JP6927401B1 - Thermoelectric conversion materials and thermoelectric conversion elements - Google Patents
Thermoelectric conversion materials and thermoelectric conversion elements Download PDFInfo
- Publication number
- JP6927401B1 JP6927401B1 JP2020195789A JP2020195789A JP6927401B1 JP 6927401 B1 JP6927401 B1 JP 6927401B1 JP 2020195789 A JP2020195789 A JP 2020195789A JP 2020195789 A JP2020195789 A JP 2020195789A JP 6927401 B1 JP6927401 B1 JP 6927401B1
- Authority
- JP
- Japan
- Prior art keywords
- thermoelectric conversion
- polymer
- conversion material
- group
- mass
- 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.)
- Active
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 162
- 239000000463 material Substances 0.000 title claims abstract description 88
- 229920000642 polymer Polymers 0.000 claims abstract description 53
- 150000001768 cations Chemical class 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 239000004020 conductor Substances 0.000 claims abstract description 31
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 150000008040 ionic compounds Chemical class 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 8
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 4
- 125000005587 carbonate group Chemical group 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 238000010586 diagram Methods 0.000 abstract 1
- -1 acryloyloxy Chemical group 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000002585 base Substances 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000002612 dispersion medium Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002109 single walled nanotube Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012673 precipitation polymerization Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002924 oxiranes Chemical group 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical class Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000004849 alkoxymethyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000036760 body temperature Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical group COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 150000003983 crown ethers Chemical group 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 150000004707 phenolate Chemical class 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- WYABBCZMFVULEF-UHFFFAOYSA-M 1-butyl-1-methylpiperidin-1-ium;bromide Chemical compound [Br-].CCCC[N+]1(C)CCCCC1 WYABBCZMFVULEF-UHFFFAOYSA-M 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- HLRQDIVVLOCZPH-UHFFFAOYSA-N 1-ethenyl-4-octylbenzene Chemical compound CCCCCCCCC1=CC=C(C=C)C=C1 HLRQDIVVLOCZPH-UHFFFAOYSA-N 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- OGMSGZZPTQNTIK-UHFFFAOYSA-N 1-methyl-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C OGMSGZZPTQNTIK-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- VBRWJLQEFUANAQ-UHFFFAOYSA-N 2-(3-ethenylphenyl)acetonitrile Chemical compound C=CC1=CC=CC(CC#N)=C1 VBRWJLQEFUANAQ-UHFFFAOYSA-N 0.000 description 1
- DUIIPHYNGUDOIM-UHFFFAOYSA-N 2-(4-ethenylphenyl)acetonitrile Chemical compound C=CC1=CC=C(CC#N)C=C1 DUIIPHYNGUDOIM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- BWVZAZPLUTUBKD-UHFFFAOYSA-N 3-(5,6,6-Trimethylbicyclo[2.2.1]hept-1-yl)cyclohexanol Chemical compound CC1(C)C(C)C2CC1CC2C1CCCC(O)C1 BWVZAZPLUTUBKD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 241000557626 Corvus corax Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 101710152403 Prosaposin Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- ZEHGKSPCAMLJDC-UHFFFAOYSA-M acetylcholine bromide Chemical compound [Br-].CC(=O)OCC[N+](C)(C)C ZEHGKSPCAMLJDC-UHFFFAOYSA-M 0.000 description 1
- JUGOREOARAHOCO-UHFFFAOYSA-M acetylcholine chloride Chemical compound [Cl-].CC(=O)OCC[N+](C)(C)C JUGOREOARAHOCO-UHFFFAOYSA-M 0.000 description 1
- 229960004266 acetylcholine chloride Drugs 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- PWOSZCQLSAMRQW-UHFFFAOYSA-N beryllium(2+) Chemical compound [Be+2] PWOSZCQLSAMRQW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical group N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 101150023172 cpb-3 gene Proteins 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- HXWGXXDEYMNGCT-UHFFFAOYSA-M decyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)C HXWGXXDEYMNGCT-UHFFFAOYSA-M 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- JMJGNDIWCVQJJZ-UHFFFAOYSA-M diphenyliodanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C=1C=CC=CC=1[I+]C1=CC=CC=C1 JMJGNDIWCVQJJZ-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KIEOLZRKTOBVMX-UHFFFAOYSA-M hexyl-dimethyl-octylazanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(C)CCCCCC KIEOLZRKTOBVMX-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910001426 radium ion Inorganic materials 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001419 rubidium ion Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 101150043270 sgo1 gene Proteins 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- YEKUWOWHPVKTCQ-UHFFFAOYSA-M tetraethylazanium;fluoride;hydrate Chemical compound O.[F-].CC[N+](CC)(CC)CC YEKUWOWHPVKTCQ-UHFFFAOYSA-M 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- HQFTZNVQVRRDLN-UHFFFAOYSA-M tetramethylazanium;fluoride;tetrahydrate Chemical compound O.O.O.O.[F-].C[N+](C)(C)C HQFTZNVQVRRDLN-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- FBLZDUAOBOMSNZ-UHFFFAOYSA-M tetrapentylazanium;iodide Chemical compound [I-].CCCCC[N+](CCCCC)(CCCCC)CCCCC FBLZDUAOBOMSNZ-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- 230000005676 thermoelectric effect Effects 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 description 1
- KKLAORVGAKUOPZ-UHFFFAOYSA-M trimethyl(phenyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)C1=CC=CC=C1 KKLAORVGAKUOPZ-UHFFFAOYSA-M 0.000 description 1
- GOTIICCWNAPLMN-UHFFFAOYSA-M trimethylsulfanium;bromide Chemical compound [Br-].C[S+](C)C GOTIICCWNAPLMN-UHFFFAOYSA-M 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
【課題】熱電変換性能と導電性とを両立できる熱電変換材料を提供すること。また、熱電変換性能と高温高湿下での経時安定性に優れた熱電変換素子を提供すること。【解決手段】本発明が解決しようとする課題は、重合体（Ａ）及び導電性材料（Ｂ）を含んでなる熱電変換材料であって、前記重合体（Ａ）が、（メタ）アクリロニトリルに由来する単量体単位とカチオン捕捉能を有する単量体単位とを含んでなる共重合体であることを特徴とする熱電変換材料によって解決できる。【選択図】なしPROBLEM TO BE SOLVED: To provide a thermoelectric conversion material capable of achieving both thermoelectric conversion performance and conductivity. Further, to provide a thermoelectric conversion element having excellent thermoelectric conversion performance and stability over time under high temperature and high humidity. A problem to be solved by the present invention is a thermoelectric conversion material containing a polymer (A) and a conductive material (B), in which the polymer (A) is converted to (meth) acrylonitrile. It can be solved by a thermoelectric conversion material characterized by being a copolymer containing a derived monomer unit and a monomer unit having a cation trapping ability. [Selection diagram] None
Description
本発明は、熱電変換材料および熱電変換素子に関する。 The present invention relates to thermoelectric conversion materials and thermoelectric conversion elements.
熱電変換材料を用いて熱を電気に変換する熱電変換技術は、自然界における様々な熱に加え、工場・車・家庭から排出される排熱や体温等の微小熱エネルギーを電気として有効活用できるクリーンエネルギーとして注目されている。熱電変換技術に活用される熱電効果は様々存在するが、半導体や金属の組合せにより構成される材料の両端に２つの異なる温度を与えた際、その温度差に応じて材料内に生じた電子勾配により起電力が発生するゼーベック効果を活用したシステムが主流である。 The thermoelectric conversion technology that converts heat into electricity using thermoelectric conversion materials is a clean that can effectively utilize minute heat energy such as waste heat and body temperature discharged from factories, cars, and homes in addition to various heat in the natural world. It is attracting attention as energy. There are various thermoelectric effects utilized in thermoelectric conversion technology, but when two different temperatures are applied to both ends of a material composed of a combination of semiconductors and metals, the electron gradient generated in the material according to the temperature difference. The mainstream is a system that utilizes the Seebeck effect, which generates electromotive force.
熱エネルギーと電気エネルギーを相互に変換できる熱電変換材料は、熱電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。熱電変換素子とは、熱を電力に変換する素子であり、半導体や金属の組合せによって構成される。代表的な熱電変換素子としては、ｐ型半導体単独、ｎ型半導体単独、またはｐ型半導体とｎ型半導体との組合せ、に分類される。より大きな電位差を得るために、熱電変換素子では、一般的に、材料としてｐ型半導体とｎ型半導体とを組合せて用いる。 Thermoelectric conversion materials capable of mutually converting thermal energy and electric energy are used in thermoelectric conversion elements such as thermoelectric power generation elements and Pelche elements. A thermoelectric conversion element is an element that converts heat into electric power, and is composed of a combination of semiconductors and metals. Typical thermoelectric conversion elements are classified into p-type semiconductors alone, n-type semiconductors alone, or combinations of p-type semiconductors and n-type semiconductors. In order to obtain a larger potential difference, a thermoelectric conversion element generally uses a combination of a p-type semiconductor and an n-type semiconductor as materials.
また、熱電変換素子は、ペルチェ素子に代表されるように、多数の素子を板状、または円筒状に組合せてなる熱電モジュールとして使用される。熱エネルギーを直接電力に変換することができるため、例えば、体温で作動する腕時計、地上用発電および人工衛星用発電における電源として利用できる。熱電変換素子の性能は、熱電変換材料の性能、およびモジュールの耐久性等に依存する。 Further, the thermoelectric conversion element is used as a thermoelectric module in which a large number of elements are combined in a plate shape or a cylindrical shape, as typified by a Pelche element. Since thermal energy can be directly converted into electric power, it can be used as a power source for, for example, a wristwatch operating at body temperature, ground power generation, and artificial satellite power generation. The performance of the thermoelectric conversion element depends on the performance of the thermoelectric conversion material, the durability of the module, and the like.
非特許文献１に記載されているとおり、熱電変換材料の性能を表す指標として、無次元熱電性能指数ＺＴが用いられる。また、熱電変換材料の性能を表す指標として、パワーファクターＰＦ（＝Ｓ2・σ）を用いる場合もある。
上記、無次元熱電性能指数ＺＴは、下記式（１）により表される。
ＺＴ＝（（Ｓ2・σ）／к）・Ｔ 式（１）
ここで、Ｓはゼーベック係数（Ｖ／Ｋ）、σは導電率（Ｓ／ｍ）、Ｔは絶対温度（Ｋ）、およびкは熱伝導率（Ｗ／（ｍ・Ｋ））である。熱伝導率кは下記式（２）で表される。
к＝α・ρ・Ｃ 式（２）
ここで、αは熱拡散率（ｍ2／ｓ）、ρは密度（ｋｇ／ｍ3）、およびＣは比熱容量（J／（ｋｇ・Ｋ））である。
すなわち、熱電変換の性能（以下、熱電特性とも称す）を向上させるには、ゼーベック係数または導電率を向上させ、その一方で熱伝導率を低下させることが重要である。
As described in Non-Patent Document 1, the dimensionless thermoelectric figure of merit ZT is used as an index showing the performance of the thermoelectric conversion material. In addition, the power factor PF (= S 2 · σ) may be used as an index showing the performance of the thermoelectric conversion material.
The dimensionless thermoelectric figure of merit ZT is represented by the following formula (1).
ZT = ((S 2 · σ ) / к) · T Equation (1)
Here, S is the Seebeck coefficient (V / K), σ is the conductivity (S / m), T is the absolute temperature (K), and к is the thermal conductivity (W / (m · K)). The thermal conductivity к is represented by the following formula (2).
к = α ・ ρ ・ C formula (2)
Here, α is the thermal diffusivity (m 2 / s), ρ is the density (kg / m 3 ), and C is the specific heat capacity (J / (kg · K)).
That is, in order to improve the thermoelectric conversion performance (hereinafter, also referred to as thermoelectric characteristics), it is important to improve the Seebeck coefficient or conductivity while lowering the thermal conductivity.
近年、従来の無機材料に代えて、有機材料を用いた熱電変換素子に関する検討が進められている。有機材料は、軽量である上に優れた成型性を有し、かつ無機材料よりも優れた可撓性を有するため、それ自身が分解しない温度範囲での汎用性が高い。また、印刷技術等を容易に活用できるため、製造エネルギーや製造コストの面でも無機材料より有利である。 In recent years, studies on thermoelectric conversion elements using organic materials instead of conventional inorganic materials have been promoted. Since organic materials are lightweight, have excellent moldability, and have superior flexibility to inorganic materials, they are highly versatile in a temperature range in which they do not decompose themselves. In addition, since printing technology and the like can be easily utilized, it is more advantageous than inorganic materials in terms of manufacturing energy and manufacturing cost.
