CN1769165A - 可用于储能装置的碳 - Google Patents
可用于储能装置的碳 Download PDFInfo
- Publication number
- CN1769165A CN1769165A CNA2005101188752A CN200510118875A CN1769165A CN 1769165 A CN1769165 A CN 1769165A CN A2005101188752 A CNA2005101188752 A CN A2005101188752A CN 200510118875 A CN200510118875 A CN 200510118875A CN 1769165 A CN1769165 A CN 1769165A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- energy storage
- carbon precursor
- carbon
- described carbon
- 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
- 238000004146 energy storage Methods 0.000 title claims abstract description 26
- 239000007833 carbon precursor Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000003990 capacitor Substances 0.000 claims abstract description 29
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 18
- 239000011280 coal tar Substances 0.000 claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 55
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 20
- 238000000197 pyrolysis Methods 0.000 claims description 15
- 125000004355 nitrogen functional group Chemical group 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002444 silanisation Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 238000002242 deionisation method Methods 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 3
- 239000003208 petroleum Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- 229910052799 carbon Inorganic materials 0.000 description 21
- 239000011521 glass Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 235000014633 carbohydrates Nutrition 0.000 description 14
- 239000011295 pitch Substances 0.000 description 13
- 229930006000 Sucrose Natural products 0.000 description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 11
- 239000005720 sucrose Substances 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 10
- 238000001994 activation Methods 0.000 description 9
