CN102354615B - Preparation method of slurry for positive plate of high-energy nickel-carbon supercapacitor - Google Patents
Preparation method of slurry for positive plate of high-energy nickel-carbon supercapacitor Download PDFInfo
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- CN102354615B CN102354615B CN 201110294390 CN201110294390A CN102354615B CN 102354615 B CN102354615 B CN 102354615B CN 201110294390 CN201110294390 CN 201110294390 CN 201110294390 A CN201110294390 A CN 201110294390A CN 102354615 B CN102354615 B CN 102354615B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002002 slurry Substances 0.000 title claims abstract description 19
- VMWYVTOHEQQZHQ-UHFFFAOYSA-N methylidynenickel Chemical compound [Ni]#[C] VMWYVTOHEQQZHQ-UHFFFAOYSA-N 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003990 capacitor Substances 0.000 claims abstract description 27
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000000853 adhesive Substances 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 11
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 11
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 210000002966 serum Anatomy 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 4
- 229920006351 engineering plastic Polymers 0.000 abstract description 4
- 239000010935 stainless steel Substances 0.000 abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000007767 bonding agent Substances 0.000 abstract 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910003075 TiO2-B Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- GDXTWKJNMJAERW-UHFFFAOYSA-J molybdenum(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mo+4] GDXTWKJNMJAERW-UHFFFAOYSA-J 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- 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)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of slurry for a positive plate of a high-energy nickel-carbon supercapacitor, and the slurry comprises a bonding agent for a positive pole and a main material, wherein the bonding agent for the positive pole accounts for 20wt%-35wt% of the total weight of the bonding agent for the positive pole and the main material. The supercapacitor is composed of a positive plate, a mixed negative plate and a diaphragm which are sealed in a stainless steel or engineering plastic shell, wherein the positive plate is prepared from a positive pole material taking nickel hydroxide as a main active substance; the mixed negative plate consists of an alkali metal hydroxide water-based electrolyte, hydrogen storage alloy powder and active carbon material utilized as an main active substance; the supercapacitor has the characteristics of large energy storage density, high discharge power and the like; and the supercapacitor prepared by the positive pole material has the working voltage up to 1.3V and the maximum energy storage density up to 65Wh/kg, can be widely applied to power supplies of electric buses, power supplies for low-temperature startup of vehicles and power supplies of military equipment, such as capacitors for aviation, aerospace, fighter planes, submarines, warships and other equipment, and be also applied to high-capacity power supplies for portable equipment, such as capacitors for notebook computers, mobile phones, electric tools and the like.
Description
Technical field
The invention belongs to the ultracapacitor field, especially a kind of preparation method of positive plate slurry of high-energy nickel/carbon super capacitor.
Background technology
Along with the iterative method that national new forms of energy are built, the track of a fast development is stepped in the research of new forms of energy, and especially the research of ultracapacitor causes the attention of various countries.By retrieval, find the publication document of following relevant ultracapacitor:
1, a kind of hickelous nydroxide mixing type ultracapacitor and preparation method thereof (CN200810111891.2), this capacitor comprises column type and square structure, by the hydroxide nickel anode, alkali metal hydroxide aqueous electrolyte and Activated carbon fiber cathode are sealed in stainless steel or the engineering plastics shell and consist of, and have that energy storage density is large, the mixing type ultracapacitor of discharge power high.The hydroxide nickel anode adopts chemical reaction method and electrochemical reaction method preparation, and an amount of carbon nano-tube of admixture and carbonyl nickel are as additive therein, and Foamed Nickel is that matrix produces anode.The activated carbon fiber that activated carbon negative electrode employing electronickelling was processed adopts nickel foil as collector as raw material.The capacitor working of assembling press and to reach 1.6V, maximum energy storage density reaches 20Wh/kg, crest discharge power reaches 8KW/kg.In field extensive uses such as industry, traffic, electronics, military affairs.
