CN104779066B - The super capacitor of a kind of rattan shape cobalt acid nickel as positive electrode and preparation method thereof - Google Patents
The super capacitor of a kind of rattan shape cobalt acid nickel as positive electrode and preparation method thereof Download PDFInfo
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- CN104779066B CN104779066B CN201510180167.5A CN201510180167A CN104779066B CN 104779066 B CN104779066 B CN 104779066B CN 201510180167 A CN201510180167 A CN 201510180167A CN 104779066 B CN104779066 B CN 104779066B
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- cobalt acid
- acid nickel
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- nickel
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 239000010941 cobalt Substances 0.000 title claims abstract description 86
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 86
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 82
- 239000002253 acid Substances 0.000 title claims abstract description 79
- 241000345998 Calamus manan Species 0.000 title claims abstract description 45
- 235000012950 rattan cane Nutrition 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003990 capacitor Substances 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 230000004888 barrier function Effects 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 48
- 239000003792 electrolyte Substances 0.000 claims description 40
- 239000003575 carbonaceous material Substances 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 26
- 239000011230 binding agent Substances 0.000 claims description 23
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000006260 foam Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 230000005611 electricity Effects 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 7
- 238000009938 salting Methods 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000005030 aluminium foil Substances 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 239000010408 film Substances 0.000 description 8
- 238000002788 crimping Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical class CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 241000257465 Echinoidea Species 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses the super capacitor of a kind of nanometer of rattan structure cobalt acid nickel as positive electrode and preparation method thereof, it includes plus plate current-collecting body, positive pole, barrier film, negative pole and negative current collector.The used positive electrode of the present invention is a kind of new cobalt acid nickel nano material, and the cobalt acid nickel material has following specific structure：The 3-D nano, structure for the rattan branch structure being made up of the crosslinking of cobalt acid nickel nano wire, rattan is connected mutually, electric conductivity is excellent, a diameter of nanoscale of rattan branch, the 3-D nano, structure of composition has great specific surface area, with excellent electro-chemical activity, good electrochemical reversible reacts, the properties such as charging rate is fast.The positive and negative electrode of the ultracapacitor or a kind of unsymmetric structure form, it is final to obtain high-energy-density and the ultracapacitor of power density.
Description
Technical field
The technical field of the present invention is ultracapacitor, and in particular to a kind of that the rattan formed is crosslinked using cobalt acid nickel nano wire
Ultracapacitor of the 3-D nano, structure material of strip as positive electrode.
Background technology
With weaponry and electronic device, the fast development of electrical equipment, requirement to power supply also more and more higher, for
Portable weapon equipment, the assembling of portable weapon and consumer electronic device and electrical equipment are, it is necessary to power supply using battery forms
Power supply.In, often pursue power density and reach preferable state with energy density, that is, require power supply energy heavy-current discharge,
And can exports very high capacity under the conditions of low discharging current, while requires that battery be able to can incite somebody to action in several minutes even in tens seconds
Battery is fully charged.But so far, both is the opposition of a comparison contradiction, also applies and has given birth to two kinds of different electricity
Pond, a kind of is the existing battery used, and it can export very high capacity under the conditions of low discharging current, but in High-current output feelings
Under condition, performance is poor, especially, charging interval all overlength of battery, can not meet modern weapons equipment and electronic equipment, electricity
The basic demand of dynamic device；Second is exactly ultracapacitor, and it can export very big electric current, but with low discharging current capacity very
It is small.Because existing battery improves, power density is very difficult, and the charging interval can not shorten enough, and research has focused on raising
In the energy density of ultracapacitor.
The method for solving this contradiction at present, it is that more than two power supplys are applied on an electronic equipment, including it is super
Capacitor and secondary cell, the high power capacity under low discharging current is provided by secondary cell, providing high current by ultracapacitor puts
Electricity.But combination is that power supply its volume is very big, and expense is also very expensive.Exploitation has large current discharging capability and low discharging current
The high ultracapacitor of capacity has the application value of reality.
Although ultracapacitor has the advantages that high power, charge/discharge rates are hurried up, the energy of current ultracapacitor is close
Degree is very low, can not also be used for separately as secondary cell in related electronics, improve the energy density of ultracapacitor
It is the focus of existing research.If its energy density can substantially catch up with lead-acid battery even lithium battery energy density, due to it
High with power, charge/discharge rates are fast, and the advantages that having extended cycle life, it will thoroughly substitute lead-acid battery even lithium battery, its
Application prospect is boundless.The priority research areas for improving its energy density at present is its positive electrode, the conduction of positive electrode
Property, discharge potential and surface area all have conclusive influence to the performance of ultracapacitor.
