CN103746091B - 一种纳米碳电极的制备方法 - Google Patents
一种纳米碳电极的制备方法 Download PDFInfo
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- CN103746091B CN103746091B CN201310484484.7A CN201310484484A CN103746091B CN 103746091 B CN103746091 B CN 103746091B CN 201310484484 A CN201310484484 A CN 201310484484A CN 103746091 B CN103746091 B CN 103746091B
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- argon
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 54
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 229910052786 argon Inorganic materials 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005011 phenolic resin Substances 0.000 claims abstract description 11
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 20
- 239000010452 phosphate Substances 0.000 claims description 20
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 15
- 229910003472 fullerene Inorganic materials 0.000 claims description 15
- 150000002505 iron Chemical class 0.000 claims description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims description 15
- 159000000002 lithium salts Chemical class 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 229910052754 neon Inorganic materials 0.000 claims description 6
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 229910013188 LiBOB Inorganic materials 0.000 claims description 5
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- XPHHIWSZCAPBGE-UHFFFAOYSA-N [N]=O.[P].[Li] Chemical class [N]=O.[P].[Li] XPHHIWSZCAPBGE-UHFFFAOYSA-N 0.000 claims description 5
- OEMGCAOEZNBNAE-UHFFFAOYSA-N [P].[Li] Chemical compound [P].[Li] OEMGCAOEZNBNAE-UHFFFAOYSA-N 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000002608 ionic liquid Substances 0.000 claims description 5