2, a kind of Vehicle-use starting super capacitor (CN03114837.9), the ultracapacitor fuse is by the sintered type nickel oxyhydroxide sheet of parcel barrier film, the thin nickel sheet that serialization activated carbon fiber cloth negative pole and afflux support consists of, capacitor core is placed in the plastic casing by making, welding current terminal, inject electrolyte, sealing just gets the ultracapacitor finished product.This ultracapacitor has higher power density and energy density, and lightweight, and cost is low, and the life-span is long, is fit to do the startup energy of all kinds vehicle, applies to have fine value.
3, a kind of carbon back multi-hole electrode film for ultracapacitor and preparation method thereof (CN200410009580.7), each constituent content of film is: active carbon content is 72mass%～99mass%, conductive carbon black or content of graphite are 0.1mass%～20mass%, the content of nm-class powder of zirconium oxide is 0.1mass%～5mass%, and the nano metal nickel powder content is 0.1mass%～3mass%; Voidage is 45%～75%, and further preferred voidage is 55%～65%.Preparing film of the present invention at first mixes deionized water, organic monomer and crosslinking agent; Then dispersant being added solution stirs and obtains premixed solution; Material powder is added, ball milling mixes, and makes slurry again; The gained slurry is added defrother and carries out froth in vacuum; Slurry with after initator and the catalyst adding de-bubble after stirring, is obtaining green compact on the casting machine behind moulding, curing and demoulding, again through the weak oxide atmosphere heat treatment, obtain the target multi-hole electrode film.Moulding process of the present invention is simple, molding time is short, easy to operate, the film thickness controllability is good, mesopore is flourishing.
4, a kind of preparation method (CN200810053475.1) of porous carbon electrode of high rate charge-discharge performance ultracapacitor, the method comprises following process, take the pore type zeolite molecular sieve as template, take gas acetylene, methane or ethene as carbon source, in quartz tube reactor, utilize the high frequency heater to carry out the porous charcoal that vapour deposition obtains being rich in micropore; Porous charcoal makes the bigger serface porous charcoal through 1000-1600 ℃ of high-temperature heat treatment reconciliation statement surface properties again; The bigger serface porous charcoal is mixed with polytetrafluoroethylene and is distributed in the ethanol, and is modulated to pulpous state, is coated in equably on the nickel foam sheet, and drying is made porous carbon electrode again.The invention has the advantages that: prepared Large ratio surface carbon deposit has the pore structure of homogeneous; The surface hydrophilicity of porous charcoal is low, and oxygen content is low, and prepared porous carbon electrode is specially adapted to the ultracapacitor of high rate charge-discharge performance.
5, a kind of hickelous nydroxide mixing type ultracapacitor and preparation method thereof (CN200810111891.2), this capacitor comprises column type and square structure, by the hydroxide nickel anode, alkali metal hydroxide aqueous electrolyte and Activated carbon fiber cathode are sealed in to consist of in stainless steel or the engineering plastics shell has that energy storage density is large, the mixing type ultracapacitor of discharge power high.The hydroxide nickel anode adopts chemical reaction method and electrochemical reaction method preparation, and an amount of carbon nano-tube of admixture and carbonyl nickel are as additive therein, and Foamed Nickel is that matrix produces anode.The activated carbon fiber that activated carbon negative electrode employing electronickelling was processed adopts nickel foil as collector as raw material.The capacitor working of assembling press and to reach 1.6V, maximum energy storage density reaches 20Wh/kg, crest discharge power reaches 8KW/kg.In field extensive uses such as industry, traffic, electronics, military affairs.