例えば、特許文献１には、有機色素骨格を有する高分子分散剤とカーボンナノチューブ（ＣＮＴ）とを含有する熱電変換材料およびそれを用いた熱電変換素子が開示されている。また、特許文献２には、キャリア輸送特性を有する多環芳香族環とアルキル基を含む置換基とが結合した導電性化合物を含む熱電変換材料およびそれを用いた熱電変換素子が開示されている。しかしながら、特許文献１の発明では、熱電変換素子として十分な性能が得られてはいなかった。また、特許文献２の発明では、導電率が１０-8〜１０-7Ｓ／ｃｍと低く、熱電変換素子として実用的な値を得ることができていない。また、熱電変換素子としての性能に加え、従来知られている熱電変換素子は、高温高湿下での経時安定性に乏しいという問題があった。 For example, Patent Document 1 discloses a thermoelectric conversion material containing a polymer dispersant having an organic dye skeleton and carbon nanotubes (CNT), and a thermoelectric conversion element using the same. Further, Patent Document 2 discloses a thermoelectric conversion material containing a conductive compound in which a polycyclic aromatic ring having a carrier transport property and a substituent containing an alkyl group are bonded, and a thermoelectric conversion element using the same. .. However, in the invention of Patent Document 1, sufficient performance as a thermoelectric conversion element has not been obtained. Further, in the invention of Patent Document 2, the conductivity is as low as 10 -8 to 10 -7 S / cm, and a practical value as a thermoelectric conversion element cannot be obtained. Further, in addition to the performance as a thermoelectric conversion element, a conventionally known thermoelectric conversion element has a problem of poor stability over time under high temperature and high humidity.
本発明が解決しようとする課題は、熱電変換性能と導電性とを両立できる熱電変換材料を提供することである。また、熱電変換性能と高温高湿下での経時安定性に優れた熱電変換素子を提供することである。 An object to be solved by the present invention is to provide a thermoelectric conversion material capable of achieving both thermoelectric conversion performance and conductivity. Another object of the present invention is to provide a thermoelectric conversion element having excellent thermoelectric conversion performance and stability over time under high temperature and high humidity.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、本発明に至った。
すなわち、本発明は、重合体（Ａ）及び導電性材料（Ｂ）を含んでなる熱電変換材料であって、上記重合体（Ａ）が、（メタ）アクリロニトリルに由来する単量体単位とカチオン捕捉能を有する単量体単位とを含んでなる共重合体であることを特徴とする熱電変換材料に関する。
The present inventors have reached the present invention as a result of repeated diligent studies to solve the above problems.
That is, the present invention is a thermoelectric conversion material containing a polymer (A) and a conductive material (B), wherein the polymer (A) is a monomer unit and a cation derived from (meth) acrylonitrile. The present invention relates to a thermoelectric conversion material, which is a copolymer containing a monomer unit having a capturing ability.
また、本発明は、上記カチオン捕捉能を有する単量体が、ポリ（オキシアルキレン）構造、エポキシド構造及びカーボネート構造からなる群より選ばれる一種以上の構造を有する単量体を含む上記熱電変換材料に関する。 Further, in the present invention, the thermoelectric conversion material in which the monomer having a cation trapping ability contains a monomer having one or more structures selected from the group consisting of a poly (oxyalkylene) structure, an epoxide structure and a carbonate structure. Regarding.
また、本発明は、上記重合体（Ａ）中、上記（メタ）アクリロニトリルに由来する単位を１質量％以上１００質量％未満含む上記熱電変換材料に関する。 The present invention also relates to the thermoelectric conversion material containing 1% by mass or more and less than 100% by mass of the unit derived from the (meth) acrylonitrile in the polymer (A).
また、本発明は、上記重合体（Ａ）中、カチオン捕捉能を有する単量体単位を１質量％以上９９質量％以下含む上記熱電変換材料に関する。 The present invention also relates to the thermoelectric conversion material containing 1% by mass or more and 99% by mass or less of a monomer unit having a cation trapping ability in the polymer (A).
また、本発明は、更に、アニオン（Ｃ）及びカチオン（Ｄ）からなるイオン性化合物を含んでなる上記熱電変換材料に関する。 The present invention further relates to the thermoelectric conversion material comprising an ionic compound composed of an anion (C) and a cation (D).
また、本発明は、上記アニオン（Ｃ）が、ＯＨ-、Ｒ1Ｏ-、Ｒ2Ｓ-、Ｒ3ＣＯＯ-、ＳＨ-、ＢＨ4 -、Ｉ-、Ｂｒ-及びＣｌ-からなる群より選択される少なくとも一つを含む上記熱電変換材料に関する。ただし、Ｒ1、Ｒ2、及びＲ3は、脂肪族炭化水素基又は芳香族炭化水素基である。 Further, the present invention, the anion (C) is, OH -, R 1 O - , R 2 S -, R 3 COO -, SH -, BH 4 -, I -, Br - and Cl - from the group consisting of With respect to the thermoelectric conversion material comprising at least one selected. However, R 1 , R 2 , and R 3 are aliphatic hydrocarbon groups or aromatic hydrocarbon groups.
また、本発明は、上記カチオン（Ｄ）が、金属カチオン又は有機塩基由来のカチオンを含む上記熱電変換材料に関する。 The present invention also relates to the thermoelectric conversion material in which the cation (D) contains a metal cation or a cation derived from an organic base.
また、本発明は、上記重合体（Ａ）の含有率が、上記導電性材料（Ｂ）の全量に対して５〜１００質量％であることを特徴とする上記熱電変換材料に関する。 The present invention also relates to the thermoelectric conversion material, wherein the content of the polymer (A) is 5 to 100% by mass with respect to the total amount of the conductive material (B).
また、本発明は、上記熱電変換材料を含んでなる熱電変換膜と、電極とを有し、上記熱電変換膜と上記電極とが、電気的に接続されていることを特徴とする熱電変換素子に関する。 Further, the present invention has a thermoelectric conversion film containing the thermoelectric conversion material and an electrode, and the thermoelectric conversion film and the electrode are electrically connected to each other. Regarding.
本発明により、熱電変換性能と導電性とを両立できる熱電変換材料を提供することができる。また、当該材料を用いて、優れた熱電変換性能と高温高湿下での経時安定性に優れた熱電変換素子を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a thermoelectric conversion material capable of achieving both thermoelectric conversion performance and conductivity. Further, by using the material, it is possible to provide a thermoelectric conversion element having excellent thermoelectric conversion performance and stability over time under high temperature and high humidity.
以下、本発明の実施形態について説明する。尚、本明細書では、「（メタ）アクリル」、「（メタ）アクリロ」、「（メタ）アクリル酸」、「（メタ）アクリレート」、および「（メタ）アクリロイルオキシ」と表記した場合には、特に説明がない限り、それぞれ、「アクリルまたはメタクリル」、「アクリロまたはメタクリロ」、「アクリル酸またはメタクリル酸」、「アクリレートまたはメタクリレート」および「アクリロイルオキシまたはメタクリロイルオキシ」を表すものとする。 Hereinafter, embodiments of the present invention will be described. In addition, in this specification, when it is described as "(meth) acrylic", "(meth) acrylo", "(meth) acrylic acid", "(meth) acrylate", and "(meth) acryloyloxy" Unless otherwise specified, they shall represent "acrylic or methacrylic acid", "acrylo or methacrylic acid", "acrylic acid or methacrylic acid", "acrylate or methacrylate" and "acryloyloxy or methacryloyloxy", respectively.
＜熱電変換材料＞
本発明の熱電変換材料は、重合体（Ａ）及び導電性材料（Ｂ）を含んでなる熱電変換材料であって、前記重合体（Ａ）が、（メタ）アクリルニトリルに由来する単量体単位とカチオン捕捉能を有する単量体単位とを含んでなる共重合体であることを特徴とする。以下、本発明の実施形態について詳細に説明する。
<Thermoelectric conversion material>
The thermoelectric conversion material of the present invention is a thermoelectric conversion material containing a polymer (A) and a conductive material (B), and the polymer (A) is a monomer derived from (meth) acrylonitrile. It is a copolymer containing a unit and a monomer unit having a cation trapping ability. Hereinafter, embodiments of the present invention will be described in detail.
＜重合体（Ａ）＞
重合体（Ａ）は、（メタ）アクリロニトリルに由来する単量体単位とカチオン捕捉能を有する単量体単位とを含んでなる共重合体である。重合体（Ａ）は、（メタ）アクリロニトリルに由来する単量体単位とカチオン捕捉能を有する単量体単位を含んでいれば、その他単量体との共重合体であっても良い。重合体（Ａ）は、ランダム共重合体、ブロック共重合体いずれの形態であってもよい。重合体（Ａ）中の（メタ）アクリロニトリル中のシアノ基の強い極性が、導電性材料（Ｂ）への吸着性を高め、導電性材料（Ｂ）の凝集を抑制すると推察される。また、熱電変換材料中にカチオン（Ｃ）が含まれる場合には、重合体（Ａ）中のカチオン捕捉能を有する単量体単位が材料中のカチオン（Ｃ）を捕捉することで、熱電変換材料中に安定に存在させることができるものと推察される。
<Polymer (A)>
The polymer (A) is a copolymer containing a monomer unit derived from (meth) acrylonitrile and a monomer unit having a cation trapping ability. The polymer (A) may be a copolymer with other monomers as long as it contains a monomer unit derived from (meth) acrylonitrile and a monomer unit having a cation trapping ability. The polymer (A) may be in the form of either a random copolymer or a block copolymer. It is presumed that the strong polarity of the cyano group in the (meth) acrylonitrile in the polymer (A) enhances the adsorptivity to the conductive material (B) and suppresses the aggregation of the conductive material (B). When the thermoelectric conversion material contains a cation (C), the monomer unit having a cation-capturing ability in the polymer (A) captures the cation (C) in the material, thereby performing thermoelectric conversion. It is presumed that it can be stably present in the material.
重合体（Ａ）の構成単位の内、（メタ）アクリロニトリルに由来する単位は、１質量％以上９９質量％以下含有することが好ましく、５０質量％以上９０質量％以下含有することがより好ましく、６０質量％以上９０質量％以下含有することがさらに好ましく、７５質量％以上９０質量％以下含有することが特に好ましい。（メタ）アクリロニトリルに由来する単位を上記範囲で含有することで、導電性材料（Ｂ）への吸着性を良好に得ることができる。 Among the constituent units of the polymer (A), the unit derived from (meth) acrylonitrile is preferably contained in an amount of 1% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 90% by mass or less. It is more preferably contained in an amount of 60% by mass or more and 90% by mass or less, and particularly preferably contained in an amount of 75% by mass or more and 90% by mass or less. By containing the unit derived from (meth) acrylonitrile in the above range, the adsorptivity to the conductive material (B) can be satisfactorily obtained.
重合体（Ａ）の構成単位の内、カチオン捕捉能を有する単量体単位は、１質量％以上９９質量％以下含有することが好ましく、１質量％以上５０質量％以下含有することがより好ましく、１質量％２０質量％以下含有することがさらに好ましい。 Among the constituent units of the polymer (A), the monomer unit having a cation trapping ability is preferably contained in an amount of 1% by mass or more and 99% by mass or less, and more preferably 1% by mass or more and 50% by mass or less. It is more preferable to contain 1% by mass of 20% by mass or less.
重合体（Ａ）の構成単位の内、カチオン捕捉能を有する単量体単位とは、カチオン（Ｄ）と配位結合を形成し得る構造を有する単量体単位を指す。本明細書中でカチオン（Ｄ）と配位結合を形成し得る構造を有する単量体の一態様として、エーテル類似構造を有する単量体が挙げられる。エーテル類似構造としては、ポリ（オキシアルキレン）構造、カーボネート構造、エポキシド構造等が挙げられるが、これに限定されない。 Among the structural units of the polymer (A), the monomer unit having a cation trapping ability refers to a monomer unit having a structure capable of forming a coordinate bond with the cation (D). In the present specification, one embodiment of a monomer having a structure capable of forming a coordination bond with a cation (D) includes a monomer having an ether-like structure. Examples of the ether-like structure include, but are not limited to, a poly (oxyalkylene) structure, a carbonate structure, and an epoxide structure.
ポリ（オキシアルキレン）構造の繰り返し単位を有する単量体として、ポリエチレングリコールモノメタクリレート、ポリプロピレングリコールモノメタクリレート、ポリエチレングリコールモノアクリレート、ポリプロピレングリコールモノアクリレート、メトキシポリエチレングリコールメタクリレート、メトキシポリエチレングリコールアクリレート、トリエチレングルコールジアクリレート等が挙げられる。カチオン捕捉能の観点から、オキシアルキレン構造の繰り返し単位は６以上が好ましく、９以上がより好ましく、２０以上が更に好ましい。また、カチオン捕捉能の観点から、ポリエチレングリコールモノメタクリレート、ポリエチレングリコールモノアクリレート、メトキシポリエチレングリコールメタクリレート、メトキシポリエチレングリコールメタクリレートが好ましい。 Polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate, and triethylene glycol as monomers having a repeating unit of poly (oxyalkylene) structure. Diacrylate and the like can be mentioned. From the viewpoint of cation trapping ability, the repeating unit of the oxyalkylene structure is preferably 6 or more, more preferably 9 or more, and even more preferably 20 or more. Further, from the viewpoint of cation trapping ability, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, methoxypolyethylene glycol methacrylate, and methoxypolyethylene glycol methacrylate are preferable.
