CN101271773A - Composite super capacitor based on cobalt oxide and ruthenium oxide and its manufacture process - Google Patents
Composite super capacitor based on cobalt oxide and ruthenium oxide and its manufacture process Download PDFInfo
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- CN101271773A CN101271773A CNA2008101118927A CN200810111892A CN101271773A CN 101271773 A CN101271773 A CN 101271773A CN A2008101118927 A CNA2008101118927 A CN A2008101118927A CN 200810111892 A CN200810111892 A CN 200810111892A CN 101271773 A CN101271773 A CN 101271773A
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- oxide
- ruthenium
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- cobalt oxide
- nickel
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- 239000003990 capacitor Substances 0.000 title claims abstract description 60
- 229910001925 ruthenium oxide Inorganic materials 0.000 title claims abstract description 55
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910000428 cobalt oxide Inorganic materials 0.000 title claims description 48
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 title claims description 46
- 239000002131 composite material Substances 0.000 title claims description 19
- 230000008569 process Effects 0.000 title claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 28
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 238000005187 foaming Methods 0.000 claims abstract description 12
- 238000004146 energy storage Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011149 active material Substances 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 230000004888 barrier function Effects 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 238000003466 welding Methods 0.000 claims description 8
- KPKACCODJBGSEQ-UHFFFAOYSA-N [C].[Co]=O Chemical compound [C].[Co]=O KPKACCODJBGSEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- -1 compound cobalt oxide Chemical class 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 6
- 239000011267 electrode slurry Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000036647 reaction Effects 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002848 electrochemical method Methods 0.000 claims description 4
- 229920006351 engineering plastic Polymers 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000010412 perfusion Effects 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 2
- 238000003487 electrochemical reaction Methods 0.000 abstract 1
- 230000008901 benefit Effects 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- JEUJLYFOFHOMTM-UHFFFAOYSA-N [C].[Ru]=O Chemical compound [C].[Ru]=O JEUJLYFOFHOMTM-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Images
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- 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
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a mixed super-capacitor based on powder blue anode and ruthenium oxide cathode and a fabrication method of the mixed super-capacitor, belonging to the fabrication technical range of capacitor. The capacitor comprises a cylindrical typed structure and a square typed structure; the mixed super-capacitor with large energy storage density and high discharging power is formed by sealing the powder blue anode, potassium hydroxide water electrolyte and ruthenium oxide cathode inside a shell. The powder blue anode takes the outcome prepared by electro-chemical reaction method as raw material, in which carbon nano-tube and nickel carbonyl with suitable quantity is mixed to be taken as additive and foaming nickel is mixed to be taken as substrate, so as to fabricate the anode. The ruthenium oxide cathode adopts nano-ruthenium prepared by chemical method as raw material, in which carbon nano-tube and nickel carbonyl with suitable quantity is mixed to be taken as additive and foaming nickel is mixed to be taken as substrate, so as to fabricate the cathode. The assembled capacitor has the working voltage of 1.4V, maximum energy storage density of 23Wh/kg, peak discharging power of 8kW/kg. The mixed super-capacitor is widely applied to the fields of industry, traffic, electrons and military, etc.
Description
Technical field
The invention belongs to the manufacturing technology scope of electrochemical capacitor, particularly be applied to a kind of the mixing type ultracapacitor and the manufacture method thereof of high energy storage density based on cobalt oxide and ruthenium-oxide.