- 229910000398 iron phosphate Inorganic materials 0.000 claims description 5
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 5
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical group O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 5
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 5
- 238000001465 metallisation Methods 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000005518 polymer electrolyte Substances 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 230000001052 transient effect Effects 0.000 claims description 5
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- -1 phenolic aldehyde Chemical class 0.000 claims 1
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000007772 electrode material Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001721 carbon Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002090 nanochannel Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
一种纳米碳电极的制备方法,包括以下步聚:1)形成前驱物气体;2)称量原料;3)将步骤2)所得的前体放入60‑70℃的真空烘箱中干燥10~30小时后放入气氛保护管式真空炉中,并置于导电基材上,然后通入氮气或氩气,再通入前驱物气体;4)将步骤3)中获得的产物制得分散粉体,并用酚醛树脂‑P123高分子共聚物‑原硅酸乙酯的溶胶等体积浸渍该分散粉体并经充分缩合;5)在步骤4)所得产物上沉积薄金属层;6)在该薄金属层上沉积电解质。该方法能降低成本,又提高性能。
Description
技术领域
本发明属于复合电极领域,涉及一种纳米碳电极的制备方法。
背景技术
诸如超级电容及锂(Li)离子电池之类的快速充电、大电容能量储存装置被用于越来越多的应用,在这些应用中的每一种中,充电时间及能量储存装置的容量是重要参数。此外,此类能量储存装置的尺寸、重量和/或费用可为重大限制。再者,对高效性能而言,低的内电阻是必须的。电阻越低,能量储存装置在传递电能上所遭遇的限制越少。因此,在本领域中需要更小、更轻且在成本上更有效地制造的更快充电、高电容能量储存装置。本领域中也需要用于电子储存装置的部件以减少储存装置的内电阻。
氢是最洁净的能源,也是一种重要的工业原料,但氢的储存与运输问题限制了氢能的广泛应用。车载氢氧燃料电池能否得到广泛的实际应用,也与这一问题能否得到解决密切相关。研究开发性能优异的储氢材料是解决氢能的储存与运输问题的关键途径之一。