カーボネート構造を有する単量体として、４−ビニル−１，３−ジオキソラン−２−オン等が挙げられる。
エポキシド構造を有する単量体として、グリシジルメタクリレート等が挙げられる。
Examples of the monomer having a carbonate structure include 4-vinyl-1,3-dioxolane-2-one.
Examples of the monomer having an epoxide structure include glycidyl methacrylate and the like.
その他カチオン捕捉能を有する単量体としては、カリックスアレーン構造を有する単量体等があげられる。カリックスアレーン構造を有する単量体としては、５−ビニルカリックス［４］アレーン（ＭＶＣ４）、５−ビニルカリックス［６］アレーン（ＭＶＣ６）、５−アクリロイルオキシカリックス［４］アレーン等があげられる。 Examples of the monomer having a cation trapping ability include a monomer having a calixarene structure. Examples of the monomer having a calixarene structure include 5-vinylcalix [4] arene (MVC4), 5-vinylcalix [6] arene (MVC6), 5-acryloyloxycalix [4] arene and the like.
その他カチオン捕捉構造を有する単量体としては、クラウンエーテル構造を有する単量体等が挙げられる。クラウンエーテル構造を有する単量体としては、マクロ環状α−(アルコキシメチル)アクリル酸エステル誘導体が挙げられる。マクロ環状α−(アルコキシメチル)アクリル酸エステル誘導体としては、例えば、以下に示す構造の化合物等が挙げられる。 Examples of the monomer having a cation trapping structure include a monomer having a crown ether structure. Examples of the monomer having a crown ether structure include a macrocyclic α- (alkoxymethyl) acrylic acid ester derivative. Examples of the macrocyclic α- (alkoxymethyl) acrylic acid ester derivative include compounds having the following structures.
重合体（Ａ）は、上記単量体以外のその他単量体を構成単位として含んでも良い。その他単量体としては、
エチルビニルエーテル、ｎ−プロピルビニルエーテル、イソプロピルビニルエーテル、ｎ−ブチルビニルエーテル、イソブチルビニルエーテル等のビニルエーテル類；
酢酸ビニル、プロピオン酸ビニル等の脂肪酸ビニル類；
テトラヒドロフルフリール（メタ）アクリレート、３−メチルオキセタニル（メタ）アクリレート等の複素環式（メタ）アクリレート類；
２−ヒドロキシエチル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート類；
（メタ）アクリル酸、クロトン酸等の脂肪族不飽和脂肪酸類；
スチレン、α−メチルスチレン、２−メチルスチレン、３−メチルスチレン、４−メチルスチレン、４−メトキシスチレン、４−メトキシスチレン、４−イソプロペニルトルエン、２−イソプロペニルトルエン、４−ｎ−オクチルスチレン、１−ビニルナフタレン、ｍ−ビニルベンジルシアニド、ｐ−ビニルベンジルシアニド等の芳香族炭化水素化合物類；
等が挙げられる。
The polymer (A) may contain other monomers other than the above-mentioned monomers as a constituent unit. As other monomers,
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate and vinyl propionate;
Heterocyclic (meth) acrylates such as tetrahydrofurfreel (meth) acrylate and 3-methyloxetanyl (meth) acrylate;
Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate;
Aliphatic unsaturated fatty acids such as (meth) acrylic acid and crotonic acid;
Styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-methoxystyrene, 4-methoxystyrene, 4-isopropenyltoluene, 2-isopropenyltoluene, 4-n-octylstyrene , 1-Vinylnaphthalene, m-vinylbenzyl cyanide, p-vinylbenzylcyanide and other aromatic hydrocarbon compounds;
And so on.
重合体（Ａ）の製造方法は、特に限定はされず、例えば、溶解重合法、懸濁重合法、塊状重合法、乳化重合法、沈殿重合等のいずれの方法を用いてもよく、溶解重合または沈殿重合法が好ましく、沈殿重合法が最も好ましい。沈殿重合法によって得られた重合体（Ａ）は重合時に使用する溶媒に溶解する低分子量成分や残存単量体を重合後速やかに除去できるため、分子量分布を狭く制御することが可能で、残存単量体量も限りなく低減でき、分散剤として機能する分子量の重合体（Ａ）を効率的に得ることができる。重合反応系としては、イオン重合、フリーラジカル重合、リビングラジカル重合等の付加重合を用いることができ、フリーラジカル重合またはリビングラジカル重合が好ましい。また、ラジカル重合開始剤としては、過酸化物、アゾ系開始剤などから選ばれた化合物またはそれらの混合物が使用でき、必要に応じて連鎖移動剤等の分子量調整剤を使用してもよい。 The method for producing the polymer (A) is not particularly limited, and for example, any method such as a solution polymerization method, a suspension polymerization method, a massive polymerization method, an emulsion polymerization method, or a precipitation polymerization method may be used, and dissolution polymerization may be used. Alternatively, the precipitation polymerization method is preferable, and the precipitation polymerization method is most preferable. Since the polymer (A) obtained by the precipitation polymerization method can quickly remove low molecular weight components and residual monomers dissolved in the solvent used during polymerization after polymerization, the molecular weight distribution can be narrowly controlled and remains. The amount of the monomer can be reduced as much as possible, and the polymer (A) having a molecular weight that functions as a dispersant can be efficiently obtained. As the polymerization reaction system, addition polymerization such as ionic polymerization, free radical polymerization, and living radical polymerization can be used, and free radical polymerization or living radical polymerization is preferable. Further, as the radical polymerization initiator, a compound selected from peroxides, azo-based initiators and the like, or a mixture thereof can be used, and if necessary, a molecular weight modifier such as a chain transfer agent may be used.
重合体（Ａ）の分子量は、ポリスチレン換算の重量平均分子量で、３０００以上５０００００以下の範囲が好ましく、４０００以上２０００００以下の範囲がより好ましく、５０００以上１０００００以下の範囲がさらに好ましく、１００００以上１０００００以下の範囲が特に好ましい。重量平均分子量を上記範囲内とすることで、導電性材料（Ｂ）への吸着性がより良好になる。 The molecular weight of the polymer (A) is a polystyrene-equivalent weight average molecular weight, preferably in the range of 3000 or more and 500,000 or less, more preferably in the range of 4000 or more and 200,000 or less, further preferably in the range of 5000 or more and 100,000 or less, and 10000 or more and 100,000 or less. The range of is particularly preferable. By setting the weight average molecular weight within the above range, the adsorptivity to the conductive material (B) becomes better.
＜導電性材料（Ｂ）＞
導電性材料（Ｂ）は、導電性向上に寄与するものである。そのため、導電性材料（Ｂ）の含有量を増やすことで導電性を向上させることができる。導電性材料（Ｂ）は、導電性を有する材料（炭素材料、金属材料、導電性高分子等）であれば、特に制限されず、例えば、炭素材料としては、黒鉛、カーボンナノチューブ、カーボンブラック、グラフェン（グラフェンナノプレートを含む）等が挙げられる。金属材料としては、例えば、金、銀、銅、ニッケル、クロム、パラジウム、ロジウム、ルテニウム、インジウム、ケイ素、アルミニウム、タングステン、モリブデン、ゲルマニウム、ガリウムおよび白金等の金属粉、並びに ＺｎＳｅ、ＣｄＳ、ＩｎＰ、ＧａＮ、ＳｉＣ、ＳｉＧｅこれらの合金、並びにこれらの複合粉が挙げられる。また、核体と、前記核体物質とは異なる物質で被覆した微粒子、具体的には、例えば、銅を核体とし、その表面を銀で被覆した銀コート銅粉等が挙げられる。また、例えば酸化銀、酸化インジウム、酸化スズ、酸化亜鉛、酸化ルテニウム、ＩＴＯ（錫ドープ酸化インジウム）、ＡＺＯ（アルミドープ酸化亜鉛）、およびＧＺＯ（ガリウムドープ酸化亜鉛）等の金属酸化物の粉末、並びにこれらの金属酸化物で表面被覆した粉末等が挙げられる。導電性高分子としては、例えば、ＰＥＤＯＴ／ＰＳＳ（ポリ（３，４−エチレンジオキシチオフェン）とポリスチレンスルホン酸から成る複合物）、ポリアニリン、ポリアセチレン、ポリピロール、ポリチオフェン、ポリパラフェニレン等が挙げられる。使用する導電性材料の種類は一種でもよいし、２種以上を組み合せて使用しても良い。また、導電性材料（Ｂ）の形状は、特に限定されず、不定形、凝集状、鱗片状、微結晶状、球状、フレーク状、ワイヤー状等を適宜用いることができる。
<Conductive material (B)>
The conductive material (B) contributes to the improvement of conductivity. Therefore, the conductivity can be improved by increasing the content of the conductive material (B). The conductive material (B) is not particularly limited as long as it is a conductive material (carbon material, metal material, conductive polymer, etc.), and examples of the carbon material include graphite, carbon nanotubes, carbon black, and the like. Graphene (including graphene nanoplates) and the like can be mentioned. Examples of the metal material include metal powders such as gold, silver, copper, nickel, chromium, palladium, rhodium, ruthenium, indium, silicon, aluminum, tungsten, molybdenum, germanium, gallium and platinum, and ZnSe, CdS, InP, etc. Examples thereof include alloys of GaN, SiC, and SiGe, and composite powders thereof. Further, a nucleolus and fine particles coated with a substance different from the nucleolus substance, specifically, for example, silver-coated copper powder having copper as a nucleolus and its surface coated with silver can be mentioned. Also, for example, powders of metal oxides such as silver oxide, indium oxide, tin oxide, zinc oxide, ruthenium oxide, ITO (tin-doped indium oxide), AZO (aluminum-doped zinc oxide), and GZO (gallium-doped zinc oxide). In addition, powders and the like whose surface is coated with these metal oxides can be mentioned. Examples of the conductive polymer include PEDOT / PSS (complex composed of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid), polyaniline, polyacetylene, polypyrrole, polythiophene, polyparaphenylene and the like. The type of conductive material used may be one type, or two or more types may be used in combination. The shape of the conductive material (B) is not particularly limited, and an amorphous shape, an agglutinated shape, a scaly shape, a microcrystalline shape, a spherical shape, a flake shape, a wire shape, or the like can be appropriately used.
ゼーベック係数と導電性との両立の観点で、カーボンナノチューブ、カーボンブラック、グラフェン（グラフェンナノプレートを含む）からなる群から選ばれる少なくとも一種が好ましく、より好ましくはカーボンナノチューブであり、特に好ましくは単層カーボンナノチューブある。 From the viewpoint of achieving both the Seebeck coefficient and conductivity, at least one selected from the group consisting of carbon nanotubes, carbon black, and graphene (including graphene nanoplates) is preferable, more preferably carbon nanotubes, and particularly preferably a single layer. There are carbon nanotubes.