6, a kind of hybrid super capacitor and preparation method thereof (CN200910079669.3), the negative active core-shell material of hybrid super capacitor is one or more among the polymorph TiO2-B of nano TiO 2 or TiO2, and positive electrode active materials is one or more in carbon nano-tube, carbon nano-fiber, graphite, conductive black, nickel hydroxide, manganous hydroxide or the molybdenum hydroxide.Hybrid super capacitor is made electrode take both positive and negative polarity active material, binding agent and conductive agent as raw material, is assembled into simulated battery and makes ultracapacitor in glove box.Preparation method provided by the invention has and can regulate and control, preparation flow is simple, processing ease, but the hybrid super capacitor model of assembling has that specific capacity is high, current potential is low, the stable performance high current charge-discharge, have extended cycle life, the easy characteristics such as realization of with low cost, mechanization large-scale production.
7, a kind of preparation method of ultracapacitor (CN200910063288.6), it comprises the steps: 1) foamed nickel substrate is put into chemical vapour deposition reactor furnace, pass into argon gas 10-60 minute, drain furnace air, then, be heated to 450-750 ℃, flow with 25-40ml/min in argon atmosphere passes into hydrocarbon gas, 450-750 ℃ of lower the reaction 30 seconds to 50 minutes, after reaction was finished, obtaining growing had the nickel foam of carbon nano-tube; 2) remove surface porosity layer product after, directly the nickel foam substrate of carbon nano-tube is arranged directly as electrode of super capacitor with growth; 3) with two thickness of step 2 gained, the pole drying that size is identical, fully soaked 1-36 hour with electrolyte, separate with the barrier film that soaks equally full electrolyte, assembling obtains ultracapacitor; Described hydrocarbon gas is acetylene, methane, ethene or propylene.Carbon nano-tube of the present invention is to be grown directly upon on the foamed nickel substrate, need not to use adhesive; Nickel foam is substrate, and the electrode substance bulk density is higher, reasonable pore distribution.
Through contrast, positive electrode and present patent application that above-mentioned all kinds of patents technology is related have more different.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, the preparation method of the positive plate slurry of the high-energy nickel/carbon super capacitor that a kind of energy storage density is large, discharge power is high is provided.
For solving the problems of the technologies described above, the present invention adopts following technical proposal:
A kind of preparation method of positive plate slurry of high-energy nickel/carbon super capacitor, preparation method's step is:
(1) positive pole is placed on adhesive puts into mixer after stirring on the mixer;
(2) with cobalt protoxide, inferior titanium oxide deionized water dissolving, deionized water will slowly add, and stirs while adding in order to avoid the powder caking forms mixed solution;
(3) mixed solution that deionized water and cobalt protoxide, inferior titanium oxide is formed is added in the mixer, stirs;
(4) in mixer, add high temperature additive;
(5) then add ball-shape nickel hydroxide, add first 1/5th, the rear continuation that stirs adds nickel hydroxide in batches, is put in the mixer to stir;
(6) add after uniform stirring half an hour again;
(7) add afterwards ptfe emulsion, stirring to form anode sizing agent.
Wherein anodal weight with adhesive is the 20%-35% of anodal adhesive and the formed total weight of major ingredient.
And described anodal raw material with adhesive consists of and the weight proportion scope is respectively:
Sodium carboxymethylcellulose 2%～4%
Deionized water 96%～98%.
And described anodal compound method with adhesive is:
(1) by weight ratio, weigh up respectively the weight of sodium carboxymethylcellulose and deionized water;
(2) deionized water that weighs up is heated to 80 ℃, water is poured in the mixer, slowly add CMC, stir while adding, stirring gets final product, and then places 24 hours, to normal temperature.
And the weight percentage ranges of described each raw material is respectively:
And described high temperature additive is the wherein at least a of zirconia, zinc oxide, oxidation Yttrium.
Advantage of the present invention and good effect are:
1, this ultracapacitor is to be that the positive electrode of main active substances is made positive plate by nickel hydroxide, alkali metal hydroxide aqueous electrolyte and hydrogen storing alloy powder are the negative plate that mixes of main active substances composition with active carbon material, and diaphragm seal consists of in stainless steel or engineering plastics shell, has that energy storage density is large, the discharge power high.