钴酸锂作为锂离子电池正极材料在移动电话、摄录像机、笔记本电脑、数码相机、媒体播放器等便携式电子产品领域表现出优异的性能,但是,它在较高温度下容易释放出氧气,带来严重的安全隐患。现在科学界和产业界普遍认为钴酸锂不适合作为电动汽车用高功率、高容量锂离子电池正极材料。同时,由于钴酸锂价格昂贵,多年来铅酸电池都压倒性占据了大部分的市场。因此,寻找低成本、高性能的正极材料是推动锂离子电池广泛应用的需要,尤其是发展电动汽车(EV)、混合电动车(HEV)的关键。可以说,从锂离子电池市场化到现在,科学家就一直在寻找性价比更高的正极材料。磷酸铁锂价格便宜、比容量高、安全性能好,是理想的锂离子电池正极材料,尤其是它较高温度下的稳定性能给高功率、高容量电池提供了安全保障,是动力电池材料的理想选择。但是磷酸铁锂电导率低,在充放电过程中易发生极化现象,大电流高倍率下容量大幅度下降,性能不很理想。磷酸铁锂要想真正实现应用,必须解决目前存在的这些问题。
已有专利CN200410054034.5公开一种纳米溶胶-凝胶膜电极、其制备方法及 应用。但是在实际使用中,这种方法由于膜厚度的改变导致电容不稳定。锂离子电池浆料固含量非常高,粘度大,采用这种方法很难使纳米碳管充分分散。因此,目前使用纳米碳管的方法不能充分发挥它的优点,同时由于纳米碳管团聚严重也不得不加大原料的用量,增加了成本,降低了复合材料的容量。
另外,电极材料是决定化学电源性能的关键之一。高性能电极材料的研究开发,一直是化学电源研究领域的核心课题。同时需要对电极材料改性来改善其导电性,从而提高高倍率性能,还要保持其高可逆电化学容量和良好的循环稳定性,并且需要成本低廉。
发明内容
本发明所要解决的技术问题是,提供一种纳米碳电极的制备方法,能防止电极材料发生团聚现象,既降低成本,又提高性能,并提供高能量密度的能量储存。由该方法制得的电极吸附氢的过程可以短时间内快速达到平衡;导电性高,内阻小并降低成本,适应工业化生产。
本发明为解决上述技术问题所采用的技术方案是:
一种纳米碳电极的制备方法,包括以下步聚:
1)将体积比为1:1:1的液态高分子量碳氢前驱物C20H40、C20H42和C22H44在500~1000℃气化以形成前驱物气体;
2)按以下组分和质量百分比含量称量原料:催化剂5%~10%、锂盐5%~10%、铁盐50%~55%和磷酸盐30~40%;所述的催化剂为金属Ni、Y、Zr和MgO的超细粉体,尺寸为500~5000nm,其重量百分比分别为催化剂总重量的85%、5%、5%和10%;所述的锂盐为碳酸锂、氢氧化锂、硝酸锂和磷酸锂的组合,其重量百分比分别为锂盐总重量的45%、25%、25%和5%;所述的铁盐为草酸亚铁和磷酸铁,其重量百分比分别为铁盐总重量的70%和30%;所述的磷酸盐为磷酸二氢铵和磷酸铵,其重量百分比分别为磷酸盐总重量的50%和50%;将上述原料加入分散剂后在球磨机中以500~800r/m的转速球磨10~15h,制得前体,加入分散剂的重量为上述原料重量的1%~5%;
3)将步骤2)所得的前体放入60~70℃的真空烘箱中干燥10~30小时后放入气氛保护管式真空炉中,并置于导电基材上,然后通入氮气或氩气,氮气或氩气流量为500~600sccm,以20~25℃/分钟的速度升温至150~200℃,再通入流量 为350~650sccm的步骤1)中的前驱物气体,保持压力在1.5~2.0Mpa;同时关掉氮气或氩气,在600~1000℃温度下恒温90~120min形成纳米碳管所连接的富勒烯葱状物三维结构材料,其长度和直径为10~20nm,比表面积为100-500m2.g-1;
4)将步骤3)中获得的产物分散于有机溶剂乙醇中,采用瞬态干燥方法制得分散粉体,并用酚醛树脂-P123高分子共聚物-原硅酸乙酯的溶胶等体积浸渍该分散粉体并经充分缩合,酚醛树脂重量含量为溶胶总重量的40~50%,P123高分子共聚物重量含量为溶胶总重量的20~30%,原硅酸乙酯重量含量为溶胶总重量的30~35%;酚醛树脂的热聚在100~105℃下进行20小时;然后对上述处理的产物恢复氮气或氩气流量,以20~25℃/分钟的速度将温度调整到600~800℃,恒温10~20h,保持压力为常压,然后将所得产物在氮气或氩气气氛保护下自然冷却到室温;
5)使用薄膜金属沉积工艺在步骤4)所得产物上沉积薄金属层,其中该薄金属层与该导电基材的表面有良好电接触;
6)在该薄金属层上沉积电解质,其中该电解质由锂磷氮氧化物(LiPON)、锂氧磷(LiOP)、锂磷(LiP)、锂聚合物电解质、双草酸硼酸锂(LiBOB)、六氟磷酸锂(LiPF6)结合碳酸乙烯酯(C3H4O3)、碳酸二甲酯(C3H6O3)或离子液体所形成。
优选的是,步骤2)中所述的分散剂为去离子水、无水乙醇或丙酮。
在上述任一方案中优选的是,步骤3)中的纳米碳管是单壁纳米碳管或多壁纳米碳管。
在上述任一方案中优选的是,该碳富勒烯洋葱状物包括C60、C70、C72、C84或C112分子和/或高深宽比链的球状碳富勒烯洋葱状物。
在上述任一方案中优选的是,可用氧化锡、氧化铜、氧化钒、氧化亚镍、氧化铬、氧化钨或其组合来代替步骤2)中的MgO,其重量百分比为催化剂总重量的10%。
在上述任一方案中优选的是,可用氦气、氖气、CO或CO2气体来代替步骤3)和4)中的氮气或氩气。
在上述任一方案中优选的是,步骤2)中的球磨机转速为600r/m。
在上述任一方案中优选的是,步骤3)中的氮气或氩气流量为550sccm,甲烷气体流量为500sccm,保持压力在1.8Mpa;所述纳米碳管和碳纤维的长度和直 径为15nm,比表面积为300-m2.g-1。
在上述任一方案中优选的是,步骤4)中的酚醛树脂热聚在102℃下进行20小时;然后对上述处理的产物恢复氮气或氩气流量,以20~25℃/分钟的速度将温度调整到700℃,恒温15h,保持压力为常压。
有益效果:
1.本发明现场生长纳米碳管,防止了团聚,纳米碳管或者碳纤维与磷酸铁锂有效接触,降低了纳米碳管或者碳纤维使用量,既降低了成本,又提高了磷酸铁锂的性能。
2.可以明显提高纳米碳纤维的储氢性能。
3.本发明与现有技术相比,形成具有导电性好的复合电极材料,从而提高高倍率性能,制得的粉体颗粒具有一定数量的纳米通道,增加了电极的有效反应面积和锂离子进出的通道,使电极材料有很高的可逆电化学容量;本发明的产品成本低廉,性能优异,满足电极材料大电流放电的要求,其制备方法简单,满足工业化生产的需求。
4.有自支撑整体结构,无需后续成型;具有利于电解质容储、离子传导和存储的三维层次孔结构;复合材料导电性好、内阻小;复合材料织构调控灵活。
5.提高了离子电导率,又提高了电子电导率。
6.提供高能量密度的能量储存。
具体实施方式
下面结合具体实施方式对本发明作进一步说明。
实施例1:
1)将体积比为1:1:1的液态高分子量碳氢前驱物C20H40、C20H42和C22H44在500℃气化以形成前驱物气体;
2)按以下组分和质量百分比含量称量原料:催化剂5g、锂盐5g、铁盐50g和磷酸盐30g;所述的催化剂为金属Ni、Y、Zr和MgO的超细粉体,尺寸为500nm,其重量百分比分别为催化剂总重量的85%、5%、5%和10%;所述的锂盐为碳酸锂、氢氧化锂、硝酸锂和磷酸锂的组合,其重量百分比分别为锂盐总重量的45%、25%、25%和5%;所述的铁盐为草酸亚铁和磷酸铁,其重量百分比分别为铁盐总重量的70%和30%;所述的磷酸盐为磷酸二氢铵和磷酸铵,其重量百 分比分别为磷酸盐总重量的50%和50%;将上述原料加入分散剂后在球磨机中以500r/m的转速球磨15h,制得前体,加入分散剂的重量为上述原料重量的1%;
3)将步骤2)所得的前体放入60℃的真空烘箱中干燥20小时后放入气氛保护管式真空炉中,并置于导电基材上,然后通入高纯氮气(N2纯度≥99.999%),流量为500sccm,以25℃/分钟的速度升温至150℃,再通入流量为350sccm的步骤1)中的前驱物气体,保持压力在1.5Mpa;同时关掉氮气,在600℃温度下恒温120min成纳米碳管所连接的富勒烯葱状物三维结构材料,其长度和直径为10~20nm,比表面积为100-500m2.g-1;该碳富勒烯洋葱状物包括C60、C70、C72、C84或C112分子和/或高深宽比链的球状碳富勒烯洋葱状物;