炭素材料としては、例えば、薄片状黒鉛として、日本黒鉛工業社製のＣＭＸ、ＵＰ−５、ＵＰ−１０、ＵＰ−２０、ＵＰ−３５Ｎ、ＣＳＳＰ、ＣＳＰＥ、ＣＳＰ、ＣＰ、ＣＢ−１５０、ＣＢ−１００、ＡＣＰ、ＡＣＰ−１０００、ＡＣＢ−５０、ＡＣＢ−１００、ＡＣＢ−１５０、ＳＰ−１０、ＳＰ−２０、Ｊ−ＳＰ、ＳＰ−２７０、ＨＯＰ、ＧＲ−６０、ＬＥＰ、Ｆ＃１、Ｆ＃２、Ｆ＃３、中越黒鉛工業所社製のＢＦ−３ＡＫ、ＦＢＦ、ＢＦ−１５ＡＫ、ＣＢＲ、ＣＰＢ−６Ｓ、ＣＰＢ−３、９６Ｌ、９６Ｌ−３、Ｋ−３、ＳＣ−１２０、ＳＣ−６０、ＨＬＰ、ＣＰ−１５０、ＳＢ−１、伊藤黒鉛工業社製のＥＣ１５００、ＥＣ１０００、ＥＣ５００、ＥＣ３００、ＥＣ１００、ＥＣ５０、西村黒鉛社製の１００９９Ｍ、ＰＢ−９９等が挙げられる。球状天然黒鉛としては、日本黒鉛工業社製のＣＧＣ−２０、ＣＧＣ−５０、ＣＧＢ−２０、ＣＧＢ−５０が挙げられる。土状黒鉛としては、日本黒鉛工業社製の青Ｐ、ＡＰ、ＡＯＰ、Ｐ＃１、中越黒鉛社製のＡＰＲ、Ｋ−５、ＡＰ−２０００、ＡＰ−６、３００Ｆ、１５０Ｆが挙げられる。人造黒鉛としては、日本黒鉛工業社製のＰＡＧ−６０、ＰＡＧ−８０、ＰＡＧ−１２０、ＰＡＧ−５、ＨＡＧ−１０Ｗ、ＨＡＧ−１５０、中越黒鉛社製のＧ−４ＡＫ、Ｇ−６Ｓ、Ｇ−３Ｇ−１５０、Ｇ−３０、Ｇ−８０、Ｇ−５０、ＳＭＦ、ＥＭＦ、ＳＦＦ、ＳＦＦ−８０Ｂ、ＳＳ−１００、ＢＳＰ−１５ＡＫ、ＢＳＰ−１００ＡＫ、ＷＦ−１５Ｃ、ＳＥＣカーボン社製のＳＧＰ−１００、ＳＧＰ−５０、ＳＧＰ−２５、ＳＧＰ−１５、ＳＧＰ−５、ＳＧＰ−１、ＳＧＯ−１００、ＳＧＯ−５０、ＳＧＯ−２５、ＳＧＯ−１５、ＳＧＯ−５、ＳＧＯ−１、ＳＧＸ−１００、ＳＧＸ−５０、ＳＧＸ−２５、ＳＧＸ−１５、ＳＧＸ−５、ＳＧＸ−１が挙げられる。 As the carbon material, for example, as flaky graphite, CMX, UP-5, UP-10, UP-20, UP-35N, CSSP, CSPE, CSP, CP, CB-150, CB- manufactured by Nippon Graphite Industry Co., Ltd. 100, ACP, ACP-1000, ACB-50, ACB-100, ACB-150, SP-10, SP-20, J-SP, SP-270, HOP, GR-60, LEP, F # 1, F # 2, F # 3, BF-3AK, FBF, BF-15AK, CBR, CPB-6S, CPB-3, 96L, 96L-3, K-3, SC-120, SC-60 manufactured by Chuetsu Graphite Industry Co., Ltd. , HLP, CP-150, SB-1, EC1500, EC1000, EC500, EC300, EC100, EC50 manufactured by Ito Graphite Industry Co., Ltd., 10099M, PB-99 manufactured by Nishimura Graphite Co., Ltd. and the like. Examples of spherical natural graphite include CGC-20, CGC-50, CGB-20, and CGB-50 manufactured by Nippon Graphite Industry Co., Ltd. Examples of earth-like graphite include blue P, AP, AOP, P # 1 manufactured by Nippon Graphite Industry Co., Ltd., and APR, K-5, AP-2000, AP-6, 300F, 150F manufactured by Chuetsu Graphite Co., Ltd. As artificial graphite, PAG-60, PAG-80, PAG-120, PAG-5, HAG-10W, HAG-150 manufactured by Nippon Graphite Industry Co., Ltd., G-4AK, G-6S, G-150 manufactured by Chuetsu Graphite Co., Ltd. 3G-150, G-30, G-80, G-50, SMF, EMF, SFF, SFF-80B, SS-100, BSP-15AK, BSP-100AK, WF-15C, SGP-100 manufactured by SEC Carbon Co., Ltd. , SGP-50, SGP-25, SGP-15, SGP-5, SGP-1, SGO-100, SGO-50, SGO-25, SGO-15, SGO-5, SGO-1, SGX-100, SGX -50, SGX-25, SGX-15, SGX-5, SGX-1 can be mentioned.
市販の導電性炭素繊維やカーボンナノチューブとしては、昭和電工社製のＶＧＣＦ等の気相法炭素繊維、名城ナノカーボン社製のＥＣ１．５，ＥＣ１．５−Ｐ、楠本化成社製のＴＵＢＡＬＬ、ゼオンナノテクノロジー社製のＺＥＯＮＡＮＯ等の単層カーボンナノチューブ、ＣＮａｎｏ社製のＦｌｏＴｕｂｅ９０００、ＦｌｏＴｕｂｅ７０００、ＦｌｏＴｕｂｅ２０００、Ｎａｎｏｃｙｌ社製のＮＣ７０００、Ｋｎａｎｏ社製の１００Ｔ、２００Ｐ等が挙げられる。 Commercially available conductive carbon fibers and carbon nanotubes include vapor-phase carbon fibers such as VGCF manufactured by Showa Denko, EC1.5 and EC1.5-P manufactured by Meijo Nanocarbon, and TUBALL and Zeon manufactured by Kusumoto Kasei. Examples thereof include single-walled carbon nanotubes such as ZEONANO manufactured by Nanotechnology, FloTube9000 and FloTube7000 manufactured by CNano, NC7000 manufactured by Nanocyl, and 100T and 200P manufactured by Knano.
市販のカーボンブラックとしては、例えば、東海カーボン社製のトーカブラック＃４３００、＃４４００、＃４５００、＃５５００、デグサ社製のプリンテックスＬ、コロンビヤン社製のＲａｖｅｎ７０００、５７５０、５２５０、５０００ＵＬＴＲＡIII、５００
０ＵＬＴＲＡ、Ｃｏｎｄｕｃｔｅｘ ＳＣ ＵＬＴＲＡ、Ｃｏｎｄｕｃｔｅｘ ９７５ ＵＬＴＲＡ、ＰＵＥＲＢＬＡＣＫ１００、１１５、２０５、三菱化学社製の＃２３５０、＃２４００Ｂ、＃２６００Ｂ、＃３０５０Ｂ、＃３０３０Ｂ、＃３２３０Ｂ、＃３３５０Ｂ、＃３４００Ｂ、＃５４００Ｂ、キャボット社製のＭＯＮＡＲＣＨ１４００、１３００、９００、ＶｕｌｃａｎＸＣ−７２Ｒ、ＢｌａｃｋＰｅａｒｌｓ２０００、ＴＩＭＣＡＬ社製のＥｎｓａｃｏ２５０Ｇ、Ｅｎｓａｃｏ２６０Ｇ、Ｅｎｓａｃｏ３５０Ｇ、ＳｕｐｅｒＰ−Ｌｉ等のファーネスブラック）、ライオン社製のＥＣ−３００Ｊ、ＥＣ−６００ＪＤ等のケッチェンブラック、電気化学工業社製のデンカブラック、デンカブラックＨＳ−１００、ＦＸ−３５等のアセチレンブラックが挙げられる。これらは特に限定されることはない。
Commercially available carbon blacks include, for example, Tokai Carbon's Toka Black # 4300, # 4400, # 4500, # 5500, Degussa's Printex L, and Colombian's Raven 7000, 5750, 5250, 5000 ULTRAIII, 500.
0ULTRA, Conductex SC ULTRA, Conductex 975 ULTRA, PUERBLACK100, 115, 205, Mitsubishi Chemical # 2350, # 2400B, # 2600B, # 3050B, # 3030B, # 3230B, # 3350B, # 3400B, # 5400B MONARCH1400, 1300, 900, Vulcan XC-72R, BlackPearls2000, Ensaco250G, Ensaco260G, Ensaco350G, SuperP-Li, etc. Examples thereof include acetylene black such as Denka Black, Denka Black HS-100, and FX-35 manufactured by Denki Kagaku Kogyo Co., Ltd. These are not particularly limited.
重合体（Ａ）は、アクリロニトリルに由来する単量体単位が、環状構造を形成すると熱電変換材料の分散性、流動性、保存安定性がより向上する。例えば、重合体（Ａ）をアルカリで処理するとアクリロニトリルに由来する単量体単位が水素化ナフチリジン環等の環状構造へ変化し、分散性がより向上する。また、詳しいメカニズムは不明であるが、環状構造を形成することで、熱電変換材料の熱電性能も向上する。環状構造を有することで、導電性材料（Ｂ）への吸着性が高まり、重合体（Ａ）から導電性材料（Ｂ）へのキャリア移動が起こりやすくなったためと考えられる。 When the monomer unit derived from acrylonitrile in the polymer (A) forms a cyclic structure, the dispersibility, fluidity, and storage stability of the thermoelectric conversion material are further improved. For example, when the polymer (A) is treated with an alkali, the monomer unit derived from acrylonitrile changes to a cyclic structure such as a hydrogenated diazanaphthalene ring, and the dispersibility is further improved. Moreover, although the detailed mechanism is unknown, the thermoelectric performance of the thermoelectric conversion material is also improved by forming the annular structure. It is considered that the cyclic structure enhances the adsorptivity to the conductive material (B) and facilitates the carrier transfer from the polymer (A) to the conductive material (B).
＜イオン性化合物＞
本発明の熱電変換材料は、アニオン（Ｃ）とカチオン（Ｄ）とからなるイオン性化合物を含有していてもよい。イオン性化合物としては、無機塩基、無機金属塩、オニウム塩以外の有機塩、オニウム塩等が挙げられるが、これらに限定されない。
<Ionic compound>
The thermoelectric conversion material of the present invention may contain an ionic compound composed of an anion (C) and a cation (D). Examples of the ionic compound include, but are not limited to, inorganic bases, inorganic metal salts, organic salts other than onium salts, and onium salts.
無機塩基としては、金属水酸化物等が挙げられる。金属水酸化物としては、アルカリ金属の水酸化物、アルカリ土類金属の水酸化物等が挙げられる。アルカリ金属の水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等が挙げられる。アルカリ土類金属の水酸化物としては、水酸化カルシウム、水酸化マグネシウム等が挙げられる。これらの中でも、アルカリ金属の水酸化物が好ましく、水酸化ナトリウム、水酸化カリウムがより好ましい。 Examples of the inorganic base include metal hydroxides and the like. Examples of the metal hydroxide include alkali metal hydroxides and alkaline earth metal hydroxides. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Examples of the hydroxide of the alkaline earth metal include calcium hydroxide and magnesium hydroxide. Among these, alkali metal hydroxides are preferable, and sodium hydroxide and potassium hydroxide are more preferable.
無機金属塩は、金属の炭酸塩等が挙げられる。金属の炭酸塩としては、アルカリ金属の炭酸塩、アルカリ土類金属の炭酸塩等が挙げられる。アルカリ金属の炭酸塩は、例炭酸リチウム、炭酸水素リチウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム等が挙げられる。アルカリ土類金属の炭酸塩は、炭酸カルシウム、炭酸マグネシウム等が挙げられる。これらの中でも、アルカリ金属の炭酸塩が好ましく、炭酸リチウム、炭酸ナトリウムがより好ましい。尚、無機塩基または無機金属塩中の金属は、遷移金属であってもよい。 Examples of the inorganic metal salt include metal carbonates and the like. Examples of metal carbonates include alkali metal carbonates and alkaline earth metal carbonates. Examples of alkali metal carbonates include lithium carbonate, lithium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate and the like. Examples of carbonates of alkaline earth metals include calcium carbonate and magnesium carbonate. Among these, alkali metal carbonates are preferable, and lithium carbonate and sodium carbonate are more preferable. The metal in the inorganic base or the inorganic metal salt may be a transition metal.
オニウム塩以外の有機塩は、カルボン酸塩、スルホン酸塩、フェノラート塩、金属アルコキシド等が挙げられる。カルボン酸塩としては、酢酸ナトリウム、安息香酸ナトリウム等が挙げられる。スルホン酸塩としては、ｐ−トルエンスルホン酸ナトリウム等が挙げられる。フェノラート塩としては、ナトリウムフェノラート等が挙げられる。金属アルコキシドとしては、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムｔｅｒｔ−ブトキシド、カリウムメトキシド、カリウムエトキシド、カリウムｔｅｒｔ−ブトキシド等が挙げられる。 Examples of organic salts other than onium salts include carboxylates, sulfonates, phenolate salts, and metal alkoxides. Examples of the carboxylate include sodium acetate, sodium benzoate and the like. Examples of the sulfonate include sodium p-toluenesulfonate and the like. Examples of the phenolate salt include sodium phenolate and the like. Examples of the metal alkoxide include sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide and the like.
オニウム塩としては、アンモニウム塩、オキソニウム塩、スルホニウム塩、ヨードニウム塩、ブロモニウム塩等が挙げられる。アンモニウム塩としては、アンモニウムヒドロキシド、アンモニウムフルオリド、アンモニウムクロリド、アンモニウムブロミド、アンモニウムヨージド等が挙げられる。 Examples of the onium salt include ammonium salt, oxonium salt, sulfonium salt, iodonium salt, bromonium salt and the like. Examples of the ammonium salt include ammonium hydroxide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide and the like.
