the same method as in Example 1, and a thermoelectric conversion layer for measurement was further produced.
〔比較例４及び５〕
＜熱電変換層形成用組成物の調製＞
比較例２の熱電変換層形成用組成物の調製において、ＣｕＯ粒子を、ＳｎＯ粒子又はＺｎＯ粒子に変えた以外は同様の方法により比較例４及び５の熱電変換層形成用組成物を調製した。
なお、ＳｎＯ粒子及びＺｎＯ粒子は、比較例２のＣｕＯ粒子分散液の調製において、酢酸銅一水和物（和光純薬工業社製）を塩化スズ（ＩＩ）二水和物（関東化学社製）、又は酢酸亜鉛二水和物（関東化学社製）に変えた以外は、同様の方法により調製したものである。
[Comparative Examples 4 and 5]
<Preparation of composition for forming thermoelectric conversion layer>
In the preparation of the thermoelectric conversion layer forming composition of Comparative Example 2, the thermoelectric conversion layer forming compositions of Comparative Examples 4 and 5 were prepared by the same method except that the CuO particles were changed to SnO particles or ZnO particles.
In addition, SnO particle | grains and ZnO particle | grains are the preparation of the CuO particle | grain dispersion liquid of the comparative example 2, copper acetate monohydrate (made by Wako Pure Chemical Industries), tin chloride (II) dihydrate (made by Kanto Chemical Co., Inc.). ), Or zinc acetate dihydrate (manufactured by Kanto Chemical Co., Inc.).
＜熱電変換層の作製＞
ついで、上記実施例１と同様の方法により、比較例４及び５の熱電変換層を作製し、さらに測定用の熱電変換層を作製した。
<Preparation of thermoelectric conversion layer>
Subsequently, the thermoelectric conversion layers of Comparative Examples 4 and 5 were produced by the same method as in Example 1, and a thermoelectric conversion layer for measurement was further produced.
〔比較例６〕
＜熱電変換層形成用組成物の調製＞
単層ＣＮＴ０．４ｇ（ＯＣＳｉＡｌ社製ＴＵＢＡＬＬ １．５ｎｍ（直径））とエタノール４００ｍＬとをメカニカルホモジナイザー（エスエムテー社製、ＨＩＧＨ−ＦＬＥＸ ＨＯＭＯＧＥＮＩＺＥＲ ＨＦ９３）を用いて、１８０００ｒｐｍで５分間混合して、ＣＮＴ分散液を得た。
次に、エタノール２００ｍＬに酢酸銅一水和物（和光純薬工業社製）を溶解させ、０．００１Ｍの酢酸銅エタノール溶液を調製した。同様に、純水２００ｍＬにチオアセトアミド（東京化成工業社製）を溶解させ、０．０１Ｍのチオアセトアミド水溶液を調製した。エタノール１００ｍＬ、上記酢酸銅エタノール溶液及びチオアセトアミド水溶液を混合し、水浴にて６０℃に昇温し、１２０分間反応させてＣｕＳ粒子を形成することにより、ＣｕＳ粒子分散液を調製した。
このＣｕＳ粒子分散液に上記ＣＮＴ分散液を混合することにより、比較例６の熱電変換層形成用組成物を得た。
なお、酢酸銅エタノール溶液はＣｕＳ粒子がＣＮＴに対して１質量％となるよう、チオアセトアミド水溶液は、添加されるチオアセトアミド水溶液中のチオアセトアミド量が、添加される酢酸銅エタノール溶液中のＣｕ量に対して４モル当量となるよう、それぞれ混合した。
[Comparative Example 6]
<Preparation of composition for forming thermoelectric conversion layer>
Single layer CNT 0.4g (TUBALL 1.5nm (diameter) manufactured by OCSiAl) and ethanol 400mL were mixed for 5 minutes at 18000rpm using mechanical homogenizer (manufactured by SMT Co., Ltd., HIGH-FLEX HOMOGENIZER HF93). Got.
Next, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 200 mL of ethanol to prepare a 0.001 M copper acetate ethanol solution. Similarly, thioacetamide (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 mL of pure water to prepare a 0.01M thioacetamide aqueous solution. A CuS particle dispersion was prepared by mixing 100 mL of ethanol, the copper acetate ethanol solution and the thioacetamide aqueous solution, raising the temperature to 60 ° C. in a water bath and reacting for 120 minutes to form CuS particles.
The composition for forming a thermoelectric conversion layer of Comparative Example 6 was obtained by mixing the CNT dispersion with this CuS particle dispersion.
In addition, the amount of thioacetamide in the thioacetamide aqueous solution added is the amount of Cu in the copper acetate ethanol solution added so that the CuS particles in the copper acetate ethanol solution is 1% by mass with respect to CNT. Each was mixed so as to be 4 molar equivalents.
＜熱電変換層の作製＞
ついで、上記実施例１と同様の方法により、比較例６の熱電変換層を作製し、さらに測定用の熱電変換層を作製した。
<Preparation of thermoelectric conversion layer>
Next, a thermoelectric conversion layer of Comparative Example 6 was produced by the same method as in Example 1, and a thermoelectric conversion layer for measurement was further produced.
〔比較例７〕
＜熱電変換層形成用組成物の調製＞
比較例６の熱電変換層形成用組成物の調製において、ＣｕＳ粒子をＡｇ２Ｓ粒子に変えた以外は同様の方法により比較例７の熱電変換層形成用組成物を調製した。
なお、Ａｇ２Ｓ粒子は、比較例６のＣｕＳ分散液の調製において、酢酸銅一水和物（和光純薬工業社製）を酢酸銀（和光純薬工業社製）に変え、溶媒をエタノールから純水に変えた以外は、同様の方法により調製したものである。
[Comparative Example 7]
<Preparation of composition for forming thermoelectric conversion layer>
In the preparation of the thermoelectric conversion layer forming composition of Comparative Example 6, the thermoelectric conversion layer forming composition of Comparative Example 7 was prepared by the same method except that the CuS particles were changed to Ag 2 S particles.