Background technology
Electric chemical super capacitor is a kind of novel energy-storing device, integrates characteristics such as high-energy-density, high power density, long-life, and it also has advantages such as non-maintaining, high reliability in addition, is a kind of new electronic component that has both electric capacity and battery behavior.It mainly is divided into and is based upon the double layer capacitor on the interfacial electric double layer basis and is based upon ultracapacitor on the pseudo capacitance basis according to the difference of energy storage mechanism.The character of material with carbon element is the decisive factor of decision double layer capacitor performance.Specific area, pore-size distribution, electrochemical stability and conductivity etc. comprising material with carbon element.The material with carbon element that meets the demands through research has active carbon, carbon nano-fiber, and CNT (carbon nano-tube) or the like, the patent " multi-electrode double layer capacitor with hermetic electrolyte seal " of relatively more typical patent of this respect such as U.S. MAXWELL company is (CA1408121A).The principle of " pseudo-capacitance " is that electrode material utilizes lithium ion or the storage of proton in the three-dimensional or accurate two-dimensional crystal lattice stereochemical structure of material to stay the purpose that reaches storage power, though its charge-discharge characteristic is extremely similar to electric double layer capacitance, but the two dimension of its energy storage mechanism and carbon material surface is adsorbed with bigger difference, and such electrode material comprises metal oxide, nitride, high molecular polymer or the like.Electric double layer capacitance is compared with pseudo capacitance, and the latter's ratio electric capacity is the former 10-100 times, but the power characteristic of the former transient large current discharge (power density) is better than the latter.At present the patent in this field mainly concentrates on the hybrid super capacitor field, as " a kind of power train in vehicle application power supply ultracapacitor " of Shanghai prestige scientific and technological development difficult to understand Co., Ltd (CN1431669).Metal oxide such as cobalt oxide and ruthenium-oxide has good electrochemical properties because of its high capacitance and relatively low resistance.Therefore the ultracapacitor based on this electrode material assembling has important use in space flight and military domain.
Anode and negative electrode are respectively by the nano oxidized cobalt electrode with pseudo capacitance characteristic and have the hybrid super capacitor that the ruthenium-oxide electrode of pseudo capacitance characteristic forms and brought into play the high inherent characteristics of pseudo capacitance energy density.Adopt nanometer cobalt oxide as anode, nano oxidized ruthenium is as negative electrode, and potassium hydroxide aqueous solution is 0V～1.4V as the composite super capacitor operating voltage range of electrolyte, and energy storage density can reach 23Wh/kg, and crest discharge power can reach 8kW/kg.Hybrid super capacitor has been brought into play the high inherent characteristics of electrode of super capacitor energy density, its energy density than aluminium electrolytic capacitor Senior Three to four orders of magnitude.In addition, hybrid super capacitor has kept that electrolytic capacitor cell voltage height, specific power height, response time are short, the advantage of simplicity of design.The performance of above-mentioned excellence makes hybrid super capacitor be widely used in fields such as industrial uninterrupted power supply, motor vehicle, high-power military power supply, radio communications.
Summary of the invention
The objective of the invention is to propose a kind of mixing type ultracapacitor and manufacture method thereof based on cobalt oxide and ruthenium-oxide, the structure of described hybrid battery container is the cobalt oxide anode, and potassium hydroxide water-based electrolyte and ruthenium-oxide negative electrode are sealed in and constitute column type or square structure in stainless steel casing or the engineering plastics shell; High energy storage characteristic and the cobalt oxide of capacitor high power characteristics and the mixing type ultracapacitor of ruthenium-oxide with storage battery.
Described anode construction forms on the porous, expanded Ni substrate for the cobalt oxide active material is sticked to, and connects banded nickel collector on the foaming Ni substrate.
Described anode construction is also for adhering to carbon nano-tube, carbonyl nickel mixed slurry formation basal body structure on porous, expanded nickel, utilize above electrochemical method is deposited on cobalt oxide, the final anode construction that forms is the composite anode that cobalt oxide-carbon nano-tube-carbonyl nickel constitutes.
Described anode cuts becomes rectangle.
Described cathode construction forms on the porous, expanded Ni substrate for the ruthenium-oxide active material is sticked to, and connects banded nickel collector on the foaming Ni substrate.
Can also add carbon nano-tube-carbonyl nickel conductive materials in the described ruthenium-oxide active material.
Described negative electrode cuts becomes rectangle.
Described electrolyte is by solute and solvent composition, and solute is a potassium hydroxide; Solvent is the aqueous solution; Concentration of electrolyte is 6mol/L～1mol/L, and concentration is big more, and the electrolyte conductance is high more.