At present, Duo Jia research institutions have carried out the correlative study of cobalt acid nickel positive electrode, are used for super capacitor to improve it
Performance during device, such as specific capacitance.Such as Chinese patent（CN102745752.A, 2012）The shape of sea urchin shape has been synthesized using hydro-thermal method
Looks, Chinese patent（CN 103979618 A, 2014）The spherical three-dimensional appearance of nano-sheet is synthesized using hydro-thermal method, China is specially
Profit（CN 104003455 A, 2014）A kind of hollow sea urchin type structure is disclosed, different methods is respectively adopted in patent above
The nanostructured of the cobalt acid nickel of globular is synthesized, to increase specific surface area and effectively improve specific capacitance.But in above patent
Nanostructure types in, the contact surface between cobalt acid nickel particles is very small, it is difficult to form efficient electric transmission network channel,
So as to cause conductive capability not to be fine, and the cobalt acid nickel spheroid of above chondritic is bigger, and mix particles compare afterwards together
Surface area or relatively small, therefore the specific capacitance increase reported is limited；On the other hand, above patent does not refer to preparation
The energy density of ultracapacitor can be lifted how many, can not be investigated it and be used for energy density scope after ultracapacitor.And
Energy density is one of most crucial parameter for electronics energy stores.
The present invention proposes a kind of 3-D nano, structure material that the rattan branch structure formed is crosslinked using cobalt acid nickel nano wire
The high-energy density super capacitor with practical value as positive electrode.Because its rattan branch is connected mutually, electric conductivity
Excellent, due to the diameter very little of its rattan branch, the surface area of the 3-D nano, structure of composition greatly increases.
The content of the invention
It is an object of the invention to obtain a kind of ultracapacitor with high-energy-density.The ultracapacitor has concurrently greatly
The characteristics of current discharge ability, current discharge capacity height and quick charge.
The present invention is realized by following technical methods.A kind of nanometer rattan shape 3-D nano, structure using synthesis
Ultracapacitor of the cobalt acid nickel as positive electrode, including positive electrode, plus plate current-collecting body, battery diaphragm, electrolyte, negative pole material
Material and negative current collector, wherein positive electrode are the nanometer rattan 3-D nano, structure materials that the cobalt acid nickel nano wire of synthesis is formed.
A kind of ultracapacitor using cobalt acid nickel as positive electrode provided by the present invention is characterised by：Prepare
Cobalt acid nickel pattern is rattan branch shape 3-D nano, structure, and forms three-dimensional netted connected structure on the whole so that between branch
Enough spaces are left so that electrolysis mass-energy is well into each nanowire surface.
A kind of ultracapacitor using cobalt acid nickel as positive electrode provided by the present invention, it is characterised in that：It is described
A diameter of 10nm-10 μm of the rattan branch of cobalt acid nickel material, cobalt acid nickel nanowire diameter are 1nm-50nm, nanowire length 20nm-1
μm, 5 μm of -1mm of length of rattan.
A kind of ultracapacitor using nanometer rattan cobalt acid nickel as positive electrode provided by the present invention is characterised by：
The plus plate current-collecting body is：The foam metals such as nickel foil, copper foil, aluminium foil, stainless steel foil, metal alloy compositions paper tinsel, nickel foam, it is stainless
The carbon materials such as the wire nettings such as steel mesh, carbon cloth.
A kind of ultracapacitor using nanometer rattan cobalt acid nickel as positive electrode provided by the present invention is characterised by：
Described battery diaphragm is to use individual layer PP（Polypropylene, PP）, individual layer PE（Polyethylene, PE）, PP+ ceramics
Coating, PE+ ceramic coateds, double-deck PP/PE, double-deck PP/PP and three layer of PP/PE/PP.And other polyolefin porous membrane classes every
Film and Kynoar etc..
A kind of ultracapacitor using nanometer rattan cobalt acid nickel as positive electrode provided by the present invention is characterised by：
The electrolyte is aqueous electrolyte, organic electrolyte and il electrolyte, and wherein aqueous electrolyte is sulfuric acid, hydroxide
The mixed aqueous solution of the single such as aqueous solutions of potassium, ammonium sulfate, sodium sulphate, potassium chloride solution saline solution or a variety of salt；Organic Electricity
Solution liquid is ethylene carbonate, propene carbonate, diethyl carbonate, dissolving or five scattered fluorine in the organic solvent such as dimethyl carbonate
Change the materials such as clear, lithium hexafluoro phosphate, tetraethyl tetrafluoro boric acid amine, methyl triethyl group tetrafluoro boric acid amine；Il electrolyte is
1- methyl -3- ethyl imidazol(e) chlorides, 1- ethyl-3-methylimidazoles, N- trimethyl-N- hexyls ammonium two（Trimethyl fluoride sulfonyl）It is sub-
The materials such as amine.