Incidentally, ethanol Ag 2 S particles, in the preparation of CuS dispersion according to Comparative Example 6, copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) instead of the silver acetate (produced by Wako Pure Chemical Industries, Ltd.), the solvent It was prepared by the same method except that it was changed from pure water to pure water.
＜熱電変換層の作製＞
ついで、上記実施例１と同様の方法により、比較例７の熱電変換層を作製し、さらに測定用の熱電変換層を作製した。
<Preparation of thermoelectric conversion layer>
Next, a thermoelectric conversion layer of Comparative Example 7 was produced by the same method as in Example 1, and a thermoelectric conversion layer for measurement was further produced.
〔比較例８及び９〕
＜熱電変換層形成用組成物の調製＞
比較例６の熱電変換層形成用組成物の調製において、ＣｕＳ粒子を、ＳｎＳ粒子又はＰｂＳ粒子に変えた以外は同様の方法により比較例８及び９の熱電変換層形成用組成物を調製した。
なお、ＳｎＳ粒子及びＰｂＳ粒子は、比較例６のＣｕＳ分散液の調製において、酢酸銅一水和物（和光純薬工業社製）を塩化スズ（ＩＩ）二水和物（関東化学社製）、又は酢酸鉛三水和物（関東化学社製）に変えた以外は、同様の方法により調製したものである。
[Comparative Examples 8 and 9]
<Preparation of composition for forming thermoelectric conversion layer>
In the preparation of the thermoelectric conversion layer forming composition of Comparative Example 6, the thermoelectric conversion layer forming compositions of Comparative Examples 8 and 9 were prepared by the same method except that the CuS particles were changed to SnS particles or PbS particles.
In addition, SnS particle | grains and PbS particle | grains WHEREIN: In preparation of the CuS dispersion liquid of the comparative example 6, copper acetate monohydrate (made by Wako Pure Chemical Industries Ltd.) is tin chloride (II) dihydrate (made by Kanto Chemical Co., Inc.). Or lead acetate trihydrate (manufactured by Kanto Chemical Co., Inc.).
＜熱電変換層の作製＞
ついで、上記実施例１と同様の方法により、比較例８及び９の熱電変換層を作製し、さらに測定用の熱電変換層を作製した。
<Preparation of thermoelectric conversion layer>
Subsequently, the thermoelectric conversion layers of Comparative Examples 8 and 9 were produced by the same method as in Example 1, and a thermoelectric conversion layer for measurement was further produced.
〔比較例１０〕
＜熱電変換層形成用組成物の調製＞
特開２０１４−１５６３７０号公報の実施例１に記載の方法において、チタン源を銅源として銅エトキシド（ＩＩ）（和光純薬工業社製）に変え、銅エトキシドをＣｕＯ粒子がＣＮＴに対して１質量％となるよう加えた以外は、同様の方法で熱電変換層形成用組成物を得た。
[Comparative Example 10]
<Preparation of composition for forming thermoelectric conversion layer>
In the method described in Example 1 of Japanese Patent Application Laid-Open No. 2014-156370, the titanium source is changed to copper ethoxide (II) (manufactured by Wako Pure Chemical Industries, Ltd.) using the copper source as the copper source, and the copper ethoxide is 1 CuO particle to CNT. A composition for forming a thermoelectric conversion layer was obtained in the same manner except that it was added in an amount of mass%.
＜熱電変換層の作製＞
ついで、上記実施例１と同様の方法により、比較例１０の熱電変換層を作製し、さらに測定用の熱電変換層を作製した。
<Preparation of thermoelectric conversion layer>
Next, a thermoelectric conversion layer of Comparative Example 10 was produced by the same method as in Example 1, and a thermoelectric conversion layer for measurement was further produced.
〔比較例１１〕
グラフェン（商品名「グラフェンナノプレートレット」東京化成社製 厚さ６〜８ｎｍ）４０ｍｇとアセトン３２ｍＬとをメカニカルホモジナイザー（エスエムテー社製、ＨＩＧＨ−ＦＬＥＸ ＨＯＭＯＧＥＮｉＺＥＲ ＨＦ９３）を用いて、１８０００ｒｐｍで５分間混合して、分散液を得た。
[Comparative Example 11]
Graphene (trade name “Graphene Nanoplatelet”, manufactured by Tokyo Chemical Industry Co., Ltd., thickness 6-8 nm) 40 mg and acetone 32 mL are mixed for 5 minutes at 18000 rpm using a mechanical homogenizer (manufactured by SMT Co., Ltd., HIGH-FLEX HOMOGENIZER HF93). A dispersion was obtained.
ついで、上記実施例２１と同様の方法により、比較例１１の熱電変換層を作製した。また、実施例２１と同様に、得られた熱電変換層を５ｃｍ角程度のサイズ（面内ばらつき用測定試料）と、１ｃｍ角程度のサイズ（熱電変換性能測定用試料）にカットし、測定用の熱電変換層を作製した。 Next, a thermoelectric conversion layer of Comparative Example 11 was produced by the same method as in Example 21 above. Similarly to Example 21, the obtained thermoelectric conversion layer was cut into a size of about 5 cm square (in-plane variation measurement sample) and a size of about 1 cm square (thermoelectric conversion performance measurement sample) for measurement. A thermoelectric conversion layer was prepared.
〔分散液の形態観察〕
実施例１〜２１で用いた各分散液（分散液１〜２１に相当）、及び比較例２〜１０で用いた各分散液を純水にて１０倍に希釈し、マイクログリッドに滴下して乾燥させた後、ＴＥＭ−ＥＤＸ（Energy Dispersive X-ray Spectroscopy）を用いて１０万倍の倍率で観察及び元素分析を実施し、無機ナノ粒子の形態観察及び組成分析を行った。この形態観察及び組成分析の結果について、本発明では以下のように定義する。
[Observation of dispersion morphology]
Each dispersion used in Examples 1 to 21 (corresponding to dispersions 1 to 21) and each dispersion used in Comparative Examples 2 to 10 were diluted 10 times with pure water and dropped onto a microgrid. After drying, observation and elemental analysis were performed at a magnification of 100,000 times using TEM-EDX (Energy Dispersive X-ray Spectroscopy), and morphology observation and composition analysis of inorganic nanoparticles were performed. The results of this morphological observation and composition analysis are defined as follows in the present invention.