A kind of mixing type ultracapacitor manufacture method based on cobalt oxide anode and ruthenium-oxide negative electrode is characterized in that, comprising:
The manufacture method of described cylindrical capacitor superposes successively for cobalt oxide anode anode, barrier film, the ruthenium-oxide negative electrode that will connect collector, coiling becomes the columnar electrode core, this electrode cores anode, cathode current collector are placed in the stainless steel casing respectively with after top cover positive pole, negative pole are connected, or anodal linking to each other of anode and top cover and cylindrical shell are as negative pole, the perfusion aqueous electrolyte is finished the capacitor sealing by welding or press seal mode;
The structure of the structure of described square hybrid battery container and column type hybrid battery container roughly the same, different is that shell mechanism is a square, manufacture method is to weld banded nickel matter collector on anode, the negative electrode respectively, anode, barrier film, the negative electrode that connects collector superposes successively becomes square shape electrode cores, be placed in stainless steel or the engineering plastics shell perfusion aqueous electrolyte after this electrode cores anode, cathode current collector connected top cover positive pole, negative pole respectively; Finish the capacitor sealing by welding, press seal or bonding again.
Described anode manufacturing process adopts the electrochemical process preparation, and as raw material, the foaming nickel porous deposits cobalt oxide as matrix on matrix with nanometer cobalt oxide; Concrete manufacture process is: electrolyte is 0.9molCo (NO
3)
2And 0.075molNaNO
3Be dissolved in the mixed liquor of 500ml second alcohol and water formulatedly, wherein the volume ratio of absolute ethyl alcohol and deionized water is 1: 1; Adopt bipolar electrode constant current cathodic reduction method deposition cobalt oxide, the anode of electrolytic cell is pure cobalt, and negative electrode is porous, expanded nickel, and controlling constant Faradaic current intensity is 1A/dm
2, the electrolytic deposition time is 4 hours, electrochemical production cobalt oxide in foaming nickel structure takes out electrode cell reaction is finished after, with behind the deionized water cyclic washing under 80 ℃ of conditions of air atmosphere drying 1 hour.
Described in the preparation anodic process of electrochemical method, an amount of carbon nano-tube of admixture and carbonyl nickel conductive materials, concrete grammar is earlier carbon nano-tube and carbonyl nickel material to be added 10wt% polytetrafluoroethylene adhesive preparation becoming slurry, wherein content of carbon nanotubes is 50～60wt%, and carbonyl nickel content is 40～30wt%; At first with above-mentioned slurry blade coating to the porous foam Ni substrate, with the negative electrode of this matrix as bipolar electrode constant current catholyte reduction apparatus, anode still is pure cobalt, electrolyte is for equally by Co (NO
3)
2And NaNO
3The electrolyte of forming; Controlling constant Faradaic current intensity is 1A/dm
2, the electrolytic deposition time is 4 hours, electrochemical production cobalt oxide-carbon nano-tube in carbon nano-tube, carbonyl nickel basal body structure-carbonyl nickel combination electrode.After finishing, cell reaction takes out electrode, with behind the deionized water cyclic washing under 80 ℃ of conditions of air atmosphere dry 1 hour.
The manufacture method of described ruthenium-oxide is a chemical method.Concrete manufacture method is: with RuCl
3The aqueous solution is as the reaction precursor body, with carbonic hydroammonium NH
4HCO
3Synthetic Ru (the HCO of reaction
3)
3, then with Ru (HCO
3)
3The heating and decomposition dehydration obtains RuO under the 240C condition
2The concrete practice takes by weighing 0.2mol RuCl
3, be dissolved in the 200mL deionized water, obtain the RuCl of brownish black
3Solution.Take by weighing 0.6mol carbonic hydroammonium NH
4HCO
3, it is even that it is dissolved in the 200mL deionized water for stirring, is added drop-wise to the RuCl of brownish black slowly
3Stir in the solution and constantly, leave standstill a few minutes, the black particle of generation also sinks to reactor bottom, and above-mentioned solution is carried out vacuum filtration, and with washed with de-ionized water with thorough removal impurity.The black powder that will obtain is at last dried down at 80 ℃ and is obtained Ru (HCO
3)
3Powdered activated material.With Ru (HCO
3)
3Powder heating and decomposition dehydration under 240 ℃ of conditions obtains RuO
2
10～25wt% carbon nano-tube, 5～15wt% carbonyl nickel that can also add ruthenium-oxide in the described ruthenium-oxide preparation process; The optimum content carbon nano-tube is 20wt%, and carbonyl nickel is 10wt%.Conductive materials can add before reaction in the ruthenic chloride presoma, carries out chemical reaction then and prepares combination electrode material.Also can after finishing, the ruthenium-oxide preparation be spiked into nanometer RuO
2Mix in the powdered activated material and fully.Adding the poly-ethene adhesive preparation that is beset with of 5wt%～20wt% in above-mentioned composite material becomes mobile and the good electrode slurry of adhesiveness, and the adhesive optimum content is 10wt%, is prepared into the ruthenium-oxide negative electrode that contains carbon nano-tube-carbonyl nickel conductive materials.