- 230000004913 activation Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- -1 carboxylic acid ion Chemical class 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 235000000346 sugar Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 150000002016 disaccharides Chemical class 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005915 ammonolysis reaction Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002402 hexoses Chemical class 0.000 description 2
- 239000012761 high-performance material Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000008101 lactose Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002972 pentoses Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- MUPFEKGTMRGPLJ-UHFFFAOYSA-N UNPD196149 Natural products OC1C(O)C(CO)OC1(CO)OC1C(O)C(O)C(O)C(COC2C(C(O)C(O)C(CO)O2)O)O1 MUPFEKGTMRGPLJ-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 150000001320 aldopentoses Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-PQMKYFCFSA-N alpha-D-mannose Chemical compound OC[C@H]1O[C@H](O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-PQMKYFCFSA-N 0.000 description 1
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 description 1
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 229960001040 ammonium chloride Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- ODEXXNNMGSAXBF-UHFFFAOYSA-N diethyl carbonate;ethyl methyl carbonate Chemical compound CCOC(=O)OC.CCOC(=O)OCC ODEXXNNMGSAXBF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 239000008103 glucose Substances 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 1
- 235000019534 high fructose corn syrup Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- BJHIKXHVCXFQLS-PQLUHFTBSA-N keto-D-tagatose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-PQLUHFTBSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229960003487 xylose Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