A kind of ultracapacitor using nanometer rattan cobalt acid nickel as positive electrode provided by the present invention is characterised by：
The negative material is activated carbon, CNT, graphene and the mixing material of other porous materials or a variety of previous materials.
A kind of ultracapacitor using nanometer rattan cobalt acid nickel as positive electrode provided by the present invention is characterised by：
The negative current collector is the foam metals such as nickel foil, copper foil, aluminium foil, stainless steel foil, metal alloy compositions paper tinsel, nickel foam, stainless
The carbon materials such as the wire nettings such as steel mesh, carbon cloth.
A kind of ultracapacitor using nanometer rattan cobalt acid nickel as positive electrode provided by the present invention is characterised by：
Preparation method as the nanometer rattan cobalt acid nickel of positive electrode includes hydro-thermal method, immersion method, bath oiling, the methods of molten-salt growth method.
The specific preparation method that the present invention prepares ultracapacitor is as follows：
1. choosing metal foil material, either nickel foam or wire netting make collector, detergent, acetone soln, ethanol are used
Solution and deionized water are cleaned by ultrasonic, and are dried for standby after cleaning；
2. controlled concentration nickel nitrate 0.01-3.0mol/L, cobalt nitrate 0.01-3.0 mol/L, above-mentioned salting liquid is mixed and stirred
Mix uniformly.0.1-20g/L kayexalates or starch are added later, are stirred；
3. adding urea in above-mentioned mixed liquor, the concentration range for controlling urea is 0.01-5.0mol/L, and then stirring is equal
It is even；
4. hydro-thermal reaction or other modes chemical reaction 1-72h are prepared by cobalt acid nickel at a temperature of 80-230 °C
The 3-D nano, structure material for the intertexture rattan branch that nano wire is formed；
5. being washed with water multiple by the cobalt acid nickel prepared and being washed repeatedly with ethanol respectively, then dry；
6. by the cobalt acid nickel of preparation, mix carbon material and polytetrafluoroethylene (PTFE) or other binding agents are mixed by certain mass ratio
Close, and be fully ground, the slurry A of underflow shape is made into using water or ethanol；
7. above-mentioned slurry A is pressed into positive electrode sheet after drying coated in metal foil using tablet press machine；
8. according to mixing carbon material or other negative materials and polytetrafluoroethylene (PTFE)（Mass content 5-20%）Mixing, and add
Enter water and ethanol is made into the slurry B of underflow shape；
9. the above-mentioned slurry B of coating is pressed into negative electrode sheet after drying in metal foil using tablet press machine；
10. space cells barrier film and crimping coiled between positive pole and negative pole, and it is soaked in 6mol/L KOH electrolyte
12h；
11. covering dresses up ultracapacitor.
The nanometer rattan 3-D nano, structure material provided by the present invention being made up of cobalt acid nickel nano wire is as positive electrode
Ultracapacitor following clear superiority：
First, the method used is to be used as ultracapacitor by the use of the cobalt acid nickel of nanometer rattan shape 3-D nano, structure of synthesis
Positive electrode, this method can realize very high energy density.The three-dimensional structure cobalt acid nickel material of prepared nanometer rattan branch shape,
With high specific surface area, the rattan branch for being interweaved connected substantially increases materials conductive performance, the cobalt acid of nanostructured
Nickel material has excellent reversible electrochemical performance again, it is possible to achieve ultrafast constant-voltage charge speed, is a kind of preferable positive pole
Material, highest energy density can reach 80Wh/kg, far above the energy density of existing ultracapacitor（Commercial at present
The energy density of ultracapacitor is respectively less than 10Wh/kg）.
2nd, the 3-D nano, structure of the rattan branch shape being made up of cobalt acid nickel nano wire prepared, has high ratio surface
Product, substantially increases the contact surface of active material and electrolyte, improves reaction rate；
3rd, cobalt acid nickel nano wire its stable chemical performance prepared, excellent reversible electrochemical during as positive electrode
Energy；
4th, the cobalt acid nickel of nano thread structure has very high electro-chemical activity；
5th, there are ultrafast charge/discharge rates；
6th, there is good energy density, energy density can reach 80Wh/kg.
Brief description of the drawings
Fig. 1 is cobalt acid nickel appearance structure schematic diagram；
Fig. 2 is cobalt acid nickel appearance structure figure scanning electron microscope (SEM) photograph；
Fig. 3 is the supercapacitor structures schematic diagram using cobalt acid nickel as positive electrode；
Fig. 4 is the constant current charge-discharge characteristic curve of ultracapacitor；
Wherein, 1 is plus plate current-collecting body, and 2 be cobalt acid nickel positive pole, and 3 be electrode diaphragm, and 4 be electrolyte, and 5 be negative pole, and 6 be negative
Pole collector.
Embodiment
The present invention is further illustrated below in conjunction with the accompanying drawings.