アンモニウムヒドロキシドとしては、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド等が挙げられる。
アンモニウムフルオリドとしては、テトラメチルアンモニウムフルオリド四水和物、テトラエチルアンモニウムフルオリド水和物、テトラブチルアンモニウムフルオリド等が挙げられる。
アンモニウムクロリドとしては、アセチルコリンクロリド、トリエチルメチルアンモニウムクロリド、テトラエチルアンモニウムクロリド、テトラプロピルアンモニウムクロリド、デシルトリメチルアンモニウムクロリド等が挙げられる。
アンモニウムブロミドとしては、アセチルコリンブロミド、テトラメチルアンモニウムブロミド、テトラエチルアンモニウムブロミド、トリメチルフェニルアンモニウムブロミド、１−ブチル−１−メチルピペリジニウムブロミド、ヘキシルジメチルオクチルアンモニウムブロミド等が挙げられる。
アンモニウムヨージドとしては、アセチルコリンヨージド、テトラメチルアンモニウムヨージド、テトラエチルアンモニウムヨージド、テトラプロピルアンモニウムヨージド、テトラブチルアンモニウムヨージド、テトラアミルアンモニウムヨージド、トリメチルフェニルアンモニウムヨージド等が挙げられる。
Examples of the ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide and the like.
Examples of ammonium fluoride include tetramethylammonium fluoride tetrahydrate, tetraethylammonium fluoride hydrate, and tetrabutylammonium fluoride.
Examples of the ammonium chloride include acetylcholine chloride, triethylmethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, decyltrimethylammonium chloride and the like.
Examples of the ammonium bromide include acetylcholine bromide, tetramethylammonium bromide, tetraethylammonium bromide, trimethylphenylammonium bromide, 1-butyl-1-methylpiperidinium bromide, hexyldimethyloctylammonium bromide and the like.
Examples of the ammonium iodide include acetylcholine ammonium iodide, tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetraamylammonium iodide, trimethylphenylammonium iodide and the like.
オキソニウム塩としては、トリメチルオキソニウムテトラフルオロボラート、トリエチルオキソニウムテトラフルオロボラート等が挙げられる。
スルホニウム塩としては、テトラフルオロほう酸ジメチル(メチルチオ)スルホニウム、トリメチルスルホニウムブロミド等が挙げられる。
ヨードニウム塩としては、ビス（２，４，６−トリメチルピリジン）ヨードニウムヘキサフルオロホスフェート、過塩素酸ジフェニルヨードニウム等が挙げられる。
ブロモニウム塩としては、ビス（２，４，６−トリメチルピリジン）ブロモニウムヘキサフルオロホスフェート等が挙げられる。
Examples of the oxonium salt include trimethyloxonium tetrafluoroborate and triethyloxonium tetrafluoroborate.
Examples of the sulfonium salt include dimethyl (methylthio) sulfonium tetrafluoroborate, trimethylsulfonium bromide and the like.
Examples of the iodonium salt include bis (2,4,6-trimethylpyridine) iodonium hexafluorophosphate, diphenyliodonium perchlorate and the like.
Examples of the bromonium salt include bis (2,4,6-trimethylpyridine) bromonium hexafluorophosphate and the like.
本発明の熱電変換材料は、アニオン（Ｃ）及びカチオン（Ｄ）からなるイオン性化合物を含んでも良い。イオン性化合物は、導電性材料（Ｂ）１００質量部に対して、１〜７０質量部配合することが好ましく、４〜６０質量部配合することがより好ましく、４〜２０質量部配合することがさらに好ましい。このような配合量とすることで分散性がより向上し、熱電変換素子の導電率、経時安定性がより向上する。 The thermoelectric conversion material of the present invention may contain an ionic compound composed of an anion (C) and a cation (D). The ionic compound is preferably blended in an amount of 1 to 70 parts by mass, more preferably 4 to 60 parts by mass, and 4 to 20 parts by mass with respect to 100 parts by mass of the conductive material (B). More preferred. With such a blending amount, the dispersibility is further improved, and the conductivity and the stability over time of the thermoelectric conversion element are further improved.
＜アニオン（Ｃ）＞
アニオン（Ｃ）は、ＯＨ-、Ｒ1Ｏ-、Ｒ2Ｓ-、Ｒ3ＣＯＯ-、ＳＨ-、ＢＨ4 -、Ｉ-、Ｂｒ-、Ｃｌ-、ＢＦ4 -、ＰＦ6 -、ＣｌＯ4 -等が挙げられる。これらの中でも、ＯＨ-、Ｒ1Ｏ-、Ｒ2Ｓ-、Ｒ3ＣＯＯ-、ＳＨ-、ＢＨ4 -、Ｉ-、Ｂｒ-およびＣｌ-からなる群より選択される少なくとも１つであることが好ましく、ＯＨ-又はＲ1Ｏ-であることがより好ましい。ここで、Ｒ1、Ｒ2、及びＲ3は、脂肪族炭化水素基または芳香族炭化水素基である。
<Anion (C)>
Anion (C) is, OH -, R 1 O - , R 2 S -, R 3 COO -, SH -, BH 4 -, I -, Br -, Cl -, BF 4 -, PF 6 -, ClO 4 -, and the like. Among these, OH -, R 1 O - , R 2 S -, R 3 COO -, SH -, BH 4 -, I -, Br - and Cl - is at least one selected from the group consisting of Is preferable, and OH − or R 1 O − is more preferable. Here, R 1 , R 2 , and R 3 are aliphatic hydrocarbon groups or aromatic hydrocarbon groups.
脂肪族炭化水素基としては、アルキル基、シクロアルキル基、アルケニル基、アルキニル基等が挙げられる。
アルキル基としては、直鎖アルキル基及び分岐アルキル基が挙げられる。
直鎖アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、ヘキサデシル基、イコシル基等が挙げられる。
分岐アルキル基としては、イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基、２−エチルヘキシル基、ターシャリーブチル基、ターシャリーペンチル基、イソペンタデシル基等が挙げられる。
シクロアルキル基としては、シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、トリシクロデシル基、ノルボルニル基、アダマンチル基等が挙げられる。
アルケニル基としては、ビニル基（エテニル基）、１−プロペニル基、２−プロペニル基、２−ブテニル基、１−ブテニル基、１−ヘキセニル基、２−ドデセニル基、ペンテニル基等等が挙げられる。
アルキニル基としては、エチニル基、１−プロピニル基、２−プロピニル基、１−ブチニル基、３−ヘキシニル基、２−ドデシニル基等が挙げられる。
Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group and an alkynyl group.
Examples of the alkyl group include a linear alkyl group and a branched alkyl group.
Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group and an icosyl group.
Examples of the branched alkyl group include an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, a 2-ethylhexyl group, a tertiary butyl group, a tertiary pentyl group, and an isopentadecyl group.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, a norbornyl group, an adamantyl group and the like.
Examples of the alkenyl group include a vinyl group (ethenyl group), a 1-propenyl group, a 2-propenyl group, a 2-butenyl group, a 1-butenyl group, a 1-hexenyl group, a 2-dodecenyl group, a pentenyl group and the like.
Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 3-hexynyl group, a 2-dodecynyl group and the like.
また、芳香族炭化水素基としては、アリール基等が挙げられる。アリール基としては、フェニル基、ビフェニリル基、ターフェニリル基、ナフチルン基、アンスリル基等が挙げられる。 Moreover, as an aromatic hydrocarbon group, an aryl group and the like can be mentioned. Examples of the aryl group include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthylun group, an anthryl group and the like.
＜カチオン（Ｄ）＞
カチオン（Ｄ）としては、金属イオンや有機塩基由来のカチオン等が挙げられる。金属イオンとしては、典型金属イオン、遷移金属イオン等が挙げられる。上記金属イオンは、リチウムイオン、ナトリウムイオン、カリウムイオン、ルビジウムイオン、セシウムイオン、フランシウムイオン、ベリリウムイオン、マグネシウムイオン、カルシウムイオン、ストロンチウムイオン、バリウムイオン、ラジウムイオン、スカンジウムイオン等が挙げられる。
<Cation (D)>
Examples of the cation (D) include cations derived from metal ions and organic bases. Examples of the metal ion include a typical metal ion, a transition metal ion, and the like. Examples of the metal ion include lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, franchium ion, beryllium ion, magnesium ion, calcium ion, strontium ion, barium ion, radium ion, scandium ion and the like.
また、有機塩基由来のカチオンとしては、一級、二級または三級アミンに由来のカチオン、その他塩基性含窒素有機化合物に由来のカチオン等が挙げられる。一級、二級または三級アミンに由来のカチオンとしては、エチルアミン、ブチルアミン、ジエチルアミン、ジブチルアミン、トリエチルアミン、トリブチルアミン等に由来のカチオンが挙げられる。その他塩基性含窒素有機化合物に由来のカチオンとしては、ピリジン、キノリン、インキノリン、ピロリジン、ピぺリジン、アジリジン、ポリエチレンイミン等に由来のカチオンが挙げられる。 Examples of the cation derived from an organic base include a cation derived from a primary, secondary or tertiary amine, a cation derived from another basic nitrogen-containing organic compound, and the like. Examples of the cation derived from the primary, secondary or tertiary amine include cations derived from ethylamine, butylamine, diethylamine, dibutylamine, triethylamine, tributylamine and the like. Examples of cations derived from other basic nitrogen-containing organic compounds include cations derived from pyridine, quinoline, inquinolin, pyrrolidine, piperidine, aziridine, polyethyleneimine and the like.
また、重合体（Ａ）は、熱電変換材料中で導電性材料（Ｂ）の分散、ゼーベック係数の向上、導電性との両立の観点から、重合体（Ａ）の含有率は、導電性材料（Ｂ）の全量に対して、上限が、４００質量％以下が好ましく、２００質量％以下がより好ましく、１２０％以下が更に好ましく、１００質量％以下が特に好ましい。また、重合体（Ａ）の効果を発揮するために、下限は、重合体（Ａ）は、導電性材料（Ｂ）の全量に対して、５質量％以上が好ましく、２０質量％以上がより好ましく、２５質量％以上が更に好ましく、４０質量％以上が特に好ましい。 Further, the polymer (A) has a conductive material (B) content in the thermoelectric conversion material, from the viewpoints of dispersion of the conductive material (B), improvement of the Seebeck coefficient, and compatibility with conductivity. With respect to the total amount of (B), the upper limit is preferably 400% by mass or less, more preferably 200% by mass or less, further preferably 120% or less, and particularly preferably 100% by mass or less. Further, in order to exert the effect of the polymer (A), the lower limit of the polymer (A) is preferably 5% by mass or more, more preferably 20% by mass or more, based on the total amount of the conductive material (B). It is preferable, 25% by mass or more is more preferable, and 40% by mass or more is particularly preferable.
また、重合体（Ａ）は、熱電変換材料中の含有率が４質量％以上８０質量％以下であることが好ましく、より好ましくは２０質量％以上６０質量％以下であり、さらに好ましくは４０質量％以上５０質量％以下である。 The content of the polymer (A) in the thermoelectric conversion material is preferably 4% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 60% by mass or less, and further preferably 40% by mass. % Or more and 50% by mass or less.
また、導電性材料（Ｂ）は、熱電変換材料中の含有率が１５質量％以上９０質量％以下であることが好ましく、より好ましくは３０質量％以上８０質量％以下であることが好ましく、さらに好ましくは５０質量％以上６０質量％以下である。 The content of the conductive material (B) in the thermoelectric conversion material is preferably 15% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 80% by mass or less, and further. It is preferably 50% by mass or more and 60% by mass or less.
本発明の熱電変換材料は、熱電特性を維持する上で、ラジカルを発生する化合物を含有しないことが好ましく、重合体（Ａ）と導電性材料（Ｂ）のみ、または、重合体（Ａ）と導電性材料（Ｂ）とイオン性化合物とからなることがより好ましいが、必要に応じてその他成分を含んでも良い。 In order to maintain the thermoelectric properties, the thermoelectric conversion material of the present invention preferably does not contain a compound that generates a radical, and contains only the polymer (A) and the conductive material (B), or the polymer (A). It is more preferably composed of the conductive material (B) and the ionic compound, but other components may be contained if necessary.
（分散媒）
分散媒は、重合体（Ａ）と導電性材料（Ｂ）とを混合する際の媒体として使用することができる。分散媒を含有することによってインキまたはペーストの状態となるため、印刷や塗工によって熱電変換膜を形成することができる。使用できる分散媒としては、重合体（Ａ）と導電性材料（Ｂ）とを溶解また良分散できるものが好ましく、有機溶剤や水を挙げることができる。分散媒は一種を単独で用いてもよく、２種以上を組み合せて用いても良い。
(Dispersion medium)
The dispersion medium can be used as a medium for mixing the polymer (A) and the conductive material (B). By containing the dispersion medium, it becomes an ink or a paste, so that a thermoelectric conversion film can be formed by printing or coating. The dispersion medium that can be used is preferably one that can dissolve or disperse the polymer (A) and the conductive material (B) well, and examples thereof include an organic solvent and water. One type of dispersion medium may be used alone, or two or more types may be used in combination.