提供了用选自天然生成的碳水化合物材料、源自煤焦油的沥青、源自石油的沥青以及它们的组合经济地制得的碳。还提供了制造这些碳的方法,以及这些碳在形成用于以下用途的电极结构中的应用:(i)电池、燃料电池和双电层电容器之类的储能用途和(ii)电容性水去离子化用途。
Description
技术领域
本发明涉及用碳前体制成的碳,这些碳前体选自天然生成的碳水化合物材料、源自煤焦油的沥青、源自石油的沥青以及它们的组合,该碳可用于储能装置。本发明还涉及制备这种碳的方法,以及电极结构形式的所述碳在以下方面的应用:(i)电池、燃料电池和双电层电容器之类的储能用途和(ii)电容性水去离子化用途。
背景技术
使用碳基电极的储能装置可在市场上购得。然而,随着例如双电层电容器(有时称为超电容器或超级电容器)之类的储能装置应用的增长,对具有改进性能的新的碳的需求也在增加。
大部分常规超电容器的电容与其电极的比表面直接相关。因此,理论上对于给定的活性碳,比表面越大,则其比电容也越大。然而,实际上比表面与电容之间的关系并非那么简单。即,一般地讲,随着给定活性碳比表面的增大,其孔体积也随之增大。随着活性碳孔体积的增大,碳的密度减小,该活性碳所显示的能量密度(体积电容)通常减小。实际上,对于大多数常规活性碳,当其单位重量的比表面约为2,000平方米/克时,其单位体积的电容(法/立方厘米)达到最大,而当单位重量的比表面超过约2,500平方米/克时,单位体积的电容反而会减小。
对更高体积电容的超电容器的市场需求,推动着对具有更大比表面的合适电极材料的发展。已经对各种材料进行了研究以满足这种需求。这些材料中的大部分使用高成本的聚合物膜,并且/或者是通过复杂的实验式制造和活化步骤制得,这些步骤太过困难或不够经济,无法用于工业大生产。
在Uehara等人的美国专利申请公开第2003/0086860号中公开了一种制造这种用于储能装置电极的低成本、高性能材料的方法。Uehara等人公开了一种生产多孔碳的方法,该方法是在羧酸离子和至少一种选自铁离子、钴离子、锰离子和镍离子的金属离子存在条件下,用碱对软碳类碳材料进行活化。Uehara等人报道,使用他们的方法可制造体积比表面≥1,000平方米/立方厘米的活性碳,并且使用这些碳的双电层电容器的单位体积的电容≥20法/立方厘米。
当制得的碳加入到超电容器之类的储能装置中时,如Uehara所述,使用金属离子可能造成稳定性方面的问题。即在制得的碳中有电活性(electroactive)金属会引起大的电流泄漏,从而使储能装置不符合要求。因此,在将这种碳加入例如超电容器之前,需要通过另外的处理步骤除去其中的电活性金属。因此,仍然需要有能够以工业化规模经济地制造的、用于超电容器之类储能装置电极的低成本高性能材料。
发明内容
我们惊异地发现,在源自碳前体的活性碳中加入较少量的氮官能团,可制得能量密度高的高比表面材料,所述碳前体选自天然生成的碳水化合物、源自煤焦油的沥青、源自石油的沥青以及它们的组合。
在本发明的一个方面,提供一种碳材料,该碳材料源自一种碳前体,该碳前体选自天然生成的碳水化合物、源自煤焦油的沥青、源自石油的沥青、以及它们的组合,所述碳材料包含大于1.0重量%的元素氮,该碳材料的比表面大于1,500平方米/克。
在本发明的另一个方面,提供一种包含本发明碳材料的电极,该碳材料源自一种碳前体,该碳前体选自天然生成的碳水化合物、源自煤焦油的沥青、源自石油的沥青、以及它们的组合,其中所述碳材料包含大于1.0重量%的元素氮,该碳材料的比表面大于1,500平方米/克。
在本发明的另一个方面,提供一种包含本发明电极的超电容器。
在本发明的另一个方面,提供一种包含本发明电极的电池。
在本发明的另一个方面,提供一种包含本发明电极的储能装置,该储能装置的工作电压高于2.5伏。
在本发明的另一个方面,提供一种本发明储能装置在选自以下的系统中的应用:汽车、功率质量(power quality)、发动机起动、光电能量存储、风车中的能量存储、医学系统、车辆推进器系统、军用电子设备、运输系统、商用电子设备、用户电子设备、便携式电子设备、声音系统和消费者电器。
在本发明的另一个方面,提供一种由碳前体制造碳材料的方法,该方法包括向碳前体中加入氮官能团,所述碳前体选自天然生成的碳水化合物、源自煤焦油的沥青、源自石油的沥青、以及它们的组合,所述碳材料包含大于1.0重量%的元素氮,该碳材料的比表面大于1,500平方米/克。
