JP2019065415A - Carbon nano-tube twist yarn - Google Patents
Carbon nano-tube twist yarn Download PDFInfo
- Publication number
- JP2019065415A JP2019065415A JP2017191185A JP2017191185A JP2019065415A JP 2019065415 A JP2019065415 A JP 2019065415A JP 2017191185 A JP2017191185 A JP 2017191185A JP 2017191185 A JP2017191185 A JP 2017191185A JP 2019065415 A JP2019065415 A JP 2019065415A
- Authority
- JP
- Japan
- Prior art keywords
- cnt
- twisted
- carbon nanotube
- twisting
- surface area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 38
- 239000011148 porous material Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003990 capacitor Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 description 31
- 238000001179 sorption measurement Methods 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 23
- 239000007789 gas Substances 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 20
- -1 1-ethyl-3-methylimidazolium tetrafluoroborate Chemical compound 0.000 description 19
- 238000005259 measurement Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000001878 scanning electron micrograph Methods 0.000 description 16
- 230000015271 coagulation Effects 0.000 description 15
- 238000005345 coagulation Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000002109 single walled nanotube Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CYKYBWRSLLXBOW-VTBMCCKRSA-N 2-hydroxy-1-[(3s,5s,8r,9s,10s,13s,14s,17s)-3-hydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]ethanone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CC[C@H]21 CYKYBWRSLLXBOW-VTBMCCKRSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003833 bile salt Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 229940093761 bile salts Drugs 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229940099352 cholate Drugs 0.000 description 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 229960003964 deoxycholic acid Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229940006477 nitrate ion Drugs 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical class [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- FHHPUSMSKHSNKW-SMOYURAASA-M sodium deoxycholate Chemical compound [Na+].C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 FHHPUSMSKHSNKW-SMOYURAASA-M 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 description 1
- VMSNAUAEKXEYGP-YEUHZSMFSA-M sodium glycodeoxycholate Chemical compound [Na+].C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 VMSNAUAEKXEYGP-YEUHZSMFSA-M 0.000 description 1
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- JAJWGJBVLPIOOH-IZYKLYLVSA-M sodium taurocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS([O-])(=O)=O)C)[C@@]2(C)[C@@H](O)C1 JAJWGJBVLPIOOH-IZYKLYLVSA-M 0.000 description 1
- 229940045946 sodium taurodeoxycholate Drugs 0.000 description 1
- YXHRQQJFKOHLAP-FVCKGWAHSA-M sodium;2-[[(4r)-4-[(3r,5r,8r,9s,10s,12s,13r,14s,17r)-3,12-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]pentanoyl]amino]ethanesulfonate Chemical compound [Na+].C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS([O-])(=O)=O)C)[C@@]2(C)[C@@H](O)C1 YXHRQQJFKOHLAP-FVCKGWAHSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- AWDRATDZQPNJFN-VAYUFCLWSA-N taurodeoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS(O)(=O)=O)C)[C@@]2(C)[C@@H](O)C1 AWDRATDZQPNJFN-VAYUFCLWSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
Description
本発明は、カーボンナノチューブ撚糸体に関する。特に、複数のカーボンナノチューブが集合したカーボンナノチューブバンドルが複数集合して構成された撚糸体に関する。 The present invention relates to a carbon nanotube twist body. In particular, the present invention relates to a twisted body in which a plurality of carbon nanotube bundles in which a plurality of carbon nanotubes are collected are assembled.
機能繊維、スマートファイバー、インテリジェント材料分野では、強度を有しつつ、比表面積が大きな新しい繊維素材の開発が期待されている。このような物性を有する繊維素材は、例えば、キャパシターや、環境中の毒性物質を吸着するフィルターなどの用途への利用が可能である。 In the functional fiber, smart fiber and intelligent material fields, development of a new fiber material having a large specific surface area while having strength is expected. A fiber material having such physical properties can be used for applications such as, for example, capacitors and filters that adsorb toxic substances in the environment.
現在、カーボンナノチューブ糸の作製方法の主流となっている非特許文献１のような乾式紡糸法を用いて作製したカーボンナノチューブ糸は、これらの用途に十分な強度を有している一方で、比表面積やキャパシタンス容量、吸着部位が不足している。 Carbon nanotube yarns produced using a dry spinning method such as Non-Patent Document 1, which is currently the mainstream of carbon nanotube yarn production methods, have sufficient strength for these applications, while There is a shortage of surface area, capacitance capacity and adsorption site.
また、例えば、非特許文献２のように、得られるカーボンナノチューブ糸の強度は高い一方で、キャパシタンス容量が３０Ｆ／ｇ未満で不足していることがわかる。 Further, for example, as in Non-Patent Document 2, it is understood that while the strength of the obtained carbon nanotube yarn is high, the capacitance capacity is insufficient at less than 30 F / g.
本発明の１つの課題は、比表面積が大きなカーボンナノチューブ撚糸体を提供する。 One object of the present invention is to provide a carbon nanotube twisted body having a large specific surface area.
本発明の一実施形態によると、長さ方向に配列した複数の帯状体を備え、前記複数の帯状体の各々は、複数のカーボンナノチューブの束が長さ方向にねじれた構造と細孔とを有する、カーボンナノチューブ撚糸体が提供される。 According to one embodiment of the present invention, the plurality of strips arranged in the longitudinal direction, each of the plurality of strips has a structure and pores in which a bundle of carbon nanotubes is twisted in the longitudinal direction. A carbon nanotube twist body is provided.
前記カーボンナノチューブ撚糸体は、ＢＪＨ法で解析される前記カーボンナノチューブ撚糸体の細孔径が２ｎｍ以上５０ｎｍ以下の範囲における積算細孔容積を０．９ｃｍ3／ｇ以上２．１ｃｍ3／ｇ以下の範囲に備える。 The carbon nanotube twisted body, the range wherein the pore diameter of the carbon nanotube twisted body a cumulative pore volume in the 50nm or less the range of 2 nm 0.9 cm 3 / g or more 2.1 cm 3 / g of the following to be analyzed by the BJH method Prepare for
前記カーボンナノチューブ撚糸体において、前記ねじれた構造は、長手方向が１０ｍｍの範囲において、１から２８００回のねじれを備えてもよい。 In the carbon nanotube twist body, the twisted structure may have 1 to 2800 twists in the range of 10 mm in the longitudinal direction.
前記カーボンナノチューブ撚糸体において、前記ねじれた構造は、前記帯状体の幅が９０ｎｍ以上１０μｍ以下を備えてもよい。 In the carbon nanotube twist body, the twisted structure may have a width of 90 nm or more and 10 μm or less of the strip.
また、本発明の一実施形態によると、前記いずれかに記載のカーボンナノチューブ撚糸体を備えるキャパシターが提供される。 Moreover, according to one embodiment of the present invention, there is provided a capacitor comprising the carbon nanotube twist body described in any of the above.
また、本発明の一実施形態によると、前記いずれかに記載のカーボンナノチューブ撚糸体を備えるフィルターが提供される。 Moreover, according to one embodiment of the present invention, there is provided a filter comprising the carbon nanotube twist body described in any of the above.
本発明によると、比表面積が大きなカーボンナノチューブ撚糸体を提供することができる。 According to the present invention, it is possible to provide a carbon nanotube twisted body having a large specific surface area.
以下、図面を参照して本発明に係るカーボンナノチューブ撚糸体について説明する。なお、本発明のカーボンナノチューブ撚糸体は、以下に示す実施の形態及び実施例の記載内容に限定して解釈されるものではない。なお、本実施の形態及び後述する実施例で参照する図面において、同一部分又は同様な機能を有する部分には同一の符号を付し、その繰り返しの説明は省略する。 Hereinafter, a carbon nanotube twist body according to the present invention will be described with reference to the drawings. In addition, the carbon nanotube twisting body of this invention is limited to the description content of embodiment shown below and an Example, and is not interpreted. Note that in the drawings referred to in this embodiment mode and the examples to be described later, the same portions or portions having similar functions are denoted by the same reference numerals, and repeated description thereof will be omitted.