Described ruthenium-oxide negative electrode manufacturing process comprises that the ruthenium-oxide powder (containing conductive carbon nanotube and carbonyl nickel) that adopts method for preparing is as raw material, porous, expanded nickel is as matrix, the adhesive that adds 5～20wt% in the ruthenium-oxide material fully mixes, and be dissolved in the aqueous solvent, abundant shear agitation, with gained electrode slurry blade coating in porous, expanded nickel collector, oven dry back continuous rolling, cut and weld or sting the nickel collector of riveting over, produce and have the ruthenium-oxide negative electrode that specific area is big, internal resistance is low and structural strength is high with ruthenium-oxide active material.
The present invention is according to hybrid capacitors purposes difference, and packaging technology is also different each other, and hybrid super capacitor of the present invention has been brought into play the high inherent characteristics of electrode of super capacitor energy density, its energy density than aluminium electrolytic capacitor Senior Three to four orders of magnitude.In addition, hybrid super capacitor has kept that electrolytic capacitor cell voltage height, specific power height, response time are short, the advantage of simplicity of design.The performance of above-mentioned excellence makes hybrid super capacitor be widely used in industry, traffic, field such as military.
Description of drawings
Fig. 1 is the cylindrical capacitor structural representation.
Fig. 2 is a square capacitor arrangement schematic diagram.
Fig. 3 prepares the microscopic appearance figure of nanometer cobalt oxide material for electrochemical process
Fig. 4 prepares the microscopic appearance figure of cobalt oxide-carbon nano-tube-carbonyl nickel composite material for electrochemical process
The microscopic appearance figure of Fig. 5 nano oxidized ruthenium material for chemical method prepares
Fig. 6 prepares the microscopic appearance figure of ruthenium-oxide-carbon nano-tube-carbonyl nickel composite material for chemical method.
Fig. 7 is the charging and discharging curve of composite super capacitor.
Fig. 8 is the energy density-power density diagram of composite super capacitor.
Embodiment
The present invention proposes a kind of mixing type ultracapacitor and manufacture method thereof based on cobalt oxide anode and ruthenium-oxide negative electrode.The structure of described hybrid battery container comprises column type and square capacitor arrangement, by cobalt oxide anode, potassium hydroxide electrolyte and ruthenium-oxide negative electrode be sealed in constitute in stainless steel or the engineering plastics shell have the operating voltage height, the metal oxide mixing type ultracapacitor of characteristics such as energy storage density is big, discharge power is high, electric leakage is little, long working life.
Figure 1 shows that the structural representation of column type hybrid battery container.Among the figure, cobalt oxide anode 1, barrier film 2, ruthenium-oxide negative electrode 3 superpose successively and reel becomes electrode cores, and anode, negative electrode respectively have collector 4 to draw, and anode 1 links to each other with positive pole 6 on the top cover 5, and negative electrode 3 links to each other with shell 7, and shell itself is as the connected mode of negative pole.Unload air valve 8 on the top cover to guarantee capacitor air pressure inside balance, between top cover 5 and the shell 7 insulated ring 9 arranged, top cover adopts welding or the press seal mode realizes and shell between sealing, the capacitor internal resistance is full of electrolyte.Its septation 2 adopts Ni-MH battery and the polypropylene dedicated barrier film of nickel-cadmium cell, and this kind barrier film has alkali resistance electrolyte characteristic, as the 50um thickness alkaline battery separator of Zhejiang Kain Co., Ltd. production.