具体实施方式
本文中所有的范围均包括端值且可互相组合。
在本文和所附的权利要求书中,术语“糖”包括许多任意的有用糖类材料。所述有用的糖包括单糖、二糖和多糖以及它们的降解产物,例如包括戊醛糖、甲基戊糖、庚戊糖(keptopentose)的戊糖,例如木糖和阿糖;鼠李糖之类的脱氧乳糖(deoxyladoses);己糖和还原糖类,例如葡萄糖、半乳糖和甘露糖之类的己糖;果糖和山梨糖之类的己酮糖;乳糖和麦芽糖之类的二糖;蔗糖之类的未还原的二糖,和其它多糖,例如糊精和蜜三糖;以及包含低聚糖的水解淀粉。常用的源料是各种颗粒和粉末形式的包含玉米糖浆、高果糖玉米糖浆等的许多糖浆。
适用于本发明用途的天然形成的碳水化合物包括例如天然形成的糖;多糖;淀粉;木素;纤维素;以及它们的混合物。
在一些实施方式中,本发明的碳材料由碳前体制造,所述碳前体是选自木材、椰壳、糖及其混合物的天然形成的碳水化合物。
在一些实施方式中,本发明的碳材料由碳前体制造,所述碳前体是选自木材、椰壳、蔗糖、果糖及其混合物的天然形成的碳水化合物。
在一些实施方式中,本发明的碳材料由碳前体制造,所述碳前体是选自蔗糖的天然形成的碳水化合物。
在一些实施方式中,本发明的碳材料由碳前体制造,所述碳前体选自源于煤焦油的沥青、源于石油的沥青、以及它们的组合。
在一些实施方式中,本发明的碳材料包含至少1.0重量%的元素氮;或者大于1.5重量%;或者大于1.75重量%;或者大于2.0重量%;或者为1.0-10.0重量%;或者为1.0-8.0重量%;或者为1.0-7.0重量%;或者为1.0-5.0重量%;或者为1.0-3.0重量%的元素氮。所述碳材料中元素氮的含量可通过传统的燃烧元素分析和X射线光电子光谱(XPS)测定。XPS能提供准确而可信的元素氮值。另外,可以用XPS测定氮官能团的种类。我们的分析表明,元素氮可以是腈、酰胺、胺、铵和环氮官能团中的形式。
在一些实施方式中,用Brunauer,Emmett,Teller(BET)法测得,本发明碳材料的比表面大于1,500平方米/克;或为1,500-3,000平方米/克;或为1,500-2,500平方米/克。
在一些实施方式中,用氮吸附法测得,本发明碳材料的孔体积为0.1-2.0立方厘米/克;或者为0.5-2.0立方厘米/克。
在一些实施方式中,用Horvath-Kawazoe(H-K)法测得,本发明碳材料的孔径分布在小于50.0纳米具有至少一个峰;或者在小于5.0纳米至少一个峰;或者在0.1-5.0纳米具有至少一个峰。
在一些实施方式中,用氮吸附法测得,本发明碳材料的孔体积小于2立方厘米/克,由H-K法测得,其孔径分布在0.1-50纳米具有至少一个峰。
本发明的碳材料可被制成或形成各种常规形状或物体,包括例如粉末、颗粒、整料、珠子、片材、块、线、丝、管、纸张、膜、毡、泡沫体、盘、织物和非织造物。
在一些实施方式中,本发明的碳材料可作为粉末提供;或者作为体积平均粒径≤50微米的粉末;或者作为体积平均粒径≤50微米的粉末;或者作为体积平均粒径≤10微米的粉末。
在一些实施方式中,本发明的碳材料可形成电极,用于各种储能装置和能量控制装置,包括例如双电层电容器(也被称为超电容器和超级电容器)、电池、燃料电池、功率稳定化装置和电容性水去离子化装置。
在一些实施方式中,可用本发明的碳材料制造用于电容器,例如用于双层电容器的电极,所述双层电容器包括至少两个电极,至少一个位于所述至少两个电极之间的多孔隔离片,以及与所述至少两个电极结构和至少一个多孔隔离片相接触的电解溶液。
适用于本发明的电解溶液包括,例如有机电解溶液和含水电解溶液。
在一些实施方式中,包含本发明碳材料的双层电容器含有有机电解溶液;或者通过将电解质溶于有机溶剂或有机溶剂混合物制得的有机电解溶液。
适用于本发明电解溶液的有机溶剂包括,例如电化学稳定的碳酸亚乙酯;碳酸亚丙酯;碳酸亚丁酯;γ-丁内酯;环丁砜;环丁砜衍生物;3-甲基环丁砜;1,2-二甲氧基乙烷;乙腈;戊二腈;戊腈;二甲基甲酰胺;二甲亚砜;四氢呋喃;二甲氧基乙烷;甲酸甲酯;碳酸二甲酯;碳酸二乙酯;碳酸乙基甲基酯以及它们的混合物。