有機溶剤としては、例えば、メタノール、エタノール、プロパノール、ブタノール、エチレングリコールメチルエーテル、ターピネオール、ジヒドロターピネオール、２，４−ジエチル−１，５−ペンタンジオール、１，３−ブチレングリコール、イソボルニルシクロヘキサノール、エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、グリセリン、トリフルオロエタノール、ｍ−クレゾール、およびチオジグリコール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、等のエーテル類、ヘキサン、ヘプタン、オクタン等の炭化水素類、ベンゼン、トルエン、キシレン、クメン等の芳香族類、酢酸エチル、酢酸ブチル等のエステル類、Ｎ−メチルピロリドン等から、必要に応じて適宜選択することができる。重合体（Ａ）と導電性材料（Ｂ）の分散性や溶解性の観点から、Ｎ−メチルピロリドンが特に好ましい。 Examples of the organic solvent include methanol, ethanol, propanol, butanol, ethylene glycol methyl ether, tarpineol, dihydroterpineol, 2,4-diethyl-1,5-pentanediol, 1,3-butylene glycol, and isobornylcyclohexanol. , Ethylene glycol, 1,3-propanediol, 1,4-butanediol, glycerin, trifluoroethanol, m-cresol, and alcohols such as thiodiglycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. , Ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, hydrocarbons such as hexane, heptane, octane, aromatics such as benzene, toluene, xylene, cumene, esters such as ethyl acetate, butyl acetate, N- From methylpyrrolidone and the like, it can be appropriately selected as needed. N-methylpyrrolidone is particularly preferable from the viewpoint of dispersibility and solubility of the polymer (A) and the conductive material (B).
（樹脂）
本発明の熱電変換材料は、成膜性や膜強度の調整等を目的として、更に、樹脂を含んでもよい。樹脂は一種を単独で用いても良く、２種以上を組み合わせて用いることもできる。また、これらの樹脂の共重合体等であっても良い。特に限定するものではないが、一実施形態において、ポリウレタン樹脂、アクリル樹脂、アクリルアミド樹脂であることが好ましい。導電性の観点から、樹脂を含む場合、樹脂の含有量は、重合体（Ａ）と導電性材料（Ｂ）との全質量を基準として、９９質量％以下の範囲が好ましく、５０質量％以下の範囲がより好ましく、２０質量％以下の範囲がさらに好ましい。
(resin)
The thermoelectric conversion material of the present invention may further contain a resin for the purpose of adjusting the film forming property and the film strength. One type of resin may be used alone, or two or more types may be used in combination. Further, it may be a copolymer of these resins or the like. Although not particularly limited, in one embodiment, a polyurethane resin, an acrylic resin, or an acrylamide resin is preferable. From the viewpoint of conductivity, when a resin is contained, the content of the resin is preferably in the range of 99% by mass or less, preferably 50% by mass or less, based on the total mass of the polymer (A) and the conductive material (B). Is more preferable, and a range of 20% by mass or less is further preferable.
（無機熱電変換材料）
本発明の熱電変換材料は、熱電変換性能を高めるために、必要に応じて、無機熱電変換材料を含んでも良い。無機熱電変換材料は特に限定されず、一般に熱電変換材料として知られているものを使用できる。
(Inorganic thermoelectric conversion material)
The thermoelectric conversion material of the present invention may contain an inorganic thermoelectric conversion material, if necessary, in order to enhance the thermoelectric conversion performance. The inorganic thermoelectric conversion material is not particularly limited, and a material generally known as a thermoelectric conversion material can be used.
＜熱電変換素子＞
本発明の熱電変換素子は、本発明の熱電変換材料を用いて形成された熱電変換膜と、電極とを有し、熱電変換膜と電極とが、電気的に接続されているものである。熱電変換膜は、導電性および熱電特性に加えて、耐熱性や可撓性の点でも優れる。そのため、高品質な熱電変換素子を容易に作製することができる。
<Thermoelectric conversion element>
The thermoelectric conversion element of the present invention has a thermoelectric conversion film formed by using the thermoelectric conversion material of the present invention and an electrode, and the thermoelectric conversion film and the electrode are electrically connected to each other. The thermoelectric conversion film is excellent in heat resistance and flexibility in addition to conductivity and thermoelectric properties. Therefore, a high-quality thermoelectric conversion element can be easily manufactured.
熱電変換膜は、基材上に熱電変換材料を塗布して得られる膜であってもよい。熱電変換材料は優れた成型性を有するため、塗布または印刷によって良好な膜を得ることが容易である。熱電変換膜の製造方法としては目的とする熱電変換膜を得ることができれば特に限定はなく、熱電変換材料の粘度等の特性や、必要とされる膜厚、面積、形状等の条件に応じて適宜選択することができる。例えば、スピンコート、スプレーコート、ロールコート、グラビアコート、フレキソコート、ダイコート、リップコート、ナイフコート、ブレードコート、コンマコート、ロールコート、カーテンコート、バーコート、ディップコート、ディスペンサー、スクリーンコート、インクジェット印刷等の各種手段を用いた方法が挙げられる。 The thermoelectric conversion film may be a film obtained by applying a thermoelectric conversion material on a base material. Since the thermoelectric conversion material has excellent moldability, it is easy to obtain a good film by coating or printing. The method for producing the thermoelectric conversion film is not particularly limited as long as the desired thermoelectric conversion film can be obtained, depending on the characteristics such as the viscosity of the thermoelectric conversion material and the required conditions such as film thickness, area and shape. It can be selected as appropriate. For example, spin coat, spray coat, roll coat, gravure coat, flexo coat, die coat, lip coat, knife coat, blade coat, comma coat, roll coat, curtain coat, bar coat, dip coat, dispenser, screen coat, inkjet printing. A method using various means such as the above can be mentioned.
熱電変換膜の膜厚は、特に限定されるものではなく、必要とされる電流値、電圧値、および抵抗等の電気的性質や、熱電特性に応じて設定できるが、後述するように、熱電変換膜の厚さ方向または面方向に温度差を生じ、かつ伝達できるように、一定以上の厚みを有するように形成されることが好ましい。熱電特性や可撓性の点から、熱電変換膜の膜厚は、０．１〜２００μｍの範囲であることが好ましく、１〜１００μｍの範囲が更に好ましく、１〜６０μｍの範囲であることが特に好ましい。 The film thickness of the thermoelectric conversion film is not particularly limited and can be set according to the required electrical properties such as current value, voltage value, resistance, and thermoelectric characteristics, but as will be described later, thermoelectric It is preferable that the conversion film is formed to have a certain thickness or more so that a temperature difference can be generated and transmitted in the thickness direction or the surface direction of the conversion film. From the viewpoint of thermoelectric characteristics and flexibility, the film thickness of the thermoelectric conversion film is preferably in the range of 0.1 to 200 μm, more preferably in the range of 1 to 100 μm, and particularly preferably in the range of 1 to 60 μm. preferable.
基材としては、特に制限はないが、不織布、紙、ポリエチレン、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート、ポリエーテルサルフォン、ポリプロピレン、ポリイミド、ポリカーボネート、およびセルローストリアセテート等の材料からなるプラスチックフィルム、またはガラス等を用いることができる。これら基材は、熱電変換材料の水や酸素の影響による劣化を防ぐために、基材表面にアルミ蒸着層やバリア層を有するものであっても良い。 The base material is not particularly limited, but is a plastic film made of a material such as non-woven fabric, paper, polyethylene, polyethylene terephthalate (PET), polyethylene naphthalate, polyether sulfone, polypropylene, polyimide, polycarbonate, and cellulose triacetate, or Glass or the like can be used. These base materials may have an aluminum vapor deposition layer or a barrier layer on the surface of the base material in order to prevent deterioration of the thermoelectric conversion material due to the influence of water or oxygen.
基材と熱電変換膜との密着性を向上させる目的で、基材表面に様々な処理を行うこともできる。具体的には、熱電変換材料の塗布に先立ち、ＵＶオゾン処理、コロナ処理、プラズマ処理、または易接着処理を行うこともできる。 Various treatments can be applied to the surface of the base material for the purpose of improving the adhesion between the base material and the thermoelectric conversion film. Specifically, prior to the application of the thermoelectric conversion material, UV ozone treatment, corona treatment, plasma treatment, or easy adhesion treatment can be performed.
熱電変換膜は、基材との積層されたものであってもよく、基材を有さない自立膜であってもよい。自立膜を作製する場合には、特に制限はないが、例えば、剥離性シート上に熱電変換膜を形成した後に、剥離コートを除去することで得ることができる。 The thermoelectric conversion film may be a laminated film with a base material, or may be a self-supporting film having no base material. When the self-supporting film is produced, there is no particular limitation, but it can be obtained, for example, by forming a thermoelectric conversion film on a peelable sheet and then removing the release coat.
剥離性シートとしては、例えば、ポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、およびポリイミドフィルム等のプラスチックフィルムに離型処理したもの等が挙げられる。 Examples of the peelable sheet include those obtained by releasing a plastic film such as a polyester film, a polyethylene film, a polypropylene film, and a polyimide film.
熱電変換素子は、上記熱電変換材料を用いて構成されることを除き、当技術分野で周知の技術を適用して構成することができる。熱電変換素子のより具体的な構成、およびその製造方法について説明する。 The thermoelectric conversion element can be configured by applying a technique well known in the art except that the thermoelectric conversion material is used. A more specific configuration of the thermoelectric conversion element and a method for manufacturing the same will be described.
熱電変換素子は、熱電変換膜と電極とが電気的に接続している。ここで、「電気的に接続する」とは、互いに接合しているか、またはワイヤー等の他の構成部分を介して通電できる状態であることを意味する。 In the thermoelectric conversion element, the thermoelectric conversion film and the electrode are electrically connected. Here, "electrically connected" means that they are joined to each other or can be energized via other components such as wires.
電極の材料は、電極として働くものであれば特に制限はないが、金属、合金、および半導体から選択することができる。一実施形態において、導電率が高く、熱電変換膜の接触抵抗が低いほうが好ましいことから、金属および合金が好ましい。例えば、金、銀、銅、白金、ニッケル、およびアルミニウムからなる群から選択される少なくとも一種を含むことが好ましい。電極は銀を含むものがさらに好ましい。 The material of the electrode is not particularly limited as long as it acts as an electrode, but can be selected from metals, alloys, and semiconductors. In one embodiment, metals and alloys are preferred because they preferably have high conductivity and low contact resistance of the thermoelectric conversion film. For example, it preferably comprises at least one selected from the group consisting of gold, silver, copper, platinum, nickel and aluminum. It is more preferable that the electrode contains silver.
電極の形成方法は特に限定されず、真空蒸着法、電極材料箔や電極材料膜を有するフィルムの熱圧着、電極材料の微粒子を分散したペーストの塗布等の方法によって形成することができる。プロセスの簡便さの観点から、電極材料箔や電極材料膜を有するフィルムの熱圧着、電極材料を分散したペーストの塗布による方法が好ましい。 The method for forming the electrode is not particularly limited, and the electrode can be formed by a method such as vacuum deposition, thermocompression bonding of a film having an electrode material foil or an electrode material film, and application of a paste in which fine particles of the electrode material are dispersed. From the viewpoint of the simplicity of the process, a method of heat-pressing a film having an electrode material foil or an electrode material film and applying a paste in which the electrode material is dispersed is preferable.
熱電変換素子の構造の典型例としては、熱電変換膜と一対の電極との位置関係から、（１）本発明による熱電変換膜の両端に電極が形成されている構造と、（２）本発明の熱電変換膜が２つの電極で挟持されている構造とに大別される。
上記（１）の構造を有する熱電変換素子は、例えば、基材上に熱電変換膜を形成した後に、その両端にそれぞれ銀ペーストを塗布して第１および第２の電極を形成することによって得ることができる。このように熱電変換膜の両端に電極が形成された熱電変換素子は、２つの電極間の距離を広くすることが容易である。そのため、２つの電極間で大きな温度差を発生させて、効率よく熱電変換を行うことが容易にできる。
Typical examples of the structure of the thermoelectric conversion element are (1) a structure in which electrodes are formed at both ends of the thermoelectric conversion film according to the present invention, and (2) the present invention, based on the positional relationship between the thermoelectric conversion film and the pair of electrodes. The thermoelectric conversion film is roughly classified into a structure in which the thermoelectric conversion film is sandwiched between two electrodes.
The thermoelectric conversion element having the structure (1) is obtained, for example, by forming a thermoelectric conversion film on a base material and then applying silver paste to both ends thereof to form first and second electrodes. be able to. In the thermoelectric conversion element in which electrodes are formed at both ends of the thermoelectric conversion film in this way, it is easy to increase the distance between the two electrodes. Therefore, it is possible to easily perform thermoelectric conversion efficiently by generating a large temperature difference between the two electrodes.