The technical scheme is that a kind of ultracapacitor using nanometer rattan cobalt acid nickel as positive electrode is provided, such as
Shown in Fig. 3, device architecture includes plus plate current-collecting body 1, cobalt acid nickel positive pole 2, electrode diaphragm 3, electrolyte 4, negative pole 5, negative pole currect collecting
Body 6.
Plus plate current-collecting body 1 in the present invention is the conductive communication of cobalt acid nickel positive electrode to the passage of device, general to require
Collector will have a larger surface area, good electric conductivity, not reacted with positive electrode and electrolyte etc., copper foil, aluminium foil, nickel
The application of paper tinsel, stainless steel, metal alloy compositions paper tinsel, it is due to that the volume after they are crimped is smaller, forms larger ratio surface
Product；The application of the carbon materials such as the wire nettings such as the foam metals such as nickel foam, stainless (steel) wire, carbon cloth, it is due to that itself just has
Micropore, remain to form larger specific surface area after preparation.
The material that cobalt acid nickel positive pole 2 in the present invention uses is by the side such as molten-salt growth method, hydro-thermal method, immersion method or bath oiling
Prepared by method.The conductive mixture and binding agent of mixing carbon, the mass ratio of each composition are specifically needed when being prepared into positive electrode
Example is cobalt acid nickel 60-90wt%, the conductive mixture 5-30wt% of carbon, binding agent 5-10wt%.Mix the mesh of the conductive mixture of carbon
Be increase cobalt acid nickel electric conductivity, reduce the internal resistance of ultracapacitor.The purpose that binding agent uses is to keep active matter
Bonding effect between matter and between collector, is prevented in charge and discharge process, and active material drops.Binding agent is generally
PVA (polyvinyl alcohol), sodium carboxymethylcellulose (CMC), polytetrafluoroethylene (PTFE)（PTFE）And Kynoar（PVDF）Deng.
The material of electrode diaphragm 3 in the present invention is individual layer PP（Polypropylene, PP）, individual layer PE
（Polyethylene, PE）, PP+ ceramic coateds, PE+ ceramic coateds, double-deck PP/PE, double-deck PP/PP and three layer of PP/PE/PP.
And other polyolefin porous membrane class barrier films and Kynoar etc..It is required that thin-film material has electronic isolation, ensure positive and negative
The electric isolution of pole；The wettability of electrolyte is got well and there is enough imbibition moisture-retaining capacities；There is certain aperture, ensure low electricity
Resistance and high ionic conductivity；Must electrolyte resistance corrosion.
Electrolyte 4 in the present invention can use aqueous electrolyte, organic electrolyte and il electrolyte, wherein water system
Electrolyte is that the single salt such as the aqueous solution, ammonium sulfate, sodium sulphate, potassium chloride solution such as sulfuric acid, potassium hydroxide, lithium hydroxide are water-soluble
The mixed aqueous solution of liquid or a variety of salt；Organic electrolyte is propene carbonate, ethylene carbonate, the organic solvent such as diethyl carbonate
The things such as middle dissolving or scattered five clear, the lithium hexafluoro phosphates of fluorination, tetraethyl tetrafluoro boric acid amine, methyl triethyl group tetrafluoro boric acid amine
Matter；Il electrolyte is 1- methyl -3- ethyl imidazol(e) chlorides, 1- ethyl-3-methylimidazoles, N- trimethyl-N- hexyls
Ammonium two（Trimethyl fluoride sulfonyl）The materials such as imines.It is 0-1.7v that aqueous electrolyte, which can reach voltage range,；Organic electrolyte
Voltage range is 0-5v, it is desirable to which electrolyte keeps stable for a long time uniformly dissolved with the ion needed for positive and negative pole material；From
Sub- liquid electrolyte voltage range is 0-5v, it is desirable to which corresponding ion has higher ionic mobility.
The material that negative pole 5 in the present invention uses is CNT, graphene, activated carbon and other porous carbon materials or more
The mixing material of kind carbon material, because the specific surface area of carbon material is big and conducts electricity very well.
Negative current collector 6 in the present invention uses the foams such as nickel foil, copper foil, aluminium foil, metal alloy compositions paper tinsel, nickel foam golden
The carbon materials such as wire netting, carbon cloth such as category, stainless (steel) wire, its requirement is similar with positive pole, to there is preferable electric conductivity and change
Learn stability.
Here is the specific embodiment of this example：
Embodiment 1
The device architecture assembled is as shown in figure 3, the assembling of wherein positive electrode and plus plate current-collecting body is by the cobalt of preparation
Sour nickel, mix carbon material and binding agent in mass ratio 80：15：It is coated on after 5 mixing on nickel foil collector, coating thickness 5-50
μm.The assembling of negative material and negative current collector is that coating thickness is 5-50 μ coated on nickel foil collector by active carbon material
m.It is positioned in KOH electrolyte and soaks after the positive pole of assembling and negative pole are separated with electrode diaphragm, is finally assembled into battery.