「均一に複合化している」：目的の組成の無機ナノ粒子がほとんど凝集せずナノ炭素材料上に担持され複合化している状態。
「不均一に複合化している」：目的の組成の無機ナノ粒子が凝集してナノ炭素材料上に担持されている状態。
「複合化していない」：目的の組成の無機ナノ粒子が凝集し、ナノ炭素材料と別々に存在している状態。
“Homogeneously composited”: A state in which inorganic nanoparticles having a target composition are hardly aggregated and are supported on a nanocarbon material and composited.
“Heterogeneously complexed”: A state in which inorganic nanoparticles of a desired composition are aggregated and supported on a nanocarbon material.
“Uncomplexed”: A state in which inorganic nanoparticles of a desired composition are aggregated and exist separately from the nanocarbon material.
この分析の結果、実施例１〜２１で用いた各分散液（分散液１〜２１に相当）は均一に複合化していた。一方、比較例２〜９の分散液は複合化していなかった。また、比較例１０の分散液は不均一に複合化していた。
なお、分散液１〜２１及び比較例２〜９の分散液中における無機ナノ粒子の短径は、いずれも５００ｎｍ以下であった。
As a result of this analysis, each dispersion used in Examples 1 to 21 (corresponding to dispersions 1 to 21) was uniformly combined. On the other hand, the dispersions of Comparative Examples 2 to 9 were not combined. Further, the dispersion of Comparative Example 10 was non-uniformly complexed.
In addition, the short diameter of the inorganic nanoparticle in the dispersion liquids 1 to 21 and the dispersion liquids of Comparative Examples 2 to 9 was 500 nm or less.
〔評価〕
各実施例及び各比較例の熱電変換層について、以下に示す各評価を実施した。
＜面内ばらつきの評価＞
ＳＥＭ−ＥＤＸ（Energy Dispersive X-ray Spectroscopy）を用いて、熱電変換層（５ｃｍ×５ｃｍサイズ）の１０か所の領域において炭素元素に対する金属元素の含有比率を測定し、下記式（１）により算出される面内ばらつきの最大値Ｔを求めた。
式（１）Ｔ＝｜最大偏差｜／｜平均値｜×１００（％）
[Evaluation]
Each evaluation shown below was implemented about the thermoelectric conversion layer of each Example and each comparative example.
<Evaluation of in-plane variation>
Using SEM-EDX (Energy Dispersive X-ray Spectroscopy), the content ratio of the metal element to the carbon element was measured in 10 regions of the thermoelectric conversion layer (5 cm × 5 cm size) and calculated by the following formula (1). The maximum value T of the in-plane variation to be performed was obtained.
Formula (1) T = | maximum deviation | / | average value | × 100 (%)
なお、熱電変換層の１０か所の領域は無作為に選択し（なお、各領域は少なくとも５００μｍ以上離れている）、各領域のサイズは２５０μｍ×２００μｍである。
式（１）中、上記平均値とは、５ｃｍ×５ｃｍサイズの熱電変換層から選ばれる任意の１０か所の領域を測定して得られる炭素元素に対する金属元素の含有比率から算出される平均値である。
また、上記最大偏差とは、任意の１０か所の領域を測定して得られる炭素元素に対する金属元素の含有比率のうち、平均値から最も離れた測定値と平均値との偏差である。結果を表２に示す。
Note that 10 regions of the thermoelectric conversion layer are randomly selected (each region is separated by at least 500 μm), and the size of each region is 250 μm × 200 μm.
In the formula (1), the average value is an average value calculated from the content ratio of the metal element to the carbon element obtained by measuring any 10 regions selected from a thermoelectric conversion layer having a size of 5 cm × 5 cm. It is.
The maximum deviation is a deviation between a measured value farthest from the average value and the average value among the content ratio of the metal element to the carbon element obtained by measuring any 10 regions. The results are shown in Table 2.
＜導電率（σ）、ゼーベック係数（Ｓ）＞
熱電特性測定装置ＭＯＤＥＬ ＲＺ２００１ｉ（オザワ科学社製）を用いて、約８０℃及び１０５℃における熱電変換層の導電率及びゼーベック係数（絶対温度１Ｋ当りの熱起電力）を測定し、内挿により、１００℃における導電率及びゼーベック係数を算出した。１実施例（比較例）につき１０試料測定し、その平均値を用いた。
なお、導電率及びゼーベック係数の評価は、各々、下記に示す式により規格化した値に基づいて実施した。
<Conductivity (σ), Seebeck coefficient (S)>
Using a thermoelectric property measuring device MODEL RZ2001i (manufactured by Ozawa Science Co., Ltd.), the conductivity and Seebeck coefficient (thermoelectromotive force per 1 K absolute temperature) of the thermoelectric conversion layer at about 80 ° C. and 105 ° C. are measured, and by interpolation, The conductivity and Seebeck coefficient at 100 ° C. were calculated. Ten samples were measured per example (comparative example), and the average value was used.
In addition, evaluation of the electrical conductivity and the Seebeck coefficient was implemented based on the value normalized by the formula shown below, respectively.
（導電率（σ））
実施例１〜２０及び比較例１〜１０は比較例１を、実施例２１及び比較例１１は比較例１１をそれぞれ基準比較例とし、下記式より各実施例及び各比較例の各規格化導電率を求めた。評価基準は下記の通りである。結果を表２及び表３に示す。
（規格化導電率）＝（各実施例又は各比較例の熱電変換層の導電率）／（基準比較例の熱電変換層の導電率）
(Conductivity (σ))
Examples 1 to 20 and Comparative Examples 1 to 10 are Comparative Example 1, Example 21 and Comparative Example 11 are Comparative Examples 11, and each normalized conductivity of each Example and each Comparative Example is expressed by the following formula. The rate was determined. The evaluation criteria are as follows. The results are shown in Tables 2 and 3.