Figure 2 shows that the structural representation of square hybrid battery container.The structure of its structure and column type hybrid battery container roughly the same, different is cobalt oxide anode 1, barrier film 2, ruthenium-oxide negative electrode 3 superposes successively and be folded into the square electrode cores, the anode negative electrode respectively has collector 4 to draw and be connected with positive pole 6, the negative pole 9 of top cover 5, top cover 5 itself guarantees between positive and negative electrode and the insulation between electrode and the shell 7, and the capacitor internal resistance is full of electrolyte.Top cover adopts the sealing between welding or bonding mode realization and shell, unloads air valve 8 on the top cover to guarantee capacitor air pressure inside balance.
The manufacture method of described composite super capacitor capacitor is made by manufacturing, the ruthenium-oxide negative electrode of cobalt oxide anode respectively and capacitor assembling three big steps are formed.
Mixing type ultracapacitor based on manufacturing of the present invention is expected to obtain extensive use in multiple field such as electronics, automobile, space flight, military affairs.The present invention is according to hybrid capacitors purposes difference, and packaging technology is also different each other, specifies as follows;
1. the cobalt oxide anode material of mixing type ultracapacitor is made
Described anode manufacturing process adopts the nanometer cobalt oxide of electrochemical process preparation as raw material, and the foaming nickel porous is as matrix.Concrete manufacture process as: electrolyte is 0.9molCo (NO
3)
2And 0.075molNaNO
3Be dissolved in the mixed liquor of 500ml second alcohol and water formulatedly, wherein the volume ratio of absolute ethyl alcohol and deionized water is 1: 1.Adopt bipolar electrode constant current cathodic reduction legal system to be equipped with cobalt oxide, the anode of electrolytic cell is pure cobalt, and negative electrode is porous, expanded nickel, and controlling constant Faradaic current intensity is 1A/dm
2, the electrolytic deposition time is 4 hours, electrochemical production cobalt oxide in foaming nickel structure.After finishing, cell reaction takes out electrode, with behind the deionized water cyclic washing under 80 ℃ of conditions of air atmosphere dry 1 hour.(as shown in Figure 3).
2. the manufacturing of mixing type ultracapacitor cobalt oxide/carbon nano-tube carbonyl nickel composite anode
Also can an amount of carbon nano-tube of admixture and carbonyl nickel conductive materials in the preparation cobalt oxide anode of described electrochemical method.Concrete grammar is earlier carbon nano-tube and the preparation of carbonyl nickel material adding 10wt% polytetrafluoroethylene adhesive to be become slurry, and wherein content of carbon nanotubes is 50～60wt%, and carbonyl nickel content is 40～30wt%.At first with above-mentioned slurry blade coating in the porous foam Ni substrate, with the negative electrode of this matrix as bipolar electrode constant current catholyte reduction apparatus, anode still is pure cobalt, electrolyte is for equally by Co (NO
3)
2And NaNO
3The electrolyte of forming.Controlling constant Faradaic current intensity is 1A/dm
2, the electrolytic deposition time is 4 hours, electrochemical production cobalt oxide-carbon nano-tube in carbon nano-tube, carbonyl nickel basal body structure-carbonyl nickel combination electrode (as shown in Figure 4).After finishing, cell reaction takes out electrode, with behind the deionized water cyclic washing under 80 ℃ of conditions of air atmosphere dry 1 hour.
3. the manufacturing of composite super capacitor ruthenium-oxide cathode active material
The manufacture method of described ruthenium-oxide is a chemical method.Concrete manufacture method is: with RuCl
3The aqueous solution is as the reaction precursor body, with carbonic hydroammonium NH
4HCO
3Synthetic Ru (the HCO of reaction
3)
3, then with Ru (HCO
3)
3The heating and decomposition dehydration obtains RuO under 240 ℃ of conditions
2The concrete practice takes by weighing 0.2mol RuCl
3, be dissolved in the 200mL deionized water, obtain the RuCl of brownish black
3Solution.Take by weighing 0.6mol carbonic hydroammonium NH
4HCO
3, it is even that it is dissolved in the 200mL deionized water for stirring, is added drop-wise to the RuCl of brownish black slowly
3Stir in the solution and constantly, leave standstill a few minutes, the black particle of generation also sinks to reactor bottom, and above-mentioned solution is carried out vacuum filtration, and with washed with de-ionized water with thorough removal impurity.The black powder that will obtain is at last dried down at 80 ℃ and is obtained Ru (HCO
3)
3Powdered activated material.With Ru (HCO
3)
3Powder heating and decomposition dehydration under 240 ℃ of conditions obtains RuO
2(as shown in Figure 5).
4. the manufacturing of composite super capacitor ruthenium-oxide-carbon nano-tube-carbonyl nickel composite cathode
Can add an amount of carbon nano-tube one carbonyl nickel conductive materials in the described ruthenium-oxide preparation process, content of carbon nanotubes is 10～25wt%, and carbonyl nickel content is 5～15wt%, and optimum content is carbon nano-tube 20wt%, carbonyl nickel 10wt%.Conductive materials can add before reaction in the ruthenic chloride presoma, carries out chemical reaction then and prepares combination electrode material (as shown in Figure 6).Also can after finishing, the ruthenium-oxide preparation be spiked into nanometer RuO
2Mix in the powdered activated material and fully.Adding the poly-ethene adhesive preparation that is beset with of 5wt%～20wt% in above-mentioned composite material becomes mobile and the good electrode slurry of adhesiveness, and the adhesive optimum content is 10wt%.In porous, expanded nickel collector, oven dry back continuous rolling cuts and welds or stings the nickel collector of riveting over gained electrode slurry blade coating, produces to have the ruthenium-oxide active electrode that specific area is big, internal resistance is low and structural strength is high.
5. the assembling of composite super capacitor and manufacturing
The structure of described column type hybrid battery container partly is made up of electrode cores, collector, end cap, shell etc.Anode, barrier film, negative electrode, barrier film are superposeed successively, reel or be folded into electrode cores.To adopt modes such as revolving riveting, ultra-sonic welded to be connected positive pole, negative pole on the top cover respectively with anode, cathode current collector.The above-mentioned electrode cores that is connected with top cover is placed in nickel matter or the stainless steel casing, under dry air atmosphere, pours into alkaline electrolyte, finish the capacitor sealing by modes such as slot rolling press seal, welding.Also can adopt anode and top cover positive pole to link to each other, negative electrode links to each other with shell, and shell itself is as the connected mode of negative pole.Top cover adopts welding or the press seal mode realizes and shell between sealing.
The structure of described its structure of square hybrid battery container and column type hybrid battery container roughly the same, different is cobalt oxide anode, barrier film, the ruthenium-oxide negative electrode superposes successively and be folded into the square electrode cores, the anode negative electrode respectively has collector to draw and be connected with the both positive and negative polarity of top cover, top cover itself guarantees between positive and negative electrode and the insulation between electrode and the shell, and the capacitor internal resistance is full of electrolyte.Top cover adopts the sealing between welding or bonding mode realization and shell.
Above-mentioned employing cobalt oxide is as anode, ruthenium-oxide is as negative electrode, potassium hydroxide reaches 1.4V (as shown in Figure 7) as the composite super capacitor operating voltage of electrolyte, energy storage density is up to 23Wh/kg, crest discharge power reaches 8kW/kg (as shown in Figure 8), brought into play the high inherent characteristics of electrode of super capacitor energy density, its energy density is than aluminium electrolytic capacitor Senior Three～four order of magnitude.In addition, hybrid super capacitor has kept that electrolytic capacitor cell voltage height, specific power height, response time are short, the advantage of simplicity of design.The performance of above-mentioned excellence makes hybrid super capacitor be widely used in fields such as military, radio communications.
Claims (8)
1. mixing type ultracapacitor based on cobalt oxide and ruthenium-oxide, it is characterized in that, the structure of described hybrid battery container is the cobalt oxide anode, and potassium hydroxide water-based electrolyte and ruthenium-oxide negative electrode are sealed in and constitute column type or square structure in stainless steel casing or the engineering plastics shell; Cobalt oxide/ruthenium-oxide mixing type ultracapacitor with high power characteristics of the high energy storage characteristic of storage battery and capacitor.
2. according to the described mixing type ultracapacitor of claim 1 based on cobalt oxide and ruthenium-oxide, it is characterized in that, described anode construction forms on the porous, expanded Ni substrate for the cobalt oxide active material with the electrochemical process preparation is deposited on, and connects banded nickel collector on the foaming Ni substrate; Its anode cuts becomes rectangle.
3. according to the described mixing type ultracapacitor of claim 1 based on cobalt oxide and ruthenium-oxide, it is characterized in that, described anode construction is also for adhering to carbon nano-tube, carbonyl nickel mixed slurry formation basal body structure on porous, expanded nickel, utilize above electrochemical method is deposited on cobalt oxide, the final anode construction that forms is the composite anode that cobalt oxide-carbon nano-tube-carbonyl nickel constitutes.
4. according to the described mixing type ultracapacitor of claim 1 based on cobalt oxide and ruthenium-oxide, it is characterized in that, described negative electrode forms on the porous, expanded Ni substrate for the ruthenium-oxide active material blade coating with the chemical method preparation sticks to, and connects banded nickel collector on the foaming Ni substrate; Its negative electrode cuts becomes rectangle.
5. according to the described mixing type ultracapacitor based on cobalt oxide and ruthenium-oxide of claim 1, it is characterized in that described electrolyte is by solute and solvent composition, solute is a potassium hydroxide; Solvent is the aqueous solution; Concentration of electrolyte is 6mol/L～1mol/L, and concentration is big more, and the electrolyte conductance is high more.
6. manufacture method based on the mixing type ultracapacitor of cobalt oxide and ruthenium-oxide, described manufacture method superposes successively for anode, barrier film, the negative electrode that will connect collector, make electrode cores, anode, cathode current collector are connected the back placement respectively in the enclosure in this electrode cores with top cover positive pole, negative pole, or anodal linking to each other of anode and top cover and shell are as negative pole, the perfusion aqueous electrolyte is finished the capacitor sealing by welding or press seal mode; It is characterized in that,
Described anode manufacturing process adopts the nanometer cobalt oxide of electrochemical process preparation as raw material, and the foaming nickel porous is 0.9molCo (NO as matrix with electrolyte
3)
2And 0.075molNaNO
3Be dissolved in the mixed liquor of 500ml second alcohol and water formulatedly, wherein the volume ratio of absolute ethyl alcohol and deionized water is 1: 1; Adopt bipolar electrode constant current cathodic reduction legal system to be equipped with cobalt oxide, the anode of electrolytic cell is pure cobalt, and negative electrode is porous, expanded nickel, and controlling constant Faradaic current intensity is 1A/dm
2, the electrolytic deposition time is 4 hours, electrochemical production cobalt oxide in foaming nickel structure.After finishing, cell reaction takes out electrode, with behind the deionized water cyclic washing under 80 ℃ of conditions of air atmosphere dry 1 hour;
The ruthenium-oxide active material blade coating with chemical method preparation of being prepared as of described negative electrode sticks on the porous, expanded Ni substrate and forms, being fabricated to of (change into: described negative electrode is prepared from porous, expanded Ni substrate by the ruthenium-oxide active material blade coating with the chemical method preparation) described ruthenium-oxide active material: with RuCl
3The aqueous solution is as the reaction precursor body, with carbonic hydroammonium NH
4HCO
3Synthetic Ru (the HCO of reaction
3)
3, then with Ru (HCO
3)
3The heating and decomposition dehydration obtains RuO under 240 ℃ of conditions
2, the concrete practice takes by weighing 0.2mol RuCl
3, be dissolved in the 200mL deionized water, obtain the RuCl of brownish black
3Solution takes by weighing 0.6mol carbonic hydroammonium NH
4HCO
3, it is even that it is dissolved in the 200mL deionized water for stirring, is added drop-wise to the RuCl of brownish black slowly
3Stir in the solution and constantly, leave standstill a few minutes, the black particle of generation also sinks to reactor bottom, and above-mentioned solution is carried out vacuum filtration, and with washed with de-ionized water with thorough removal impurity, the black powder that will obtain is at last dried down at 80 ℃ and is obtained Ru (HCO
3)
3Powdered activated material is with Ru (HCO
3)
3Powder heating and decomposition dehydration under 240 ℃ of conditions obtains RuO
2
7. according to the manufacture method of the described mixing type ultracapacitor based on cobalt oxide and ruthenium-oxide of claim 6, it is characterized in that, in above-mentioned electrochemical production cobalt oxide anodic process, also admixture carbon nano-tube and carbonyl nickel conductive materials, prepare the compound cobalt oxide anode of another kind of cobalt oxide-carbon nano-tube-carbonyl nickel, be specially earlier carbon nano-tube and carbonyl nickel material are added 10wt% polytetrafluoroethylene adhesive preparation becoming slurry, wherein content of carbon nanotubes is 50～60wt%, and carbonyl nickel content is 40～30wt%; In the porous foam Ni substrate, with the negative electrode of this matrix as bipolar electrode constant current catholyte reduction apparatus, anode still is pure cobalt with above-mentioned slurry blade coating, and electrolyte is for equally by Co (NO
3)
2And NaNO
3The electrolyte of forming.Controlling constant Faradaic current intensity is 1A/dm
2, the electrolytic deposition time is 4 hours, takes out electrode after cell reaction is finished, and with behind the deionized water cyclic washing under 80 ℃ of conditions of air atmosphere dry 1 hour, obtains the compound cobalt oxide anode of cobalt oxide-carbon nano-tube-carbonyl nickel.
8. according to the manufacture method of the described mixing type ultracapacitor based on cobalt oxide and ruthenium-oxide of claim 6, it is characterized in that, in the preparation process of described ruthenium-oxide active material, can also in ruthenium-oxide, add an amount of carbon nano-tube-carbonyl nickel hybrid conductive material; Wherein content of carbon nanotubes is 10～25wt%, and carbonyl nickel content is 5～15wt%, and optimum content is carbon nano-tube 20wt%, carbonyl nickel 10wt%; Conductive materials can add before reaction in the ruthenic chloride presoma, carries out chemical reaction then and prepares combination electrode material.Also can after finishing, the ruthenium-oxide preparation be spiked into nanometer RuO
2Mix in the powdered activated material and fully, adding the poly-ethene adhesive preparation that is beset with of 5wt%～20wt% in above-mentioned composite material becomes mobile and the good electrode slurry of adhesiveness, and the adhesive optimum content is 10wt%; In porous, expanded nickel collector, oven dry back continuous rolling cuts and welds or stings the nickel collector of riveting over gained electrode slurry blade coating, produces to have the ruthenium-oxide active electrode that specific area is big, internal resistance is low and structural strength is high.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101894683A (en) * | 2010-06-24 | 2010-11-24 | 王庆刚 | Cathode blanked non-inert anode super pseudo-capacitor |
| CN102918613A (en) * | 2010-04-23 | 2013-02-06 | Ug投资有限公司 | A multi-element electrochemical capacitor and a method for manufacturing the same |
| CN109137023A (en) * | 2018-10-29 | 2019-01-04 | 南昌航空大学 | A kind of electrochemical preparation method of cobalt/cobalt oxide composite material and its application |
-
2008
- 2008-05-19 CN CNB2008101118927A patent/CN100552841C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102918613A (en) * | 2010-04-23 | 2013-02-06 | Ug投资有限公司 | A multi-element electrochemical capacitor and a method for manufacturing the same |
| CN102918613B (en) * | 2010-04-23 | 2017-04-19 | Ug投资有限公司 | A multi-element electrochemical capacitor and a method for manufacturing the same |
| CN101894683A (en) * | 2010-06-24 | 2010-11-24 | 王庆刚 | Cathode blanked non-inert anode super pseudo-capacitor |
| CN101894683B (en) * | 2010-06-24 | 2012-06-13 | 王庆刚 | Cathode blanked non-inert anode super pseudo-capacitor |
| CN109137023A (en) * | 2018-10-29 | 2019-01-04 | 南昌航空大学 | A kind of electrochemical preparation method of cobalt/cobalt oxide composite material and its application |
| CN109137023B (en) * | 2018-10-29 | 2020-07-03 | 南昌航空大学 | Application of cobalt oxide composite material |
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