Its preparation method is as follows：
1. choosing nickel foil makees collector, clear using metal detergent, acetone soln, ethanol solution and deionized water ultrasound
Wash, be dried for standby after cleaning；
2. controlled concentration nickel nitrate 0.01-3.0mol/L, cobalt nitrate 0.01-3.0 mol/L, above-mentioned salting liquid is mixed
Stir.0.1-20g/L kayexalates are added later, are stirred.
3. adding urea in above-mentioned mixed liquor, the concentration range for controlling urea is 0.01-5mol/L, and then stirring is equal
It is even.
4. hydro-thermal reaction 1-72h is to prepare the friendship being made up of cobalt acid nickel nano wire at a temperature of 80-220 degrees Celsius
Knit the 3-D nano, structure material of rattan branch.
5. being washed with water multiple by the cobalt acid nickel prepared and being washed repeatedly with ethanol respectively, then dry.
6. by the cobalt acid nickel of preparation, carbon material and PTFE binding agents in mass ratio 80 are mixed：15：5 mixing, and fully grind
Mill, underflow shape is made into using water or ethanol.
7. above-mentioned slurry is pressed into positive electrode sheet after drying coated on nickel foil using tablet press machine.
8, are according to mixing carbon material and PTFE mass ratioes 95：5 mixing, and add water and ethanol is made into underflow shape.
9. the above-mentioned slurry of coating is pressed into negative electrode sheet after drying on nickel foil using tablet press machine.
10. space cells barrier film and crimping coiled between positive pole and negative pole, and it is soaked in 6mol/L KOH electrolyte
12h。
11. it is assembled into unsymmetric structure ultracapacitor.
The constant current charge-discharge characteristic curve of the ultracapacitor of preparation is as shown in Figure 4.In perseverance it can be seen from characteristic curve
Banish in electric process, have an obviously discharge platform in very wide voltage range, voltage is with the time enough into a class
Triangular structure in rectangular configuration, rather than conventional Super capacitor, thus higher energy density can be obtained, because energy
Metric density is by I（Discharge current）×U（Discharge voltage）×t（Discharge time）Determine.
Embodiment 2
The nickel foil in embodiment 1 is mainly changed into nickel foam, the assembling of wherein positive electrode and plus plate current-collecting body is to make
Standby cobalt acid nickel, mix carbon material and binding agent in mass ratio 80：15：Coated on nickel foil collector after 5 mixing.Negative material
Assembling with negative current collector is that coating thickness is 20 μm coated on nickel foil collector by active carbon material.By assembling just
Pole and negative pole are positioned in KOH electrolyte after being separated with electrode diaphragm to be soaked, and is finally assembled into battery.
Preparation flow is similar to Example 1.
Embodiment 3
The device architecture assembled is as shown in figure 3, the assembling of wherein positive electrode and plus plate current-collecting body is by the cobalt of preparation
Sour nickel, mix carbon material and binding agent in mass ratio 85：10：It is coated on after 5 mixing in foamed nickel current collector, coating thickness 40
μm.The assembling of negative material and negative current collector is that coating thickness is 40 μ coated in foamed nickel current collector by active carbon material
m.It is positioned in KOH electrolyte and soaks after the positive pole of assembling and negative pole are separated with electrode diaphragm, is finally assembled into battery.
Preparation flow is similar to Example 1.
Embodiment 4
The device architecture assembled is as shown in figure 3, the assembling of wherein positive electrode and plus plate current-collecting body is by the cobalt of preparation
Sour nickel, mix carbon material and binding agent in mass ratio 80：15：It is coated on after 5 mixing in foamed nickel current collector, coating thickness 50
μm.The assembling of negative material and negative current collector is that coating thickness is 50 μ coated in foamed nickel current collector by active carbon material
m.LiPF is placed after the positive pole of assembling and negative pole are separated with electrode diaphragm6Soaked in electrolyte, be finally assembled into battery.
Preparation flow is similar to Example 1.
Embodiment 5
The device architecture assembled is as shown in figure 3, the assembling of wherein positive electrode and plus plate current-collecting body is by the cobalt of preparation
Sour nickel, mix carbon material and binding agent in mass ratio 80：15：Coated on nickel foil collector after 5 mixing, coating thickness is 20 μ
m.The assembling of negative material and negative current collector is that coating thickness is 20 μm coated on nickel foil collector by active carbon material.
It is positioned in KOH electrolyte and soaks after the positive pole of assembling and negative pole are separated with electrode diaphragm, is finally assembled into battery.