2, the present invention's prepared ultracapacitor operating voltage of positive electrode of inventing reaches 1.3V, and maximum energy storage density reaches 65Wh/kg.Can be widely used in the electrical source of power, vehicle cold-starting of electric bus with the electrical source of power of electrical source of power, military hardware, such as the equipments such as Aero-Space, fighter plane, submarine, naval vessels capacitor, also can be applicable to portable set high power capacity electrical source of power, such as notebook computer, mobile phone, electric-tool container etc.Application relates to vehicle, traffic, industry, aviation, military affairs, consumer electronics, green energy resource etc., has very widely application prospect.
Embodiment
Below in conjunction with embodiment the present invention is further set forth, but the scope of protection of present invention is not limited to following execution mode.
Its compound method of positive plate slurry of high-energy nickel/carbon super capacitor involved in the present invention at first is that the preparation positive pole is used adhesive in two steps, need propose the preparation of time the previous day, prepares positive pole and is mixed with positive electrode with preparing with major ingredient behind the adhesive again.
Embodiment 1:
A kind of positive plate slurry of high-energy nickel/carbon super capacitor, the preparation method is:
One, preparation is anodal uses adhesive, and the weight proportion of its raw material is respectively:
Sodium carboxymethylcellulose 2%
Deionized water 98%.
The step of compound method is:
1, weighs up respectively the weight of sodium carboxymethylcellulose and deionized water;
2, the deionized water that weighs up is heated to about 80 ℃, water is poured in the mixer, slowly add sodium carboxymethylcellulose, stir while adding, stir and evenly get final product after 3-5 minute, then placed 24 hours, to normal temperature, for subsequent use.
Two, the raw material of major ingredient formation and percentage by weight are as follows:
This positive plate slurry preparation method's concrete steps following (take 100 kilograms as example):
The positive pole that 1, will prepare is placed on adhesive and puts into mixer after stirring on the mixer, and its weight is 30 kilograms.
2,1.4 kilograms of 5.6 kilograms of cobalt protoxides, inferior titanium oxide are used deionized water dissolving, note deionized water will be repeatedly, slowly add on a small quantity, stir while adding, in order to avoid the powder caking forms mixed serum.
3, the mixed serum that deionized water and cobalt protoxide, inferior titanium oxide is formed is added in the mixer, stirs.
4, in mixer, add 1.4 kilograms of high temperature additive zirconias.
5, then add 59.5 kilograms of ball-shape nickel hydroxides, approximately 12 kilograms of first a small amount of addings, the rear continuation that stirs divides 4 batches to add nickel hydroxides, is put in the mixer and stirs.
6, add after uniform stirring half an hour again.
7, add afterwards 2.1 kilograms of PTFE (polytetrafluoroethylene) emulsions, the PTFE emulsion that adds is concentration commonly used, and concentration is 60%, and solution is stirred, and can form anode sizing agent.
Embodiment 2:
A kind of positive plate slurry of high-energy nickel/carbon super capacitor, the preparation method is:
One, preparation is anodal uses adhesive, and the weight proportion of its raw material is respectively:
Sodium carboxymethylcellulose 4%
Deionized water 96%.
The step of compound method is:
1, weighs up respectively the weight of sodium carboxymethylcellulose and deionized water;
2, the deionized water that weighs up is heated to about 80 ℃, water is poured in the mixer, slowly add sodium carboxymethylcellulose, stir while adding, stirring evenly got final product after a few minutes, then placed 24 hours, and is to normal temperature, for subsequent use.
Two, the raw material of major ingredient formation and percentage by weight are as follows:
This positive plate slurry preparation method's concrete steps following (take 100 kilograms as example):
1, be ready to the positive pole adhesive that prepared, be placed on and put into mixer after stirring on the mixer, its weight is 25 kilograms.
2,2.25 kilograms of 3 kilograms of cobalt protoxides, inferior titanium oxide are used deionized water dissolving, note deionized water will be repeatedly, slowly add on a small quantity, stir while adding, in order to avoid the powder caking forms mixed solution.