図１は、本発明の一実施形態に係るカーボンナノチューブ撚糸体１０（以下、ＣＮＴ撚糸体ともいう）の模式図である。ＣＮＴ撚糸体１０は、長手方向に配列した複数の帯状体１３を備える。帯状体１３は、複数のカーボンナノチューブバンドル（以下、ＣＮＴバンドルともいう）を備えるカーボンナノチューブ集合体（以下、ＣＮＴ集合体ともいう）を含み、ＣＮＴ集合体は長手方向に配列する。複数の帯状体１３の各々は、複数のカーボンナノチューブ（以下、ＣＮＴともいう）１１の束が長さ方向にねじれた構造と細孔１５とを有する。 FIG. 1 is a schematic view of a carbon nanotube twisted body 10 (hereinafter also referred to as a CNT twisted body) according to an embodiment of the present invention. The CNT twisting body 10 is provided with a plurality of strip-shaped members 13 arranged in the longitudinal direction. The strip 13 includes a carbon nanotube assembly (hereinafter, also referred to as a CNT assembly) including a plurality of carbon nanotube bundles (hereinafter, also referred to as a CNT bundle), and the CNT assembly is aligned in the longitudinal direction. Each of the plurality of strip-shaped members 13 has a structure in which a bundle of a plurality of carbon nanotubes (hereinafter, also referred to as CNT) 11 is twisted in the length direction, and a pore 15.
ここで、ＣＮＴバンドルとは、複数のＣＮＴ１１がファンデルワールス力によって、相互に束状（バンドル化）及び縄状に凝集した集合体である。ＣＮＴ１１を製造する場合、基材表面に形成された触媒層に対して垂直又は略垂直な方向にＣＮＴ１１が成長する。隣接するＣＮＴ１１はファンデルワールス力によって、相互に結合し、配向性を有するＣＮＴ集合体を構成する。このため、ＣＮＴ集合体を解す、又は分散させる場合にも、ＣＮＴ１１を１本の単位までＣＮＴ集合体を解す又は分散させることはできず、隣接するＣＮＴ１１がファンデルワールス力によって凝集したＣＮＴバンドルを構成する。ＣＮＴ撚糸体１０は、複数のＣＮＴバンドルを備えるＣＮＴ集合体が長手方向に配列した帯状体１３を備え、複数の帯状体１３の各々は、複数のＣＮＴ１１の束が長さ方向にねじれた構造と細孔１５とを有することにより、ＣＮＴ撚糸体１０全体として大きな比表面積と物質を吸着するための無数の空隙により構成される大きな細孔容積を有する。 Here, the CNT bundle is an aggregate in which a plurality of CNTs 11 are aggregated into a bundle (bundling) and a rope shape by van der Waals' force. When manufacturing CNTs 11, CNTs 11 grow in a direction perpendicular or substantially perpendicular to the catalyst layer formed on the substrate surface. Adjacent CNTs 11 are mutually connected by van der Waal's force to form a CNT aggregate having orientation. Therefore, even when the CNT assembly is dissolved or dispersed, the CNT assembly can not be dissolved or dispersed up to one unit, and a CNT bundle in which adjacent CNTs 11 are aggregated by van der Waals force is obtained. Configure. The CNT twisting body 10 is provided with a strip 13 in which a CNT aggregate including a plurality of CNT bundles is arranged in the longitudinal direction, and each of the plurality of strips 13 has a structure in which a bundle of a plurality of CNTs 11 is twisted in the longitudinal direction By having the pores 15, the entire CNT twisting body 10 has a large specific surface area and a large pore volume constituted by innumerable voids for adsorbing a substance.
［ＣＮＴ撚糸体の比表面積］
一実施形態において、ＣＮＴ撚糸体１０は、ＢＥＴ比表面積が２００ｍ2／ｇ以上１１００ｍ2／ｇ以下の範囲を備える。ここで、ＢＥＴ比表面積とは、液体窒素温度（７７Ｋ）での窒素分子の吸着等温線からBrunauer-Emmett-Teller(BET)の方法で求めた比表面積である。ＣＮＴ１１の自体の比表面積が、理論的計算によれば、未開口のもので１３００ｍ2／ｇ程度であることから、ＣＮＴ撚糸体１０は、それに匹敵する大きなＢＥＴ比表面積を最大値として有する。一方、ＢＥＴ比表面積が２００ｍ2／ｇより小さいと、キャパシターやフィルターとして十分な機能を発揮できない。
[Specific Surface Area of CNT Twisted Yarn]
In one embodiment, the CNT twisted body 10 has a BET specific surface area in the range of 200 m 2 / g or more and 1100 m 2 / g or less. Here, the BET specific surface area is a specific surface area determined by the method of Brunauer-Emmett-Teller (BET) from the adsorption isotherm of nitrogen molecules at liquid nitrogen temperature (77 K). Since the specific surface area of the CNTs 11 themselves is about 1300 m 2 / g in the unopened one according to theoretical calculation, the CNT twisting body 10 has a comparable large BET specific surface area as the maximum value. On the other hand, if the BET specific surface area is smaller than 200 m 2 / g, it can not exhibit sufficient function as a capacitor or a filter.
［ＣＮＴ撚糸体の細孔］
一実施形態において、ＣＮＴ撚糸体１０は、ガス吸着法から求められる吸脱着等温線の相対圧が０．９５以下に相当するサイズの細孔１５が５００ｃｍ3／ｇ（ＳＴＰ）以上１３００ｃｍ3／ｇ（ＳＴＰ）以下の細孔容積を備える。ガス吸着法から求められる吸脱着等温線の相対圧が０．９５以下に相当するサイズの細孔１５は、直径が２ｎｍ以下のマイクロ孔と直径が２ｎｍを超えて５０ｎｍ以下のメソ孔を含む。一実施形態において、ＣＮＴ撚糸体１０は、マイクロ孔とメソ孔のガス吸着量の合計が５００ｃｍ3／ｇ（ＳＴＰ）以上１３００ｃｍ3／ｇ（ＳＴＰ）以下であり、ＣＮＴ撚糸体１０全体として、このような大きな細孔容積を備える。ガス吸着法から求められる吸脱着等温線の相対圧は、標準状態（０℃、１ａｔｍ）での平衡圧力／飽和蒸気圧により求めることができる。
[Pore of CNT Twisted Yarn]
In one embodiment, CNT twisting member 10, the size of the pores 15 is 500cm 3 / g (STP) or 1300 cm 3 / g relative pressure of adsorption and desorption isotherms obtained from gas adsorption method is equivalent to 0.95 (STP) with a pore volume less than or equal to The pores 15 having a size corresponding to the relative pressure of the adsorption / desorption isotherm determined by the gas adsorption method equal to or less than 0.95 include micropores having a diameter of 2 nm or less and mesopores having a diameter of more than 2 nm and 50 nm or less. In one embodiment, CNT twisted body 10 is the sum of the gas adsorption amount of micropores and mesopores 500cm 3 / g (STP) or 1300cm 3 / g (STP) hereinafter, as a whole CNT twisted body 10, the With such a large pore volume. The relative pressure of the adsorption-desorption isotherm determined from the gas adsorption method can be determined by the equilibrium pressure / saturation vapor pressure at standard conditions (0 ° C., 1 atm).
［ガス吸着法の測定精度］
液体窒素温度（７７Ｋ）での窒素吸着等温線を用いた場合、全表面積１０ｍ2に対して±０．４％の精度で、全表面積０．１ｍ2に対して±８％の精度で再現性が得られる。吸着ガスとしてＫｒを用いた場合が最も測定精度が高く、全表面積０．１ｍ2に対して±１％の精度で、全表面積５ｃｍ2に対して±８％の精度で再現性が得られる。市販の汎用装置では全表面積が５ｃｍ2以上の試料量を用いた測定が可能である。
[Measurement accuracy of gas adsorption method]
When using the nitrogen adsorption isotherm at liquid nitrogen temperature (77K), with 0.4% accuracy ± relative to the total surface area of 10 m 2, reproducible ± 8% accuracy with respect to the total surface area of 0.1 m 2 Is obtained. The measurement accuracy is highest when Kr is used as the adsorption gas, and the reproducibility is obtained with an accuracy of ± 1% with respect to the total surface area of 0.1 m 2 and with an accuracy of ± 8% with respect to the total surface area of 5 cm 2 . A commercially available general-purpose device can measure using a sample amount having a total surface area of 5 cm 2 or more.
細孔分布の解析に用いる窒素吸脱着等温線は、例えば、マイクロトラック・ベル製BELSOR seriesで測定することができる。 The nitrogen adsorption-desorption isotherm used for analysis of pore distribution can be measured, for example, with Microtrack Bell BELSOR series.