适用于本发明电解溶液的电解质包括,例如具有由R1R2R3R4N+或R1R2R3R4P+表示的季鎓阳离子、和选自例如BF4 -、PF6 -、ClO4 -、CF3SO3 -和(SO2R5)(SO2R6)N-的阴离子的盐,其中R1、R2、R3和R4各自独立地为C1-6烷基,R5和R6各自独立地为C1-4烷基、亚烷基和共同地为环结构。在一些实施方式中,所述电解质选自(C2H5)4NBF4、(C2H5)3(CH3)NBF4、(C2H5)4PBF4和(C2H5)3(CH3)PBF4。在一些实施方式中,将一种所示的盐以0.1-2.5摩尔/升,或者0.5-2摩尔/升的浓度溶解于有机溶液中。
在一些实施方式中,包含本发明碳材料的双层电容器含有含水电解溶液。
适用于本发明的含水电解溶液,可通过将电解质溶于水溶液制得。
适用于本发明电解溶液的水溶液包含,例如氢氧化钾和硫酸。
适用于本发明双层电容的隔离片包括,例如聚丙烯纤维的非织造织物、玻璃纤维的非织造织物、合成纤维素、天然纤维素以及它们的组合。
在一些实施方式中,包含本发明碳材料的电极在有机电解质中的电容大于80法/克;或者大于100法/克。
在一些实施方式中,本发明双层电容器的工作电压≥2.5伏。
在一些实施方式中,可将本发明的储能装置用于各种系统,包括例如汽车、功率质量(power quality)、发动机起动、光电能量存储、风车中的能量存储、医学系统、车辆推进器系统、军用电子设备、运输系统、商用电子设备、用户电子设备、便携式电子设备、声音系统和消费者电器。
在一些实施方式中,可通过以下步骤的组合对碳前体进行处理,制备本发明的碳材料:
a)脱水;
b)热解;
c)活化;
d)引入氮官能团。
可将操作(a)-(d)中的两项或两项以上结合在单个操作中。例如可将热解和活化操作结合在单个操作中。另外,操作(a)-(d)也可以依照任意的顺序进行。例如,可在热解之前或之后,或者在活化之前或之后引入氮官能团。也可略去操作(a)-(d)中的一项或多项。
在一些实施方式中,可通过向碳前体中引入氮官能团,并进行以下步骤中的至少两项,从而由天然生成的碳水化合物碳前体制造本发明的碳材料:
a)对碳前体进行脱水;
b)对碳前体进行热解;
c)对碳前体进行活化。
可将操作(a)-(c)中的两项或两项以上结合在单个操作中。例如可将热解和活化操作结合在单个操作中。另外,操作(a)-(c)也可以依照任意的顺序进行,可以在向碳前体中引入氮官能团之前或之后进行。例如,可在热解之前或之后,或者在活化之前或之后引入氮官能团。
在本发明的方法中,可使用常规方法对碳前体、特别是天然生成的碳水化合物碳前体,进行脱水,这些方法可包括加入活性添加剂。适用于所述天然形成的碳水化合物的脱水处理的活性添加剂,包括例如硫酸和磷酸之类的酸和酸式盐。使用活性添加剂可以加速所述碳水化合物或糖环结构中-OH基团以水形式的去除和双键的形成。
在本发明的方法中,用常规方法对碳前体进行热解。例如,可在惰性气氛或活性气氛或二者组合的情况下对碳前体进行热解。热解温度可在例如400-2000℃;或者在700-1500℃;或者800-1200℃的范围内。热解时间可为1-12小时;或者2-10小时;或者3-8小时。热解气氛可为惰性或活性或这两者的组合。惰性热解气氛包括惰性、非氧化气体,例如氮气、氩气和氦气。活性气氛包括,例如一氧化碳、二氧化碳、水汽和空气。或者也可用氢氧化钾之类的碱金属氢氧化物、硫酸之类的无机酸或二氯化锌之类的Lewis酸完成化学活化。在一些实施方式中,可在惰性热解之后完成活化过程,以增加碳材料的孔隙率和比表面。
可通过使用空气、二氧化碳和水汽的活化操作在碳材料中引入含氧的非氮官能团。这些官能团包括羟基和羧基部分。这些官能团可通过提高假电容来提高总电容。然而,这种假电容会随时间降低,导致储能装置不稳定。可以用例如有机硅硅烷化试剂的衍生作用使含氧的官能团稳定,所述有机硅硅烷化试剂包括例如六甲基乙硅烷和三甲基氯硅烷。
可以在制造本发明碳材料过程中的任何时候向碳前体中引入氮官能团。例如可在脱水、热解或活化之前或之后引入氮官能团。
引入氮官能团的方法包括,例如氨氧化反应和含氮添加剂的使用。氨氧化反应包括在制造所述碳材料过程的某个时候,使碳前体材料与氨气或氨气/氧气混合物接触。含氮添加剂的使用包括在制造所述碳材料过程的某个时候,使碳前体材料与在升高的温度下能与碳前体反应的含氮添加剂接触。这种含氮添加剂包括,例如氯化铵、聚烯丙胺、聚二烯丙基二甲基氯化铵、聚乙烯亚胺、三乙醇胺、三聚氰胺、硫酸铵、磷酸二氢铵、尿素、硫酸铝铵、硫酸氢铵、甜菜碱、乙酸铵以及它们的混合物。
实施例
在下面的实施例中将详细描述本发明的一些实施方式。
