CN104779066A - Super capacitor using cane-shaped nickel cobaltate as positive electrode material and preparation method of super capacitor - Google Patents

Super capacitor using cane-shaped nickel cobaltate as positive electrode material and preparation method of super capacitor Download PDF

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Publication number
CN104779066A
CN104779066A CN201510180167.5A CN201510180167A CN104779066A CN 104779066 A CN104779066 A CN 104779066A CN 201510180167 A CN201510180167 A CN 201510180167A CN 104779066 A CN104779066 A CN 104779066A
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positive electrode
nickel
acid nickel
nano
ultracapacitor
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CN104779066B (en
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陈泽祥
张继君
王艳
李海
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Sichuan Angen Based Technology Co., Ltd.
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University of Electronic Science and Technology of China
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their materials
    • H01G11/32Carbon-based, e.g. activated carbon materials
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/52Separators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/58Liquid electrolytes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors [EDLCs]; Processes specially adapted for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The invention discloses a super capacitor using cane-shaped nickel cobaltate as a positive electrode material and a preparation method of the super capacitor. The super capacitor comprises a positive electrode current collector, a positive electrode, a diaphragm, a negative electrode and a negative electrode current collector. According to the invention, the positive electrode is made of a novel nickel cobaltate nanomaterial, the nickel cobaltate nanomaterial adopts the following specific structures: a three-dimensional structure of a cane branch structure formed by cross-linking nickel cobaltate nanowires, wherein canes are connected to each other, the conductivity is excellent, the cane branches have the diameter in nanometer, the formed three-dimensional nanostructure has the properties of large specific surface area, excellent electrochemical activity, excellent electrochemical reversible reaction, high charge speed and the like. Positive and negative electrodes of the super capacitor are further in the form of an asymmetrical structure; ultimately, the super capacitor with high energy density and power density is obtained.

Description

A kind of rattan shape cobalt acid nickel is as the super capacitor and preparation method thereof of positive electrode
Technical field
Technical field of the present invention is ultracapacitor, is specifically related to a kind of ultracapacitor of 3-D nano, structure material as positive electrode using cobalt acid nickel nano wire to be cross-linked the Rattan-shaped of formation.
Background technology
Along with the fast development of weaponry and electronic device, electrical equipment, also more and more higher to the requirement of power supply, for portable weapon equipment, the assembling of portable weapon and consumer electronic device and electrical equipment, need the Power supply adopting battery forms.In application, often pursuit power density and energy density reach desirable state, namely require power supply energy heavy-current discharge, very high capacity can be exported under low discharging current condition again, require that battery even can be full of electricity in tens seconds by battery in several minutes simultaneously.But so far, both is an opposition comparing contradiction, also apply and given birth to two kinds of different batteries, be a battery for existing use, it can export very high capacity under low discharging current condition, but in High-current output situation, show poor, especially, charging interval all overlength of battery, cannot meet modern weapons equipment and electronic equipment, electric device basic demand; The second is exactly ultracapacitor, and it can export very large electric current, but very little with low discharging current capacity.Because existing battery raising power density is very difficult, the charging interval cannot enough shorten, and having focused on of research improves in the energy density of ultracapacitor.
The method of this contradiction of current solution, is apply plural power supply on an electronic equipment, comprises ultracapacitor and secondary cell, provide the high power capacity under low discharging current, provide heavy-current discharge by ultracapacitor by secondary cell.But it is very large that combination is its volume of power supply, and expense is also very expensive.Exploitation has the application value that large current discharging capability and the high ultracapacitor of low discharging current capacity have reality.
Although ultracapacitor has high power, charge/discharge rates such as to be hurried up at the advantage, but the energy density of ultracapacitor is very low at present, also cannot be used in relevant electronics as secondary cell separately, the energy density improving ultracapacitor be the focus of existing research.If its energy density can catch up with lead-acid battery even lithium battery energy density substantially, due to it, to have power high, and charge/discharge rates is fast, and the advantage such as have extended cycle life, and it will replace lead-acid battery even lithium battery thoroughly, and its application prospect is boundless.The priority research areas of current its energy density of raising is the conductivity of its positive electrode, positive electrode, and discharge potential and surface area all have conclusive impact to the performance of ultracapacitor.