［ＢＪＨ法による細孔の評価］
また、一実施形態において、ＣＮＴ撚糸体１０は、ＢＪＨ法（Barrett-Joyner-Hallender法）で解析される細孔径が２ｎｍ以上５０ｎｍ以下の範囲において、０．９ｃｍ3／ｇ以上２．１ｃｍ3／ｇ以下の範囲に積算細孔容積を備える。２ｎｍを超えて５０ｎｍ以下のメソ孔の細孔分布は、ＢＪＨ法で窒素吸脱着等温線を解析することにより求めることができる。ＣＮＴ撚糸体１０においては、メソ孔の積算細孔容積が０．９ｃｍ3／ｇ以上２．１ｃｍ3／ｇ以下である。
[Evaluation of pores by BJH method]
Also, in one embodiment, CNT twisting member 10, BJH method in (Barrett-Joyner-Hallender method) range pore diameter to be analyzed following 50nm over 2nm by, 0.9 cm 3 / g or more 2.1 cm 3 / Integral pore volume is provided in the range of g or less. The pore distribution of mesopores of more than 2 nm and less than or equal to 50 nm can be determined by analyzing a nitrogen adsorption and desorption isotherm by the BJH method. In the CNT twisting body 10, the cumulative pore volume of mesopores is 0.9 cm 3 / g or more and 2.1 cm 3 / g or less.
［ＣＮＴ撚糸体のねじれ構造］
一実施形態において、ＣＮＴ撚糸体１０におけるねじれ構造は、長手方向に１０ｍｍの範囲に、１から２８００回のねじれを備える。ここで、ねじれは、ＣＮＴ撚糸体１０の走査型電子顕微鏡（ＳＥＭ）像において、ＣＮＴ撚糸体１０の長手方向が１０ｍｍの範囲の平均ねじれ回数値として算出される。具体的には、ＳＥＭ像に任意の直線を引き、長手方向に１０ｍｍの範囲に、図６（ｄ）に示すように、その直線と帯状体１３が交わった点の個数をカウントすることにより求めることができる。
[Twist structure of CNT twisting body]
In one embodiment, the twisted structure in the CNT twisted body 10 is provided with 1 to 2800 twists in the range of 10 mm in the longitudinal direction. Here, in the scanning electron microscope (SEM) image of the CNT twisting body 10, the twist is calculated as an average twisting number value in the range of 10 mm in the longitudinal direction of the CNT twisting body 10. Specifically, an arbitrary straight line is drawn on the SEM image, and as shown in FIG. 6D, the number is determined by counting the number of points where the straight line intersects the strip 13 in a range of 10 mm in the longitudinal direction. be able to.
［帯状体の幅］
一実施形態において、ＣＮＴ撚糸体１０におけるねじれ構造は、帯状体１３の幅が９０ｎｍ以上１０μｍ以下である。ここで、帯状体１３の幅は、ＣＮＴ撚糸体１０のＳＥＭ像において、帯状体１３の幅を測定することにより求めることができる。
[Band width]
In one embodiment, in the twisted structure in the CNT twisting body 10, the width of the band 13 is 90 nm or more and 10 μm or less. Here, the width of the strip 13 can be obtained by measuring the width of the strip 13 in the SEM image of the CNT twisting body 10.
［機械的強度］
一実施形態において、ＣＮＴ撚糸体１０を０％以上１５％以下の範囲で延伸させた際にヤング率が２０ＧＰａ以上８４ＧＰａ以下である。ＣＮＴ撚糸体１０の破断強度は、３０７ＭＰａ以上１０５４ＭＰａ以下である。ＣＮＴ撚糸体１０は、ねじれ構造を有する帯状体１３を備えることにより、十分な強度を実現することができる。
[Mechanical strength]
In one embodiment, the Young's modulus is 20 GPa or more and 84 GPa or less when the CNT twisted body 10 is stretched in the range of 0% or more and 15% or less. The breaking strength of the CNT twisting body 10 is 307 MPa or more and 1054 MPa or less. The CNT twisting body 10 can achieve sufficient strength by providing the strip 13 having a twist structure.
［キャパシタンス］
ＣＮＴ撚糸体１０は、走査速度が１０ｍＶ／ｓである時に、キャパシタンスが３０Ｆ／ｇ以上８０Ｆ／ｇ以下である。大きな比表面積と電解液のアクセスが良好な無数の空隙により構成される大きな細孔容積を備えるため、このように大きなキャパシタンスを実現することができる。
[capacitance]
The CNT twisting body 10 has a capacitance of 30 F / g to 80 F / g when the scanning speed is 10 mV / s. Such large capacitances can be realized because of the large specific surface area and the large pore volume constituted by the innumerable voids with good access of the electrolyte.
尚、キャパシタンス測定には、図２に示す様に、３ｃｍのＣＮＴ撚糸体１０を治具５１に装着して作用極ＷＥとする。治具５１には、ＣＮＴ撚糸体１０の両端を固定する２つの白金電極５３が対向して配置される。白金電極５３は、ポリイミドテープ等で保護される。また、参照電極ＲＥとして銀／塩化銀線５７が配置され、カウンター電極ＣＥとして白金箔５５を用い、０．１ｍｏｌ／Ｌの１−エチル−３−メチルイミダゾリウムテトラフルオロボラート（ＥＭＩＢＦ4）水溶液５９の中に、これらの電極を浸漬してキャパシタンス測定を実施することができる。測定条件としては参照電極に対し、作用極に−０．２Ｖから＋０．５Ｖの電圧を印加した際に、電圧の印加速度（走査電圧）および得られる電流波形、ＣＮＴ撚糸体の重量から単位重量当たりのキャパシタンスの値を算出することができる。 In addition, as shown in FIG. 2, 3 cm of CNT twisting body 10 is mounted | worn with a jig | tool 51, and it is set as the working electrode WE for capacitance measurement. In the jig 51, two platinum electrodes 53 for fixing the both ends of the CNT twisting body 10 are disposed to face each other. The platinum electrode 53 is protected by a polyimide tape or the like. In addition, a silver / silver chloride wire 57 is disposed as a reference electrode RE, and a platinum foil 55 is used as a counter electrode CE, and a 0.1 mol / L 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4 ) aqueous solution These electrodes can be immersed in 59 to perform capacitance measurements. As the measurement conditions, when a voltage of -0.2 V to +0.5 V is applied to the working electrode with respect to the reference electrode, the application speed (scanning voltage) of the voltage and the obtained current waveform, the weight of the CNT twisting body to unit weight The value of the per-capacitance can be calculated.
［ＣＮＴ］
本発明に係るＣＮＴ撚糸体１０を構成するＣＮＴとしては、単層、二層又は多層のＣＮＴを用いることができる。例えば、国際公開第２００６／０１１６５５号に記載された方法（スーパーグロース法：ＳＧ）で作製した単層カーボンナノチューブや、改良直噴熱分解合成法（enhanced Direct Injection Pyrolytic Synthesis method：ｅＤｉｐｓ）で作製した単層カーボンナノチューブを好適に用いることができるが、これらに限定されるものではない。
[CNT]
As a CNT which comprises the CNT twisting body 10 which concerns on this invention, CNT of single layer, two layers, or multiple layers can be used. For example, single-walled carbon nanotubes prepared by the method (super growth method: SG) described in WO 2006/011655, or prepared by the improved Direct Injection Pyrolytic Synthesis method (eDips) Although single-walled carbon nanotubes can be suitably used, it is not limited thereto.
高比表面積を有するＣＮＴほど、比表面積の高いＣＮＴ撚糸体１０を得るのに好適である。ＣＮＴ自身の比表面積は、ＣＮＴの層数や結晶性に依存し、単層ＣＮＴが最も比表面積が高く、層数が多くなるほど比表面積は低くなる。単層ＣＮＴであっても、合成方法やＣＮＴの結晶性、長さによってＣＮＴ撚糸体１０の比表面積は異なる。 The higher the specific surface area of the CNT, the more preferable it is to obtain a CNT twisting body 10 having a high specific surface area. The specific surface area of the CNT itself depends on the number of layers and crystallinity of the CNT, and the single-walled CNT has the highest specific surface area, and the larger the number of layers, the lower the specific surface area. Even in the single-walled CNT, the specific surface area of the CNT twisted body 10 varies depending on the synthesis method, the crystallinity of the CNT, and the length.