对比例1
依照如下步骤,用蔗糖制备不含元素氮的活性碳材料:
(a)将500克蔗糖溶解在350克蒸馏水中;
(b)边剧烈搅拌,边向(a)的产物中缓慢加入56克96重量%的硫酸;
(c)将(b)的产物倒入一玻璃盘内;
(d)在室温下将该玻璃盘放入烘箱;
(e)将烘箱的温度升高到120℃,在此温度下保持过夜;
(f)第二天,观察到在玻璃盘中形成了炭黑;
(g)将炭黑从玻璃盘中取出,研磨成粒径小于10目(mesh),用标称筛孔为2.00毫米的筛子测定,所用筛子为:美国标准试验筛ASTME-11规格第10号和TylerEquivalent 9目。
(h)将100克上述(g)的产物放入氧化铝管内,在5C/分钟的氮气流下,在管式炉内加热到500℃,并在此温度下保持3.0小时;
(i)然后将(h)制得的材料加热到1000℃,用CO2活化2.5小时,得到比表面为2058平方米/克、孔体积为1.0立方厘米/克的活性碳材料产物。
本实施例制得的产物通过XPS分析,证明其不含元素氮。
对比例2
将购自Kuraray化学公司、商品名为BP-20的活性碳材料用于对比目的,该活性碳材料不含元素氮。
实施例3
依照如下步骤,用蔗糖制备含元素氮的活性碳材料:
(a)将150克氯化铵溶解在350克蒸馏水中;
(b)将500克蔗糖缓慢加入(a)的产物进行混合;
(c)边剧烈搅拌,边向(b)的产物中缓慢加入120克96重量%的硫酸;
(d)将(c)的产物倒入一玻璃盘内;
(e)在室温下将该玻璃盘放入烘箱;
(f)将烘箱的温度升高到120℃,在此温度下保持过夜;
(g)第二天,观察到在玻璃盘中形成了炭黑;
(h)将炭黑从玻璃盘中取出,研磨成粒径小于10目,用标称筛孔为2.00毫米的筛子测定,所用筛子为:美国标准试验筛ASTME-11规格第10号和TylerEquivalent 9目。
(i)将100克上述(h)的产物放入氧化铝管内,在5C/分钟的氮气流下,在管式炉内加热到500℃,并在此温度下保持3.0小时;
(j)然后将(i)制得的材料加热到1000℃,用CO2活化4.5小时,得到比表面为2064平方米/克、孔体积为0.885立方厘米/克的活性碳材料产物。
XPS分析测得,本实施例制得的产物中元素氮含量为1.5重量%。
实施例4
依照如下步骤,用蔗糖制备含元素氮的活性碳材料:
(a)将100克氯化铵溶解在350克蒸馏水中;
(b)将500克蔗糖缓慢加入(a)的产物进行混合;
(c)边剧烈搅拌下,边向(b)的产物中缓慢加入120克96重量%的硫酸;
(d)将(c)的产物倒入一玻璃盘内;
(e)在室温下将该玻璃盘放入烘箱;
(f)将烘箱的温度升高到120℃,并在此温度下保持过夜;
(g)第二天,观察到在玻璃盘中形成了炭黑;
(h)将炭黑从玻璃盘中取出,研磨成粒径小于10目,用标称筛孔为2.00毫米的筛子测定,所用筛子为:美国标准试验筛ASTME-11规格第10号和TylerEquivalent 9目。
(i)将100克(h)的产物放入氧化铝管内,在5C/分钟的氮气流下,在管式炉内加热到500℃,并在此温度下保持3.0小时;
(j)然后将(i)制得的材料加热到1000℃,用CO2活化4.0小时,得到比表面为2227平方米/克、孔体积为1.0立方厘米/克的活性碳材料产物。
XPS分析测得,本实施例制得的产物中元素氮含量为1.5重量%。
实施例5
依照如下步骤,用蔗糖制备含元素氮的活性碳材料:
(a)将100克氯化铵溶解在350克蒸馏水中;
(b)将500克蔗糖缓慢加入(a)的产物进行混合;
(c)边剧烈搅拌下,边向(b)的产物中缓慢加入120克96重量%的硫酸;
(d)将(c)的产物倒入一玻璃盘内;
(e)在室温下将该玻璃盘放入烘箱;
(f)将烘箱的温度升高到120℃,并在此温度下保持过夜;
(g)第二天,观察到在玻璃盘中形成了炭黑;
(h)将炭黑从玻璃盘中取出,研磨成粒径小于10目,用标称筛孔为2.00毫米的筛子测定,所用筛子为:美国标准试验筛ASTME-11规格第10号和TylerEquivalent 9目。
(i)将100克(h)的产物放入氧化铝管内,在5C/分钟的氮气流下,在管式炉内加热到500℃,并在此温度下保持3.0小时;
(j)然后将(i)制得的材料加热到1000℃,并用CO2活化3.0小时,得到比表面为1703平方米/克、孔体积为0.726立方厘米/克的活性碳材料产物。