At present, Duo Jia research institution has carried out the correlative study of cobalt acid nickel positive electrode, to improve it for performance during ultracapacitor, as ratio capacitance.As Chinese patent (CN102745752.A, 2012) pattern of water heat transfer sea urchin shape is utilized, Chinese patent (CN 103979618 A, 2014) the spherical three-dimensional appearance of water heat transfer nano-sheet is utilized, Chinese patent (CN 104003455 A, 2014) disclose a kind of hollow sea urchin type structure, patent above adopts diverse ways to synthesize the nanostructure of the cobalt acid nickel of globular, to increase specific area and effectively to improve ratio capacitance respectively.But in the nanostructure types in above patent, contact-making surface between cobalt acid nickel particles is very little, be difficult to form efficient electric transmission network channel, thus cause conductive capability not to be fine, and the cobalt acid nickel spheroid of above chondritic is larger, mix particles together rear specific area is still relatively little, and the ratio capacitance therefore reported increases limited; On the other hand, above patent does not all mention the energy density of the ultracapacitor of preparation can rise to how many, cannot investigate it for energy density scope after ultracapacitor.And energy density is one of the most crucial parameter for electronics stored energy.
The present invention proposes a kind of high-energy density super capacitor with practical value of 3-D nano, structure material as positive electrode using cobalt acid nickel nano wire to be cross-linked the rattan branch structure of formation.Because its rattan branch is connected mutually, electric conductivity is excellent, and because the diameter of its rattan branch is very little, the surface area of the 3-D nano, structure of formation increases greatly.
Summary of the invention
The object of the invention is to obtain a kind of ultracapacitor with high-energy-density.This ultracapacitor has the feature of the high and quick charge of large current discharging capability, current discharge capacity concurrently.
The present invention is realized by following technical method.A kind of ultracapacitor of nanometer rattan shape 3-D nano, structure cobalt acid nickel as positive electrode using synthesis, comprise positive electrode, plus plate current-collecting body, battery diaphragm, electrolyte, negative material and negative current collector, wherein positive electrode is the nanometer rattan 3-D nano, structure material of the cobalt acid nickel nano wire formation of synthesis.
A kind of cobalt acid nickel that uses provided by the present invention is as the feature of the ultracapacitor of positive electrode: the cobalt acid nickel pattern of preparation is rattan branch shape 3-D nano, structure, and form three-dimensional netted connected structure on the whole, make between branch, to leave enough spaces and fully enter each nanowire surface to make electrolysis mass-energy.
A kind of cobalt acid nickel that uses provided by the present invention is as the ultracapacitor of positive electrode, it is characterized in that: the rattan branch diameter of described cobalt acid nickel material is 10nm-10 μm, cobalt acid nickel nanowire diameter is 1nm-50nm, and nanowire length is 20nm-1 μm, length 5 μm of-1mm of rattan.
A kind of nanometer rattan cobalt acid nickel that uses provided by the present invention is as the feature of the ultracapacitor of positive electrode: described 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, the wire nettings such as stainless (steel) wire, the material with carbon elements such as carbon cloth.
A kind of nanometer rattan cobalt acid nickel that uses provided by the present invention is as the feature of the ultracapacitor of positive electrode: described battery diaphragm adopts individual layer PP(polypropylene, PP), individual layer PE(polyethylene, PE), PP+ ceramic coated, PE+ ceramic coated, double-deck PP/PE, double-deck PP/PP and three layer PP/PE/PP.And other polyolefin porous membrane class barrier film and Kynoar etc.
A kind of nanometer rattan cobalt acid nickel that uses provided by the present invention is as the feature of the ultracapacitor of positive electrode: described electrolyte is aqueous electrolyte, organic electrolyte and il electrolyte, wherein aqueous electrolyte is the mixed aqueous solution of sulfuric acid, potassium hydroxide aqueous solution, the single saline solutions such as ammonium sulfate, sodium sulphate, potassium chloride solution or multiple salt; Organic electrolyte is ethylene carbonate, propene carbonate, diethyl carbonate, dissolve in the organic solvents such as dimethyl carbonate or dispersion five fluoridize the materials such as clear, lithium hexafluoro phosphate, tetraethyl tetrafluoro boric acid amine, methyl triethyl group tetrafluoro boric acid amine; Il electrolyte is the materials such as 1-methyl-3-ethyl imidazol(e) chloride, 1-ethyl-3-methylimidazole, N-trimethyl-N-hexyl ammonium two (trimethyl fluoride sulfonyl) imines.
A kind of nanometer rattan cobalt acid nickel that uses provided by the present invention is as the feature of the ultracapacitor of positive electrode: described negative material is the composite material of active carbon, carbon nano-tube, Graphene and other porous materials or multiple previous materials.
A kind of nanometer rattan cobalt acid nickel that uses provided by the present invention is as the feature of the ultracapacitor of positive electrode: described 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, the wire nettings such as stainless (steel) wire, the material with carbon elements such as carbon cloth.
A kind of nanometer rattan cobalt acid nickel that uses provided by the present invention is as the feature of the ultracapacitor of positive electrode: the preparation method as the nanometer rattan cobalt acid nickel of positive electrode comprises hydro thermal method, immersion method, bath oiling, the methods such as molten salt growth method.
The concrete preparation method that the present invention prepares ultracapacitor is as follows:
1. choose metal foil material or nickel foam or wire netting and make collector, use washing agent, acetone soln, ethanolic solution and deionized water ultrasonic cleaning, cleaning post-drying is for subsequent use;
2. controlled concentration nickel nitrate 0.01-3.0mol/L, cobalt nitrate 0.01-3.0 mol/L, by above-mentioned salting liquid mixing and stirring.Add 0.1-20g/L kayexalate or starch later, stir;
3. in above-mentioned mixed liquor, add urea, the concentration range controlling urea is 0.01-5.0mol/L, then stirs;
4. at the temperature of 80-230 ° of C, namely hydro-thermal reaction or other mode chemical reactions 1-72h prepare the 3-D nano, structure material of the intertexture rattan branch be made up of cobalt acid nickel nano wire;
5. the cobalt prepared acid nickel is washed with water respectively repeatedly and washs repeatedly with ethanol, then dry;
6., by the cobalt of preparation acid nickel, mix material with carbon element and polytetrafluoroethylene or other binding agents by the mixing of certain mass ratio, and fully grind, use water or ethanol to be made into the slurry A of underflow shape;
7. above-mentioned slurry A is coated in metal forming, after drying, uses tablet press machine to be pressed into positive electrode sheet;
8. according to mixing material with carbon element or other negative materials and polytetrafluoroethylene (mass content 5-20%) mixing, and add the slurry B that water and ethanol are made into underflow shape;
9. apply above-mentioned slurry B in metal forming, after drying, use tablet press machine to be pressed into negative electrode sheet;
10. space cells barrier film curling rolling between positive pole and negative pole, and be soaked in 12h in the KOH electrolyte of 6mol/L;
11. coverings dress up ultracapacitor.
The nanometer rattan 3-D nano, structure material be made up of cobalt acid nickel nano wire provided by the present invention is as the following clear superiority of the ultracapacitor of positive electrode:
One, the method used utilizes the cobalt acid nickel of the nanometer rattan shape 3-D nano, structure synthesized as super capacitor anode material, and the method can realize very high energy density.The three-dimensional structure cobalt acid nickel material of prepared nanometer rattan branch shape, there is high specific area, the rattan branch being interweaved connected substantially increases materials conductive performance, the cobalt acid nickel material of nanostructure has again excellent reversible electrochemical performance, ultrafast constant voltage charge speed can be realized, it is a kind of desirable positive electrode, highest energy density can reach 80Wh/kg, far above the energy density (energy density of ultracapacitor commercial at present is all less than 10Wh/kg) of existing ultracapacitor.
Two, the 3-D nano, structure of the rattan branch shape be made up of cobalt acid nickel nano wire of preparation, has high specific area, substantially increases the contact-making surface of active material and electrolyte, improve reaction rate;
Three, its stable chemical performance of cobalt acid nickel nano wire of preparation, as reversible electrochemical performance excellent during positive electrode;
Four, the cobalt acid nickel of nano thread structure has very high electro-chemical activity;
Five, there is ultrafast charge/discharge rates;
Six, have good energy density, energy density can reach 80Wh/kg.
Accompanying drawing explanation
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 uses cobalt acid nickel as the supercapacitor structures schematic diagram of positive electrode;
Fig. 4 is the constant current charge-discharge characteristic curve of ultracapacitor;
Wherein, 1 is plus plate current-collecting body, and 2 is cobalt acid nickel positive pole, and 3 is electrode diaphragm, and 4 is electrolyte, and 5 is negative pole, and 6 is negative current collector.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Technical scheme of the present invention is to provide a kind of nanometer rattan cobalt acid nickel that uses as the ultracapacitor of positive electrode, and as shown in Figure 3, device architecture comprises plus plate current-collecting body 1, cobalt acid nickel positive pole 2, electrode diaphragm 3, electrolyte 4, negative pole 5, negative current collector 6.
Plus plate current-collecting body 1 in the present invention is the passage of conductive communication to device of cobalt acid nickel positive electrode, General Requirements collector will have larger surface area, good electric conductivity, not with the reaction such as positive electrode and electrolyte, the application of Copper Foil, aluminium foil, nickel foil, stainless steel, metal alloy compositions paper tinsel, be due to they curling after volume smaller, form larger specific area; The foam metals such as nickel foam, the wire nettings such as stainless (steel) wire, the application of the material with carbon elements such as carbon cloth, is because itself just has micropore, still can forms larger specific area after preparation.
The material that cobalt acid nickel positive pole 2 in the present invention uses is prepared by methods such as molten salt growth method, hydro thermal method, immersion method or bath oilings.Specifically need the conductive mixture and the binding agent that mix carbon when being prepared into positive electrode, the mass ratio of each composition is cobalt acid nickel 60-90wt%, the conductive mixture 5-30wt% of carbon, binding agent 5-10wt%.The object of the conductive mixture of mixing carbon is the conductivity increasing cobalt acid nickel, reduces the internal resistance of ultracapacitor.The object that binding agent uses be in order to keep between active material and and collector between bonding effect, prevent in charge and discharge process, dropping of active material.Binding agent is generally PVA (polyvinyl alcohol), sodium carboxymethylcellulose (CMC), polytetrafluoroethylene (PTFE) and Kynoar (PVDF) etc.
The material of the electrode diaphragm 3 in the present invention is individual layer PP(polypropylene, PP), individual layer PE(polyethylene, PE), PP+ ceramic coated, PE+ ceramic coated, double-deck PP/PE, double-deck PP/PP and three layer PP/PE/PP.And other polyolefin porous membrane class barrier film and Kynoar etc.Require that thin-film material has electronic isolation, ensure the electric isolution of both positive and negative polarity; The wettability of electrolyte is got well and there is enough imbibition moisture-retaining capacity; There is certain aperture, ensure low resistance and high ionic conductivity; Must electrolyte resistance corrosion.
Electrolyte 4 in the present invention can adopt aqueous electrolyte, organic electrolyte and il electrolyte, wherein aqueous electrolyte is the mixed aqueous solution of the aqueous solution such as sulfuric acid, potassium hydroxide, lithium hydroxide, the single saline solutions such as ammonium sulfate, sodium sulphate, potassium chloride solution or multiple salt; Organic electrolyte is propene carbonate, ethylene carbonate, dissolve in the organic solvents such as diethyl carbonate or dispersion five fluoridize the materials such as clear, lithium hexafluoro phosphate, tetraethyl tetrafluoro boric acid amine, methyl triethyl group tetrafluoro boric acid amine; Il electrolyte is the materials such as 1-methyl-3-ethyl imidazol(e) chloride, 1-ethyl-3-methylimidazole, N-trimethyl-N-hexyl ammonium two (trimethyl fluoride sulfonyl) imines.It is 0-1.7v that aqueous electrolyte can reach voltage range; The voltage range of organic electrolyte is 0-5v, requires that electrolyte is dissolved with the ion needed for positive and negative pole material uniformly, and keeps stable for a long time; Il electrolyte voltage range is 0-5v, requires that corresponding ion has higher ionic mobility.
The material that negative pole 5 in the present invention uses is carbon nano-tube, Graphene, the composite material of active carbon and other porous carbon materials or various carbon materials, because the specific area of material with carbon element is large and conduct electricity very well.
Negative current collector 6 in the present invention adopts nickel foil, Copper Foil, aluminium foil, metal alloy compositions paper tinsel, the foam metals such as nickel foam, the wire nettings such as stainless (steel) wire, the material with carbon elements such as carbon cloth, and it requires with positive pole similar, have good electric conductivity and chemical stability.
Here is the specific embodiment of this example:
Embodiment 1
As shown in Figure 3, wherein the assembling of positive electrode and plus plate current-collecting body is that mixing material with carbon element and binding agent in mass ratio 80:15:5 are coated on nickel foil collector after mixing, and coating thickness is 5-50 μm by the cobalt of preparation acid nickel to the device architecture assembled.The assembling of negative material and negative current collector is coated on by active carbon material on nickel foil collector, and coating thickness is 5-50 μm.Be positioned in KOH electrolyte after the positive pole of assembling and negative pole electrode diaphragm are separated and soak, be finally assembled into battery.
Its preparation method is as follows:
1. choose nickel foil and make collector, use metal detergent, acetone soln, ethanolic solution and deionized water ultrasonic cleaning, cleaning post-drying is for subsequent use;
2. controlled concentration nickel nitrate 0.01-3.0mol/L, cobalt nitrate 0.01-3.0 mol/L, by above-mentioned salting liquid mixing and stirring.Add 0.1-20g/L kayexalate later, stir.
3. in above-mentioned mixed liquor, add urea, the concentration range controlling urea is 0.01-5mol/L, then stirs.
4. at the temperature of 80-220 degree Celsius, namely hydro-thermal reaction 1-72h prepares the 3-D nano, structure material of the intertexture rattan branch be made up of cobalt acid nickel nano wire.
5. the cobalt prepared acid nickel is washed with water respectively repeatedly and washs repeatedly with ethanol, then dry.
6. by the cobalt of preparation acid nickel, the 80:15:5 mixing in mass ratio of mixing material with carbon element and PTFE binding agent, and fully grind, use water or ethanol to be made into underflow shape.
7. above-mentioned slurry is coated on nickel foil, after drying, uses tablet press machine to be pressed into positive electrode sheet.
8. mix according to mixing material with carbon element and PTFE mass ratio 95:5, and add water and ethanol is made into underflow shape.
9. apply above-mentioned slurry on nickel foil, after drying, use tablet press machine to be pressed into negative electrode sheet.
10. space cells barrier film curling rolling between positive pole and negative pole, and be soaked in 12h in the KOH electrolyte of 6mol/L.
11. are assembled into unsymmetric structure ultracapacitor.
The constant current charge-discharge characteristic curve of the ultracapacitor of preparation as shown in Figure 4.As can be seen from characteristic curve, in constant-current discharge process, an obviously discharge platform is had in very wide voltage range, voltage and time enough become a class rectangular configuration, instead of the triangular structure in conventional Super capacitor, thus higher energy density can be obtained, because energy density is by I(discharging current) × U(discharge voltage) × t(discharge time) determine.
Embodiment 2
Mainly the nickel foil in embodiment 1 is become nickel foam, wherein the assembling of positive electrode and plus plate current-collecting body is that mixing material with carbon element and binding agent in mass ratio 80:15:5 are coated on nickel foil collector after mixing by the cobalt of preparation acid nickel.The assembling of negative material and negative current collector is coated on by active carbon material on nickel foil collector, and coating thickness is 20 μm.Be positioned in KOH electrolyte after the positive pole of assembling and negative pole electrode diaphragm are separated and soak, be finally assembled into battery.
Preparation flow is similar to embodiment 1.
Embodiment 3
As shown in Figure 3, wherein the assembling of positive electrode and plus plate current-collecting body is that mixing material with carbon element and binding agent in mass ratio 85:10:5 are coated on nickel foam collector after mixing, and coating thickness is 40 μm by the cobalt of preparation acid nickel to the device architecture assembled.The assembling of negative material and negative current collector is coated on by active carbon material on nickel foam collector, and coating thickness is 40 μm.Be positioned in KOH electrolyte after the positive pole of assembling and negative pole electrode diaphragm are separated and soak, be finally assembled into battery.
Preparation flow is similar to embodiment 1.
Embodiment 4
As shown in Figure 3, wherein the assembling of positive electrode and plus plate current-collecting body is that mixing material with carbon element and binding agent in mass ratio 80:15:5 are coated on nickel foam collector after mixing, and coating thickness is 50 μm by the cobalt of preparation acid nickel to the device architecture assembled.The assembling of negative material and negative current collector is coated on by active carbon material on nickel foam collector, and coating thickness is 50 μm.LiPF is placed after the positive pole of assembling and negative pole electrode diaphragm being separated 6soak in electrolyte, be finally assembled into battery.
Preparation flow is similar to embodiment 1.
Embodiment 5
As shown in Figure 3, wherein the assembling of positive electrode and plus plate current-collecting body is that mixing material with carbon element and binding agent in mass ratio 80:15:5 are coated on nickel foil collector after mixing, and coating thickness is 20 μm by the cobalt of preparation acid nickel to the device architecture assembled.The assembling of negative material and negative current collector is coated on by active carbon material on nickel foil collector, and coating thickness is 20 μm.Be positioned in KOH electrolyte after the positive pole of assembling and negative pole electrode diaphragm are separated and soak, be finally assembled into battery.
Its preparation method is as follows:
1. cut out the nickel foil being used as collector, use washing agent, acetone soln, ethanolic solution and deionized water ultrasonic cleaning, cleaning post-drying is for subsequent use;
2. controlled concentration nickel nitrate 0.01-3.0mol/L, cobalt nitrate 0.01-3.0 mol/L, by above-mentioned salting liquid mixing and stirring.Add 0.1-20g/L kayexalate later, stir.
3. in above-mentioned mixed liquor, add urea, the concentration range controlling urea is 0.01-5mol/L, then stirs.
4. at the temperature of 70-230 degree Celsius, namely hydro-thermal reaction 24h prepares cobalt acid nickel material.
5. the product prepared is washed with water respectively and wash several for several times and with ethanol, then dry.
6. in tube furnace 200-700 degree Celsius burn 1-5 hour, form cobalt acid nickel.
7. by the cobalt of preparation acid nickel, the 80:15:5 mixing in mass ratio of mixed active charcoal and PTFE binding agent, and fully grind, use water or ethanol to be made into underflow shape.
8. by above-mentioned slurry blade coating on nickel foil, electrode slice is made in drying-compressing tablet-oven dry.
9. mix according to mixed active charcoal and PTFE mass ratio 95:5, and add water and ethanol is made into underflow shape.
10. by above-mentioned slurry blade coating on nickel foil, electrode slice is made in drying-compressing tablet-oven dry.
11. between positive pole and negative pole space cells barrier film curling rolling, and be soaked in 12h in the KOH electrolyte of 3 mol/L.
12. are assembled into battery.
Embodiment 6
As shown in Figure 3, wherein the assembling of positive electrode and plus plate current-collecting body is that mixing material with carbon element and binding agent in mass ratio 75:20:5 are coated on nickel foil collector after mixing, and coating thickness is 10 μm by the cobalt of preparation acid nickel to the device architecture assembled.The assembling of negative material and negative current collector is coated on by active carbon material on nickel foil collector, and coating thickness is 10 μm.Be positioned in LiOH electrolyte after the positive pole of assembling and negative pole electrode diaphragm are separated and soak, be finally assembled into battery.
Preparation flow is similar to embodiment 5.
Embodiment 7
As shown in Figure 2, wherein the assembling of positive electrode and plus plate current-collecting body is that mixing material with carbon element and binding agent in mass ratio 85:10:5 are coated on nickel foil collector after mixing, and coating thickness is 5 μm by the cobalt of preparation acid nickel to the device architecture assembled.The assembling of negative material and negative current collector is coated on by active carbon material on nickel foil collector, and coating thickness is 5 μm.LiPF is positioned over after the positive pole of assembling and negative pole electrode diaphragm being separated 6soak in electrolyte, be finally assembled into battery.
Preparation flow is similar to embodiment 5.
Embodiment 8
As shown in Figure 3, wherein the assembling of positive electrode and plus plate current-collecting body is that mixing material with carbon element and binding agent in mass ratio 80:15:5 are coated on nickel foil collector after mixing, and coating thickness is about 10 μm by the cobalt of preparation acid nickel to the device architecture assembled.The assembling of negative material and negative current collector is coated on by active carbon material on nickel foil collector, and coating thickness is about 10 μm.Be positioned in KOH electrolyte after the positive pole of assembling and negative pole electrode diaphragm are separated and soak, be finally assembled into battery.
Its preparation method is as follows:
1. choose nickel foil and make collector, use metal detergent, acetone soln, ethanolic solution and deionized water ultrasonic cleaning, cleaning post-drying is for subsequent use;
2. controlled concentration nickel nitrate 0.01 mol/L, cobalt nitrate 0.01 mol/L, by above-mentioned salting liquid mix and blend 20 min.Add 1 g/L kayexalate later, stir.
3. in above-mentioned mixed liquor, add urea, the concentration range controlling urea is 0.05mol/L, then stirs.
4. at the temperature of 120 degrees Celsius, namely hydro-thermal reaction 12h prepares the 3-D nano, structure material of the intertexture rattan branch be made up of cobalt acid nickel nano wire.
5. the cobalt prepared acid nickel is washed with water respectively repeatedly and washs repeatedly with ethanol, then dry.
6. by the cobalt of preparation acid nickel, the 80:15:5 mixing in mass ratio of mixing material with carbon element and PTFE binding agent, and fully grind, use water or ethanol to be made into underflow shape.
7. above-mentioned slurry is coated on nickel foil, after drying, uses tablet press machine to be pressed into positive electrode sheet.
8. mix according to mixing material with carbon element and PTFE mass ratio 95:5, and add water and ethanol is made into underflow shape.
9. apply above-mentioned slurry on nickel foil, after drying, use tablet press machine to be pressed into negative electrode sheet.
10. space cells barrier film curling rolling between positive pole and negative pole, and be soaked in 12h in the KOH electrolyte of 2 mol/L.
Embodiment 9
As shown in Figure 3, wherein the assembling of positive electrode and plus plate current-collecting body is that mixing material with carbon element and binding agent in mass ratio 80:15:5 are coated on nickel foil collector after mixing, and coating thickness is about 20 μm by the cobalt of preparation acid nickel to the device architecture assembled.The assembling of negative material and negative current collector is coated on by active carbon material on nickel foil collector, and coating thickness is about 20 μm.Be positioned in KOH electrolyte after the positive pole of assembling and negative pole electrode diaphragm are separated and soak, be finally assembled into battery.
Its preparation method is as follows:
1. choose nickel foil and make collector, use metal detergent, acetone soln, ethanolic solution and deionized water ultrasonic cleaning, cleaning post-drying is for subsequent use;
2. controlled concentration nickel nitrate 1.5mol/L, cobalt nitrate 1.5mol/L, by above-mentioned salting liquid mix and blend 10 min.Add 0.5 g/L kayexalate later, stir.
3. in above-mentioned mixed liquor, add urea, the concentration range controlling urea is 0.1mol/L, then stirs 10min.
4. at the temperature of 150 degrees Celsius, namely hydro-thermal reaction 12h prepares the 3-D nano, structure material of the intertexture rattan branch be made up of cobalt acid nickel nano wire.
5. the cobalt prepared acid nickel is washed with water respectively repeatedly and washs repeatedly with ethanol, then dry.
6. by the cobalt of preparation acid nickel, the 80:15:5 mixing in mass ratio of mixing material with carbon element and PTFE binding agent, and fully grind, use water or ethanol to be made into underflow shape.
7. above-mentioned slurry is coated on nickel foil, after drying, uses tablet press machine to be pressed into positive electrode sheet.
8. mix according to mixing material with carbon element and PTFE mass ratio 95:5, and add water and ethanol is made into underflow shape.
9. apply above-mentioned slurry on nickel foil, after drying, use tablet press machine to be pressed into negative electrode sheet.
10. space cells barrier film curling rolling between positive pole and negative pole, and be soaked in 12h in the KOH electrolyte of 6mol/L.
Embodiment 10
As shown in Figure 3, wherein the assembling of positive electrode and plus plate current-collecting body is that mixing material with carbon element and binding agent in mass ratio 80:15:5 are coated on nickel foil collector after mixing, and coating thickness is about 10 μm by the cobalt of preparation acid nickel to the device architecture assembled.The assembling of negative material and negative current collector is coated on by active carbon material on nickel foil collector, and coating thickness is about 10 μm.Be positioned in KOH electrolyte after the positive pole of assembling and negative pole electrode diaphragm are separated and soak, be finally assembled into battery.
Its preparation method is as follows:
1. choose nickel foil and make collector, use metal detergent, acetone soln, ethanolic solution and deionized water ultrasonic cleaning, cleaning post-drying is for subsequent use;
2. controlled concentration nickel nitrate 3mol/L, cobalt nitrate 3mol/L, by above-mentioned salting liquid mixing and stirring.Add 1 g/L kayexalate later, stir.
3. in above-mentioned mixed liquor, add urea, the concentration range controlling urea is 0.05mol/L, then stirs.
4. at the temperature of 100 degrees Celsius, namely hydro-thermal reaction 36h prepares the 3-D nano, structure material of the intertexture rattan branch be made up of cobalt acid nickel nano wire.
5. the cobalt prepared acid nickel is washed with water respectively repeatedly and washs repeatedly with ethanol, then dry.
6. by the cobalt of preparation acid nickel, the 80:15:5 mixing in mass ratio of mixing material with carbon element and PTFE binding agent, and fully grind, use water or ethanol to be made into underflow shape.
7. above-mentioned slurry is coated on nickel foil, after drying, uses tablet press machine to be pressed into positive electrode sheet.
8. mix according to mixing material with carbon element and PTFE mass ratio 95:5, and add water and ethanol is made into underflow shape.
9. apply above-mentioned slurry on nickel foil, after drying, use tablet press machine to be pressed into negative electrode sheet.
10. space cells barrier film curling rolling between positive pole and negative pole, and be soaked in 12h in the KOH electrolyte of 4 mol/L.

Claims (9)

1. the rattan shape 3-D nano, structure cobalt acid nickel be made up of nano wire is as the ultracapacitor of positive electrode, comprise the plus plate current-collecting body (1) set gradually, positive pole (2), electrode diaphragm (3), electrolyte (6), negative pole (4), negative current collector (5), it is characterized in that, the nanometer rattan 3-D nano, structure material that positive pole (2) adopts cobalt acid nickel nano wire to form.
2. a kind of nanometer rattan shape 3-D nano, structure cobalt acid nickel according to claim 1 is as the ultracapacitor of positive electrode, it is characterized in that: cobalt acid nickel pattern is be cross-linked by cobalt acid nickel nano wire the rattan branch shape 3-D nano, structure formed, and forms three-dimensional netted connected structure on the whole.
3. a kind of nanometer rattan shape 3-D nano, structure cobalt acid nickel according to claim 1 is as the ultracapacitor of positive electrode, it is characterized in that: the rattan branch diameter of described cobalt acid nickel material is 10nm-10 μm, cobalt acid nickel nanowire diameter is 1nm-50nm, nanowire length is 20nm-1 μm, length 5 μm of-1mm of rattan.
4. a kind of nanometer rattan shape 3-D nano, structure cobalt acid nickel according to claim 1 as positive electrode ultracapacitor its, be characterised in that: described plus plate current-collecting body is nickel foil, Copper Foil, aluminium foil, stainless steel foil, metal alloy compositions paper tinsel, nickel foam, stainless (steel) wire or carbon cloth.
5. a kind of rattan shape nanostructure cobalt acid nickel according to claim 1 is as the ultracapacitor of positive electrode, it is characterized in that: described battery diaphragm adopts any one in individual layer PP, individual layer PE, PP+ ceramic coated, PE+ ceramic coated, double-deck PP/PE, double-deck PP/PP or three layer PP/PE/PP.
6. a kind of nanometer rattan shape 3-D nano, structure cobalt acid nickel according to claim 1 is as the ultracapacitor of positive electrode, it is characterized in that: described electrolyte is aqueous electrolyte, organic electrolyte or il electrolyte;
Wherein aqueous electrolyte is sulfuric acid, potassium hydroxide aqueous solution, the mixed aqueous solution of ammonium sulfate, sodium sulphate, potassium chloride solution or multiple salt;
Organic electrolyte is ethylene carbonate, propene carbonate, diethyl carbonate, in dimethyl carbonate organic solvent dissolve or dispersion five fluoridize 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) chloride, 1-ethyl-3-methylimidazole, N-trimethyl-N-hexyl ammonium diimine.
7. one kind according to the preparation method of the arbitrary described a kind of nanometer rattan shape 3-D nano, structure cobalt acid nickel of claim 1-6 as the ultracapacitor of positive electrode:
Step 1, choose in metal foil material or nickel foam or wire netting that any one makes collector, use the ultrasonic cleaning successively of washing agent, acetone soln, ethanolic solution and deionized water, cleaning post-drying is for subsequent use;
Step 2, controlled concentration nickel nitrate 0.01-3.0mol/L, cobalt nitrate 0.01-3.0 mol/L, by above-mentioned salting liquid mix and blend 5-60 min, add 0.1-20.0g/L kayexalate or starch later, stirs 5-60 min;
Step 3, in the mixed liquor that step 2 is obtained, add urea, the concentration range controlling urea is 0.01-5.0 mol/L, then stirs 5-60min;
Step 4, at the temperature of 70-230 ° of C, namely hydro-thermal reaction or other mode chemical reactions 1-72h prepare the 3-D nano, structure material of the intertexture rattan branch be made up of cobalt acid nickel nano wire;
Step 5, the cobalt prepared acid nickel washed with water repeatedly respectively and with ethanol washing repeatedly, then dry;
Step 6, by the cobalt of preparation acid nickel, mixing material with carbon element and binding agent by (70-90): (10-20): the mass ratio mixing of (2-7), and fully grind, uses water or ethanol to be made into the slurry A of underflow shape;
Step 7, above-mentioned slurry A is coated in metal forming, after drying, uses tablet press machine to be pressed into positive electrode sheet;
Step 8, negative material to be mixed with binding agent, and add the slurry B that water and ethanol are made into underflow shape;
Step 9, apply above-mentioned slurry B in metal forming, after drying, use tablet press machine to be pressed into negative electrode sheet;
Step 10, between positive pole and negative pole space cells barrier film curling rolling, and be soaked in 12h in the KOH electrolyte of 6mol/L;
Step 11, covering dress up unsymmetric structure ultracapacitor.
8. a kind of nanometer rattan shape 3-D nano, structure cobalt acid nickel according to claim 7 is as the preparation method of the ultracapacitor of positive electrode, it is characterized in that: binding agent is polytetrafluoroethylene.
9. a kind of nanometer rattan shape 3-D nano, structure cobalt acid nickel according to claim 8 is as the preparation method of the ultracapacitor of positive electrode, and negative material is the composite material of material with carbon element or carbon nanomaterial or multiple carbon.
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