単層ＣＮＴの比表面積は、６００ｍ2／ｇ以上１５００ｍ2／ｇ以下、好ましくは８００ｍ2／ｇ以上１５００ｍ2／ｇ以下、より好ましくは１０００ｍ2／ｇ以上１５００ｍ2／ｇ以下である。 The specific surface area of the single-walled CNT is 600 m 2 / g or more and 1500 m 2 / g or less, preferably 800 m 2 / g or more and 1500 m 2 / g or less, more preferably 1000 m 2 / g or more and 1500 m 2 / g or less.
［ＣＮＴ長さ］
ＣＮＴの長さは、０．１μｍ以上５００μｍ以下、より好ましくは０．５μｍ以上１ｍｍ以下、さらに好ましくは１μｍ以上１０ｍｍ以下である。このようなＣＮＴは優れた変形能を有し、ＣＮＴがたわみやすいために、ＣＮＴ同士の結合による比表面積のロスが起こりにくいため、高比表面積の糸構造体を得るのに好適である。
[CNT length]
The length of the CNT is 0.1 μm or more and 500 μm or less, more preferably 0.5 μm or more and 1 mm or less, and further preferably 1 μm or more and 10 mm or less. Such CNTs have excellent deformability, and because the CNTs are flexible, loss of the specific surface area due to the bonding of the CNTs is unlikely to occur, and thus they are suitable for obtaining a high specific surface area yarn structure.
［ＣＮＴ撚糸体の製造方法］
本発明に係るＣＮＴ撚糸体の製造方法の一実施形態としては、例えば、ＣＮＴを溶媒へ分散させるＣＮＴ分散液の製造工程、得られたＣＮＴ分散液を凝固浴へ注入し、ＣＮＴバンドルを凝集させ、湿潤下にてＣＮＴ糸の形状を得るＣＮＴ紡糸体の製造工程、乾燥時に延伸しＣＮＴ糸を得るＣＮＴ撚糸体の製造工程を含む工程で構成される。
[Method of producing CNT twisted yarn]
In one embodiment of the method for producing a CNT twisted body according to the present invention, for example, a production process of a CNT dispersion in which CNTs are dispersed in a solvent, the obtained CNT dispersion is injected into a coagulation bath to aggregate CNT bundles. The method comprises the steps of manufacturing a CNT spinner which obtains the shape of a CNT yarn under wet conditions, and manufacturing a CNT twisted body which is stretched at the time of drying to obtain a CNT yarn.
ＣＮＴ分散液の製造工程としては、界面活性剤を用いてＣＮＴを分散させる工程であり、ＣＮＴと界面活性剤を水に加え、ＣＮＴを分散させる。分散工程としては、予備分散と本分散を行うことが好ましい。分散時に用いる界面活性剤としては、例えば、ノニオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤のいずれを使用しても良い。 The step of producing the CNT dispersion liquid is a step of dispersing CNTs using a surfactant, and the CNTs and the surfactant are added to water to disperse the CNTs. In the dispersing step, it is preferable to perform preliminary dispersion and main dispersion. As surfactant used at the time of dispersion | distribution, you may use any of nonionic surfactant, anionic surfactant, cationic surfactant, and amphoteric surfactant, for example.
分散時に用いる界面活性剤としては、好ましくは、アニオン界面活性剤であり、アニオン界面活性剤の種類としてはアルキルベンゼンスルホン酸塩（例えば、ドデシルベンゼンスルホン酸ナトリウム等）、アルキルアルコール硫酸エステル塩（例えば、ドデシル硫酸ナトリウム等）、アルキルジフェニルエーテルジスルホン酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸エステルナトリウム、ジアルキルスルホコハク酸ナトリウム、アルキルアリルスルホコハク酸ナトリウム、Ｎ−ラウロイルサルコシンナトリウム、ポリオキシエチレンアルキルフェニルエーテル硫酸エステルナトリウム、（メタ）アクリロイルポリオキシアルキレン硫酸エステルナトリウム、アルキルアルコールリン酸エステル塩、胆汁酸塩（例えばコール酸ナトリウム、デオキシコール酸ナトリウム、ヒオデオキシコール酸ナトリウム、グリココール酸ナトリウム、グリコデオキシコール酸ナトリウム、タウロコール酸ナトリウム及びタウロデオキシコール酸ナトリウム）からなる群から選択される界面活性剤の1つ以上を用いることができる。より好ましくは胆汁酸塩、特にタウロデオキシコール酸塩を用いることができる。 The surfactant used at the time of dispersion is preferably an anionic surfactant, and as the type of anionic surfactant, alkylbenzene sulfonate (eg, sodium dodecylbenzene sulfonate etc.), alkyl alcohol sulfate ester salt (eg, Sodium dodecyl sulfate), sodium alkyl diphenyl ether disulfonate, sodium sodium polyoxyethylene alkyl ether sulfate, sodium dialkyl sulfosuccinate, sodium alkyl allyl sulfosuccinate, sodium N-lauroyl sarcosine, sodium polyoxyethylene alkyl phenyl ether sulfate ( ) Acryloyl polyoxyalkylene sulfate sodium ester, alkyl alcohol phosphate ester salt, bile salt (eg cholate) Using one or more of the surfactants selected from the group consisting of sodium deoxycholate, sodium hypodeoxycholate, sodium glycocholate, sodium glycodeoxycholate, sodium taurocholate and sodium taurodeoxycholate). be able to. More preferably, bile salts, in particular taurodeoxycholate can be used.
予備分散には、例えば、超音波攪拌装置や攪拌装置を用いることができる。また、本分散には、例えば、超音波ホモジナイザー、せん断力をかけて分散させるジェットミル装置や湿式微粒化装置を用いることができる。 For the preliminary dispersion, for example, an ultrasonic stirring device or a stirring device can be used. Further, for the main dispersion, for example, an ultrasonic homogenizer, a jet mill apparatus for dispersing by applying a shear force, or a wet atomization apparatus can be used.
ＣＮＴ紡糸体の製造工程としてはＣＮＴ分散液を注入ノズルから凝固浴へ注入し、ＣＮＴバンドルを凝集させることにより、ＣＮＴ紡糸体を得る。 In the production process of the CNT spinner, the CNT dispersion is injected from the injection nozzle into the coagulation bath, and the CNT bundle is coagulated to obtain the CNT spinner.
凝固浴としては、例えば、有機用溶媒や塩水水溶液などが挙げられる。凝固浴中の有機溶媒としては、水と混和する有機溶媒が好ましく、例えば、エタノール、メタノール、プロパノール及びイソプロパノール（ＩＰＡ）等の低級アルコール、アセトン、メチルエチルケトン及び４−メチル−２−ペンタノン(ＭＩＢＫ)などのケトン類、テトラヒドロフラン及びジオキサンなどのエーテル類、（Ｎ，Ｎ−ジメチルホルムアミド）ＤＭＦ、アセトアミド、ホルムアミド、ジメチルアセトアミド及びＮ−メチルピロリドンなどのアミド類、エチレングリコール、プロピレングリコール、ジエチレングリコール及びジプロピレングリコールなどのグリコール類、エチレングリコールモノメチルエーテル及びエチレングリコールモノエチルエーテルなどのアルキレングリコールモノアルキルエーテル、グリセリン、ジメチルスルホキシド、アセトニトリルからなる群から選択される有機溶媒が挙げられる。凝固浴の有機溶媒としては含水有機溶媒が好ましい。また、混合した上記の２種以上の有機溶媒であっても良い。凝固浴の温度は５〜５０℃程度、好ましくは室温程度の温度であればよい。吐出されたＣＮＴ紡糸体はすぐに次の水への浸漬工程に供してもよく、１分以上、例えば５分以上凝固浴中に維持してもよい。 Examples of the coagulation bath include organic solvents and aqueous saline solutions. The organic solvent in the coagulation bath is preferably an organic solvent miscible with water, such as lower alcohols such as ethanol, methanol, propanol and isopropanol (IPA), acetone, methyl ethyl ketone and 4-methyl-2-pentanone (MIBK) Ketones, ethers such as tetrahydrofuran and dioxane, (N, N-dimethylformamide) DMF, acetamide, amides such as formamide, dimethylacetamide and N-methylpyrrolidone, ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, etc. Glycols, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, glycerin, Sulfoxides include organic solvent selected from the group consisting of acetonitrile. As an organic solvent of a coagulation bath, a water-containing organic solvent is preferable. In addition, the above two or more organic solvents may be mixed. The temperature of the coagulation bath may be about 5 to 50 ° C., preferably about room temperature. The discharged CNT spinning body may be immediately subjected to the next water immersion step, or may be maintained in the coagulation bath for 1 minute or more, for example 5 minutes or more.