3, the mixed solution that deionized water and cobalt protoxide, inferior titanium oxide is formed is added in the mixer, stirs.
4, in mixer, add 0.75 kilogram in zinc oxide.
5, then add 67.5 kilograms of ball-shape nickel hydroxides, 13.5 kilograms of first a small amount of addings, the rear continuation that stirs divides 5 batches to add nickel hydroxides, is put in the mixer and stirs.
6, add after uniform stirring half an hour again.
7, add afterwards 1.5 kilograms of PTFE (polytetrafluoroethylene) emulsions, the PTFE emulsion that adds is concentration commonly used, and concentration is 60%, and solution is stirred, and can form anode sizing agent.
High temperature, low-temperature characteristics testing result by the made capacitor of this anode sizing agent see the following form:
Detect unit: Ministry of Information Industry Chemical Physics power supply product quality supervision and test center
Claims (5)
1. the preparation method of a positive plate slurry of high-energy nickel/carbon super capacitor, it is characterized in that: preparation method's step is:
⑴ be placed on positive pole and put into mixer after stirring on the mixer with adhesive;
⑵ with cobalt protoxide, inferior titanium oxide deionized water dissolving, and deionized water will slowly add, and stirs while adding in order to avoid the powder caking forms mixed serum;
⑶ be added to the mixed serum that deionized water and cobalt protoxide, inferior titanium oxide form in the mixer, stirs;
⑷ add high temperature additive in mixer;
⑸ add ball-shape nickel hydroxide then, adds first 1/5th, and the rear continuation that stirs adds nickel hydroxide in batches, is put in the mixer to stir;
⑹ uniform stirring half an hour again after add;
⑺ add ptfe emulsion after, stirring to form anode sizing agent;
Wherein anodal weight with adhesive is the anodal 20%-35% that uses the total weight of adhesive and other all raw materials.
2. the preparation method of high-energy nickel/carbon super capacitor positive electrode according to claim 1 is characterized in that: described anodal raw material formation and weight proportion scope thereof with adhesive is respectively:
Sodium carboxymethylcellulose 2%～4%
Deionized water 96%～98%.
3. the preparation method of positive plate slurry of high-energy nickel/carbon super capacitor according to claim 2 is characterized in that: described anodal compound method with adhesive is:
⑴ weigh up respectively the weight of sodium carboxymethylcellulose and deionized water by weight ratio;
⑵ be heated to 80 ℃ with the deionized water that weighs up, and water is poured in the mixer, slowly adds sodium carboxymethylcellulose, stirs while adding, and stirring gets final product, and then placed 24 hours, to normal temperature.
4. the preparation method of positive plate slurry of high-energy nickel/carbon super capacitor according to claim 1, it is characterized in that: the weight percentage ranges of described other all raw materials is respectively:
5. the preparation method of positive plate slurry of high-energy nickel/carbon super capacitor according to claim 1 is characterized in that: described high temperature additive is the wherein at least a of zirconia, zinc oxide, yittrium oxide.
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| CN 201110294390 CN102354615B (en) | 2011-09-30 | 2011-09-30 | Preparation method of slurry for positive plate of high-energy nickel-carbon supercapacitor |
| PCT/CN2012/079631 WO2013044683A1 (en) | 2011-09-30 | 2012-08-03 | Method for preparing positive plate slurry of high-energy nickel/carbon super capacitor |
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| CN104064371B (en) * | 2014-06-20 | 2017-07-07 | 四川能宝电源制造有限公司 | For the Ni/C anode sizing agents and anode pole piece preparation method of super capacitance cell |
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| CA2380954A1 (en) * | 2002-04-08 | 2003-10-08 | Powergenix Systems, Inc. | Supercapacitor device with extended capability |
| CN101276692B (en) * | 2008-05-19 | 2010-06-23 | 清华大学 | Nickelous hydroxide composite super capacitor and manufacture process thereof |
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