上記（２）の構造を有する熱電変換素子は、例えば、基材上に銀ペーストを塗布して第１の電極を形成し、その上に本発明の熱電変換膜を形成し、さらにその上に銀ペーストを塗工して第２の電極を形成することによって得ることができる。このように２つの電極で本発明の熱電変換膜を挟持する熱電変換素子では、熱電変換膜の膜厚方向、つまり基材に対して垂直な方向の温度差を利用できることから、発熱原に貼り付ける形態での利用が可能である。そのため、熱源から広範囲で熱を取り出すことができる等の利点があるため好ましい。上記（２）の構造を有する熱電変換素子では、膜厚を厚くすることで２つの電極間の距離を広くし、温度差を確保することも可能である。 In the thermoelectric conversion element having the structure (2), for example, a silver paste is applied on a base material to form a first electrode, a thermoelectric conversion film of the present invention is formed on the first electrode, and the thermoelectric conversion film of the present invention is further formed on the first electrode. It can be obtained by applying a silver paste to form a second electrode. In the thermoelectric conversion element in which the thermoelectric conversion film of the present invention is sandwiched between the two electrodes in this way, the temperature difference in the film thickness direction of the thermoelectric conversion film, that is, in the direction perpendicular to the base material can be utilized, so that the thermoelectric conversion film is attached to the heat generating source. It can be used in the form of attachment. Therefore, it is preferable because it has an advantage that heat can be extracted from a heat source in a wide range. In the thermoelectric conversion element having the structure (2) described above, it is possible to increase the distance between the two electrodes and secure the temperature difference by increasing the film thickness.
熱電変換素子は、直列に接続することで高い電圧を発生させることが可能であり、並列に接続することで大きな電流を発生させることが可能である。また、熱電変換素子は、２つ以上の熱電変換素子を接続したものであってもよい。本発明によれば、熱電変換素子が優れた可撓性を有するため、平面ではない形状を有する熱源に対しても追随して良好に設置することが可能である。
熱電変換素子は、熱源から効率良く熱を伝えるための吸熱層や蓄熱層を有していても良く、また、温度差を確保するために断熱層や放熱層を有していても良い。更に、用途や必要な電力量に応じ、取り出した電気を昇圧回路を用いて昇圧したり、取り出した電気エネルギーをコンデンサーやキャパシタ、あるいは二次電池等に一時的に溜めて使用することもできる。
The thermoelectric conversion elements can generate a high voltage by connecting them in series, and can generate a large current by connecting them in parallel. Further, the thermoelectric conversion element may be one in which two or more thermoelectric conversion elements are connected. According to the present invention, since the thermoelectric conversion element has excellent flexibility, it can be satisfactorily installed even with respect to a heat source having a non-planar shape.
The thermoelectric conversion element may have an endothermic layer or a heat storage layer for efficiently transferring heat from a heat source, or may have a heat insulating layer or a heat radiating layer for ensuring a temperature difference. Further, depending on the application and the required amount of electric power, the extracted electricity can be boosted by using a booster circuit, or the extracted electric energy can be temporarily stored in a capacitor, a capacitor, a secondary battery, or the like for use.
以下、実験例により、本発明をより具体的に説明するが、本発明はこれらの実施例に限定されない。尚、例中、「部」は「質量部」を、「％」は「質量％」をそれぞれ意味するものとする。また、「ＮＭＰ」とは、Ｎ−メチルピロリドンを示す。 Hereinafter, the present invention will be described in more detail with reference to Experimental Examples, but the present invention is not limited to these Examples. In the example, "part" means "part by mass" and "%" means "% by mass". Moreover, "NMP" means N-methylpyrrolidone.
（重量平均分子量（Ｍｗ）の測定方法）
重量平均分子量（Ｍｗ）は、示差屈折率（ＲＩ）検出器を装備したゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定した。装置は、ＨＬＣ−８３２０ＧＰＣ（東ソー社製）を用い、分離カラムを３本直列に繋ぎ、充填剤には順に東ソー社製「ＴＳＫ−ＧＥＬＳＵＰＥＲＡＷ−４０００」、「ＡＷ−３０００」及び「ＡＷ−２５００」を用い、オーブン温度４０℃、溶離液として３０ｍＭトリエチルアミン及び１０ｍＭＬｉＢｒのＮ，Ｎ−ジメチルホルムアミド溶液を用い、流速０．６ｍＬ／分で測定した。測定用試料は、上記溶離液からなる分散媒に１％の濃度で調整し、２０μＬ注入した。分子量は、ポリスチレン換算値である。
(Measuring method of weight average molecular weight (Mw))
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) equipped with a differential refractive index (RI) detector. The device used HLC-8320GPC (manufactured by Tosoh Co., Ltd.), three separation columns were connected in series, and the fillers were "TSK-GELSUPERAW-4000", "AW-3000" and "AW-2500" manufactured by Tosoh Co., Ltd. in order. Was used at an oven temperature of 40 ° C., and a solution of 30 mM triethylamine and 10 mM LiBr in N, N-dimethylformamide was used as an eluent, and the measurement was carried out at a flow rate of 0.6 mL / min. The measurement sample was adjusted to a concentration of 1% in a dispersion medium composed of the above eluent, and 20 μL was injected. The molecular weight is a polystyrene-equivalent value.
＜重合体（Ａ）の製造＞
（製造例１）
（重合体（Ａ−１）の製造）
ガス導入管、温度計、コンデンサー、攪拌機を備えた反応容器に、アセトニトリル１００部、アクリロニトリル９９部、ＰＭＥ４００ １部、３−メルカプト−１，２−プロパンジオール１部を仕込み、窒素ガスで置換した。反応容器内を７０℃に加熱してアセトニトリル１０部、２，２’−アゾビス（２，４−ジメチルバレロニトリル）（富士フイルム和光純薬社製：Ｖ−６５）０．４部からなる混合物を６時間かけて反応容器内に滴下し、重合反応を行った。滴下終了後、７０℃で１時間反応させた後、Ｖ−６５を０．１部添加し、さらに７０℃で１時間反応を続け目的物を沈殿物として得た。その後、不揮発分測定にて転化率が９８％を超えたことを確認した。生成物を減圧濾過によって濾別し、アセトニトリル１００部にて洗浄を行い、減圧乾燥によって溶媒を完全に除去して重合体（Ａ−１）を得た。
<Production of polymer (A)>
(Manufacturing Example 1)
(Production of polymer (A-1))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 100 parts of acetonitrile, 99 parts of acrylonitrile, 1 part of PME400, and 1 part of 3-mercapto-1,2-propanediol, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 70 ° C. to prepare a mixture consisting of 10 parts of acetonitrile and 0.4 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd .: V-65). The mixture was added dropwise to the reaction vessel over 6 hours to carry out a polymerization reaction. After completion of the dropping, the reaction was carried out at 70 ° C. for 1 hour, 0.1 part of V-65 was added, and the reaction was further continued at 70 ° C. for 1 hour to obtain the desired product as a precipitate. After that, it was confirmed by measuring the non-volatile content that the conversion rate exceeded 98%. The product was filtered off under reduced pressure, washed with 100 parts of acetonitrile, and dried under reduced pressure to completely remove the solvent to obtain a polymer (A-1).
（製造例２〜２１）
（重合体（Ａ−２）〜（Ａ−２１）の製造）
単量体の種類と配合量を表１に示すように変更した以外は、製造例１と同様にして、それぞれ重合体（Ａ−２）〜（Ａ−２１）を製造した。各重合体のＭｗを表１に示す。尚、重合体（Ａ−２）〜（Ａ−２１）の合成は、連鎖移動剤の添加、重合開始剤量の調整、および反応条件等を適宜変更してＭｗを調整した。また、連鎖移動剤として３−メルカプト−１，２−プロパンジオールを用いた。
(Manufacturing Examples 2 to 21)
(Production of Polymers (A-2) to (A-21))
Polymers (A-2) to (A-21) were produced in the same manner as in Production Example 1 except that the type and blending amount of the monomers were changed as shown in Table 1. The Mw of each polymer is shown in Table 1. In the synthesis of the polymers (A-2) to (A-21), Mw was adjusted by adding a chain transfer agent, adjusting the amount of the polymerization initiator, and appropriately changing the reaction conditions. Moreover, 3-mercapto-1,2-propanediol was used as a chain transfer agent.
表１中、数値は特に断りのない限り「部」を表し、空欄は配合していないことを意味する。本明細書中の略号は以下のとおりである。
ＨＥＡ：ヒドロキシエチルアクリレート
ＢＡ：ブチルアクリレート
ＰＭＥ４００：（日油社製 「ブレンマーＰＭＥ４００」メトキシポリエチレングリコールメタクリレート、ポリエチレングリコールの繰り返し単位が約９）
ＡＭＥ４００：（日油社製 「ブレンマーＡＭＥ４００」メトキシポリエチレングリコールアクリレート、ポリエチレングリコールの繰り返し単位が約９）
ＰＭＥ１０００：（日油社製 「ブレンマーＰＭＥ１０００」メトキシポリエチレングリコールメタクリレート、ポリエチレングリコールの繰り返し単位が約２３）
ＰＰ８００：（日油社製 「ブレンマーＰＰ８００」ポリプロピレングリコールモノメタクリレート）
ＧＭＡ：グリシジルメタクリレート
３ＥＧ−Ａ：（共栄社製 ライトアクリレート３ＥＧ−Ａ：トリエチレングルコールジアクリレート）
マクロ環状α−アルコキシメチルアクリル酸エステル（下記構造の化合物）
In Table 1, the numerical values represent "parts" unless otherwise specified, and blanks mean that they are not mixed. The abbreviations in this specification are as follows.
HEA: Hydroxyethyl acrylate BA: Butyl acrylate PME400: (Nichiyu Co., Ltd. "Blemmer PME400" methoxypolyethylene glycol methacrylate, polyethylene glycol repeating unit is about 9)
AME400: (NOF Corporation "Blemmer AME400" methoxypolyethylene glycol acrylate, polyethylene glycol repeating unit is about 9)
PME1000: (NOF Corporation "Blemmer PME1000" methoxypolyethylene glycol methacrylate, repeating unit of polyethylene glycol is about 23)
PP800: (NOF Corporation "Blemmer PP800" Polypropylene Glycol Monomethacrylate)
GMA: Glycidyl methacrylate 3EG-A: (Light acrylate 3EG-A manufactured by Kyoei Co., Ltd .: Triethylene glucol diacrylate)
Macrocyclic α-alkoxymethylacrylic acid ester (compound with the following structure)
＜熱電変換材料を含む分散液の製造＞
［実施例１］
（分散液１）
重合体（Ａ−１）０．３部、ＳＷＣＮＴ（ＯＣＳｉＡｌ社製単層カーボンナノチューブ「ＴＵＢＡＬＬ」）０．４部、ＮＭＰ７９．３部、イオン性化合物として水酸化ナトリウム０．０３６部、カチオン捕捉剤（Ｅ）としてＤＢ１５Ｃ５の〇部をそれぞれ秤量して混合した。さらにビーズを加え、スキャンデックスで４時間振とう後、ろ過してビーズを取り除き、熱電変換材料の分散液１を得た。
<Manufacturing of dispersion liquid containing thermoelectric conversion material>
[Example 1]
(Dispersion liquid 1)
Polymer (A-1) 0.3 parts, SWCNT (OCSiAl single-walled carbon nanotube "TUBALL") 0.4 parts, NMP 79.3 parts, sodium hydroxide 0.036 parts as an ionic compound, cation scavenger As (E), 0 parts of DB15C5 were weighed and mixed. Further, beads were added, and after shaking with Scandex for 4 hours, the beads were removed by filtration to obtain a dispersion liquid 1 of a thermoelectric conversion material.
［実施例２〜３４、比較例１〜２］
（分散液２〜３４、１０１〜１０２）
材料の種類および配合量を表２に示す内容にそれぞれ変更した以外は、分散液１の製造方法と同様にして、熱電変換材料の分散液２〜３４、１０１〜１０２をそれぞれ得た。
[Examples 2-34, Comparative Examples 1-2]
(Dispersions 2-34, 101-102)
Dispersions 2-34 and 101-102 of the thermoelectric conversion material were obtained in the same manner as in the production method of the dispersion 1 except that the types and blending amounts of the materials were changed to the contents shown in Table 2.
表２に記載した略号の材料を以下に示す。
導電性材料（Ｂ）
ＳＷＣＮＴ：ＯＣＳｉＡｌ社製単層カーボンナノチューブ「ＴＵＢＡＬＬ」
ＭＷＣＮＴ：（ＫＵＭＨＯ ＰＥＴＲＯＣＨＥＭＩＣＡＬ社製多層カーボンナノチューブ「Ｋｎａｎｏｓ１００Ｐ」）
ＣＢ：（ライオン社製 ケッチェンブラック「ＥＣ−３００Ｊ」）
重合体（Ａ）ではない重合体
ＰＶＡ：エクセバール ＲＳ−２１１７（クラレ社製）
イオン性化合物
ＴＢＡＯＨ：水酸化テトラブチルアンモニウム
The materials with the abbreviations listed in Table 2 are shown below.