Its preparation method is as follows：
1. the handy nickel foil for making collector is cut out, it is clear using detergent, acetone soln, ethanol solution and deionized water ultrasound
Wash, be dried for standby after cleaning；
2. controlled concentration nickel nitrate 0.01-3.0mol/L, cobalt nitrate 0.01-3.0 mol/L, above-mentioned salting liquid is mixed and stirred
Mix uniformly.0.1-20g/L kayexalates are added later, are stirred.
3. adding urea in above-mentioned mixed liquor, the concentration range for controlling urea is 0.01-5mol/L, and then stirring is equal
It is even.
4. hydro-thermal reaction 24h prepares cobalt acid nickel material at a temperature of 70-230 degrees Celsius.
Wash for several times for several times and with ethanol 5. the product prepared is washed with water respectively, then dry.
6. the 200-700 degrees Celsius of 1-5 hour of burning in tube furnace, form cobalt acid nickel.
7. by the cobalt acid nickel of preparation, mixed active charcoal and PTFE binding agents in mass ratio 80：15：5 mixing, and fully grind
Mill, underflow shape is made into using water or ethanol.
8. above-mentioned slurry is scratched on nickel foil, electrode slice is made in drying-tabletting-drying.
9. according to mixed active charcoal and PTFE mass ratioes 95：5 mixing, and add water and ethanol is made into underflow shape.
10. above-mentioned slurry is scratched on nickel foil, electrode slice is made in drying-tabletting-drying.
11. space cells barrier film and crimping coiled between positive pole and negative pole, and it is soaked in 3 mol/L KOH electrolyte
12h。
12. it is assembled into battery.
Embodiment 6
The device architecture assembled is as shown in figure 3, the assembling of wherein positive electrode and plus plate current-collecting body is by the cobalt of preparation
Sour nickel, mix carbon material and binding agent in mass ratio 75：20：Coated on nickel foil collector after 5 mixing, coating thickness is 10 μ
m.The assembling of negative material and negative current collector is that coating thickness is 10 μm coated on nickel foil collector by active carbon material.
It is positioned in LiOH electrolyte and soaks after the positive pole of assembling and negative pole are separated with electrode diaphragm, is finally assembled into battery.
Preparation flow is similar to Example 5.
Embodiment 7
The device architecture assembled is as shown in Fig. 2 the assembling of wherein positive electrode and plus plate current-collecting body is by the cobalt of preparation
Sour nickel, mix carbon material and binding agent in mass ratio 85：10：Coated on nickel foil collector after 5 mixing, coating thickness is 5 μ
m.The assembling of negative material and negative current collector is that coating thickness is 5 μm coated on nickel foil collector by active carbon material.Will
The positive pole and negative pole of assembling are positioned over LiPF after being separated with electrode diaphragm6Soaked in electrolyte, be finally assembled into battery.
Preparation flow is similar to Example 5.
Embodiment 8
The device architecture assembled is as shown in figure 3, the assembling of wherein positive electrode and plus plate current-collecting body is by the cobalt of preparation
Sour nickel, mix carbon material and binding agent in mass ratio 80：15：Coated on nickel foil collector after 5 mixing, coating thickness is about 10
μm.The assembling of negative material and negative current collector is that coating thickness is about 10 μ coated on nickel foil collector by active carbon material
m.It is positioned in KOH electrolyte and soaks after the positive pole of assembling and negative pole are separated with electrode diaphragm, is finally assembled into battery.
Its preparation method is as follows：
1. choosing nickel foil makees collector, clear using metal detergent, acetone soln, ethanol solution and deionized water ultrasound
Wash, be dried for standby after cleaning；
2. the mol/L of controlled concentration nickel nitrate 0.01, the mol/L of cobalt nitrate 0.01, above-mentioned salting liquid is mixed 20
min.1 g/L kayexalates are added later, are stirred.
3. adding urea in above-mentioned mixed liquor, the concentration range for controlling urea is 0.05mol/L, is then stirred.
4. hydro-thermal reaction 12h is to prepare the intertexture rattan branch being made up of cobalt acid nickel nano wire at a temperature of 120 degrees Celsius
The 3-D nano, structure material of bar.
5. being washed with water multiple by the cobalt acid nickel prepared and being washed repeatedly with ethanol respectively, then dry.
6. by the cobalt acid nickel of preparation, carbon material and PTFE binding agents in mass ratio 80 are mixed：15：5 mixing, and fully grind
Mill, underflow shape is made into using water or ethanol.
7. above-mentioned slurry is pressed into positive electrode sheet after drying coated on nickel foil using tablet press machine.
8, are according to mixing carbon material and PTFE mass ratioes 95：5 mixing, and add water and ethanol is made into underflow shape.
9. the above-mentioned slurry of coating is pressed into negative electrode sheet after drying on nickel foil using tablet press machine.