(Standardized conductivity) = (Conductivity of thermoelectric conversion layer of each example or comparative example) / (Conductivity of thermoelectric conversion layer of reference comparative example)
≪評価基準≫
「Ａ」：規格化導電率が１．５０以上
「Ｂ」：規格化導電率が１．３０以上、１．５０未満
「Ｃ」：規格化導電率が１．１０以上、１．３０未満
「Ｄ」：規格化導電率が１．１０未満
≪Evaluation criteria≫
“A”: normalized conductivity is 1.50 or more “B”: normalized conductivity is 1.30 or more and less than 1.50 “C”: normalized conductivity is 1.10 or more and less than 1.30 “ D ": normalized conductivity is less than 1.10
（ゼーベック係数（Ｓ））
実施例１〜２０及び比較例１〜１０は比較例１を、実施例２１及び比較例１１は比較例１１をそれぞれ基準比較例とし、下記式より各実施例及び各比較例の各規格化ゼーベック係数を求めた。評価基準は下記の通りである。結果を表２及び表３に示す。
（規格化ゼーベック係数）＝（各実施例又は各比較例の熱電変換層のゼーベック係数）／（基準比較例の熱電変換層のゼーベック係数）
(Seebeck coefficient (S))
Examples 1 to 20 and Comparative Examples 1 to 10 are Comparative Example 1, Example 21 and Comparative Example 11 are Comparative Examples 11, and each standardized Seebeck of each Example and each Comparative Example is given by the following formula. The coefficient was obtained. The evaluation criteria are as follows. The results are shown in Tables 2 and 3.
(Standardized Seebeck coefficient) = (Seebeck coefficient of thermoelectric conversion layer of each example or comparative example) / (Seebeck coefficient of thermoelectric conversion layer of reference comparative example)
≪評価基準≫
「Ａ」：規格化ゼーベック係数が１．５０以上
「Ｂ」：規格化ゼーベック係数が１．３０以上、１．５０未満
「Ｃ」：規格化ゼーベック係数が１．１０以上、１．３０未満
「Ｄ」：規格化ゼーベック係数が１．１０未満
≪Evaluation criteria≫
“A”: Normalized Seebeck coefficient is 1.50 or more “B”: Normalized Seebeck coefficient is 1.30 or more and less than 1.50 “C”: Normalized Seebeck coefficient is 1.10 or more and less than 1.30 “ D ": Normalized Seebeck coefficient is less than 1.10
＜熱伝導率κ、性能指数Ｚ比の評価＞
（性能指数Ｚ比の評価）
以下の式により性能指数Ｚを算出した。
（性能指数Ｚ）＝［（導電率）×（ゼーベック係数）２］／熱伝導率
なお、性能指数Ｚの算出にあたり、以下の式により各実施例及び各比較例の熱電変換層の熱伝導率を算出した。なお、熱拡散率、比熱、及び、密度についても、導電率及びゼーベック係数と同様に１実施例（比較例）につき１０試料測定し、その平均値を用いた。
（熱伝導率[Ｗ／ｍＫ]）＝（比熱［Ｊ／ｋｇ・Ｋ]）×（密度[ｋｇ／ｍ３］）×（熱拡散率［ｍ２／ｓ］）
なお、上記式において、「比熱」はＤＳＣ法（示差走査熱量測定法）により測定し、「密度」は質量／体積より測定した。「熱拡散率」は、熱拡散率測定装置ａｉ−Ｐｈａｓｅ Ｍｏｂｉｌｅ １ｕ（アイフェイズ株式会社製）を用いて測定した。
<Evaluation of thermal conductivity κ and figure of merit Z ratio>
(Evaluation of performance index Z ratio)
The figure of merit Z was calculated by the following formula.
(Performance index Z) = [(Conductivity) × (Seebeck coefficient) 2 ] / thermal conductivity In calculating the performance index Z, the thermal conductivity of the thermoelectric conversion layer of each example and each comparative example is expressed by the following formula. Was calculated. As for the thermal diffusivity, specific heat, and density, 10 samples were measured for each example (comparative example) as in the case of the conductivity and Seebeck coefficient, and the average values were used.
(Thermal conductivity [W / mK]) = (specific heat [J / kg · K]) × (density [kg / m 3 ]) × (thermal diffusivity [m 2 / s])
In the above formula, “specific heat” was measured by DSC method (differential scanning calorimetry), and “density” was measured from mass / volume. “Thermal diffusivity” was measured using a thermal diffusivity measuring apparatus ai-Phase Mobile 1u (manufactured by Eye Phase Co., Ltd.).
算出された各実施例及び各比較例の性能指数Ｚの値を用いて、下記に示す式により規格化性能指数Ｚ比（以下、「Ｚ比」ともいう。）を算出した。具体的には、下記式より各実施例及び各比較例のＺ比を求めた。なお、実施例１〜２０及び比較例１〜１０は比較例１を、実施例２１及び比較例１１は比較例１１をそれぞれ基準比較例に用いた。結果を表２及び表３に示す。
（Ｚ比）＝（各実施例又は各比較例の熱電変換層の性能指数Ｚ）／（基準比較例の熱電変換層の性能指数Ｚ）
Using the calculated value of the performance index Z of each example and each comparative example, a normalized performance index Z ratio (hereinafter also referred to as “Z ratio”) was calculated by the following formula. Specifically, Z ratio of each Example and each comparative example was calculated | required from the following formula. In Examples 1 to 20 and Comparative Examples 1 to 10, Comparative Example 1 was used, and in Examples 21 and 11, Comparative Example 11 was used as a reference comparative example. The results are shown in Tables 2 and 3.
(Z ratio) = (Performance index Z of thermoelectric conversion layer of each example or each comparative example) / (Performance index Z of thermoelectric conversion layer of the reference comparative example)
≪評価基準≫
「ＡＡ」：規格化性能指数Ｚが７．００以上
「Ａ」：規格化性能指数Ｚが５．００以上、７．００未満
「Ｂ」：規格化性能指数Ｚが３．５０以上、５．００未満
「Ｃ」：規格化性能指数Ｚが２．５０以上、３．５０未満
「Ｄ」：規格化性能指数Ｚが２．００以上、２．５０未満
「Ｅ」：規格化性能指数Ｚが２．００未満
≪Evaluation criteria≫
“AA”: standardized performance index Z is 7.00 or more “A”: standardized performance index Z is 5.00 or more and less than 7.00 “B”: standardized performance index Z is 3.50 or more; Less than 00 “C”: normalized performance index Z is 2.50 or more and less than 3.50 “D”: normalized performance index Z is 2.00 or more and less than 2.50 “E”: normalized performance index Z is Less than 2.00
（熱伝導率κの評価）
熱伝導率κの評価は、下記に示す式により規格化した値に基づいて実施した。具体的には、実施例１〜２０及び比較例１〜１０は比較例１を、実施例２１及び比較例１１は比較例１１をそれぞれ基準比較例とし、下記式より各実施例及び各比較例の各規格化熱伝導率（以下、「規格化熱伝導率」ともいう。）を求めた。評価基準は下記の通りである。結果を表２及び表３に示す。
（規格化熱伝導率）＝（各実施例又は各比較例の熱電変換層の熱伝導率）／（基準比較例の熱電変換層の熱伝導率）
(Evaluation of thermal conductivity κ)
Evaluation of thermal conductivity (kappa) was implemented based on the value normalized by the formula shown below. Specifically, Examples 1 to 20 and Comparative Examples 1 to 10 are Comparative Examples 1, and Examples 21 and 11 are Comparative Examples 11 as reference comparative examples. Each normalized thermal conductivity (hereinafter, also referred to as “normalized thermal conductivity”) was obtained. The evaluation criteria are as follows. The results are shown in Tables 2 and 3.
(Standardized thermal conductivity) = (Thermal conductivity of the thermoelectric conversion layer of each example or each comparative example) / (Thermal conductivity of the thermoelectric conversion layer of the reference comparative example)
≪評価基準≫
「Ａ」：規格化熱伝導率が０．５００未満
「Ｂ」：規格化熱伝導率が０．５００以上、０．７００未満
「Ｃ」：規格化熱伝導率が０．７００以上、０．９００未満
「Ｄ」：規格化熱伝導率が０．９００以上
≪Evaluation criteria≫
“A”: normalized thermal conductivity is less than 0.500 “B”: normalized thermal conductivity is 0.500 or more and less than 0.700 “C”: normalized thermal conductivity is 0.700 or more, 0.00 Less than 900 “D”: normalized thermal conductivity is 0.900 or more
＜密着性の評価＞
各実施例及び各比較例の熱電変換層をそれぞれ１０個ずつ準備し、ニチバン株式会社製セロハンテープ（幅２４ｍｍ）を密着させてから剥がした。剥がした後の熱電変換層の外観を目視で観察することにより、密着性を評価した。評価基準は下記の通りである。結果を表１に示す。
<Evaluation of adhesion>
Ten thermoelectric conversion layers of each Example and each Comparative Example were prepared, and the cellophane tape (width 24 mm) manufactured by Nichiban Co., Ltd. was brought into close contact, and then peeled off. The adhesion was evaluated by visually observing the appearance of the thermoelectric conversion layer after peeling. The evaluation criteria are as follows. The results are shown in Table 1.
「Ａ」:１０個の試料のいずれにも剥離が観察されなかった。
「Ｂ」:１０個の試料のうち、１個以上の試料で剥離が観察された。
“A”: no peeling was observed in any of the ten samples.
“B”: Peeling was observed in one or more of 10 samples.
以下に表２及び表３を示す。
なお、表２及び表３の無機ナノ粒子欄に記載される「ナノ炭素材料に対する含有量」は、ナノ炭素材料に対する無機ナノ粒子の含有量に相当する。
また、表２及び表３の「複合化の有無」は、ナノ炭素材料と無機ナノ粒子との状態を示す。ナノ炭素材料の存在下にて無機ナノ粒子を形成した場合（複合化されている場合）には「有」、そうでない場合（複合化されていない場合）には「無」で表す。
Tables 2 and 3 are shown below.
In addition, "content with respect to nanocarbon material" described in the inorganic nanoparticle column of Table 2 and Table 3 corresponds to the content of inorganic nanoparticles with respect to the nanocarbon material.
“Presence / absence of complexation” in Tables 2 and 3 indicates the state of the nanocarbon material and the inorganic nanoparticles. When inorganic nanoparticles are formed in the presence of the nanocarbon material (when combined), “present” is indicated, and when not (when not combined), “not present” is indicated.
表２に示す結果から、実施例１〜２１の熱電変換層は、いずれも面内ばらつきの最大値Ｔが３０％以下であることが確認された。また、実施例１〜２１の熱電変換層は、いずれも規格化Ｚに優れ、且つ、密着性にも優れていることが確認された。 From the results shown in Table 2, it was confirmed that in each of the thermoelectric conversion layers of Examples 1 to 21, the maximum value T of in-plane variation was 30% or less. Moreover, it was confirmed that the thermoelectric conversion layers of Examples 1 to 21 are both excellent in standardization Z and excellent in adhesion.
また、表２の実施例１〜８の対比から、熱電変換層中、無機ナノ粒子の含有量が、ナノ炭素材料に対して０．０１〜３００質量％である場合（好ましくは０．０１〜２５０質量％、より好ましくは０．０５〜３質量％である場合）に、性能指数Ｚにより優れることが確認された。
また、実施例５、９〜２０の対比から、無機ナノ粒子として金属硫化物粒子又は金属酸化物粒子を含有する場合（より好ましくは金属硫化物粒子を含有する場合）には、熱電変換性能がより一層優れることが確認された。また、実施例５、９〜１３、１５〜２０の対比から、無機ナノ粒子が、銅、銀、鉛、及び錫からなる群より選ばれる少なくとも１種の金属元素を含有する場合には、熱電変換性能がより優れることが確認された。なかでも無機ナノ粒子が、銅、銀、鉛、又は錫からなる群より選ばれる少なくとも１種の金属元素を含有する硫化物である場合に、ゼーベック係数Ｓ、導電性σ、熱伝導性κ、性能指数Ｚのいずれについても優れることが確認された。
Further, from the comparison of Examples 1 to 8 in Table 2, when the content of inorganic nanoparticles in the thermoelectric conversion layer is 0.01 to 300% by mass with respect to the nanocarbon material (preferably 0.01 to 250% by mass, more preferably 0.05 to 3% by mass), it was confirmed that the figure of merit Z was superior.
Further, from the comparison of Examples 5 and 9 to 20, when metal sulfide particles or metal oxide particles are contained as inorganic nanoparticles (more preferably, metal sulfide particles are contained), thermoelectric conversion performance is obtained. It was confirmed that it was even better. Further, in contrast to Examples 5, 9-13, and 15-20, when the inorganic nanoparticles contain at least one metal element selected from the group consisting of copper, silver, lead, and tin, thermoelectric It was confirmed that the conversion performance was better. Among them, when the inorganic nanoparticles are sulfides containing at least one metal element selected from the group consisting of copper, silver, lead, or tin, Seebeck coefficient S, conductivity σ, thermal conductivity κ, It was confirmed that any of the figure of merit Z was excellent.
一方、比較例２〜１０の熱電変換層は、面内ばらつきの最大値Ｔが大きく、この結果として熱電変換性能及び密着性のいずれにおいても所望の効果が得られなかった。
なお、比較例１０の方法で形成される複合粒子は、金属酸化物粒子のカーボンナノチューブへの被覆性は高くなるが、電磁波照射により急速に加熱されることにより粒子形成が素早く進行するため、金属酸化物粒子同士の凝集が避けられないことを明らかとした。つまり、比較例１０の方法で形成される複合粒子は、無機ナノ粒子がナノ炭素材料上に担持されてはいるものの、金属酸化物同士の凝集もある程度存在するため、熱電変換性能及び密着性において所望の効果が発現しなかったと考えられる。
On the other hand, the thermoelectric conversion layers of Comparative Examples 2 to 10 have a large in-plane variation maximum value T, and as a result, the desired effect was not obtained in either thermoelectric conversion performance or adhesion.
Note that the composite particles formed by the method of Comparative Example 10 have a higher coverage of the metal oxide particles on the carbon nanotubes, but the particles are rapidly formed by rapid heating by electromagnetic wave irradiation. It was clarified that aggregation of oxide particles is inevitable. That is, in the composite particles formed by the method of Comparative Example 10, although inorganic nanoparticles are supported on the nanocarbon material, there is some aggregation of metal oxides, so in thermoelectric conversion performance and adhesion It is considered that the desired effect was not exhibited.
（実施例２２）熱電変換モジュールの作製
熱電変換層を４ｍｍ×８ｍｍのサイズにカットしたこと以外は実施例５と同様にして熱電変換層を１６個作製した。
次いで、上記熱電変換層を用いて図６に示す熱電変換モジュールを作製した。
まず、幅１．６ｃｍ×長さ１４ｃｍの基板１２０（ポリイミド基板）に、スクリーン印刷により、銀ペーストを印刷し、銀ペーストの印刷物を１２０℃で１時間乾燥させて、電極１３０を１６対と配線１３２を同時に形成した。なお、電極１つ当たりのサイズは、幅４ｍｍ×長さ２．５ｍｍで、電極間距離は５ｍｍである。また、後述する１６個の熱電変換層１５０が直列に接続されるように、１対の電極１３０間が幅１ｍｍの配線により接続される。
次に、幅４ｍｍ×長さ８ｍｍのサイズにカットした熱電変換層を、両面テープを用いて電極間に張り付けた。電極と熱電変換層の接触部に銀ペーストを塗布し、１２０℃で１時間乾燥することにより電極と熱電変換層を接着させ電気的に接続した。このようにして得られた熱電変換モジュール２００を実施例２２の熱電変換モジュールとして用いた。
(Example 22) Production of thermoelectric conversion module Sixteen thermoelectric conversion layers were produced in the same manner as in Example 5 except that the thermoelectric conversion layer was cut into a size of 4 mm x 8 mm.
Subsequently, the thermoelectric conversion module shown in FIG. 6 was produced using the thermoelectric conversion layer.
First, a silver paste is printed on a substrate 120 (polyimide substrate) having a width of 1.6 cm and a length of 14 cm by screen printing, and the printed matter of silver paste is dried at 120 ° C. for 1 hour to wire 16 pairs of electrodes 130. 132 was formed simultaneously. The size per electrode is 4 mm wide × 2.5 mm long, and the distance between the electrodes is 5 mm. Further, a pair of electrodes 130 are connected by a wiring having a width of 1 mm so that 16 thermoelectric conversion layers 150 described later are connected in series.
Next, the thermoelectric conversion layer cut into a size of 4 mm wide × 8 mm long was attached between the electrodes using a double-sided tape. A silver paste was applied to the contact portion between the electrode and the thermoelectric conversion layer, and dried at 120 ° C. for 1 hour to adhere and electrically connect the electrode and the thermoelectric conversion layer. The thermoelectric conversion module 200 thus obtained was used as the thermoelectric conversion module of Example 22.