Conductive material (B)
SWCNT: OCSiAl single-walled carbon nanotube "TUBALL"
MWCNT: (Multi-walled carbon nanotube "Knanos100P" manufactured by KUMHO PETROCHEMICAL)
CB: (Lion's Ketjen Black "EC-300J")
Polymer PVA that is not polymer (A): Excelval RS-2117 (manufactured by Kuraray)
Ionic compound TBAOH: Tetrabutylammonium hydroxide
＜熱電変換材料の評価＞
得られた分散液１〜３４、１０１〜１０２を、それぞれ基材としてシート状基材である厚さ７５μｍのＰＥＴフィルムにアプリケータを用いて塗布した後、１２０℃で３０分間乾燥して、膜厚５μｍの熱電変換膜を有する積層体をそれぞれを得た。また、得られた熱電変換膜（以下、塗膜ともいう）を有する積層体について、以下の方法に従って、導電率、ゼーベック係数、８５℃、湿度８５％の環境下での経時安定性を評価した。結果を表２に示す。
<Evaluation of thermoelectric conversion materials>
The obtained dispersions 1-34 and 101-102 are each applied to a PET film having a thickness of 75 μm, which is a sheet-like base material, using an applicator, and then dried at 120 ° C. for 30 minutes to form a film. Laminates having a thermoelectric conversion film having a thickness of 5 μm were obtained. Further, the obtained laminate having the thermoelectric conversion film (hereinafter, also referred to as a coating film) was evaluated for stability over time in an environment of conductivity, Seebeck coefficient, 85 ° C. and humidity of 85% according to the following method. .. The results are shown in Table 2.
（導電率（抵抗率））
作製直後の積層体を２．５ｃｍ×５ｃｍの大きさに切り取り、ＪＩＳ−Ｋ７１９４に準じて、ロレスタＧＸ ＭＣＰ−Ｔ７００（三菱化学アナリテック社製）を用いて四探針法で導電率を測定した。比較例１の導電率を１としたときの相対値として表２に示す。
(Conductivity (resistivity))
The laminated body immediately after production was cut into a size of 2.5 cm × 5 cm, and the conductivity was measured by a four-probe method using a Loresta GX MCP-T700 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) according to JIS-K7194. .. Table 2 shows the relative values when the conductivity of Comparative Example 1 is 1.
（ゼーベック係数）
作製直後の積層体を３ｍｍ×１０ｍｍの大きさに切り取り、アドバンス理工株式会社製のＺＥＭ−３ＬＷを用いて、８０℃におけるゼーベック係数（μＶ／Ｋ）を測定した。比較例１のゼーベック係数を１としたときの相対値を表２に示す。
(Seebeck coefficient)
The laminate immediately after production was cut into a size of 3 mm × 10 mm, and the Seebeck coefficient (μV / K) at 80 ° C. was measured using ZEM-3LW manufactured by Advance Riko Co., Ltd. Table 2 shows the relative values when the Seebeck coefficient of Comparative Example 1 is 1.
（高温高湿条件下での経時安定性）
作製直後の積層体を、８５℃、湿度８５％の環境下で１０日間静置した後にゼーベック係数を測定した。作製直後の積層体のゼーベック係数（表２に挙げたゼーベック係数）に対するゼーベック係数の変化率を求め、下記基準に基づいて評価した。
◎：ゼーベック係数の変化率が１０％以下。（非常に良好）
○：ゼーベック係数の変化率が１０％より大きく２０％以下。（良好）
△：ゼーベック係数の変化率が２０％より大きく５０％以下。（使用可能）
×：ゼーベック係数の変化率が５０％より大きい。また、ｎ型熱電素子の場合は、マイナスのゼーベック係数がプラスに転じる場合も含む。（不良）
(Stability over time under high temperature and high humidity conditions)
The Seebeck coefficient was measured after allowing the laminate immediately after production to stand in an environment of 85 ° C. and 85% humidity for 10 days. The rate of change of the Seebeck coefficient with respect to the Seebeck coefficient (Seebeck coefficient listed in Table 2) of the laminated body immediately after production was determined and evaluated based on the following criteria.
⊚: The rate of change of the Seebeck coefficient is 10% or less. (Very good)
◯: The rate of change of the Seebeck coefficient is greater than 10% and 20% or less. (Good)
Δ: The rate of change of the Seebeck coefficient is greater than 20% and 50% or less. (Available)
X: The rate of change of the Seebeck coefficient is greater than 50%. Further, in the case of an n-type thermoelectric element, the case where the negative Seebeck coefficient turns positive is also included. (Defective)
表２が示すように、本発明の熱電変換材料は、高い導電率とゼーベック係数を示した。更に、高温高湿条件下での経時安定性に優れていることが確認された。これは、重合体Ａ（Ａ）がカチオン捕捉能を有することによって、膜中のカチオンを捕捉し、系中の酸素等からの酸化を防ぐことができたためであると考えられる。 As shown in Table 2, the thermoelectric conversion material of the present invention showed high conductivity and Seebeck coefficient. Furthermore, it was confirmed that it was excellent in stability over time under high temperature and high humidity conditions. It is considered that this is because the polymer A (A) has a cation trapping ability, so that the cation in the membrane can be trapped and oxidation from oxygen or the like in the system can be prevented.
＜熱電変換素子の製造＞
厚さ５０μｍのＰＥＴフィルム上に、上記分散液をそれぞれ塗布し、厚さ２０μｍ、５ｍｍ×３０ｍｍの形状を有する熱電変換層を、それぞれ１０ｍｍ間隔に５つ作製した。次いで、各熱電変換層がそれぞれ直列に接続されるように、銀ペーストを用いて、厚さ１０μｍ、５ｍｍ×３３ｍｍの形状を有する銀回路（電極）を４つ作製して熱電変換素子をそれぞれ製造した。上記銀ペーストとしては、東洋インキ株式会社製のＲＥＸＡＬＰＨＡ ＲＡ−ＦＳ ０７４を使用した。各熱電変換素子について起電力を測定したところ、実施例１〜３４で製造した分散液を用いて製造した熱電変換素子は、いずれも比較例１および２で製造した分散液を用いて製造した熱電変換素子よりもゼーベック係数が優れていることを確認した。
<Manufacturing of thermoelectric conversion element>
The above dispersions were applied onto a PET film having a thickness of 50 μm, and five thermoelectric conversion layers having a thickness of 20 μm and a shape of 5 mm × 30 mm were prepared at intervals of 10 mm. Next, four silver circuits (electrodes) having a thickness of 10 μm and a shape of 5 mm × 33 mm were produced using silver paste so that each thermoelectric conversion layer was connected in series, and each thermoelectric conversion element was manufactured. bottom. As the silver paste, REXALPHA RA-FS 074 manufactured by Toyo Ink Co., Ltd. was used. When the electromotive force was measured for each thermoelectric conversion element, the thermoelectric conversion elements produced using the dispersions produced in Examples 1 to 34 were all thermoelectrics produced using the dispersions produced in Comparative Examples 1 and 2. It was confirmed that the Seebeck coefficient was superior to that of the conversion element.
Claims (8)
A thermoelectric conversion film comprising the thermoelectric conversion material according to any one of claims 1 to 7 and an electrode, and the thermoelectric conversion film and the electrode are electrically connected to each other. Conversion element.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020195789A JP6927401B1 (en) | 2020-11-26 | 2020-11-26 | Thermoelectric conversion materials and thermoelectric conversion elements |
| JP2021121694A JP2022084510A (en) | 2020-11-26 | 2021-07-26 | Thermoelectric conversion material and thermoelectric conversion element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020195789A JP6927401B1 (en) | 2020-11-26 | 2020-11-26 | Thermoelectric conversion materials and thermoelectric conversion elements |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021121694A Division JP2022084510A (en) | 2020-11-26 | 2021-07-26 | Thermoelectric conversion material and thermoelectric conversion element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP6927401B1 true JP6927401B1 (en) | 2021-08-25 |
| JP2022084128A JP2022084128A (en) | 2022-06-07 |
Family
ID=77364627
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020195789A Active JP6927401B1 (en) | 2020-11-26 | 2020-11-26 | Thermoelectric conversion materials and thermoelectric conversion elements |
| JP2021121694A Pending JP2022084510A (en) | 2020-11-26 | 2021-07-26 | Thermoelectric conversion material and thermoelectric conversion element |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021121694A Pending JP2022084510A (en) | 2020-11-26 | 2021-07-26 | Thermoelectric conversion material and thermoelectric conversion element |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP6927401B1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014199837A (en) * | 2013-03-29 | 2014-10-23 | 東洋インキＳｃホールディングス株式会社 | Thermoelectric conversion material, composition for thermoelectric conversion element, thermoelectric conversion film, and thermoelectric conversion element using them |
| JP2015115447A (en) * | 2013-12-11 | 2015-06-22 | 高圧ガス工業株式会社 | Power generation device |
| WO2015198980A1 (en) * | 2014-06-26 | 2015-12-30 | 国立大学法人奈良先端科学技術大学院大学 | Nanomaterial dopant composition composite, dopant composition, and method for manufacturing nanomaterial dopant composition composite |
-
2020
- 2020-11-26 JP JP2020195789A patent/JP6927401B1/en active Active
-
2021
- 2021-07-26 JP JP2021121694A patent/JP2022084510A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014199837A (en) * | 2013-03-29 | 2014-10-23 | 東洋インキＳｃホールディングス株式会社 | Thermoelectric conversion material, composition for thermoelectric conversion element, thermoelectric conversion film, and thermoelectric conversion element using them |
| JP2015115447A (en) * | 2013-12-11 | 2015-06-22 | 高圧ガス工業株式会社 | Power generation device |
| WO2015198980A1 (en) * | 2014-06-26 | 2015-12-30 | 国立大学法人奈良先端科学技術大学院大学 | Nanomaterial dopant composition composite, dopant composition, and method for manufacturing nanomaterial dopant composition composite |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2022084510A (en) | 2022-06-07 |
| JP2022084128A (en) | 2022-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | Flexible, sandwich-like Ag-nanowire/PEDOT: PSS-nanopillar/MnO 2 high performance supercapacitors | |
| Liu et al. | Development of graphene oxide/polyaniline inks for high performance flexible microsupercapacitors via extrusion printing | |
| Lu et al. | Flexible solid-state supercapacitors: design, fabrication and applications | |
| Wang et al. | A synthesis method of MnO2/activated carbon composite for electrochemical supercapacitors | |
| Ogata et al. | All-graphene oxide flexible solid-state supercapacitors with enhanced electrochemical performance | |
| Yang et al. | Polyoxometalate‐coupled graphene via polymeric ionic liquid linker for supercapacitors | |
| Zhao et al. | PEDOT-based composites as electrode materials for supercapacitors | |
| Wang et al. | Super‐aligned carbon nanotube films as current collectors for lightweight and flexible lithium ion batteries | |
| Singu et al. | Benzoyl peroxide oxidation route to nano form polyaniline salt containing dual dopants for pseudocapacitor | |
| Wei et al. | Electropolymerized polyaniline nanocomposites from multi-walled carbon nanotubes with tuned surface functionalities for electrochemical energy storage | |
| Gong et al. | High-performance flexible in-plane micro-supercapacitors based on vertically aligned CuSe@ Ni (OH) 2 hybrid nanosheet films | |
| US20120028127A1 (en) | Apparatus and associated methods | |
| TWI601330B (en) | Electrode material and energy storage apparatus | |
| Ramirez-Castro et al. | Electrochemical performance of carbon/MnO2 nanocomposites prepared via molecular bridging as supercapacitor electrode materials | |
| Aoki et al. | Acrylic acid-based copolymers as functional binder for silicon/graphite composite electrode in lithium-ion batteries | |
| Varzi et al. | The effects of pristine and carboxylated multi-walled carbon nanotubes as conductive additives on the performance of LiNi0. 33Co0. 33Mn0. 33O2 and LiFePO4 positive electrodes | |
| CN105186004A (en) | Copper current collector for lithium-ion battery anodes as well as preparation method and application of copper current collector | |
| Kwak et al. | Flexible transparent symmetric solid-state supercapacitors based on NiO-decorated nanofiber-based composite electrodes with excellent mechanical flexibility and cyclability | |
| JP7249583B2 (en) | Solid electrolyte and secondary battery using the same | |
| Sohn et al. | Impact of different nanostructures of a PEDOT decorated 3D multilayered graphene foam by chemical methods on supercapacitive performance | |
| KR102052416B1 (en) | Electrically conductive ink and manufacturing method of conductive film and micro-supercapacitor therefrom | |
| Liu et al. | Carbon fabric supported manganese and ruthenium oxide thin films for supercapacitors | |
| US10981794B1 (en) | Stable aqueous dispersion of carbon | |
| JP6927401B1 (en) | Thermoelectric conversion materials and thermoelectric conversion elements | |
| JP6827657B2 (en) | Electrochemical device and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20201215 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20201215 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20210308 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210316 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210427 |
|
| 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: 20210706 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210719 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6927401 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |