CN109003830A - A kind of supercapacitor and preparation method thereof - Google Patents
A kind of supercapacitor and preparation method thereof Download PDFInfo
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- CN109003830A CN109003830A CN201810981474.7A CN201810981474A CN109003830A CN 109003830 A CN109003830 A CN 109003830A CN 201810981474 A CN201810981474 A CN 201810981474A CN 109003830 A CN109003830 A CN 109003830A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 98
- 239000007772 electrode material Substances 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 65
- 239000003990 capacitor Substances 0.000 claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 67
- 239000002131 composite material Substances 0.000 claims description 65
- 239000002121 nanofiber Substances 0.000 claims description 51
- 239000000725 suspension Substances 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002019 doping agent Substances 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical group C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 150000003233 pyrroles Chemical class 0.000 abstract description 45
- 230000000694 effects Effects 0.000 abstract description 13
- 241000894006 Bacteria Species 0.000 abstract description 9
- 229920002678 cellulose Polymers 0.000 abstract description 8
- 239000001913 cellulose Substances 0.000 abstract description 8
- 238000005253 cladding Methods 0.000 abstract 1
- 229920000128 polypyrrole Polymers 0.000 description 132
- 238000000034 method Methods 0.000 description 30
- 239000004020 conductor Substances 0.000 description 22
- 239000002109 single walled nanotube Substances 0.000 description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000013049 sediment Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000033116 oxidation-reduction process Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920002749 Bacterial cellulose Polymers 0.000 description 3
- 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 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 3
- 239000005016 bacterial cellulose Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UYVVLXVBEQAATF-UHFFFAOYSA-N 4-(1,3,7,12-tetrahydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl)pentanoic acid Chemical compound OC1CC2CC(O)CC(O)C2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 UYVVLXVBEQAATF-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229960003964 deoxycholic acid Drugs 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 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
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a kind of supercapacitors and preparation method thereof, belong to electrochemical capacitor field.In order to solve the problems, such as that conductivity is low existing for electrode material film, capacitance is small and at high cost, the present invention provides a kind of electrode materials, mainly formed by bacteria cellulose BC, pyrroles Py, multi-walled carbon nanotube Material cladding, not only meet flexible electronic devices to elastic properties of materials stretching and curved requirement, simultaneously meet preparation cost is low, preparation method simplify, material structure is stablized, conductivity height and the big electrode material of capacitance.The material is applied in capacitor, the technical effects such as the good rate capability charge and discharge time for obtaining electrode is longer, fake capacitance better performances, specific capacitance significantly improve, the capacitor performance of the material and its application is preferable, and application is wider.
Description
Technical field
The present invention relates to electrochemical capacitor field, in particular to a kind of supercapacitor and preparation method thereof.
Background technique
Supercapacitor is a kind of novel energy-storing element between traditional capacitor and common batteries, relative to traditional capacitance
Device has higher energy density to have higher power density relative to battery.Its charge/discharge speed is fast, has extended cycle life, and work model
It encloses extensively, therefore causes the extensive concern of people.As a kind of biggish emerging energy storage dress of the good and electric stored energy capacitance of charge-discharge performance
It sets.Although the energy density of supercapacitor is lower than lithium battery, supercapacitor is because it is with fast charging and discharging and function
The advantages that rate density is high can be improved in future to the improvement that supercapacitor field according to applied by it is different and carries out
Its energy density.
Traditional metallic conductor conductive material, such as Cu, Ag.The metal materials such as Ni, although there is higher electric conductivity,
Be not able to satisfy flexible electronic devices to elastic properties of materials stretch and curved requirement, be not able to satisfy fuel cell, ion battery,
Requirement of the electrochemical appliances such as flexible super capacitor to conductive electrode material, and pollution level is high, it is not degradable.With the epoch
Development, in electrode material for super capacitor, with high-specific surface area, good chemical stability carbon material be super capacitor
Electrode material is studied and be widely used to device.Bacteria cellulose bacteria cellulose (hereinafter referred to as BC) is synthesized by microbial fermentation
Porosity mesh nano grade biopolymer, hyperfine structure interconnected assign the porosity and Bi Biao of BC abundance
Area has three-dimensional porous property mesh nano level structure, and surface contains great amount of hydroxy group, also has good stretching and bending etc.
Mechanical performance has biodegradability, has good compatibility with environment, can be used as the base material of composite material.
Increase with people to demand for energy, needs to produce the energy storage device with higher energy density, it is wanted
Ask electrode material electric conductivity with higher and capacitance.However, BC-PPy film still has, conductivity is low and capacitance is small
The problem of.Ma(Ma L,Liu R,Niu H,et al.Freestanding conductive film based on
polypyrrole/bacterial cellulose/graphene paper for flexible supercapacitor:
Large areal mass exhibits excellent areal capacitance[J].Electrochimica Acta,
Pass through simple vacuum filtration process in 2016,222:429-437) for BC-PPy nanofiber and redox graphene dispersion liquid
Mixing is made BC/PPY/RGO (redox graphene) composite membrane, realizes after being assembled into supercapacitor in 1mAcm-2
3.66Fcm-2With in 50mAcm-22.59Fcm-2High area capacitance.
Peng et al. is prepared for BC/PPy/CuS (Peng S, Fan L, Wei C, et al.Flexible
polypyrrole/copper sulfide/bacterial cellulose nanofibrous composite
membranes as supercapacitor electrodes[J].Carbohydrate Polymers,2017,157:344-
352)、BC/PPy/NiS(nanofibrous composite membranes for flexible supercapacitor
Electrodes [J] .Cellulose, 2016,23 (4): 2639-2651) and BC/PPy/CoS (Peng S, Xu Q, Fan
L,et al.Flexible polypyrrole/cobalt sulfide/bacterial cellulose c omposite
membranes for supercapacitor application[J].Synthetic Metals,2016,222(B):285-
292) flexible super capacitor electrode material, the addition of CuS, NiS, CoS improve the specific capacitance of BC base electrode, reach it respectively
To 580Fg-1、713F·g-1、614F·g-1。
In order to solve the problems, such as that conductivity is low existing for electrode material film, capacitance is small and at high cost, it is desirable to provide one
Kind of electrode material not only meets flexible electronic devices and stretches to elastic properties of materials and curved requirement, while it is low to meet preparation cost,
Preparation method simplifies, and material structure is stablized, conductivity height and the big electrode material of capacitance.
Summary of the invention
The present invention provides a kind of supercapacitor, including positive and negative electrode, diaphragm, current-collector and electrolyte, described positive and negative
Electrode is specially combination electrode material, and the combination electrode material is mainly received by bacteria cellulose (BC), pyrroles (Py), multi wall carbon
Mitron (MWCNTs) is combined, and the preparation of the combination electrode material includes: to be beaten BC film, disperse to obtain nanofiber
After being mixed the nanofiber suspension with oxidant and dopant, Py monomer is added into mixed liquor for suspension,
Bacteria cellulose film/polypyrrole (BC/PPy) composite pulp is obtained, BC/PPy compound is obtained after composite pulp is removed water, by BC/PPy
Compound is added in the MWCNTs dispersion liquid for being mixed with dispersing agent, obtains BC/PPy/MWCNTs after mixing, dehydration, drying
Combination electrode material.
Preferably, the oxidant has one of iron chloride, ferric perchlorate, ammonium persulfate or hydrogen peroxide；It is described to mix
Miscellaneous dose has one of hydrochloric acid, sulfuric acid or dust technology.
Preferably, the dispersing agent is cetyl trimethylammonium bromide (CTAB), lauryl sodium sulfate (SDS), takes off
One of oxycholic acid sodium (DOC) or neopelex (SDBS).
It is highly preferred that the dispersing agent is cetyl trimethylammonium bromide (CTAB).
Preferably, the electrolyte is one of potassium chloride, sodium hydroxide, sulfuric acid, lithium chloride.
It is highly preferred that the electrolyte is lithium chloride, concentration 2.0mol/L.
Preferably, the diaphragm material is one in filter paper, PVDF membrane or polypropylene, polyethylene film combined films
Kind.
It is highly preferred that the diaphragm material is polypropylene, polyethylene combined films.
Preferably, the current-collector is metal foil, metal mesh, conducting polymer composite material, expanding metal or stainless steel
One of material.
It is highly preferred that the current-collector is stainless steel material.
It is a further object of the present invention to provide the preparation methods of above-mentioned supercapacitor, the specific steps are as follows:
(a) preparation of positive and negative electrode:
(1) BC film is beaten, disperses to obtain BC nanofiber suspension, the BC nanofiber suspension is added to
In mixed liquor containing oxidant and dopant, through ultrasound, stirring, cooling, mixed liquor A is obtained, Py monomer is added to mixing
In liquid A, and at 2-6 DEG C, reaction time 150-210min obtains BC/PPy composite pulp, and the BC/PPy composite pulp is passed through
After water removal, BC/PPy compound is obtained, it is spare；The molar ratio of the dopant and Py are (1.25-25): 1, oxidant and Py's
Molar ratio is (0.09-3.1): 1；
(2) MWCNTs, dispersing agent and water are mixed, obtains mixed liquid B, wherein MWCNTs concentration is 0.8-1mg/mL；
The BC/PPy compound is added in mixed liquid B according to adding proportion 3g:50-100mL, is obtained after agitated dehydration, drying
BC/PPy/MWCNTs combination electrode material；
(b) capacitor is organized:
After BC/PPy/MWCNTs combination electrode material is cut out, as positive and negative pole material；It is used between positive and negative pole material
Diaphragm separates, and injects electrolyte, and adds current-collector on the outside of positive and negative pole material to get symmetric form supercapacitor is arrived.
Preferably, in the step (1), the oxidant is iron chloride, and the dopant is hydrochloric acid.
It is highly preferred that the molar ratio of the hydrochloric acid and Py are (2.5-25): 1, the molar ratio of iron chloride and Py are (2.3-
3.1): 1.
Preferably, in the step (1), in the step (1), the concentration of the BC nanofiber suspension is 1-4mg/
mL。
Preferably, in the step (1), the Py monomer and initial BC nanofiber suspension volume ratio are (0.2-
0.4):50。
Preferably, in the step (1), BC nanofiber suspension the preparation method comprises the following steps: BC is crushed, be beaten 5-
10min is dispersed 10-15min at 8500-10000r/min using high speed disperser and obtains nanofiber suspension.
Preferably, in the step (1), ultrasonic time 15-20min, mixing time 15-20min, cooling temperature is
2-6℃。
Preferably, in the step (1), the water-eliminating method of the BC/PPy compound are as follows: by BC/PPy composite pulp with
7000-8000rpm is centrifuged 10-15min, removes supernatant, leaves sediment.
Preferably, in the step (2), the dispersant concentration is 3-6mg/mL.
Preferably, in the step (2), the mixed liquid B is received the preparation method comprises the following steps: being proportionally added into multi wall carbon into water
Mitron and dispersing agent obtain mixed liquid B through ultrasonic disperse 2-3h.
Beneficial effect
1, the present invention is raw material using bacteria cellulose, polypyrrole, multi-walled carbon nanotube, provide it is a kind of efficiently, it is economical,
The preparation method of the electrode material of environmental protection, and can be applied in supercapacitor.
2, preparation method of the present invention is simple and efficient, among the BC/PPy in production procedure, is not dialysed or is eluted
This routine operation, it not only simplifies the preparation method, and surprisingly obtains significantly more technical effect, without dialysis
The conductivity of the BC/PPy/MWCNTs composite conducting material of BC/PPy preparation is up to 1.60S/cm2, specific capacitance is up to
1.398F/cm2, relatively by the BC/PPy, the BC/PPy/ being prepared according to the same method of the embodiment of the present invention 14 of dialysis
MWCNTs compound conductivity (additive amount of multi-walled carbon nanotube is 50mg) high 1.25S/cm2, the high 1.092F/cm of specific capacitance2。
3, the control of the ratio of hydrochloric acid and pyrroles is often the point usually ignored in material preparation process.And the present invention passes through control
The ratio of salt manufacturing acid and pyrroles, unexpectedly obtain its ratio can be obtained the significant skill of conductivity raising in small range section
Art effect.
4, the selection of multi-walled carbon nanotube:
Carbon nanotube is as monodimension nanometer material, and light-weight, hexagonal structure connection is perfect, has many abnormal power
, electricity and chemical property.TEM is utilized for the first time and measures temperature multi wall in from room temperature to 800 degree of variation ranges by Treacy etc.
The mean square amplitude of carbon nanotube, to derive that the average Young's modulus of multi-walled carbon nanotube is about 1.8Tpa (M M J
Treacy,T W Ebbesen,J M Gibson et al.Exceptionally high young’s modulus
Observed for individual carbon nanotubes [J] .Nature, 1996,381 (6584): 678~680).
And Salvetat etc. measures the Young's modulus of the single-walled carbon nanotube of minor diameter, and exporting its modulus of shearing is 1Tpa (J P
Salvetat,A D Briggs,J M Bonard et al.Elastic and shear module of single wall
Cathon nanotube ropes [J] .phys Rev Lett, 1999,82 (5): 944~947).Wong etc. is aobvious with atomic force
The bending strength average value that micro mirror measures multi-walled carbon nanotube is 14.2 ± 10.8GPa, and the bending strength of carbon fiber only has
1GPa(E W Wong,P E Sheechan,C M Liebe et al.Nanobeam Mechanics:Elasticity,
Strength and Toughness of Nanorods and Nanotubes [J] .Science, 1997,277 (5334):
1971~1975).Multi-walled carbon nanotube either intensity or toughness, all far superior to any fiber.Meanwhile multi-wall carbon nano-tube
Pipe is wrapped by multilayer carbon atom, and interlamellar spacing is about 0.34nm, and for outer diameter in several nanometers to several hundred nanometers, length is general
In micron dimension, the longest can meet the needs of different materials processing up to several millimeters.Cost is relatively low for multi-walled carbon nanotube,
It is ten parts of single-walled carbon nanotube price, thus Selection utilization multi-walled carbon nanotube of the present invention prepares conductive material,
The present invention selects multi-walled carbon nanotube for raw material, not only realizes low cost but also realizes efficient technology effect
Fruit.
Detailed description of the invention
Fig. 1 is scanning electron microscope (hereinafter referred to as SEM) photo in the embodiment of the present invention, wherein the SEM photograph of (I) pure BC material
(II) SEM photograph of SEM photograph (III) BC-PPy-MWCNTs material of BC-PPy material；
Fig. 2 is the CV curve graph of electrode material in the embodiment of the present invention；Wherein (I) BC-PPy-MWCNTs-1 (II) BC-
PPy-MWCNTs-2；
Fig. 3 is the CV curve graph of two electrode materials under 20mV/s scanning speed in the embodiment of the present invention；
Fig. 4 is GCD curve graph of the electrode material under different current densities in the embodiment of the present invention, wherein (I) BC-PPy-
MWCNTs-1, (II) BC-PPy-MWCNTs-2；
Fig. 5 is two electrode materials in the embodiment of the present invention in 3mA/cm2GCD curve under current density；
Fig. 6 is the specific capacitance value line chart in the embodiment of the present invention under different current densities；
Fig. 7 is power density and energy density figure in the embodiment of the present invention；
Fig. 8 is the EIS figure of electrode material in the embodiment of the present invention, wherein two electrode material of (I) BC-PPy-MWCNTs
EIS figure；(II) two electrode material EIS figure low frequency range enlarged drawing of BC-PPy-MWCNTs；
Fig. 9 is the CV test curve of the supercapacitor in the embodiment of the present invention under different scanning rates, wherein (I) is
BC-PPy-MWCNTs-1, (II) are BC-PPy-MWCNTs-2；
Figure 10 is the CV curve graph of two supercapacitors under 20mV/s scanning speed in the embodiment of the present invention；
Figure 11 is GCD curve graph of the supercapacitor under different current densities in the embodiment of the present invention, wherein (I) BC-
PPy-MWCNTs-1, (II) BC-PPy-MWCNTs-2；
Figure 12 is supercapacitor in the embodiment of the present invention in 3mA cm-2Current density under GCD curve；
Figure 13 is that the EIS that electrode material is applied to supercapacitor in the embodiment of the present invention schemes；
Figure 14 is specific capacitance value of the supercapacitor under different current densities in the embodiment of the present invention；
Figure 15 is the relationship in the embodiment of the present invention between the power density and energy density of supercapacitor；
Figure 16 is the relational graph in the embodiment of the present invention between (I) pyrroles dosage and BC/PPy electrode material sheet resistance, (II)
Relational graph between pyrroles's dosage and BC/PPy electrode material conductivity；
Figure 17 is (I) HCl and Py molar ratio (n in the embodiment of the present inventionHCL: nPy) and BC/PPy electrode material sheet resistance between
Relational graph, the relational graph between (II) HCl and Py molar ratio and BC/PPy electrode material conductivity；
Figure 18 is (I) FeCl in the embodiment of the present invention3With Py different mol ratio (nFeCl3: nPy) and the electrode material side BC/PPy
Relational graph between resistance, (II) FeCl3Relational graph between Py different mol ratio and BC/PPy electrode material conductivity.
Content is embodied
The present invention is described below by specific embodiment.Unless stated otherwise, technological means used in the present invention
It is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, it is not intended to limit the present invention
Range, the spirit and scope of the invention are limited only by the claims that follow.To those skilled in the art, without departing substantially from this
Under the premise of invention spirit and scope, to the various changes or change of material component and dosage progress in these embodiments
It belongs to the scope of protection of the present invention.
The preparation of 1 electrode material of embodiment and capacitor
(1) BC crushed, be beaten 5min, high speed disperser is used to disperse 10min at 8500r/min, be made
The BC nanofiber suspension of 1mg/mL；
(2) BC nanofiber suspension is added in the hydrochloric acid mixed solution containing iron chloride, through ultrasonic 15min, stirring
15min, 2 DEG C of cooling, obtain mixed liquor A, and Py monomer is added according to initial BC nanofiber suspension volume ratio 0.2:50
Into mixed liquor A, and at 2 DEG C, reaction time 150min obtains BC/PPy composite pulp, and the BC/PPy composite pulp is passed through
After water removal, BC/PPy compound is obtained, it is spare；
Wherein the molar ratio of hydrochloric acid and pyrroles are 2.5:1, and the molar ratio of iron chloride and pyrroles are 2.3:1；
Wherein, the water-eliminating method of BC/PPy compound are as follows: BC/PPy composite pulp is centrifuged 10min with 7000rpm, in removing
Clearly, sediment is left.
(3) it takes water as a solvent, prepares multi-walled carbon nanotube and cetyl trimethylammonium bromide mixed liquor, obtain mixed liquor
The BC/PPy compound is added in mixed liquid B according to adding proportion 3g:50mL, stirs 30min, take out through vacuum filter by B
Filter forms a film, is freeze-dried, obtaining BC/PPy/MWCNTs composite conducting material；
Wherein, in mixed liquid B, multi-walled carbon nanotube concentration is 0.8mg/mL, and cetyl trimethylammonium bromide concentration is
3mg/mL,
Wherein, mixed liquid B the preparation method comprises the following steps: being proportionally added into multi-walled carbon nanotube and cetyl front three into water
Base ammonium bromide obtains mixed liquid B through ultrasonic disperse 2h.
After BC/PPy/MWCNTs composite conducting material is cut out, as positive and negative pole material；It is used between positive and negative pole material
Diaphragm separates, and injects the potassium chloride electrolyte of 2.0mol/L, and adds current-collector on the outside of positive and negative pole material to get symmetric form is arrived
Supercapacitor.
Its septation material is filter paper, and current-collector uses metal foil material.
The preparation of 2 electrode material of embodiment and capacitor
(1) BC crushed, be beaten 10min, high speed disperser is used to disperse 15min at 10000r/min, be made
The BC nanofiber suspension of 4mg/mL；
(2) BC nanofiber suspension is added in the hydrochloric acid mixed solution containing iron chloride, through ultrasonic 20min, stirring
20min, 6 DEG C of cooling, obtain mixed liquor A, and Py monomer is added according to initial BC nanofiber suspension volume ratio 0.4:50
Into mixed liquor A, and at 6 DEG C, reaction time 210min obtains BC/PPy composite pulp, and the BC/PPy composite pulp is passed through
After water removal, BC/PPy compound is obtained, it is spare；
The molar ratio of the hydrochloric acid and pyrroles are 25:1, and the molar ratio of iron chloride and pyrroles are 3.1:1；
Wherein, the water-eliminating method of BC/PPy compound are as follows: BC/PPy composite pulp is centrifuged 15min with 8000rpm, in removing
Clearly, sediment is left.
(3) it takes water as a solvent, prepares multi-walled carbon nanotube and cetyl trimethylammonium bromide mixed liquor, obtain mixed liquor
The BC/PPy compound is added in mixed liquid B according to adding proportion 3g:100mL, 60min is stirred, through vacuum filter by B
Suction filtration forms a film, is freeze-dried, obtaining BC/PPy/MWCNTs composite conducting material；
Wherein, in mixed liquid B, multi-walled carbon nanotube concentration is 1mg/mL, and cetyl trimethylammonium bromide concentration is
6mg/mL,
Wherein, mixed liquid B the preparation method comprises the following steps: being proportionally added into multi-walled carbon nanotube and cetyl front three into water
Base ammonium bromide obtains mixed liquid B through ultrasonic disperse 3h.
After BC/PPy/MWCNTs composite conducting material is cut out, as positive and negative pole material；It is used between positive and negative pole material
Diaphragm separates, and injects the chlorination lithium electrolyte of 2.0mol/L, and adds current-collector on the outside of positive and negative pole material to get symmetric form is arrived
Supercapacitor.
Its septation material is PVDF membrane, and current-collector uses metal mesh material.
The preparation of 3 electrode material of embodiment and capacitor
(1) BC crushed, be beaten 8min, high speed disperser is used to disperse 12min at 9000r/min, be made
The BC nanofiber suspension of 2.5mg/mL；
(2) BC nanofiber suspension is added in the hydrochloric acid mixed solution containing iron chloride, through ultrasonic 18min, stirring
18min, 4 DEG C of cooling, obtain mixed liquor A, and Py monomer is added according to initial BC nanofiber suspension volume ratio 0.3:50
Into mixed liquor A, and at 4 DEG C, reaction time 190min obtains BC/PPy composite pulp, and the BC/PPy composite pulp is passed through
After water removal, BC/PPy compound is obtained, it is spare；
The molar ratio of the hydrochloric acid and pyrroles are 20:1, and the molar ratio of iron chloride and pyrroles are 2.7:1；
Wherein, the water-eliminating method of BC/PPy compound are as follows: BC/PPy composite pulp is centrifuged 12min with 7500rpm, in removing
Clearly, sediment is left.
(3) it takes water as a solvent, prepares multi-walled carbon nanotube and cetyl trimethylammonium bromide mixed liquor, obtain mixed liquor
The BC/PPy compound is added in mixed liquid B according to adding proportion 3g:60mL, stirs 40min, take out through vacuum filter by B
Filter forms a film, is freeze-dried, obtaining BC/PPy/MWCNTs composite conducting material；
Wherein, in mixed liquid B, multi-walled carbon nanotube concentration is 0.9mg/mL, and cetyl trimethylammonium bromide concentration is
5mg/mL,
Wherein, mixed liquid B the preparation method comprises the following steps: being proportionally added into multi-walled carbon nanotube and cetyl front three into water
Base ammonium bromide obtains mixed liquid B through ultrasonic disperse 2.5h.
After BC/PPy/MWCNTs composite conducting material is cut out, as positive and negative pole material；It is used between positive and negative pole material
Diaphragm separates, and injects the sulfuric acid electrolyte of 2.5mol/L, and surpasses on the outside of positive and negative pole material plus current-collector to get to symmetric form
Grade capacitor.
Its septation material is polypropylene, polyethylene film combined films, and current-collector uses conducting polymer composite material.
The preparation of 4 electrode material of embodiment and capacitor
(1) BC crushed, be beaten 10min, high speed disperser is used to disperse 10min at 8500r/min, be made
The BC nanofiber suspension of 3mg/mL；
(2) BC nanofiber suspension is added in the hydrochloric acid mixed solution containing iron chloride, through ultrasonic 15min, stirring
20min, 6 DEG C of cooling, obtain mixed liquor A, and Py monomer is added according to initial BC nanofiber suspension volume ratio 0.4:50
Into mixed liquor A, and at 2 DEG C, reaction time 150min obtains BC/PPy composite pulp, and the BC/PPy composite pulp is passed through
After water removal, BC/PPy compound is obtained, it is spare；
The molar ratio of the hydrochloric acid and pyrroles are 10:1, and the molar ratio of iron chloride and pyrroles are 2.5:1；
Wherein, the water-eliminating method of BC/PPy compound are as follows: BC/PPy composite pulp is centrifuged 10min with 7000rpm, in removing
Clearly, sediment is left.
(3) it takes water as a solvent, prepares multi-walled carbon nanotube and neopelex mixed liquor, obtain mixed liquid B, it will
The BC/PPy compound according to adding proportion 3g:60mL be added mixed liquid B in, stir 40min, through vacuum filter filter at
Film is freeze-dried, obtains BC/PPy/MWCNTs composite conducting material；
Wherein, in mixed liquid B, multi-walled carbon nanotube concentration is 0.9mg/mL, and neopelex concentration is 4mg/
ML,
Wherein, mixed liquid B the preparation method comprises the following steps: being proportionally added into multi-walled carbon nanotube and detergent alkylate sulphur into water
Sour sodium obtains mixed liquid B through ultrasonic disperse 2h.
After BC/PPy/MWCNTs composite conducting material is cut out, as positive and negative pole material；It is used between positive and negative pole material
Diaphragm separates, and injects the NaOH electrolyte of 2.5mol/L, and symmetrical to get arriving plus current-collector on the outside of positive and negative pole material
Type supercapacitor.
Its septation material is polypropylene, polyethylene film combined films, and current-collector uses expanding metal material.
The preparation of 5 electrode material of embodiment and capacitor
(1) BC crushed, be beaten 5min, high speed disperser is used to disperse 10min at 8500r/min, be made
The BC nanofiber suspension of 3mg/mL；
(2) BC nanofiber suspension is added in the dust technology mixed liquor containing hydrogen peroxide, through ultrasonic 15min, is stirred
15min, 2 DEG C of cooling are mixed, mixed liquor A is obtained, Py monomer is added according to initial BC nanofiber suspension volume ratio 0.2:50
Enter into mixed liquor A, and at 2 DEG C, reaction time 150min obtains BC/PPy composite pulp, and the BC/PPy composite pulp is passed through
After crossing water removal, BC/PPy compound is obtained, it is spare；
Wherein the molar ratio of dust technology and pyrroles are 2.5:1, and the molar ratio of hydrogen peroxide and pyrroles are 1.15-1.55:1；
Wherein, the water-eliminating method of BC/PPy compound are as follows: BC/PPy composite pulp is centrifuged 10min with 7000rpm, in removing
Clearly, sediment is left.
(3) it takes water as a solvent, prepares multi-walled carbon nanotube and NaTDC mixed liquor, obtain mixed liquid B, it will be described
BC/PPy compound is added in mixed liquid B according to adding proportion 3g:70mL, stirs 30min, form a film through vacuum filter suction filtration,
It is freeze-dried, obtains BC/PPy/MWCNTs composite conducting material；
Wherein, in mixed liquid B, multi-walled carbon nanotube concentration be 1mg/mL, sodium deoxycholate concentration 3mg/mL,
Wherein, mixed liquid B the preparation method comprises the following steps: be proportionally added into multi-walled carbon nanotube and NaTDC into water,
Through ultrasonic disperse 2h, mixed liquid B is obtained.
After BC/PPy/MWCNTs composite conducting material is cut out, as positive and negative pole material；It is used between positive and negative pole material
Diaphragm separates, and injects the potassium chloride electrolyte of 2.0mol/L, and adds current-collector on the outside of positive and negative pole material to get symmetric form is arrived
Supercapacitor.
Its septation material is polypropylene, polyethylene combined films, and current-collector is stainless steel material.
The preparation of 6 electrode material of embodiment and capacitor
Capacitor is prepared according to the method for embodiment 5, unique the difference is that the molar ratio of control dust technology and pyrroles are 5:
1, the molar ratio of hydrogen peroxide and pyrroles are 1.15:1.
The preparation of 7 electrode material of embodiment and capacitor
Capacitor is prepared according to the method for embodiment 5, unique the difference is that the molar ratio of control dust technology and pyrroles are 10:
1, the molar ratio of hydrogen peroxide and pyrroles are 1.55:1.
The preparation of 8 electrode material of embodiment and capacitor
Capacitor is prepared according to the method for embodiment 5, unique the difference is that the molar ratio of control dust technology and pyrroles are 20:
1, the molar ratio of hydrogen peroxide and pyrroles are 1.35:1.
The preparation of 9 electrode material of embodiment and capacitor
(1) BC crushed, be beaten 8min, high speed disperser is used to disperse 12min at 8500r/min, be made
The BC nanofiber suspension of 2.5mg/mL；
(2) BC nanofiber suspension is added in the sulfuric acid mixture liquid containing ammonium persulfate, through ultrasonic 18min, is stirred
18min, 4 DEG C of cooling are mixed, mixed liquor A is obtained, Py monomer is added according to initial BC nanofiber suspension volume ratio 0.3:50
Enter into mixed liquor A, and at 4 DEG C, reaction time 150min obtains BC/PPy composite pulp, and the BC/PPy composite pulp is passed through
After crossing water removal, BC/PPy compound is obtained, it is spare；
The molar ratio of the sulfuric acid and pyrroles are 1.25:1, and the molar ratio of ammonium persulfate and pyrroles are 1.15-1.55:1；
Wherein, the water-eliminating method of BC/PPy compound are as follows: BC/PPy composite pulp is centrifuged 12min with 7500rpm, in removing
Clearly, sediment is left.
(3) it takes water as a solvent, prepares multi-walled carbon nanotube and lauryl sodium sulfate mixed liquor, obtain mixed liquid B, by institute
State BC/PPy compound according to adding proportion 3g:60mL be added mixed liquid B in, stir 40min, through vacuum filter filter at
Film is freeze-dried, obtains BC/PPy/MWCNTs composite conducting material；
Wherein, in mixed liquid B, multi-walled carbon nanotube concentration is 0.9mg/mL, and lauryl sodium sulfate concentration is 5mg/mL,
Wherein, mixed liquid B the preparation method comprises the following steps: being proportionally added into multi-walled carbon nanotube and dodecyl sulphate into water
Sodium obtains mixed liquid B through ultrasonic disperse 2.5h.
After BC/PPy/MWCNTs composite conducting material is cut out, as positive and negative pole material；It is used between positive and negative pole material
Diaphragm separates, and injects the sulfuric acid electrolyte of 2.5mol/L, and surpasses on the outside of positive and negative pole material plus current-collector to get to symmetric form
Grade capacitor.
Its septation material is PVDF membrane, and current-collector uses conducting polymer.
The preparation of 10 electrode material of embodiment and capacitor
Capacitor is prepared according to the method for embodiment 9, it is unique the difference is that the molar ratio of control dust technology and pyrroles are
The molar ratio of 2.5:1, hydrogen peroxide and pyrroles are 1.15:1.
The preparation of 11 electrode material of embodiment and capacitor
Capacitor is prepared according to the method for embodiment 9, unique the difference is that the molar ratio of control dust technology and pyrroles are 5:
1, the molar ratio of hydrogen peroxide and pyrroles are 1.35:1.
The preparation of 12 electrode material of embodiment and capacitor
Capacitor is prepared according to the method for embodiment 9, unique the difference is that the molar ratio of control dust technology and pyrroles are 10:
1, the molar ratio of hydrogen peroxide and pyrroles are 1.55:1.
The preparation of 13 electrode material of embodiment and capacitor
Capacitor is prepared according to the method for embodiment 9, it is unique that the difference is that oxidant is perchloric acid, dopant is hydrochloric acid,
The molar ratio of hydrochloric acid and pyrroles are controlled as 10:1, the molar ratio of perchloric acid and pyrroles are 0.09-0.13:1.
The preparation of 14 electrode material of embodiment and capacitor
(1) method specifically prepared includes: that BC film is cut into small cubes first, is then beaten 5min using soy bean milk making machine,
It reuses high speed disperser and disperses 10min at 10000r/min, the BC nanofiber suspension of 1.5mg/mL is made.
(2) it then measures 50mLBC suspension to be added in hydrochloric acid (2.0M) and chlorination iron mixed solution, be ultrasonically treated
15min is stirred for 15min and is cooled to 4 DEG C, obtains mixed liquor A.By Py monomer according to initial BC nanofiber suspension body
Product is added in mixed liquor A than 0.2:50, and at 4 DEG C, reaction time 180min obtains BC/PPy composite pulp.After reacting
Slurries are centrifuged 10min with 8000rpm, sufficiently remove extra moisture, it is spare to weigh 3g.
The molar ratio of hydrochloric acid and pyrroles are 20:1 in mixed liquor A, and the molar ratio of iron chloride and pyrroles are 2.3:1.
(3) 40mg, 50mg multi-walled carbon nanotube (MWCNTs) are added separately in 50ml distilled water, and are separately added into
0.2g cationic surfactant cetyl trimethylammonium bromide (CTAB), ultrasonic disperse 2h.By above-mentioned spare 3gBC/
PPy slurry is added in multi-walled carbon nanotube dispersion liquid, is stirred 30min, is then filtered film forming using vacuum filter, obtain BC/
PPy/MWCNTs composite conducting material.
(4) by freeze-drying, BC/PPy/MWCNTs is cut into the small square of 1cm × 1cm, as positive and negative pole material
BC-PPy-MWCNTs。
During assembling, it is put into positive electrode in anode cover center, 3-5 drop electrolyte (2.0mol/L LiCl is added dropwise
Solution) infiltration electrode material, successively assemble diaphragm, negative electrode material, gasket, spring leaf finally covers negative electrode casing, and with hydraulic pressure
It picks and compresses it, symmetric form supercapacitor can be obtained.
Its septation material is polypropylene, polyethylene combined films, and current-collector is stainless steel material.
Even if it should be noted that diaphragm material selection filter paper or the polyvinylidene fluoride of 14 capacitor of the present embodiment
Film, though current-collector selection use metal foil, metal mesh, conducting polymer composite material or expanding metal, technical effect and
Embodiment 15,16,17 can equally obtain the similar technical effect of same embodiment 15,16,17 there is no apparent difference.
BC-PPy-MWCNTs-1 and BC-PPy-MWCNTs-2 is to be added respectively in the test of following example 15,16,17
40mg, 50mg multi-walled carbon nanotube obtained electrode material.
Experimental example 15BC/PPy/MWCNTs composite conducting material structure and performance test
The conducting performance test of structure is carried out to BC/PPy/MWCNTs composite conducting material prepared by embodiment 14: (1) being swept
Retouch the structure observation of Electronic Speculum:
Referring to attached drawing 1 as can be seen that (a) pure BC film surface is smooth, there is porous network structure.(b) BC-PPyc material table
Face is coarse, and BC uniformly adheres to one layer of PPy polymer, forms core-shell structure, and after polymerization, BC-PPy is remained carefully
The reticulated porous structures of fungin.(c) contain a small amount of multi-walled carbon nanotube, attachment or edge on BC-PPy-MWCNTs film
In BC-PPy film, to form stable BC-PPy-MWCNTs structure of composite membrane.
Single-walled carbon nanotube made of being wrapped as single layer of carbon atom (SWCNTs) diameter change is small, relative to MWCNTs,
SWCNTs is distributed more uniform, BC-PPy-SWCNTs close structure in BC-PPy film.And made of multilayer carbon atom wraps
MWCNTs length is usually 10-100 times of SWCNTs, can establish wider connection, the core-shell structure of MWCNTs and BC-PPy
Intertexture is spiraled, and the quick transmitting of electronics, ion is advantageously implemented, in BC-PPy-MWCNTs, it can be seen that MWCNTs locally reunites
Phenomenon.
Single-walled carbon nanotube made of being wrapped as single layer of carbon atom (SWCNTs), generally in 1-6nm, diameter is greater than diameter
6nm is later especially unstable, is easy to happen collapsing for single-walled carbon nanotube, diameter change is small, exists relative to MWCNTs, SWCNTs
More uniform, BC-PPy-SWCNTs close structure is distributed in BC-PPy film.And MWCNTs is wrapped by multilayer carbon atom,
Interlamellar spacing is about 0.34nm, and outer diameter is in several nanometers to several hundred nanometers.Its length is generally in micron dimension, and the longest is up to number milli
Rice, is approximately 10-100 times of SWCNTs, can establish wider connection, and the core-shell structure of MWCNTs and BC-PPy, which interweave, to spiral,
It is advantageously implemented the quick transmitting of electronics, ion, in BC-PPy-MWCNTs, it can be seen that the part MWCNTs agglomeration.
(2) conductivity is tested:
Gather with the BC/PPy/MWCNTs composite conducting material of the preparation of embodiment 14 and BC-PPy compound, using in situ
The BC/PAni/SWCNTs material of legal preparation carries out the test and comparison of conductivity:
1 conductivity test and comparison of table
Note: PAni: polyaniline
SWCNTs: single-walled carbon nanotube
The synergistic effect of multi-walled carbon nanotube and polypyrrole improves the chemical property of conductive composite film.After tested, more
The higher BC/PPy/MWCNTs conductive composite film chemical property of wall carbon nano tube content is more excellent, and conductivity is up to 1.6S/
cm2, it is 15 times of BC-PPy electrode material, with increasing for multi-walled carbon nanotube, this value likely continues to increase.
It should be understood that the electrode material of 1-13 of embodiment of the present invention preparation equally has above-mentioned experiment effect, each reality
It applies between example and little with above-mentioned experiment effect otherness.
The electro-chemical test of experimental example 16BC/PPy/MWCNTs composite conducting material
Test is the electro-chemical test of the BC/PPy/MWCNTs composite conducting material prepared using embodiment 14 below
(1) cyclic voltammetric (CV) is tested
Referring to attached drawing 2,3 as can be seen that in -0.2v-0.6v range, each cv curve shows class rectangle shape, and
Curve about zero current baseline almost symmetry, substantially may be used by the oxidation-reduction process for illustrating that material is occurred in charge and discharge process
It is inverse, with good capacitance behavior.The size of CV curve represents the performance of electrode capacitance, with multi-walled carbon nanotube
Increase and increases.As sweep speed increases, the shape of curve shows the good rate capability of electrode without very big deformation.
(2) constant current charge-discharge (GCD) is tested
Referring to attached drawing 4,5 it can be seen that by GCD curve it is found that its charging curve and discharge curve are mirrored into symmetrically, approximation
It is in equilateral triangle, illustrate the oxidation-reduction process Basic Reversible that material is occurred in charge and discharge process, in charge and discharge process
There is good invertibity.
(3) power density and energy density
The specific capacitance of electrode material and the relationship of charging current are referring to attached drawing 6,7, under identical current density, multi wall carbon
The high specific capacitance of nanotube content is high, is 3mA cm in current density-2When, the area capacitance 0.814F of BC-PPy-MWCNTs--1
cm-2, energy density reach 0.0635mWh cm-2, power density reaches 1.1140mW cm-2.It is 3mA cm in current density-2When,
The area capacitance of BC-PPy-MWCNTs-2 electrode material can reach 1.398F cm-2, energy density reach 0.1127mWh cm-2, function
Rate density reaches 1.1143mW cm-2.Show excellent chemical property.
Table 2BC-PPy-MWCNTs electrode material chemical property table
In formula, i is discharge current, and Δ t is discharge time, and Δ V is the potential difference in charge and discharge process.
In formula, E is face energy density, Wh/cm2；CsFor the area specific capacitance of capacitor, F/cm2；Δ V is electro-chemical test
Voltage range, V.
In formula, P is surface power density, W/cm2；E is face energy density, Wh/cm2；When Δ t is that constant current charge-discharge is tested
Between, h.
When one timing of multi-walled carbon nanotube content, with the increase of current density, the operating voltage section of electrode material is contracted
Short, discharge time also shortens, and area capacitance reduces, and energy density reduces, and power density increases.And in identical current density
Under, the parameters of BC-PPy-MWCNTs-2 are above BC-PPy-MWCNTs-1, i.e., increase multi wall carbon in a certain range and receive
The content of mitron is conducive to the chemical property for improving electrode material.
(4) AC impedance (EIS) test of electrode material
Referring to attached drawing 8, the Nyquist figure of each electrode is made of the semicircular ring of high frequency section and the vertical line of low frequency part,
Wherein the real part of high frequency region impedance reflects the complexity that charged particle is spread in hole, and the straight line of low-frequency range then reflects
The fake capacitance performance of electrode, the deviation imaginary axis is closer, and fake capacitance performance is better.It can be seen that by EIS figure, contain multi-walled carbon nanotube
More electrode material fake capacitances is good, but internal resistance is higher.
It should be understood that the electrode material of 1-13 of embodiment of the present invention preparation equally has above-mentioned experiment effect, each reality
It applies between example and little with above-mentioned experiment effect otherness.
Embodiment 17BC/PPy/MWCNTs is applied to the electro-chemical test of capacitor
Test is the electro-chemical test of the capacitor prepared using embodiment 14 below.
(1) the CV test of supercapacitor
Test voltage range illustrates material referring to attached drawing 9,10 it is found that each CV curve shows class rectangle shape for 0-0.8V
The oxidation-reduction process Basic Reversible occurred in charge and discharge process is expected, with good capacitance behavior.The face of CV curve
Product size represents the performance of electrode capacitance, and the high supercapacitor capacitive character of multi-walled carbon nanotube content can be good.Referring to attached drawing 10
It knows to increase with sweep speed, the shape of curve shows the good rate capability of electrode without very big deformation.
(2) constant current charge-discharge (GCD) is tested
Charging curve and discharge curve are mirrored into symmetrically, approximate in equilateral triangle, illustrate material in charge and discharge process
The oxidation-reduction process Basic Reversible occurred has good invertibity in charge and discharge process.By referring to attached drawing 11,12 it is found that
In 3mA/cm2Under sweep speed, the charge and discharge time of the high supercapacitor of multi-walled carbon nanotube content is longer.
(3) AC impedance (EIS) is tested
Electrode material containing different content multi-walled carbon nanotube is applied in supercapacitor, EIS figure such as Figure 13
It is shown.The Nyquist figure of each electrode is made of the semicircular ring of high frequency section and the vertical line of low frequency part, wherein high frequency region impedance
Real part reflect the complexity that charged particle is spread in hole, the straight line of low-frequency range then reflects the fake capacitance of electrode
Can, the deviation imaginary axis is closer, and fake capacitance performance is better.Containing the electrode material more than multi-walled carbon nanotube, fake capacitance better performances,
And transfer impedance is small.
(4) power density and energy density
Chemical property of 3 supercapacitor of table under different current densities
BC-PPy-MWCNTs-1 and BC-PPy-MWCNTs-2 are respectively applied in supercapacitor, in different electric currents
Under density, specific capacitance, energy density and the power density of supercapacitor are as shown in Figure 14,15 and table 3.Multi-walled carbon nanotube contains
The area capacitance for measuring high supercapacitor is more stable.It is 3mA cm in current density-2When, it is super containing BC-PPy-MWCNTs--1
The area capacitance 0.810F cm of capacitor-2, energy density reach 0.0338mWh cm-2, power density reaches 1.644mW cm-2。
The area capacitance of the supercapacitor containing BC-PPy-MWCNTs-2 can reach 0.788F cm-2, energy density reach 0.0491mWh cm-2, power density reaches 2.01mW cm-2。
It should be understood that the capacitor of 1-13 of embodiment of the present invention preparation equally has above-mentioned experiment effect, it is each to implement
Example between and with above-mentioned experiment effect otherness it is little.
18 electrode material intermediate B C/PPy electrode material comparative experiments of embodiment
1, different pyrroles's dosage BC/PPy electrode material conductivity tests
Intermediate B C/PPy preparation is as follows:
(1) preparation of BC nanofiber suspension: with 14 step of embodiment (1)
(2) BC nanofiber suspension is added in the hydrochloric acid mixed solution containing iron chloride, through ultrasonic 18min, stirring
18min, 4 DEG C of cooling, obtain mixed liquor A, Py monomer and initial BC nanofiber suspension are added in mixed liquor A, and 4
At DEG C, reaction time 180min obtains BC/PPy composite pulp, by the BC/PPy composite pulp after water removal, obtains BC/PPy
Compound, it is spare；Molar ratio (the n of the hydrochloric acid and pyrrolesHCl:nPy) it is 10:1, the molar ratio (n of iron chloride and pyrrolesFeCl3:
nPy) it is 2.3:1.
Experimental group 1,2,3 be respectively as follows: Py monomer and initial BC nanofiber suspension volume ratio 0.2:50,0.3:50,
0.4:50
Control group 1,2,3,4 be respectively as follows: Py monomer and initial BC nanofiber suspension volume ratio 0.1:50,0.5:50,
0.6:50、0.7:50。
Conductivity test is carried out, it is as a result as follows.
The different pyrroles's dosage BC/PPy electrode material conductivity tests of table 4
As the concentration of pyrrole monomer improves, the conductivity of BC/PPy composite material reduces after gradually increasing.Bacterial fibers
Element is a kind of insulating materials.In low concentration, discontinuous polypyrrole particle is coated on the table of bacteria cellulose nanofiber
Face gradually forms the complete path of a uniformly continuous with the increase of concentration, obtains optimal electric conductivity, and pyrroles uses at this time
Amount is 0.2mL.In higher concentration, it may lead and react excessively acutely, lead to polypyrrole being unevenly distributed in matrix surface
Even and side reaction generation has an impact to complete conductive path is formed, to influence its electric conductivity.
2, the BC/PPy electrode material conductivity of difference HCl and Py molar ratio is tested
Intermediate B C/PPy preparation is as follows:
(1) preparation of BC nanofiber suspension: with 14 step of embodiment (1)
(2) BC nanofiber suspension is added in the hydrochloric acid mixed solution containing iron chloride, through ultrasonic 18min, stirring
18min, 4 DEG C of cooling, obtain mixed liquor A, Py monomer and initial BC nanofiber suspension are added in mixed liquor A, Py is mono-
Body and initial BC nanofiber suspension volume ratio are 0.3:50, and at 4 DEG C, and it is multiple to obtain BC/PPy by reaction time 180min
Slurry is closed, by the BC/PPy composite pulp after water removal, obtains BC/PPy compound, it is spare；Wherein, iron chloride and pyrroles rub
You are than (nFeCl3:nPy) it is 2.7:1.
Experimental group 1,2,3,4 respectively corresponds hydrochloric acid and the molar ratio (n of pyrrolesHCl:nPy) it is 2.5:1,5:1,10:1,20:1.
Control group 1,2,3 respectively corresponds hydrochloric acid and the molar ratio (n of pyrrolesHCl:nPy) it is 30:1,50:1,100:1.
5 difference n of tableHCl:nPyThe test of BC/PPy electrode material conductivity
The control of the ratio of hydrochloric acid and pyrroles is often the point usually ignored in material preparation process.And the present invention passes through control
The ratio of hydrochloric acid and pyrroles, unexpectedly obtain its ratio can be obtained the significant technology of conductivity raising in small range section
Effect.
When the ratio of hydrochloric acid and pyrroles are lower, to a certain extent, increase the electricity that its ratio is conducive to improve electrode material
Conductance, but be more than a certain range, continue scaling up, the conductivity of electrode material can be substantially reduced.As shown in Figure 17-(II),
The molar ratio of hydrochloric acid and pyrroles control within the scope of 2,5-20, and BC/PPy electrode material has higher conductivity, the portion more than 20
Point, the trend being substantially reduced is presented with the raising of molar ratio in conductivity, and when molar ratio is increased to 100, conductivity is reduced to original
The one third come.
In this experiment, hydrochloric acid is as dopant, on the one hand, carries the proton translocation of positive charge to polypyrrole strand
On, and disperse and spread apart to come in one section of conjugated chain, cause the distribution of charge to change, is equivalent to polymer molecule
It loses electronics and is oxidized, and then mention high molecular electric conductivity, turn between polymer molecule and dopant there is no charge
It moves；On the other hand, a kind of acidic environment is provided, guarantees Fe3+Exist in the form of an ion in the solution, so that oxidation occur.
But the intake of excessive hydrochloric acid may hinder the interaction between pyrrole monomer and bacteria cellulose fibre, make to be combined to bacterium
The polypyrrole of cellulose fiber surface is reduced, and cannot form a complete conductive path, to make the reduction of its conductivity.But subtract
Few hydrochloric acid additive amount but never has well-known technique to disclose with the limit section for obtaining high conductivity.
Other dopants include surfactant, dyestuff, cyclodextrin and its derivative etc. in polypyrrole synthesis process.Surface
Activating agent, such as neopelex (SDBS), lauryl sodium sulfate (SDS), cetyl trimethylammonium bromide
(CTAB) etc., there are special molecular structure and working mechanism, due to emulsification, polypyrrole synthesis is introduced using it as dopant
The three dimensional growth that will limit pyrroles in the process, directly affects partial size, the pattern of polypyrrole particle, and then influences its electric conductivity.
Dyestuff can play the role of surfactant-like in aqueous solution, but general dyestuff is because have very strong π-π interaction
Solubility is lower, the hydrophilic radicals such as sulfonic group need to be introduced between dye molecule to improve its dissolubility.Cyclodextrin due to cavity and
Crystal packing structure can also limit pyrroles's Growth In Space, influence the microstructure of polypyrrole.
3, difference FeCl3It is tested with the BC/PPy electrode material conductivity of Py molar ratio
Intermediate B C/PPy preparation is as follows:
(1) preparation of BC nanofiber suspension: with 14 step of embodiment (1)
(2) BC nanofiber suspension is added in the hydrochloric acid mixed solution containing iron chloride, through ultrasonic 18min, stirring
18min, 4 DEG C of cooling, obtain mixed liquor A, Py monomer and initial BC nanofiber suspension are added in mixed liquor A, Py is mono-
Body and initial BC nanofiber suspension volume ratio are 0.2:50, and at 4 DEG C, and it is multiple to obtain BC/PPy by reaction time 180min
Slurry is closed, by the BC/PPy composite pulp after water removal, obtains BC/PPy compound, it is spare；Wherein, mole of hydrochloric acid and pyrroles
Than (nFeCl3:nPy) it is 20:1.
Experimental group 1,2,3,4 respectively corresponds iron chloride and the molar ratio (n of pyrrolesHCl:nPy) it is 2.3:1,2.7:1,3.1:1.
Control group 1,2,3,4 respectively corresponds hydrochloric acid and the molar ratio (n of pyrrolesHCl:nPy) it is 1.1:1,1.5:1,1.9:1,
3.5:1。
6 difference n of tableFeCl3:nPyThe test of BC/PPy electrode material conductivity
In the case where other conditions are certain, FeCl3It is 2.3 with the ratio between the amount of pyrrole monomer substance, the composite membrane of acquisition
Conductivity highest.
Claims (10)
1. a kind of supercapacitor, including positive and negative electrode, diaphragm, current-collector and electrolyte, the positive and negative electrode is specially multiple
Composite electrode material, the combination electrode material are mainly combined by BC, Py, MWCNTs, the preparation of the combination electrode material
It include: that BC film is beaten, disperses to obtain nanofiber suspension, by the nanofiber suspension and oxidant and doping
After agent is mixed, Py monomer is added into mixed liquor, obtains BC/PPy composite pulp, obtains BC/PPy after composite pulp is removed water and answer
Object is closed, BC/PPy compound is added in the MWCNTs dispersion liquid for being mixed with dispersing agent, is obtained after mixing, dehydration, drying
BC/PPy/MWCNTs combination electrode material.
2. a kind of supercapacitor as described in claim 1, it is characterised in that: the oxidant be iron chloride, ferric perchlorate,
One of ammonium persulfate or hydrogen peroxide；The dopant is one of hydrochloric acid, sulfuric acid or dust technology.
3. a kind of supercapacitor as described in claim 1, it is characterised in that: the dispersing agent is cetyl trimethyl bromine
Change one of ammonium, lauryl sodium sulfate, NaTDC or neopelex.
4. a kind of supercapacitor as described in claim 1, it is characterised in that: the electrolyte be potassium chloride, sodium hydroxide,
One of sulfuric acid, lithium chloride；The diaphragm material is filter paper, PVDF membrane or polypropylene, polyethylene film combined films
One of.
5. a kind of supercapacitor as described in claim 1, it is characterised in that: the current-collector is metal foil, metal mesh, leads
One of electric polymer composite material, expanding metal or stainless steel material.
6. the preparation method of any supercapacitor of claim 1-5, it is characterised in that: specific step is as follows:
(a) preparation of positive and negative electrode:
(1) BC film is beaten, disperses to obtain BC nanofiber suspension, by the BC nanofiber suspension be added to containing
In the mixed liquor of oxidant and dopant, through ultrasound, stirring, cooling, mixed liquor A is obtained, Py monomer is added to mixed liquor A
In, and at 2-6 DEG C, reaction time 150-210min obtains BC/PPy composite pulp, by the BC/PPy composite pulp by removing water
Afterwards, BC/PPy compound is obtained, it is spare；The molar ratio of the dopant and Py are (1.25-25): 1, mole of oxidant and Py
Than for (0.09-3.1): 1；
(2) MWCNTs, dispersing agent and water are mixed, obtains mixed liquid B, wherein MWCNTs concentration is 0.8-1mg/mL；By institute
It states BC/PPy compound to be added in mixed liquid B according to adding proportion 3g:50-100mL, obtains BC/ after agitated dehydration, drying
PPy/MWCNTs combination electrode material；
(b) capacitor is organized:
After BC/PPy/MWCNTs combination electrode material is cut out, as positive and negative pole material；It is used between the positive and negative pole material
Diaphragm separates, and injects electrolyte, and adds current-collector on the outside of positive and negative pole material to get symmetric form supercapacitor is arrived.
7. a kind of preparation method of supercapacitor as claimed in claim 6, it is characterised in that: described in the step (1)
The concentration of BC nanofiber suspension is 1-4mg/mL.
8. a kind of preparation method of supercapacitor as claimed in claim 6, it is characterised in that: described in the step (1)
Py monomer and initial BC nanofiber suspension volume ratio are (0.2-0.4): 50.
9. a kind of preparation method of supercapacitor as claimed in claim 6, it is characterised in that: described in the step (1)
BC nanofiber suspension the preparation method comprises the following steps: BC is crushed, 5-10min is beaten, using high speed disperser in 8500-
Disperse 10-15min under 10000r/min and obtains nanofiber suspension.
10. a kind of preparation method of supercapacitor as claimed in claim 6, it is characterised in that: in the step (2), institute
Stating dispersant concentration is 3-6mg/mL.
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