10. space cells barrier film and crimping coiled between positive pole and negative pole, and it is soaked in 2 mol/L KOH electrolyte
12h。
Embodiment 9
The device architecture assembled is as shown in figure 3, the assembling of wherein positive electrode and plus plate current-collecting body is by the cobalt of preparation
Sour nickel, mix carbon material and binding agent in mass ratio 80：15：Coated on nickel foil collector after 5 mixing, coating thickness is about 20
μm.The assembling of negative material and negative current collector is that coating thickness is about 20 μ coated on nickel foil collector by active carbon material
m.It is positioned in KOH electrolyte and soaks after the positive pole of assembling and negative pole are separated with electrode diaphragm, is finally assembled into battery.
Its preparation method is as follows：
1. choosing nickel foil makees collector, clear using metal detergent, acetone soln, ethanol solution and deionized water ultrasound
Wash, be dried for standby after cleaning；
2. controlled concentration nickel nitrate 1.5mol/L, cobalt nitrate 1.5mol/L, above-mentioned salting liquid is mixed into 10 min.
0.5 g/L kayexalates are added later, are stirred.
3. adding urea in above-mentioned mixed liquor, the concentration range for controlling urea is 0.1mol/L, then stirs 10min.
4. hydro-thermal reaction 12h is to prepare the intertexture rattan branch being made up of cobalt acid nickel nano wire at a temperature of 150 degrees Celsius
The 3-D nano, structure material of bar.
5. being washed with water multiple by the cobalt acid nickel prepared and being washed repeatedly with ethanol respectively, then dry.
6. by the cobalt acid nickel of preparation, carbon material and PTFE binding agents in mass ratio 80 are mixed：15：5 mixing, and fully grind
Mill, underflow shape is made into using water or ethanol.
7. above-mentioned slurry is pressed into positive electrode sheet after drying coated on nickel foil using tablet press machine.
8, are according to mixing carbon material and PTFE mass ratioes 95：5 mixing, and add water and ethanol is made into underflow shape.
9. the above-mentioned slurry of coating is pressed into negative electrode sheet after drying on nickel foil using tablet press machine.
10. space cells barrier film and crimping coiled between positive pole and negative pole, and it is soaked in 6mol/L KOH electrolyte
12h。
Embodiment 10
The device architecture assembled is as shown in figure 3, the assembling of wherein positive electrode and plus plate current-collecting body is by the cobalt of preparation
Sour nickel, mix carbon material and binding agent in mass ratio 80：15：Coated on nickel foil collector after 5 mixing, coating thickness is about 10
μm.The assembling of negative material and negative current collector is that coating thickness is about 10 μ coated on nickel foil collector by active carbon material
m.It is positioned in KOH electrolyte and soaks after the positive pole of assembling and negative pole are separated with electrode diaphragm, is finally assembled into battery.
Its preparation method is as follows：
1. choosing nickel foil makees collector, clear using metal detergent, acetone soln, ethanol solution and deionized water ultrasound
Wash, be dried for standby after cleaning；
2. controlled concentration nickel nitrate 3mol/L, cobalt nitrate 3mol/L, above-mentioned salting liquid is mixed evenly.Add later
Enter 1 g/L kayexalates, stir.
3. adding urea in above-mentioned mixed liquor, the concentration range for controlling urea is 0.05mol/L, is then stirred.
4. hydro-thermal reaction 36h is to prepare the intertexture rattan branch being made up of cobalt acid nickel nano wire at a temperature of 100 degrees Celsius
The 3-D nano, structure material of bar.
5. being washed with water multiple by the cobalt acid nickel prepared and being washed repeatedly with ethanol respectively, then dry.
6. by the cobalt acid nickel of preparation, carbon material and PTFE binding agents in mass ratio 80 are mixed：15：5 mixing, and fully grind
Mill, underflow shape is made into using water or ethanol.
7. above-mentioned slurry is pressed into positive electrode sheet after drying coated on nickel foil using tablet press machine.
8, are according to mixing carbon material and PTFE mass ratioes 95：5 mixing, and add water and ethanol is made into underflow shape.
9. coating above-mentioned slurry on nickel foil, negative electrode sheet is pressed into using tablet press machine after drying.
10. space cells barrier film and crimping coiled between positive pole and negative pole, and it is soaked in 4 mol/L KOH electrolyte
12h。
Claims (7)
1. a kind of ultracapacitor of rattan shape 3-D nano, structure cobalt acid nickel being made up of nano wire as positive electrode, including
The plus plate current-collecting body set gradually（1）, positive pole（2）, electrode diaphragm（3）, electrolyte（6）, negative pole（4）, negative current collector（5）,
Characterized in that, positive pole（2）The nanometer rattan 3-D nano, structure material formed using cobalt acid nickel nano wire；
The cobalt acid nickel pattern is to be crosslinked the rattan branch shape 3-D nano, structure formed, and shape on the whole by cobalt acid nickel nano wire
Into three-dimensional netted connected structure, a diameter of 10nm-10 μm of the rattan branch of the cobalt acid nickel material, cobalt acid nickel nanowire diameter is 1nm-
50nm, nanowire length are 20nm-1 μm, 5 μm of -1mm of length of rattan.
2. super electricity of a kind of nanometer of rattan shape 3-D nano, structure cobalt acid nickel according to claim 1 as positive electrode
Container, it is characterised in that：The plus plate current-collecting body is nickel foil, copper foil, aluminium foil, stainless steel foil, metal alloy compositions paper tinsel, foam
Nickel, stainless (steel) wire or carbon cloth.
3. a kind of ultracapacitor of the rattan shape nanostructured cobalt acid nickel according to claim 1 as positive electrode, its
It is characterised by：Described electrode diaphragm be using individual layer PP, individual layer PE, PP+ ceramic coated, PE+ ceramic coateds, double-deck PP/PE,
It is any in double-deck PP/PP or three layer of PP/PE/PP.
4. super electricity of a kind of nanometer of rattan shape 3-D nano, structure cobalt acid nickel according to claim 1 as positive electrode
Container, it is characterised in that：The electrolyte is aqueous electrolyte；
Wherein aqueous electrolyte is sulfuric acid, potassium hydroxide aqueous solution, ammonium sulfate, sodium sulphate, potassium chloride solution or a variety of salt
Mixed aqueous solution.
5. it is a kind of according to a kind of any described nanometer rattan shape 3-D nano, structure cobalt acid nickel of claim 1-3 as positive pole material
The preparation method of the ultracapacitor of material：
Step 1, selection metal foil material make collector, are surpassed successively using detergent, acetone soln, ethanol solution and deionized water
Sound cleans, and is dried for standby after cleaning；
Step 2, controlled concentration nickel nitrate 0.01-3.0mol/L, cobalt nitrate 0.01-3.0 mol/L, above-mentioned salting liquid is mixed and stirred
5-60 min are mixed, add 0.1-20.0g/L kayexalates or starch, stirring 5-60 min later；
Step 3, urea is added in mixed liquor made from step 2, the concentration range for controlling urea is 0.01-5.0 mol/L, so
After stir 5-60min；
Step 4, hydro-thermal reaction reaction 1-72h is to prepare the intertexture being made up of cobalt acid nickel nano wire at a temperature of 70-230 °C
The 3-D nano, structure material of rattan branch；
Step 5, the cobalt acid nickel prepared is washed with water multiple respectively and washed repeatedly with ethanol, then dried；
Step 6, by the cobalt acid nickel of preparation, mixing carbon material and binding agent press（70-90）：( 10-20)：（2-7）Mass ratio mix
Close, and be fully ground, the slurry A of underflow shape is made into using water or ethanol；
Step 7, by above-mentioned slurry A coated in metal foil, be pressed into positive electrode sheet using tablet press machine after drying；
Step 8, negative material mixed with binding agent, and add water and ethanol is made into the slurry B of underflow shape；
Step 9, the above-mentioned slurry B of coating are pressed into negative electrode sheet after drying in metal foil using tablet press machine；
Step 10, spaced electrode barrier film and crimp coiled between positive pole and negative pole, and be soaked in 6mol/L KOH electrolyte
12h；
Step 11, covering dress up unsymmetric structure ultracapacitor.
6. super electricity of a kind of nanometer of rattan shape 3-D nano, structure cobalt acid nickel according to claim 5 as positive electrode
The preparation method of container, it is characterised in that：Binding agent is polytetrafluoroethylene (PTFE).
7. super electricity of a kind of nanometer of rattan shape 3-D nano, structure cobalt acid nickel according to claim 5 as positive electrode
The preparation method of container, it is characterised in that：Negative material is carbon material.
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| CN105304352B (en) * | 2015-10-12 | 2018-07-13 | 哈尔滨工业大学深圳研究生院 | Nickel foam autoreaction prepares the method and its supercapacitor applications of manganese dioxide/nickel hydroxide composite nano plate |
| CN107731552B (en) * | 2017-08-15 | 2018-10-02 | 湖北大学 | A kind of nickel nano wire collector and preparation method thereof |
| CN110195235A (en) * | 2019-06-21 | 2019-09-03 | 盐城工学院 | A kind of phosphorus doping cobalt acid nickel/foam nickel electrode and its preparation method and application |
| CN110648861B (en) * | 2019-09-12 | 2021-10-15 | 陕西国防工业职业技术学院 | In-situ growth of braided porous channel NiCo2O4Method of nanosheet |
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