分散液及び凝固浴いずれの溶媒としても、水を用いてもよい。その場合、分散液と凝固浴のいずれか一方又は両方に塩類を添加する。分散液と凝固浴の両方に塩類が含まれない場合、紡糸体（紡糸原糸）を得ることができない。塩類は無機塩及び有機塩のいずれでもよいが、無機塩類が好ましい。なお、塩類は水溶性である。一実施形態において、塩類としては、アルカリ金属塩又はアルカリ土類金属塩が好ましく、より好ましくはナトリウム塩、カリウム塩、リチウム塩、カルシウム塩、マグネシウム塩、バリウム塩又はストロンチウム塩が挙げられ、さらに好ましくはナトリウム塩、カルシウム塩又はマグネシウム塩が挙げられる。塩類のアニオンとしては、例えば、塩素イオン、フッ素イオン、臭素イオン、ヨウ素イオン、硫酸イオン、亜硫酸イオン、リン酸イオン、硝酸イオン、亜硝酸イオン、メタンスルホン酸イオン、ベンゼンスルホン酸イオン、トルエンスルホン酸イオン、クエン酸イオン、シュウ酸イオン、リンゴ酸イオン、酒石酸イオン、マレイン酸イオン、フマル酸イオン及び酢酸イオンからなる群から選択されるアニオンが挙げられる。 Water may be used as a solvent for either the dispersion liquid or the coagulation bath. In that case, salts are added to either or both of the dispersion and the coagulation bath. If both the dispersion and the coagulation bath do not contain salts, it is not possible to obtain a spun body (spun raw yarn). The salts may be either inorganic salts or organic salts, but inorganic salts are preferred. The salts are water soluble. In one embodiment, the salts are preferably alkali metal salts or alkaline earth metal salts, more preferably sodium salts, potassium salts, lithium salts, calcium salts, magnesium salts, barium salts or strontium salts, and more preferably Include sodium salts, calcium salts or magnesium salts. As the anion of salts, for example, chloride ion, fluoride ion, bromide ion, iodide ion, sulfate ion, sulfite ion, sulfite ion, phosphate ion, nitrate ion, nitrite ion, methanesulfonate ion, benzenesulfonate ion, toluenesulfonate And anions selected from the group consisting of ions, citrate ions, oxalate ions, malate ions, tartrate ions, maleate ions, fumarate ions and acetate ions.
一実施形態において、好ましい塩類としては、例えば、塩化ナトリウム、塩化カリウム、塩化リチウム、塩化カルシウム、塩化マグネシウム、臭化ナトリウム、臭化カリウム、臭化カルシウム、臭化マグネシウム、硫酸ナトリウム、硫酸カリウム、硝酸ナトリウム、硝酸カリウム、硝酸カルシウム、硝酸マグネシウム、リン酸ナトリウム、リン酸一水素二ナトリウム、リン酸二水素一ナトリウム、リン酸カリウム、リン酸一水素二カリウム及びリン酸二水素一カリウムからなる群から選択される塩類が挙げられる。 In one embodiment, preferred salts are, for example, sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, sodium bromide, potassium bromide, calcium bromide, magnesium bromide, magnesium bromide, sodium sulfate, potassium sulfate, nitrate Selected from the group consisting of sodium, potassium nitrate, calcium nitrate, magnesium nitrate, sodium phosphate, disodium monohydrogen phosphate, monosodium dihydrogen phosphate, potassium phosphate, dipotassium monohydrogen phosphate and monopotassium dihydrogen phosphate Salts are included.
一実施形態において、塩類の濃度は、例えば、分散液中では０質量％〜２５質量％程度、好ましくは０質量％〜２０質量％程度であり、凝固浴中では０質量％〜４０質量％程度、好ましくは０質量％〜３５質量％程度である。塩類は単独、あるいは２種以上の塩類を組み合わせて分散液及び／又は凝固浴に溶解される。凝固浴又は分散液中に塩類が含まれるので、分散液を吐出後の凝固浴には塩類が含まれる。分散液を吐出後の凝固浴中の塩類濃度は０．５質量％〜４０質量％程度、好ましくは１質量％〜３５質量％程度である。塩類は、分散液のみ又は凝固液のみに含まれていてもよいので、分散液又は凝固液の塩類濃度の下限は各々０質量％であるが、塩類を含む分散液又は凝固液の塩類濃度の下限は、０．５質量％程度、好ましくは１質量％程度であり、上限は、４０質量％程度、好ましくは３５質量％程度である。 In one embodiment, the concentration of the salt is, for example, about 0% by mass to about 25% by mass, preferably about 0% by mass to about 20% by mass in the dispersion, and about 0% by mass to about 40% by mass in the coagulation bath Preferably, it is about 0% by mass to 35% by mass. The salts may be dissolved alone or in combination of two or more salts in the dispersion and / or coagulation bath. Since the coagulation bath or the dispersion contains salts, the coagulation bath after discharging the dispersion contains salts. The salt concentration in the coagulation bath after discharging the dispersion is about 0.5 mass% to 40 mass%, preferably about 1 mass% to 35 mass%. Since the salts may be contained only in the dispersion or in the coagulating liquid, the lower limit of the salt concentration of the dispersion or coagulating liquid is 0% by mass, but the salt concentration of the dispersion or coagulating liquid containing salts is The lower limit is about 0.5% by mass, preferably about 1% by mass, and the upper limit is about 40% by mass, preferably about 35% by mass.
得られたＣＮＴ紡糸体を水に浸漬し、溶媒を水に置換する。 The obtained spun CNTs are immersed in water, and the solvent is replaced with water.
ＣＮＴ撚糸体の製造工程としては、例えば、ＣＮＴ紡糸体を乾燥時に、荷重をかけて乾燥させ延伸する工程であり、本製造工程を行う事により、ＣＮＴ同士の結合力を用い適切な密度を有するＣＮＴ撚糸体を製造することができる。本製造工程は水に浸漬したＣＮＴ紡糸体を有機溶媒に一度浸漬した後に、本製造工程を実施することも可能である。 A step of manufacturing a CNT twisted body is, for example, a step of drying and stretching a spun CNT body under load, and performing this manufacturing step to have an appropriate density using the bonding strength between CNTs. A CNT twisted body can be manufactured. It is also possible to carry out the present production step after the CNT spun body soaked in water is once dipped in an organic solvent.
上述した本発明に係るＣＮＴ撚糸体は、キャパシターやフィルターに適用することができる。図３（ａ）は、本発明の一実施形態に係るＣＮＴ撚糸体１０を編み込んで作製したキャパシター１００の一例を示す模式図である。キャパシター１００は、ＣＮＴ撚糸体１０で構成された一対の電極膜１０１を有し、２枚の電極膜１０１は、電解質膜１０３を介して対向するように配置される。また、一対の電極膜１０１を電解質膜液に浸して、キャパシター１００を構成してもよい。電極膜１０１として、ＣＮＴ撚糸体１０を１本又は複数本合わせた織物状もしくは膜状の部材、又は図３（ｂ）に示したようなＣＮＴ撚糸体１０を編み込んだ織物状の部材を用いることができる。なお、電解質膜液および電解質膜には、公知の材料を用いることができるため、詳細な説明は省略する。 The CNT twisting body according to the present invention described above can be applied to a capacitor or a filter. Fig.3 (a) is a schematic diagram which shows an example of the capacitor 100 produced by knitting in the CNT twisting body 10 which concerns on one Embodiment of this invention. The capacitor 100 has a pair of electrode films 101 formed of the CNT twisting body 10, and the two electrode films 101 are disposed to face each other through the electrolyte film 103. Alternatively, the capacitor 100 may be configured by immersing the pair of electrode films 101 in an electrolyte film solution. As the electrode film 101, a fabric-like or film-like member in which one or a plurality of CNT twisted yarns 10 are combined, or a woven-like member in which the CNT twisted yarns 10 as illustrated in FIG. Can. In addition, since a well-known material can be used for electrolyte membrane liquid and an electrolyte membrane, detailed description is abbreviate | omitted.
図３（ｃ）は、本発明の一実施形態に係るＣＮＴ撚糸体１０を編み込んで作製したフィルター２００の一例を示す模式図である。フィルター２００としては、ＣＮＴ撚糸体１０を１本から複数本、一方向に配列させた部材、又はＣＮＴ撚糸体１０を編み込んだ部材を用いることができる。フィルター２００は、気体成分、液体成分又は固形成分を吸着することができる。 FIG.3 (c) is a schematic diagram which shows an example of the filter 200 which weaved and produced the CNT twisting body 10 which concerns on one Embodiment of this invention. As the filter 200, a member in which one to a plurality of CNT twisted yarns 10 are arranged in one direction, or a member in which the CNT twisted yarns 10 are woven can be used. The filter 200 can adsorb gas components, liquid components or solid components.
以下、図面を参照して本発明に係るＣＮＴ撚糸体の実施例について説明する。なお、本発明のＣＮＴ撚糸体は、以下の実施例の記載内容に限定して解釈されるものではない。 Hereinafter, with reference to the drawings, an embodiment of a CNT twisting body according to the present invention will be described. In addition, the CNT twisting body of this invention is limited to the description content of the following example, and is not interpreted.
（実施例１）
実施例１として、スーパーグロース法により製造された単層ＣＮＴ（以下、ＳＧとも記述する） ５０ｍｇとＴＤＯＣ ４５０ｍｇを２４．５ｇの水に加え、超音波攪拌装置（株式会社日本精機製作所製、ＵＳＳ−１）を用いて予備分散した。その後、超音波ホモジナイザー（株式会社日本精機製作所製、ＵＳ−５０）を用いて、超音波照射３０分間の条件で本分散を行うことで実施例１のＣＮＴ分散液を得た。
Example 1
As Example 1, 50 mg of single layer CNT (hereinafter also described as SG) manufactured by the super growth method and 450 mg of TDOC were added to 24.5 g of water, and an ultrasonic stirrer (made by Nippon Seiki Co., Ltd., USS-) Predispersed using 1). Then, using the ultrasonic homogenizer (manufactured by Nippon Seiki Co., Ltd., US-50), the CNT dispersion liquid of Example 1 was obtained by performing the main dispersion under the conditions of ultrasonic irradiation for 30 minutes.
実施例１のＣＮＴ分散液を注入ノズル（内径１．２５ｍｍ）から１００ｍＬのイソプロピルアルコール（ＩＰＡ）を満たしたシャーレに注入し、ＣＮＴを凝集させ、実施例１のＣＮＴ紡糸体を作製した。 The CNT dispersion liquid of Example 1 was injected from an injection nozzle (inner diameter 1.25 mm) into a petri dish filled with 100 mL of isopropyl alcohol (IPA) to aggregate CNTs, and a CNT spun body of Example 1 was produced.
実施例１のＣＮＴ紡糸体をＩＰＡ中にて１日間放置した後、水に置換し３日以上浸漬した。水中から取り出した実施例１のＣＮＴ紡糸体の両端を治具に固定し、延伸装置を用い片端を駆動させることより荷重をかけて乾燥し、実施例１のＣＮＴ撚糸体を得た。 After leaving the spun CNTs of Example 1 in IPA for 1 day, it was replaced with water and immersed for 3 days or more. The both ends of the spun CNT product of Example 1 taken out from water were fixed to a jig and dried by applying a load by driving one end using a stretching apparatus to obtain a CNT twisted body of Example 1.
［ＣＮＴ紡糸体及びＣＮＴ撚糸体の幅の評価］
ＩＰＡへ注入直後の実施例１のＣＮＴ紡糸体の写真を図４に示す。画像解析ソフト（三谷商事社製、ｗｉｎＲＯＯＦ）を用い、図４より、実施例１のＣＮＴ紡糸体の幅を測定した。また、実施例１のＣＮＴ撚糸体についてハイスピードカメラ（株式会社キーエンス社製、ＶＷ−６００Ｃ）を用いて画像を取り込み、ハイスピードマイクロスコープ（株式会社キーエンス社製、ＶＷ−９０００）を用い、取り込んだ画像から実施例１のＣＮＴ撚糸体の幅を測定した。
[Evaluation of widths of spun CNTs and twisted CNTs]
A photograph of the spun CNTs of Example 1 immediately after injection into IPA is shown in FIG. The width of the spun CNTs of Example 1 was measured from FIG. 4 using an image analysis software (winROOF manufactured by Mitani Corporation). In addition, an image is captured using the high speed camera (VW-600C manufactured by Keyence Corporation) for the CNT twisting body of Example 1, and captured using the high speed microscope (VW-9000 manufactured by Keyence Corporation) The width of the CNT twisting body of Example 1 was measured from the base image.
［ヤング率、破断強度］
熱・応力・歪測定装置（Ｓｅｉｋｏ Ｉｎｓｔｒｕｍｅｎｔｓ Ｉｎｃ．社製、ＴＭＡ／ＳＳ６０００）を用い、実施例１のＣＮＴ撚糸体のヤング率及び破断強度を測定した。
[Young's modulus, breaking strength]
The Young's modulus and breaking strength of the CNT twisting body of Example 1 were measured using a heat / stress / strain measurement device (manufactured by Seiko Instruments Inc., TMA / SS6000).
表１に実施例１のＣＮＴ紡糸体及びＣＮＴ撚糸体の平均幅、ＣＮＴ撚糸体の幅に対するＣＮＴ紡糸体の幅の割合、ＣＮＴ撚糸体のヤング率及びＣＮＴ撚糸体の破断強度の値を示す。 Table 1 shows the average widths of the CNT spun yarn and the CNT twisted yarn of Example 1, the ratio of the width of the CNT spun yarn to the width of the CNT twisted yarn, the Young's modulus of the CNT twisted yarn and the breaking strength of the CNT twisted yarn.
表１より、ＣＮＴ撚糸体の幅が、ＣＮＴ紡糸体の幅に比べて著しく小さい(１０分の１未満)ことが明らかとなった。これは分散液中のＣＮＴ同士の凝集力が大きいこと、分散によるＣＮＴのダメージを最小限にとどめ、水中に均一に分散させていること、乾燥時に収縮が起こることを示しており、本実施例において、特性が良好なＣＮＴ撚糸体を得るために必要な一つの指標となることが明らかである。また、表１より実施例１のＣＮＴ撚糸体のヤング率及び破断強度の値は高く強度に優れた撚糸体であることが明らかとなった。 From Table 1, it became clear that the width of the CNT twisted body is extremely small (less than one tenth) as compared with the width of the CNT spun body. This indicates that the cohesion of the CNTs in the dispersion is large, the damage of the CNTs due to the dispersion is minimized, the particles are uniformly dispersed in water, and shrinkage occurs upon drying. In the above, it is clear that the characteristic is one indicator necessary to obtain a good CNT twisted body. Moreover, it became clear from Table 1 that the values of the Young's modulus and breaking strength of the CNT twisted yarn of Example 1 are high and the yarn is excellent in strength.
（実施例２）
実施例１においては、スーパーグロース法により製造された単層ＣＮＴを用いたが、実施例２においては、ｅＤｉｐｓ法により製造された単層ＣＮＴを用いた例を示す。ｅＤｉｐｓ法により製造された単層ＣＮＴ（株式会社名城ナノカーボン社製、ＥＣ１．４、以下、ｅＤｉｐｓと記述する） ５０ｍｇとＴＤＯＣ ４５０ｍｇを２４．５ｇの水に加え、超音波攪拌装置（株式会社日本精機製作所製、ＵＳＳ−１）を用いて予備分散した。その後、超音波ホモジナイザー（株式会社日本精機製作所製、ＵＳ−５０）を用いて、超音波照射３０分間の条件で本分散を行うことで実施例２のＣＮＴ分散液を得た。
(Example 2)
In Example 1, single-walled CNT manufactured by the super growth method was used, but in Example 2, an example using single-walled CNT manufactured by the eDips method is shown. 50 mg of single-layer CNT (manufactured by Meijo Nano Carbon Co., Ltd., EC 1.4, hereinafter referred to as eDips) manufactured by the eDips method and 450 mg of TDOC are added to 24.5 g of water, and an ultrasonic stirrer (Japan Co., Ltd.) It predispersed using Seiki Seisakusho make, USS-1). Thereafter, main dispersion was performed under the conditions of ultrasonic irradiation for 30 minutes using an ultrasonic homogenizer (US-50, manufactured by Nippon Seiki Co., Ltd.) to obtain a CNT dispersion liquid of Example 2.
実施例２のＣＮＴ分散液を注入ノズル（内径１．２５ｍｍ）から１００ｍＬのＩＰＡを満たしたシャーレに注入し、ＣＮＴを凝集させ、実施例２のＣＮＴ紡糸体を作製した。 The CNT dispersion liquid of Example 2 was injected from an injection nozzle (inner diameter 1.25 mm) into a petri dish filled with 100 mL of IPA to aggregate CNTs, and a CNT spun body of Example 2 was produced.
実施例２のＣＮＴ紡糸体をＩＰＡ中にて１日間放置した後、水に置換し３日以上浸漬した。水中から取り出した実施例２のＣＮＴ紡糸体の、両端を治具に固定し、延伸装置を用い片端を駆動させることより荷重をかけて乾燥し、実施例２のＣＮＴ撚糸体を得た。 After leaving the spun CNTs of Example 2 in IPA for 1 day, they were replaced with water and immersed for 3 days or more. The both ends of the CNT spinning body of Example 2 taken out from water were fixed to a jig and a load was applied by driving one end using a stretching apparatus to dry, thereby obtaining a CNT twisted body of Example 2.
［ＣＮＴ紡糸体及びＣＮＴ撚糸体の幅の評価］
ＩＰＡへ注入直後の実施例２のＣＮＴ紡糸体の写真を図５に示す。画像解析ソフト（三谷商事社製ｗｉｎＲＯＯＦ）を用い、図５を用い、実施例２のＣＮＴ紡糸体の幅を測定した。また、実施例２のＣＮＴ撚糸体についてハイスピードカメラ（株式会社キーエンス社製、ＶＷ−６００Ｃ）を用いて画像を取り込み、ハイスピードマイクロスコープ（株式会社キーエンス社製、ＶＷ−９０００）を用い、取り込んだ画像から実施例２のＣＮＴ撚糸体の幅を測定した。
[Evaluation of widths of spun CNTs and twisted CNTs]
A photograph of the spun CNTs of Example 2 immediately after injection into IPA is shown in FIG. Using the image analysis software (winROOF manufactured by Mitani Corporation), the width of the spun CNTs of Example 2 was measured using FIG. In addition, an image is captured using a high speed camera (VW-600C manufactured by Keyence Corporation) for the CNT twisting body of Example 2, and captured using a high speed microscope (VW-9000 manufactured by Keyence Corporation) The width of the CNT twisting body of Example 2 was measured from the base image.
［ヤング率、破断強度］
熱・応力・歪測定装置（Ｓｅｉｋｏ Ｉｎｓｔｒｕｍｅｎｔｓ Ｉｎｃ社製、ＴＭＡ／ＳＳ ６０００）を用い、実施例２のＣＮＴ撚糸体のヤング率及び破断強度を測定した。
[Young's modulus, breaking strength]
The Young's modulus and breaking strength of the CNT twisting body of Example 2 were measured using a heat / stress / strain measurement device (manufactured by Seiko Instruments Inc., TMA / SS 6000).
表２に実施例２のＣＮＴ紡糸体及びＣＮＴ撚糸体の平均幅、ＣＮＴ撚糸体の幅に対するＣＮＴ撚糸体の幅の割合、ＣＮＴ撚糸体のヤング率及びＣＮＴ撚糸体の破断強度の値を示す。 Table 2 shows the average widths of the CNT spun yarn and the CNT twisted yarn of Example 2, the ratio of the width of the CNT twisted yarn to the width of the CNT twisted yarn, the Young's modulus of the CNT twisted yarn and the breaking strength of the CNT twisted yarn.
表２よりＣＮＴ撚糸体の幅が、ＣＮＴ紡糸体の幅に比べて著しく小さい(６分の１未満)ことが明らかとなった。これは、分散液中のＣＮＴ同士の凝集力が大きいこと、分散によるＣＮＴのダメージを最小限にとどめ、水中に均一に分散させていること、乾燥時に収縮が起こることを示しており、本実施例において、特性が良好なＣＮＴ撚糸体を得るために必要な一つの指標となることが明らかである。また、表２より実施例２のＣＮＴ撚糸体のヤング率及び破断強度の値は高く、強度に優れた撚糸体であることが明らかとなった。 It is clear from Table 2 that the width of the CNT twisted body is extremely small (less than one-sixth) as compared with the width of the CNT spun body. This indicates that the cohesion of the CNTs in the dispersion is large, the damage of the CNTs due to the dispersion is minimized, the particles are uniformly dispersed in water, and shrinkage occurs upon drying. In the example, it is clear that the characteristic is one indicator necessary to obtain a good CNT strand. Moreover, it became clear from Table 2 that the values of Young's modulus and breaking strength of the CNT twisted yarn of Example 2 are high, and the twisted yarn is excellent in strength.
［表面構造の評価、ガス吸着量、細孔分布、比表面積測定、キャパシタンス測定］
実施例１のＣＮＴ撚糸体について、表面構造の評価、ガス吸着量、細孔分布、比表面積測定、キャパシタンス測定を実施した。
[Evaluation of surface structure, gas adsorption amount, pore distribution, specific surface area measurement, capacitance measurement]
Evaluation of surface structure, gas adsorption amount, pore distribution, specific surface area measurement, and capacitance measurement were carried out for the CNT twisting body of Example 1.
実施例１のＣＮＴ撚糸体の表面構造は、走査型電子顕微鏡（日本電子株式会社、ＪＳＭ−６５１０）による観察像を元に画像解析ソフト（三谷商事社製、ｗｉｎＲＯＯＦ）を用い、ＣＮＴ撚糸体を形成する帯状体の幅の範囲及び平均ねじれ回数を測定した。図６（ａ）〜図６（ｃ）は、実施例１のＣＮＴ撚糸体のＳＥＭ像である。ねじれ回数のカウント法の一例として、図６（ａ）〜図６（ｃ）に示すように実施例１のＣＮＴ撚糸体の観察像において、任意の直線を引き、図６（ｄ）に示すように、その直線と帯状体が交わった点の個数をカウントし１０ｍｍ当たりの平均ねじれ回数値を算出した。 The surface structure of the CNT twisted yarn of Example 1 uses the image analysis software (winROOF manufactured by Mitani Corp.) based on the observation image by a scanning electron microscope (Nippon Denshi Co., Ltd., JSM-6510). The range of width of the formed band and the average number of twists were measured. 6 (a) to 6 (c) are SEM images of the CNT twisting body of Example 1. FIG. As shown in FIGS. 6 (a) to 6 (c), an arbitrary straight line is drawn on the observation image of the CNT twisting body of Example 1 as shown in FIGS. 6 (a) to 6 (c) as shown in FIG. 6 (d). Then, the number of points at which the straight line intersected with the strip was counted to calculate an average number of twists per 10 mm.
高精度ガス／蒸気吸着量測定装置（マイクロトラック・ベル株式会社製、ＢＥＬＳＯＲＰＭＡＸ）を用い、実施例１のＣＮＴ撚糸体のガス吸着量、細孔分布、比表面積を測定した。吸着ガスとして不活性ガスである窒素ガスを使用し、相対圧の変化に対するガス吸着量変化を測定することで得られた吸脱着等温線から、相対圧０．９５以下に相当するメソ孔とマイクロ孔のガス吸着量を求めた。 The gas adsorption amount, pore distribution, and specific surface area of the CNT twisting body of Example 1 were measured using a high-precision gas / vapor adsorption amount measuring device (BELSORPMAX, manufactured by Microtrac Bell Inc.). From the adsorption and desorption isotherm obtained by using nitrogen gas which is an inert gas as the adsorption gas and measuring the change in gas adsorption amount with respect to the change in relative pressure, mesopores and micropores corresponding to a relative pressure of 0.95 or less The gas adsorption amount of the holes was determined.
ＢＪＨ法で吸脱着等温線を解析することで実施例１のＣＮＴ撚糸体の細孔分布を求め、細孔径２ｎｍから５０ｎｍのメソ孔の積算細孔容積を求めた。また吸脱着等温線をＢＥＴ法で解析することで実施例１のＣＮＴ撚糸体ＢＥＴ比表面積を求めた。 The pore distribution of the CNT twisting body of Example 1 was determined by analyzing the adsorption / desorption isotherm by the BJH method, and the integrated pore volume of mesopores with a pore diameter of 2 nm to 50 nm was determined. Further, by analyzing the adsorption / desorption isotherm by the BET method, the CNT twisted body BET specific surface area of Example 1 was determined.
実施例１のＣＮＴ撚糸体のキャパシタンスは、０．１ｍｏｌ／Ｌ １−エチル−３−メチルイミダゾリウムテトラフルオロボラート（ＥＭＩＢＦ4）水溶液中にて、走査速度を１０ｍＶ／ｓ、２０ｍＶ／ｓ、５０ｍＶ／ｓ、１００ｍＶ／ｓの条件でＡｇ／ＡｇＣｌ線に対して−０．２Ｖ〜＋０．５Ｖの電圧を印加することによりキャパシタンス波形を得た。得られた数値を用い、実施例１のＣＮＴ撚糸体の重量から単位重量当たりのキャパシタンスの値を算出した。 The capacitance of the CNT twisted body of Example 1 is 10 mV / s, 20 mV / s, 50 mV at a scanning speed of 0.1 mol / L in 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4 ) aqueous solution. A capacitance waveform was obtained by applying a voltage of -0.2 V to +0.5 V with respect to the Ag / AgCl line under the conditions of 100 mV / s / s. The value of the capacitance per unit weight was calculated from the weight of the CNT twisting body of Example 1 using the obtained numerical values.
実施例２のＣＮＴ撚糸体について、実施例１と同様の評価手法で表面構造の評価、表面構造の評価、ガス吸着量、細孔分布、比表面積測定、キャパシタンス測定を実施した。 Evaluation of the surface structure, evaluation of the surface structure, gas adsorption amount, pore distribution, specific surface area measurement, and capacitance measurement were performed on the CNT twisted body of Example 2 by the same evaluation method as in Example 1.
(比較例１)
比較例１として、乾式紡糸法の多層ＣＮＴ撚糸体（村田機械株式会社製）について、実施例１と同様の評価手法で表面構造の評価、表面構造の評価、ガス吸着量、細孔分布、比表面積測定及びキャパシタンス測定を実施した。多層ＣＮＴ撚糸体のＳＥＭ像を図７（図７（ａ）倍率１０００、図７（ｂ）倍率１０，０００）に示す。
(Comparative example 1)
As Comparative Example 1, evaluation of surface structure, evaluation of surface structure, amount of adsorbed gas, distribution of pores, ratio with the same evaluation method as in Example 1 for multilayer CNT twisted yarn (made by Murata Machinery Co., Ltd.) of dry spinning method Surface area measurements and capacitance measurements were performed. The SEM image of the multilayer CNT twisted yarn is shown in FIG. 7 (FIG. 7 (a) magnification 1000, FIG. 7 (b) magnification 10,000).
表３に実施例１、実施例２、比較例１のＣＮＴ撚糸体を形成する帯状体の幅の範囲及び平均ねじれ回数、ガス吸着量、細孔分布及びＢＥＴ比表面積の測定結果を示す。
表３の結果より、実施例１および実施例２のＣＮＴ撚糸体は比較例１と比較し、帯状体幅の範囲が広く、平均ねじれ回数が少なく、積算細孔容積、ガス吸着量及びＢＥＴ面積が大きいことが明らかとなった。 From the results of Table 3, compared to Comparative Example 1, the CNT twisted yarns of Example 1 and Example 2 have a wider band width range and a smaller average number of twists, and the accumulated pore volume, gas adsorption amount, and BET area Was found to be large.
表４に実施例１、実施例２、比較例１のＣＮＴ撚糸体のキャパシタンスの測定結果を示す。
表４の結果より実施例１、実施例２のＣＮＴ撚糸体のキャパシタンスの値は比較例１と比較し明らかに高いことが明らかになった。 From the results of Table 4, it was revealed that the value of the capacitance of the CNT twisting body of Example 1 and Example 2 was clearly higher than that of Comparative Example 1.
（実施例３）
ＳＧ及びｅＤｉｐｓの２種類のＣＮＴの配合量を変化させ、ＣＮＴ全量が合計５０ｍｇとなるように秤量し、ＴＤＯＣ ４５０ｍｇを２４．５ｇの水に加えた後、実施例１と同様の作製方法で、５種類のＣＮＴ撚糸体を作製した。表９にＳＧ及びｅＤｉｐｓの配合量と、該当するＣＮＴ配合量を用いて作製したＣＮＴ撚糸体の表記を示す。
The compounding amount of two kinds of CNTs of SG and eDips was changed, and weighed so that the total amount of CNTs became 50 mg in total, and after adding 450 mg of TDOC to 24.5 g of water, Five types of CNT twisted yarns were produced. Table 9 shows the notations of CNT twisted yarns produced using the blending amounts of SG and eDips and the corresponding blending amounts of CNT.
得られた５種のＣＮＴ撚糸体について、ＣＮＴ撚糸体の表面形状をＳＥＭにより観察した。図８に５種類のＣＮＴ撚糸体のＳＥＭ像を示す。図８（ａ）にＳＧの配合量を１００％として作製したＣＮＴ撚糸体の表面構造を示し、図８（ｅ）にｅＤｉｐｓの配合量を１００％で作製したＣＮＴ撚糸体の表面構造を示す。図８（ｂ）〜図８（ｄ）のＳＥＭ像より、ＳＧの配合量を１００％から減らしてｅＤｉｐｓの配合量を増やすことにより、ｅＤｉｐｓの配合量を１００％で作製したＣＮＴ撚糸体の表面構造に近づくことが明らかとなった。この結果より、ＳＧ及びｅＤｉｐｓの配合比率を変化させることにより、得られるＣＮＴ撚糸体の表面構造を自由に制御であることが明らかとなった。 The surface shape of the CNT twisting body was observed by SEM about five types of obtained CNT twisting bodies. The SEM image of five types of CNT twisting bodies is shown in FIG. FIG. 8 (a) shows the surface structure of a CNT twisting body produced with the blending amount of SG being 100%, and FIG. 8 (e) shows the surface structure of a CNT twisting body produced with the blending amount of eDips 100%. From the SEM images of FIG. 8 (b) to FIG. 8 (d), the surface of the CNT twisting yarn produced with 100% of the compounded amount of eDips by reducing the compounded amount of SG from 100% and increasing the compounded amount of eDips. It became clear to approach the structure. From this result, it was revealed that the surface structure of the obtained CNT twisted body can be freely controlled by changing the blending ratio of SG and eDips.
表６に実施例３のＣＮＴ撚糸体のヤング率、破断強度、ガス吸着量、細孔分布、ＢＥＴ比表面積の測定結果を示す。このように、ＳＧおよびｅＤｉｐｓの配合比率を変化させることにより、ＣＮＴ撚糸体の構造制御を行い、ヤング率、破断強度、ガス吸着量、細孔分布、ＢＥＴ比表面積を制御可能であることが明らかとなった。 Table 6 shows the measurement results of Young's modulus, breaking strength, gas adsorption amount, pore distribution, and BET specific surface area of the CNT twisted body of Example 3. As described above, it is apparent that the structure control of the CNT twisting body can be performed by changing the mixing ratio of SG and eDips, and the Young's modulus, breaking strength, gas adsorption amount, pore distribution, and BET specific surface area can be controlled. It became.
１０：ＣＮＴ撚糸体、１１：ＣＮＴ、１３：帯状体、１５：細孔、１００：キャパシター、５１：治具、５３：白金電極、５５：白金箔、５７：銀／塩化銀線、５９：水溶液、１０１：電極膜、１０３：電解質膜、２００：フィルター 10: CNT twisting body, 11: CNT, 13: strip, 15: pore, 100: capacitor, 51: jig, 53: platinum electrode, 55: platinum foil, 57: silver / silver chloride wire, 59: aqueous solution , 101: electrode membrane, 103: electrolyte membrane, 200: filter
Claims (6)
前記複数の帯状体の各々は、複数のカーボンナノチューブの束が長さ方向にねじれた構造と細孔とを有する、ことを特徴とするカーボンナノチューブ撚糸体。 Comprising a plurality of strips arranged in the longitudinal direction,
A carbon nanotube twisted body, wherein each of the plurality of bands has a structure in which a bundle of carbon nanotubes is twisted in the longitudinal direction and a pore.
ＢＪＨ法で解析される前記カーボンナノチューブ撚糸体の細孔径が２ｎｍ以上５０ｎｍ以下の範囲における積算細孔容積を０．９ｃｍ3／ｇ以上２．１ｃｍ3／ｇ以下の範囲に備える、ことを特徴とする請求項１に記載のカーボンナノチューブ撚糸体。 The carbon nanotube twist body is
The carbon nanotube twisted yarn body characterized in that the integrated pore volume in the range of 2 nm to 50 nm is in the range of 0.9 cm 3 / g to 2.1 cm 3 / g, which is analyzed by the BJH method. The carbon nanotube twist body according to claim 1.
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