XPS分析测得,本实施例制得的产物中元素氮含量为1.65重量%。
实施例6
测试实施例1-5制得的活性炭在下表1中所示的各种性能参数。使用下列的仪器获得表1中的数据:
a)频率特性分析器(FRA),Schlumberger Solartron型1250;
b)稳压器,EG&G型273;
c)数字万用表,Keithley型197。
d)电容测试盒S/N 005,100欧姆设置(setting)。
e)RLC仪,Philips PM6303
f)电源,Hewlett-Packard型E3610A
g)天平,Mettler H10;
h)测微计,Brown/Sharp;
i)泄漏电流仪;
j)电池/电容器测试仪,Arbin型HSP-2042
有机电解质电容器性能测试
对实施例1-5提供的各种碳样品在具有有机电解质的电容器中作为电极材料的性质和性能进行测试。所有的碳样品为由颗粒形成的直径1.59厘米、厚0.005厘米的分离电极。在测试电容器系统中所用隔离片的厚度约为0.0076厘米。各测试电极在195℃的真空条件下(粗真空(roughing)泵)干燥18小时。然后将干燥的测试电极浸泡在电解液中。然后将冷却的测试电极(仍处于真空)移入一干盒(drybox)。所有随后的组装操作都在该干盒内进行。然后再将该测试电极再在有机电解液中浸泡10分钟,然后将其装入电容器电池中。所述电解液包含含有1.0M四乙胺的四氟硼酸盐(TEATFB)的碳酸丙二酯(PC)和碳酸二甲酯(DMC)的等体积混合物。所用的隔离片为“开放电池泡沫型”材料,该材料当装入电池中时厚度约为0.0076厘米。从干盒中取出已组装的电池进行测试。将金属板夹在各导电面板上用作集电器。然后将这些测试电容器电池在1.0V下调适10分钟,再测试其性质。然后将这些测试电容器电池在2.0V下调适10分钟,再次测试其性质。
电容器电池测试
所有对电容器电池的测试在室温下进行。
在1.0V的顺序如下:使用RCL仪的1千赫ESR,用电容测试盒对带100欧姆串联电阻的电容器充电,30分钟后用泄漏电流仪泄漏电流,用稳压器和FRA进行电化学阻抗光谱(EIS)测量。
在2.0V的顺序与1.0V所用的顺序相同。最后的测量是用Arbin进行的恒定电流充电/放电测量。在四导线结构中以0.010-V-振幅正弦-波-信号进行EIS测量。
在将1.0或2.0伏的电压施加于电容器和串联的100Ω电阻器后,测量使电容器从0V(1-1/e)V=0.632V的充电时间,从而测定C100充电电容。
然后将充电时间(以秒为单位)除以100(串联电阻值)计算重量电容(以法/克为单位)。将重量电容与碳的密度相乘计算体积电容。
表1
样品 | 比表面 | 孔体积 | 重量%氮 | 体积电容(2伏) | 重量电容(2伏) |
对比例1 | 2058平方米/克 | 1.0立方厘米/克 | 0% | 72法/立方厘米 | 96法/克 |
对比例2 | 2039平方米/克 | 0.88立方厘米/克 | 0% | 69法/立方厘米 | 97法/克 |
实施例3 | 2064平方米/克 | 0.88立方厘米/克 | 1.5% | 94法/立方厘米 | 114法/克 |
实施例4 | 2227平方米/克 | 1.0立方厘米/克 | 1.5% | 92法/立方厘米 | 118法/克 |
实施例5 | 1703平方米/克 | 0.73立方厘米/克 | 1.65% | 94法/立方厘米 | 106法/克 |
实施例7:对包含氧官能团碳的硅烷化(预示(prophetic))
向包含90%碳、5%氧、2%氮和3%氢的5克碳样品(比表面2000平方米/克,1.0立方厘米/克)中加入100毫升无水甲苯和2.0克三甲基氯硅烷。将该混合物加热至回流并保持12小时。通过过滤回收碳,用过量的甲苯清洗,然后在真空干燥,制得含2.5%Si的碳。
所得碳材料是稳定的,可用作超电容装置的电极。
实施例8:煤焦油沥青碳前体(预示)
按照以下步骤,用煤焦油沥青制备碳材料:
(a)将100克三聚氰胺与500克煤焦油沥青混合;
(b)将(a)的混合物倒入玻璃盘;
(c)在室温下将该玻璃盘放入烘箱;
(d)在氮气流下,将烘箱的温度缓慢升高到800℃,并在此温度下保持8小时;
(e)然后将(d)制得的材料加热到1000℃,并用CO2活化2.5小时,得到比表面为2000平方米/克、孔体积为1.0立方厘米/克、元素氮含量大于1.0重量%的活性碳材料产物。
制得的碳材料可用作超电容器的电极。
Claims (10)
1.一种碳材料,所述碳材料由碳前体获得,所述碳前体选自天然生成的碳水化合物材料、源自煤焦油的沥青、源自石油的沥青以及它们的组合,所述碳材料包含大于1.0重量%的元素氮,所述碳材料的比表面大于1500平方米/克。
2.如权利要求1所述的碳材料,其特征在于,所述碳材料的孔体积小于2立方厘米/克,其孔径分布在0.1-50纳米具有至少一个峰。
3.一种电极,包含如权利要求1所述的碳材料。
4.一种超电容器,包含如权利要求3所述的电极。
5.一种电池,包含如权利要求3所述的电极。
6.一种储能装置,包含如权利要求3所述的电极,其中所述储能装置的工作电压大于2.5伏。
7.如权利要求6所述的储能装置在以下系统中的应用:汽车、功率质量、发动机启动、光电能量存储、风车的能量存储、医学系统、车辆推进器系统、军用电子设备、运输系统、商用电子设备、用户电子设备、便携式电子设备、声音系统和消费者电器。
8.一种由碳前体制造碳材料的方法,所述碳前体选自天然生成的碳水化合物材料、源自煤焦油的沥青、源自石油的沥青以及它们的组合,所述方法包括向所述碳前体中加入氮官能团,所述碳材料包含大于1.0重量%的元素氮,所述碳材料的比表面大于1500平方米/克。
9.如权利要求8所述的方法,其特征在于,所述碳前体是天然生成的碳水化合物,所述方法还包括以下步骤中的至少两项:
a)对碳前体进行脱水;
b)对碳前体进行热解;
c)对碳前体进行活化。
10.如权利要求8所述的方法,其特征在于,所述碳材料具有含氧官能团,其中所述方法还包括对所述含氧官能团进行硅烷化处理。
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EP (1) | EP1655267B1 (zh) |
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CN102317205A (zh) * | 2008-12-15 | 2012-01-11 | 康宁股份有限公司 | 用于高能量密度超级电容器的活性炭材料 |
CN102317205B (zh) * | 2008-12-15 | 2014-04-09 | 康宁股份有限公司 | 用于高能量密度超级电容器的活性炭材料 |
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CN102712479B (zh) * | 2010-01-22 | 2015-06-17 | 康宁股份有限公司 | 用于edlc的高电容低氧多孔碳 |
CN107634225A (zh) * | 2017-08-31 | 2018-01-26 | 福建新峰二维材料科技有限公司 | 一种采用硬碳正极材料的双离子电池制备方法 |
CN108726517A (zh) * | 2018-07-21 | 2018-11-02 | 吉林大学 | 提高稻壳基电容炭体积比电容的方法 |
CN108726517B (zh) * | 2018-07-21 | 2022-03-18 | 吉林大学 | 提高稻壳基电容炭体积比电容的方法 |
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TW200630301A (en) | 2006-09-01 |
EP1655267B1 (en) | 2016-03-16 |
AU2005225138A1 (en) | 2006-05-18 |
KR20060052242A (ko) | 2006-05-19 |
JP2006160597A (ja) | 2006-06-22 |
EP1655267A2 (en) | 2006-05-10 |
KR100817745B1 (ko) | 2008-03-31 |
JP4313357B2 (ja) | 2009-08-12 |
HK1087683A1 (en) | 2006-10-20 |
CN100355651C (zh) | 2007-12-19 |
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US20060093915A1 (en) | 2006-05-04 |
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