（比較例１２）
熱電変換層を４ｍｍ×８ｍｍサイズにカットした比較例２の熱電変換層を用いたこと以外は実施例２２と同様にして熱電変換モジュールを作製した。
(Comparative Example 12)
A thermoelectric conversion module was produced in the same manner as in Example 22 except that the thermoelectric conversion layer of Comparative Example 2 in which the thermoelectric conversion layer was cut to a size of 4 mm × 8 mm was used.
（熱電変換モジュールの評価）
図７は、実施例における熱電変換モジュールの評価方法を説明するための図である。図７に示すように、熱電変換モジュール２００の発電層側をアラミドフィルム３１０により保護した。そして、熱電変換モジュール２００の下部をホットプレート３３０上に設置した銅プレート３２０で挟みこんで固定することにより、熱電変換モジュール２００の下部を効率的に加熱できるようにした。
次いで、熱電変換モジュール２００の両端における取り出し電極（図示せず）にソースメーター（ケースレーインスツルメンツ社製）の端子（図示せず）を取り付け、ホットプレート３３０の温度を１００℃で一定に保って、熱電変換モジュール２００に温度差を付与した。
電流−電圧特性を測定し、短絡電流及び開放電圧を測定した。測定結果から、「（出力）＝［（電流）×（電圧）／４］」によって出力を算出した。その結果、出力は実施例２２＞比較例１２となり、実施例２２の熱電変換層の性能を支持する結果が得られた。
(Evaluation of thermoelectric conversion module)
FIG. 7 is a diagram for explaining a thermoelectric conversion module evaluation method in the embodiment. As shown in FIG. 7, the power generation layer side of the thermoelectric conversion module 200 was protected by an aramid film 310. Then, the lower part of the thermoelectric conversion module 200 is sandwiched and fixed by the copper plate 320 installed on the hot plate 330 so that the lower part of the thermoelectric conversion module 200 can be efficiently heated.
Next, a terminal (not shown) of a source meter (manufactured by Keithley Instruments) is attached to extraction electrodes (not shown) at both ends of the thermoelectric conversion module 200, and the temperature of the hot plate 330 is kept constant at 100 ° C. A temperature difference was given to the conversion module 200.
Current-voltage characteristics were measured, and short-circuit current and open-circuit voltage were measured. From the measurement result, the output was calculated by “(output) = [(current) × (voltage) / 4]”. As a result, the output was Example 22> Comparative Example 12, and a result supporting the performance of the thermoelectric conversion layer of Example 22 was obtained.
１１０、１２０、１３０、１４０ 熱電変換素子
１１、１７ 金属板
１２、２２ 第１の基材
１３、２３ 第１の電極
１４、２４ 熱電変換層
１５、２５ 第２の電極
１６、２６ 第２の基材
３０ 第２基板
３２ 第１基板
３２ａ，３０ａ 低熱伝導部
３２ｂ，３０ｂ 高熱伝導部
３４ 熱電変換層
３６ 第１の電極
３８ 第２の電極
４１ ｎ型熱電変換層
４２ ｐ型熱電変換層
４３ 下側基材
４４ 第２の電極
４５ 第１及び第３の電極
４５Ａ 第１の電極
４５Ｂ 第３の電極
４６ 上側基材
４７ 電子
４８ ホール
１２０ 基板
１３０ 電極
１３２ 配線
１５０ 熱電変換層
２００ 熱電変換モジュール
３１０ アラミドフィルム
３２０ 銅プレート
３３０ ホットプレート
110, 120, 130, 140 Thermoelectric conversion element 11, 17 Metal plate 12, 22 First base material 13, 23 First electrode 14, 24 Thermoelectric conversion layer 15, 25 Second electrode 16, 26 Second group Material 30 Second substrate 32 First substrate 32a, 30a Low heat conduction portion 32b, 30b High heat conduction portion 34 Thermoelectric conversion layer 36 First electrode 38 Second electrode 41 n-type thermoelectric conversion layer 42 p-type thermoelectric conversion layer 43 lower side Base material 44 Second electrode 45 First and third electrode 45A First electrode 45B Third electrode 46 Upper base material 47 Electron 48 Hole 120 Substrate 130 Electrode 132 Wiring 150 Thermoelectric conversion layer 200 Thermoelectric conversion module 310 Aramid film 320 Copper plate 330 Hot plate
Claims (8)
前記熱電変換層を走査型電子顕微鏡にて観察し、エネルギー分散型Ｘ線分析により得られる前記ナノ炭素材料由来の炭素元素に対する前記金属元素の含有比率を用いて、下記式（１）により算出される面内ばらつきの最大値Ｔが、０〜３０％である熱電変換層。
式（１）Ｔ＝｜最大偏差｜／｜平均値｜×１００
前記平均値とは、走査型電子顕微鏡にて観察した前記熱電変換層の１０か所の領域における前記ナノ炭素材料由来の炭素元素に対する前記金属元素の含有比率をそれぞれ算出し、それらを算術平均して得られる平均値である。
前記最大偏差とは、走査型電子顕微鏡にて観察した前記熱電変換層の１０か所の領域における前記ナノ炭素材料由来の炭素元素に対する前記金属元素の含有比率のうち前記平均値から最も離された測定値と、前記平均値との偏差である。 A thermoelectric conversion layer containing a nanocarbon material and inorganic nanoparticles containing a metal element,
The thermoelectric conversion layer is observed with a scanning electron microscope and is calculated by the following formula (1) using the content ratio of the metal element to the carbon element derived from the nanocarbon material obtained by energy dispersive X-ray analysis. A thermoelectric conversion layer having a maximum in-plane variation T of 0 to 30%.
Formula (1) T = | maximum deviation | / | average value | × 100
The average value is calculated by calculating the content ratio of the metal element to the carbon element derived from the nanocarbon material in 10 regions of the thermoelectric conversion layer observed with a scanning electron microscope, and arithmetically averaging them. Is the average value obtained.