4)将步骤3)中获得的产物分散于有机溶剂乙醇中,采用瞬态干燥方法制得分散粉体,并用酚醛树脂-P123高分子共聚物-原硅酸乙酯的溶胶等体积浸渍该分散粉体并经充分缩合,酚醛树脂重量含量为溶胶总重量的40%,P123高分子共聚物重量含量为溶胶总重量的20%,原硅酸乙酯重量含量为溶胶总重量的35%;酚醛树脂的热聚在105℃下进行20小时;然后对上述处理的产物恢复氮气或氩气流量,以20℃/分钟的速度将温度调整到600℃,恒温20h,保持压力为常压,然后将所得产物在氮气或氩气气氛保护下自然冷却到室温;
5)使用薄膜金属沉积工艺在步骤4)所得产物上沉积薄金属层,其中该薄金属层与该导电基材的表面有良好电接触;
6)在该薄金属层上沉积电解质,其中该电解质由锂磷氮氧化物(LiPON)、锂氧磷(LiOP)、锂磷(LiP)、锂聚合物电解质、双草酸硼酸锂(LiBOB)、六氟磷酸锂(LiPF6)结合碳酸乙烯酯(C3H4O3)、碳酸二甲酯(C3H6O3)或离子液体所形成。
以制备的电极作为正极,然后以锂片为对电极,美国Celgard 2400为隔膜,以1.0mol·L-1LiPF6/EC+DMC[V(EC):V(DMC)=1:1]为电解液,在充满氩气的不锈钢手套箱中装配成扣式电池。在Land-BTL10(蓝电)全自动电池程控测试仪上进行恒流恒压充放电测试,放电倍率分别为0.5~3C,充放电电压范围为4.5~5.5V。在1C倍率下放电容量为150mAh·g-1。
在20℃和60atm的压力下测得该方法制得的电极材料的氢吸附能力为10min内大于等于0.8(gH2/100g)。
实施例2:
1)将体积比为1:1:1的液态高分子量碳氢前驱物C20H40、C20H42和C22H44在500℃气化以形成前驱物气体;
2)按以下组分和质量百分比含量称量原料:催化剂5g、锂盐10g、铁盐55g和磷酸盐40g;所述的催化剂为金属Ni、Y、Zr和MgO的超细粉体,尺寸为500nm,其重量百分比分别为催化剂总重量的85%、5%、5%和10%;所述的锂盐为碳酸锂、氢氧化锂、硝酸锂和磷酸锂的组合,其重量百分比分别为锂盐总重量的45%、25%、25%和5%;所述的铁盐为草酸亚铁和磷酸铁,其重量百分比分别为铁盐总重量的70%和30%;所述的磷酸盐为磷酸二氢铵和磷酸铵,其重量百分比分别为磷酸盐总重量的50%和50%;将上述原料加入分散剂后在球磨机中以800r/m的转速球磨10h,制得前体,加入分散剂的重量为上述原料重量的5%;
3)将步骤2)所得的前体放入70℃的真空烘箱中干燥20小时后放入气氛保护管式真空炉中,并置于导电基材上,然后通入高纯氮气(N2纯度≥99.999%),流量为600sccm,以20℃/分钟的速度升温至200℃,再通入流量为650sccm的步骤1)中的前驱物气体,保持压力在2Mpa;同时关掉氮气,在1000℃温度下恒温90min成纳米碳管所连接的富勒烯葱状物三维结构材料,其长度和直径为10~20nm,比表面积为100-500m2.g-1;该碳富勒烯洋葱状物包括C60、C70、C72、C84或C112分子和/或高深宽比链的球状碳富勒烯洋葱状物;
4)将步骤3)中获得的产物分散于有机溶剂乙醇中,采用瞬态干燥方法制得分散粉体,并用酚醛树脂-P123高分子共聚物-原硅酸乙酯的溶胶等体积浸渍该分散粉体并经充分缩合,酚醛树脂重量含量为溶胶总重量的40%,P123高分子共聚物重量含量为溶胶总重量的20%,原硅酸乙酯重量含量为溶胶总重量的35%;酚醛树脂的热聚在100℃下进行20小时;然后对上述处理的产物恢复氮气或氩气流量,以20℃/分钟的速度将温度调整到800℃,恒温10h,保持压力为常压,然后将所得产物在氮气或氩气气氛保护下自然冷却到室温;
5)使用薄膜金属沉积工艺在步骤4)所得产物上沉积薄金属层,其中该薄金属层与该导电基材的表面有良好电接触;
6)在该薄金属层上沉积电解质,其中该电解质由锂磷氮氧化物(LiPON)、锂 氧磷(LiOP)、锂磷(LiP)、锂聚合物电解质、双草酸硼酸锂(LiBOB)、六氟磷酸锂(LiPF6)结合碳酸乙烯酯(C3H4O3)、碳酸二甲酯(C3H6O3)或离子液体所形成。
以制备的电极作为正极,然后以锂片为对电极,美国Celgard 2400为隔膜,以1.0mol·L-1LiPF6/EC+DMC[V(EC):V(DMC)=1:1]为电解液,在充满氩气的不锈钢手套箱中装配成扣式电池。在Land-BTL10(蓝电)全自动电池程控测试仪上进行恒流恒压充放电测试,放电倍率分别为2.5~3.3C,充放电电压范围为5~6V。在1C倍率下放电容量为165mAh·g-1。
在20℃和60atm的压力下测得该方法制得的电极材料的氢吸附能力为10min内大于等于0.92(gH2/100g)。
实施例3:
1)将体积比为1:1:1的液态高分子量碳氢前驱物C20H40、C20H42和C22H44在500℃气化以形成前驱物气体;
2)按以下组分和质量百分比含量称量原料:催化剂10g、锂盐5g、铁盐50g和磷酸盐35g;所述的催化剂为金属Ni、Y、Zr和MgO的超细粉体,尺寸为500nm,其重量百分比分别为催化剂总重量的85%、5%、5%和10%;所述的锂盐为碳酸锂、氢氧化锂、硝酸锂和磷酸锂的组合,其重量百分比分别为锂盐总重量的45%、25%、25%和5%;所述的铁盐为草酸亚铁和磷酸铁,其重量百分比分别为铁盐总重量的70%和30%;所述的磷酸盐为磷酸二氢铵和磷酸铵,其重量百分比分别为磷酸盐总重量的50%和50%;将上述原料加入分散剂后在球磨机中以600r/m的转速球磨10h,制得前体,加入分散剂的重量为上述原料重量的2.5%;
3)将步骤2)所得的前体放入65℃的真空烘箱中干燥20小时后放入气氛保护管式真空炉中,并置于导电基材上,然后通入高纯氮气(N2纯度≥99.999%),流量为500sccm,以22℃/分钟的速度升温至180℃,再通入流量为500sccm的步骤1)中的前驱物气体,保持压力在1.8Mpa;同时关掉氮气,在800℃温度下恒温100min成纳米碳管所连接的富勒烯葱状物三维结构材料,其长度和直径为10~20nm,比表面积为100-500m2.g-1;该碳富勒烯洋葱状物包括C60、C70、C72、C84或C112分子和/或高深宽比链的球状碳富勒烯洋葱状物;
4)将步骤3)中获得的产物分散于有机溶剂乙醇中,采用瞬态干燥方法制得 分散粉体,并用酚醛树脂-P123高分子共聚物-原硅酸乙酯的溶胶等体积浸渍该分散粉体并经充分缩合,酚醛树脂重量含量为溶胶总重量的50%,P123高分子共聚物重量含量为溶胶总重量的30%,原硅酸乙酯重量含量为溶胶总重量的30%;酚醛树脂的热聚在102℃下进行20小时;然后对上述处理的产物恢复氮气或氩气流量,以22℃/分钟的速度将温度调整到700℃,恒温15h,保持压力为常压,然后将所得产物在氮气或氩气气氛保护下自然冷却到室温;
5)使用薄膜金属沉积工艺在步骤4)所得产物上沉积薄金属层,其中该薄金属层与该导电基材的表面有良好电接触;
6)在该薄金属层上沉积电解质,其中该电解质由锂磷氮氧化物(LiPON)、锂氧磷(LiOP)、锂磷(LiP)、锂聚合物电解质、双草酸硼酸锂(LiBOB)、六氟磷酸锂(LiPF6)结合碳酸乙烯酯(C3H4O3)、碳酸二甲酯(C3H6O3)或离子液体所形成。
以制备的电极作为正极,然后以锂片为对电极,美国Celgard 2400为隔膜,以1.0mol·L-1LiPF6/EC+DMC[V(EC):V(DMC)=1:1]为电解液,在充满氩气的不锈钢手套箱中装配成扣式电池。在Land-BTL10(蓝电)全自动电池程控测试仪上进行恒流恒压充放电测试,放电倍率分别为3~3.5C,充放电电压范围为5.5~6.5V。在1C倍率下放电容量为170mAh·g-1。
在20℃和60atm的压力下测得该方法制得的电极材料的氢吸附能力为10min内大于等于0.88(gH2/100g)。
上述实施例中所提供的催化剂可按照下列步骤制备:
(1)溶液的配制
将50ml含8.5gNi的硝酸镍水溶液与50ml含5gY的硝酸钇水溶液和50ml含8.5gNi的硝酸锆水溶液混合,得溶液A;将15g碳酸氢钠配成150ml水溶液,得溶液B。
(2)沉淀的制备
将溶液B在0℃以约8ml/min的速度滴入以氖气强烈搅拌下的溶液A中,得沉淀,氖气的充入速度为100ml/s。
(3)催化剂的制备
将(2)所得沉淀经去离子水洗涤、过滤,然后加入10g的氧化镁粉末,充分混合均匀,经120℃干燥5小时,氩气气氛下400℃焙烧6小时后制得催化剂。
以上所述,仅是本发明的较佳实施例而已,并非是对本发明作其它形式的限制,任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型,仍属于本发明技术方案的保护范围。
Claims (2)
1.一种纳米碳电极的制备方法,其特征在于,包括以下步聚:
1)将体积比为1:1:1的液态高分子量碳氢前驱物C20H40、C20H42和C22H44在500~1000℃气化以形成前驱物气体;
2)按以下组分和质量百分比含量称量原料:催化剂5%~10%、锂盐5%~10%、铁盐50%~55%和磷酸盐30~40%;所述的锂盐为碳酸锂、氢氧化锂、硝酸锂和磷酸锂的组合,其重量百分比分别为锂盐总重量的45%、25%、25%和5%;所述的铁盐为草酸亚铁和磷酸铁,其重量百分比分别为铁盐总重量的70%和30%;所述的磷酸盐为磷酸二氢铵和磷酸铵,其重量百分比分别为磷酸盐总重量的50%和50%;将上述原料加入分散剂后在球磨机中以球磨机转速为600r/m的转速球磨10~15h,制得前体,加入分散剂的重量为上述原料重量的1%~5%;所述催化剂按照下列步骤制备:
(1)溶液的配制
将50ml含8.5gNi的硝酸镍水溶液与50ml含5gY的硝酸钇水溶液和50ml含8.5gZr的硝酸锆水溶液混合,得溶液A;将15g碳酸氢钠配成150ml水溶液,得溶液B;
(2)沉淀的制备
将溶液B在0℃以约8ml/min的速度滴入以氖气强烈搅拌下的溶液A中,得沉淀,氖气的充入速度为100ml/s;
(3)催化剂的制备
将(2)所得沉淀经去离子水洗涤、过滤,然后加入10g的氧化镁粉末,充分混合均匀,经120℃干燥5小时,氩气气氛下400℃焙烧6小时后制得催化剂;
3)将步骤2)所得的前体放入60~70℃的真空烘箱中干燥10~30小时后放入气氛保护管式真空炉中,并置于导电基材上,然后通入氮气或氩气,氮气或氩气流量为500~600sccm,以20~25℃/分钟的速度升温至150~200℃,再通入流量为350~650sccm的步骤1)中的前驱物气体,保持压力在1.5~2.0Mpa;同时关掉氮气或氩气,在600~1000℃温度下恒温90~120min形成纳米碳管所连接的碳富勒烯洋葱状物三维结构材料,其长度和直径为10~20nm,比表面积为100-500m2.g-1;
4)将步骤3)中获得的产物分散于有机溶剂乙醇中,采用瞬态干燥方法制得分散粉体,并用酚醛树脂-P123高分子共聚物-原硅酸乙酯的溶胶等体积浸渍该分散粉体并经充分缩合,酚醛树脂重量含量为溶胶总重量的40~50%,P123高分子共聚物重量含量为溶胶总重量的20~30%,原硅酸乙酯重量含量为溶胶总重量的30~35%;酚醛树脂的热聚在102℃下进行20小时;然后对上述处理的产物恢复氮气或氩气流量,以20~25℃/分钟的速度将温度调整到700℃,恒温15h,保持压力为常压,然后将所得产物在氮气或氩气气氛保护下自然冷却到室温;
5)使用薄膜金属沉积工艺在步骤4)所得产物上沉积薄金属层,其中该薄金属层与该导电基材的表面有良好电接触;
6)在该薄金属层上沉积电解质,其中该电解质由锂磷氮氧化物(LiPON)、锂氧磷(LiOP)、锂磷(LiP)、锂聚合物电解质、双草酸硼酸锂(LiBOB)、六氟磷酸锂(LiPF6)结合碳酸乙烯酯(C3H4O3)、碳酸二甲酯(C3H6O3)或离子液体所形成;
步骤2)中所述的分散剂为去离子水、无水乙醇或丙酮;
步骤3)中的纳米碳管是单壁纳米碳管或多壁纳米碳管;
所述碳富勒烯洋葱状物包括C60、C70、C72、C84或C112分子和/或高深宽比链的球状碳富勒烯洋葱状物。
2.根据权利要求1所述的纳米碳电极的制备方法,其特征在于,可用氦气、氖气、CO或CO2气体来代替步骤3)和4)中的氮气或氩气。
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