The maximum deviation is the most distant from the average value among the content ratio of the metal element to the carbon element derived from the nanocarbon material in 10 regions of the thermoelectric conversion layer observed with a scanning electron microscope. It is a deviation between the measured value and the average value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017036457A JP6698565B2 (en) | 2017-02-28 | 2017-02-28 | Thermoelectric conversion layer, thermoelectric conversion element, thermoelectric conversion module |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017036457A JP6698565B2 (en) | 2017-02-28 | 2017-02-28 | Thermoelectric conversion layer, thermoelectric conversion element, thermoelectric conversion module |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018142639A true JP2018142639A (en) | 2018-09-13 |
| JP6698565B2 JP6698565B2 (en) | 2020-05-27 |
Family
ID=63528317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017036457A Expired - Fee Related JP6698565B2 (en) | 2017-02-28 | 2017-02-28 | Thermoelectric conversion layer, thermoelectric conversion element, thermoelectric conversion module |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6698565B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200071001A (en) * | 2018-12-10 | 2020-06-18 | 연세대학교 산학협력단 | Ionic thermoelectric materials and ionic thermoelectric devices comprising the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001055028A1 (en) * | 2000-01-25 | 2001-08-02 | Nippon Aerosil Co., Ltd. | Oxide powder and method for preparing the same, and product using the same |
| WO2010002004A1 (en) * | 2008-07-04 | 2010-01-07 | 保土谷化学工業株式会社 | Carbon fiber and composite material |
| JP2015170766A (en) * | 2014-03-07 | 2015-09-28 | 学校法人東京理科大学 | Thermoelectric conversion material-containing resin composition, and film formed by thermoelectric conversion material-containing resin composition |
| JP2016058475A (en) * | 2014-09-08 | 2016-04-21 | 富士フイルム株式会社 | Thermoelectric conversion element |
-
2017
- 2017-02-28 JP JP2017036457A patent/JP6698565B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001055028A1 (en) * | 2000-01-25 | 2001-08-02 | Nippon Aerosil Co., Ltd. | Oxide powder and method for preparing the same, and product using the same |
| WO2010002004A1 (en) * | 2008-07-04 | 2010-01-07 | 保土谷化学工業株式会社 | Carbon fiber and composite material |
| JP2015170766A (en) * | 2014-03-07 | 2015-09-28 | 学校法人東京理科大学 | Thermoelectric conversion material-containing resin composition, and film formed by thermoelectric conversion material-containing resin composition |
| JP2016058475A (en) * | 2014-09-08 | 2016-04-21 | 富士フイルム株式会社 | Thermoelectric conversion element |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200071001A (en) * | 2018-12-10 | 2020-06-18 | 연세대학교 산학협력단 | Ionic thermoelectric materials and ionic thermoelectric devices comprising the same |
| KR102324383B1 (en) * | 2018-12-10 | 2021-11-11 | 연세대학교 산학협력단 | Ionic thermoelectric materials and ionic thermoelectric devices comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6698565B2 (en) | 2020-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | Screen-printing of a highly conductive graphene ink for flexible printed electronics | |
| Zhao et al. | PEDOT-based composites as electrode materials for supercapacitors | |
| Khan et al. | Comprehensive review on carbon nanotubes embedded in different metal and polymer matrix: fabrications and applications | |
| Pan et al. | Fabrication of sandwich-structured PPy/MoS2/PPy nanosheets for polymer composites with high dielectric constant, low loss and high breakdown strength | |
| JP6110818B2 (en) | Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using the same, and power source for sensor | |
| JP6806898B2 (en) | Conductive film, thermoelectric conversion layer, thermoelectric conversion element, thermoelectric conversion module, method for manufacturing conductive film, composition | |
| Song et al. | An ultra-long and low junction-resistance Ag transparent electrode by electrospun nanofibers | |
| KR20180122319A (en) | A composition for a thermoelectric conversion element, a method for producing a carbon nanotube on which metal nanoparticles are supported, a molded article for a thermoelectric conversion element, a method for producing the same, | |
| WO2014119468A1 (en) | Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using thermoelectric conversion element, and power supply for sensors using thermoelectric conversion element | |
| KR101843795B1 (en) | Method for Preparing Nano-sized Thin Film Coating | |
| JP5931764B2 (en) | Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using the same, and power supply for sensor | |
| JP6535106B2 (en) | Thermoelectric conversion layer, thermoelectric conversion element and composition for forming thermoelectric conversion layer | |
| Zhao et al. | EMI shielding effectiveness of silver nanoparticle-decorated multi-walled carbon nanotube sheets | |
| JP6698565B2 (en) | Thermoelectric conversion layer, thermoelectric conversion element, thermoelectric conversion module | |
| JP6586665B2 (en) | Transparent conductive film, dye-sensitized solar cell photoelectrode and touch panel, and dye-sensitized solar cell | |
| JP2015214734A (en) | Spherical composite copper fine particle containing extra-fine carbon fiber and manufacturing method therefor | |
| JP5931763B2 (en) | Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using the same, and power supply for sensor | |
| WO2014178284A1 (en) | Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation, and power supply for sensors | |
| JP6744406B2 (en) | N-type semiconductor layer, thermoelectric conversion layer, thermoelectric conversion element, thermoelectric conversion module, and composition for forming n-type semiconductor layer | |
| WO2018159685A1 (en) | Thermoelectric conversion layer, thermoelectric conversion layer forming composition, thermoelectric conversion element, thermoelectric conversion module | |
| JP5931762B2 (en) | Thermoelectric conversion material, thermoelectric conversion element, article for thermoelectric power generation using the same, and power supply for sensor | |
| Yin et al. | Improved thermoelectric performance of flexible film based on polypyrrole/silver nanocomposites | |
| WO2019039239A1 (en) | Nanomaterial complex and method for manufacturing same | |
| EP3041009A1 (en) | Light power generation device and method for manufacturing same | |
| WO2015002029A1 (en) | Thermoelectric conversion element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190125 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20191023 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20191024 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200421 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200428 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6698565 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |