CN101685713B - Method for manufacturing Active carbon fiber electrode super capacitor and electrode - Google Patents
Method for manufacturing Active carbon fiber electrode super capacitor and electrode Download PDFInfo
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- CN101685713B CN101685713B CN2009100917113A CN200910091711A CN101685713B CN 101685713 B CN101685713 B CN 101685713B CN 2009100917113 A CN2009100917113 A CN 2009100917113A CN 200910091711 A CN200910091711 A CN 200910091711A CN 101685713 B CN101685713 B CN 101685713B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000003990 capacitor Substances 0.000 title claims abstract description 37
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 23
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 64
- 239000004744 fabric Substances 0.000 claims abstract description 64
- 239000011888 foil Substances 0.000 claims abstract description 20
- 239000004411 aluminium Substances 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 22
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- 230000008020 evaporation Effects 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 15
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- 239000005030 aluminium foil Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 229920000297 Rayon Polymers 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 230000008901 benefit Effects 0.000 claims description 7
- 239000007772 electrode material Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004026 adhesive bonding Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000005255 carburizing Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
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- 239000001301 oxygen Substances 0.000 claims description 3
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- 239000007787 solid Substances 0.000 claims description 3
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 3
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- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000002964 rayon Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 239000011255 nonaqueous electrolyte Substances 0.000 abstract description 8
- 238000004146 energy storage Methods 0.000 abstract description 6
- 238000007789 sealing Methods 0.000 abstract description 6
- 238000004891 communication Methods 0.000 abstract description 3
- 238000010248 power generation Methods 0.000 abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 3
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- 229910052799 carbon Inorganic materials 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- NTBYNMBEYCCFPS-UHFFFAOYSA-N azane boric acid Chemical compound N.N.N.OB(O)O NTBYNMBEYCCFPS-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
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- 230000004888 barrier function Effects 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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Classifications
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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 an active carbon fiber cloth material-based super capacitor and a manufacturing method thereof, which belongs to the technical field of manufacturing capacitors. The super capacitor is a fully sealed type super capacitor which is assembled by superposing and coiling a positive electrode, a diaphragm and a negative electrode into an electrode core, pouring a non-aqueous electrolyte into the electrode core and sealing the electrode core in a stainless steel or aluminum shell to form a cylindrical or square structure, wherein the positive electrode and the negative electrode are prepared by adhering an active carbon fiber material to two sides of a positive electrode aluminum foil collector and a negative electrode aluminum foil collector; the internal resistance of the capacitor is reduced; the working voltage of the capacitor is improved and is between 0 and 2.8 volts; and the energy-storage density reaches 6 Wh/kg. The super capacitor has good high-temperature environment operation characteristics, and the service life can reach over 0.2 million times at a temperature of 70 DEG C. The super capacitor has very wide application in the fields of industrial uninterrupted power supplies, electric vehicles, wind power generation, military high-power power supplies, radio communication and the like.
Description
Technical field
The invention belongs to based on ultracapacitor manufacturing technology scope, particularly have a kind of ultracapacitor of active carbon fiber electrode of high energy storage characteristic and high discharge power and the manufacture method of electrode.
Background technology
Ultracapacitor 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 " electric double layer type " ultracapacitor on the interfacial electric double layer basis and is based upon " pseudo-capacitance type " 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 " electric double layer type " ultracapacitor 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 activated carbon, activated carbon fiber, CNT (carbon nano-tube) or the like, the patent " multi-electrode double layer capacitor " of relatively typical patent of this respect such as U.S. MAXWELL company with hermetic electrolyte seal (CA1408121A), the patent of patent of Tsing-Hua University " a kind of ultracapacitor and manufacture method thereof based on active carbon electrode " (200910086835.2) and Sino Power Star Co., Ltd. (SPSCAP) " activated carbon fiber cloth/spraying aluminium compound polar plate double electric layer capacitor and preparation method thereof " is (ZL03124290.1).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, such electrode material comprises metal oxide, nitride, high molecular polymer or the like, the patent in this field mainly concentrates on the hybrid super capacitor field at present, 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), the patent of Tsing-Hua University " based on the composite super capacitor and the manufacture method thereof of cobalt oxide and ruthenium-oxide " (200810111892.7), " a kind of poly-bile mixed super capacitor and manufacture method thereof " (200810101688.7).The key index of ultracapacitor comprises energy density and discharge power etc., and the key factor that wherein restricts These parameters is the packaging technology of electrode material and capacitor.Therefore by the good novel active carbon electrode material of processability and prepare on this basis the novel active carbon electrode can effectively improve capacitor pure can density and improve the capacitor discharge power, in electronics, information, industry, traffic, space flight and military domain, have important use based on the ultracapacitor of above-mentioned novel active carbon fiber electrode.
Summary of the invention
The objective of the invention is to propose a kind of manufacture method of ultracapacitor and electrode of active carbon fiber electrode, the structure of described ultracapacitor is after superposition is wound into electrode cores successively by anode, barrier film and negative electrode, the perfusion nonaqueous electrolyte, be sealed in and constitute column type or square structure in stainless steel or the aluminium shell, assembling becomes the full seal type ultracapacitor, it is characterized in that described anode and negative electrode stick to the anode aluminium foil collector respectively by active-carbon fibre material and make cathode aluminum foil collector both sides; Described perfusion nonaqueous electrolyte is by electrolyte triethyl group monomethyl tetrafluoro boric acid ammonium salt, solvent is gamma-butyrolacton and 6: 3 by ratio of weight and the number of copies mixed solution of propene carbonate, the additive sulfolane is formed, three's ratio of weight and number is 6: 3: 1, and wherein the concentration of tetrafluoro boric acid ammonium salt is 0.5mol/L～1mol/L.
The preparation method of described active carbon fiber electrode
(1) active-carbon fibre material is that employing proportion is 100～200g/m
2Viscose rayon cloth adopts diammonium hydrogen phosphate as impregnating agent as raw material, finishes by five step such as dipping, oven dry, carbonization, activation, reprocessing operation,
1) impregnation technology is dissolved in for raw material are adopted that to be mixed with concentration in the deionized water be that the diammonium hydrogen phosphate of 25wt%～40wt% soaks, and soak time was controlled at 40 minutes～60 minutes;
2) stoving process dries under sunshine and draughty situation for the raw material that immersion is finished, and the airing time should be no more than 72 hours, and after the airing, moisture is no more than 5wt% in the cloth;
3) carbonization technique is controlled between 250～420 ℃ in carburizing temperature for the raw material after will drying, and carries out carbonization treatment under water vapour-air mixed atmosphere protection.
4) activating process for raw material that carbonization treatment is crossed in 900～920 ℃ of temperature ranges, activating pore-creating under water vapour-nitrogen mixture atmosphere protection handled 40～60 minutes, if fall flat after an activation processing is finished is then carried out twice above same process and is handled until thorough activation;
5) aftertreatment technology is immersed in the 5wt% aqueous sulfuric acid for the activated carbon fiber that activation processing is crossed, and residual tar is removed in supersound washing, cleans repeatedly with a large amount of deionized waters at last and thoroughly oven dry.
Activated carbon fiber phosphorus impurities content by above-mentioned prepared is lower than 1wt%, and oxygen impurities content is lower than 4wt%, and specific area is greater than 1500m
2/ g is suitable as the electrode material of ultracapacitor very much.
(2) active carbon fiber electrode is to adopt the method for spraying or evaporation to adhere to one deck minute metallic alumina particles as conductive layer in a side of activated carbon fiber cloth, the inside that the minute metallic alumina particles penetrates into activated carbon fiber cloth constitutes the conductive network structure, above-mentioned activated carbon fiber cloth is adhered to the side of conductive layer and adopts conductive adhesive to stick to both sides preparation the becoming novel active carbon fiber electrode of serialization aluminum foil current collector.
Spraying coating process is for to be contained in unreeling on the station of flush coater with activated carbon fiber cloth, be wound on the rolling station after cloth passed coldplate (spray coating plate), start thermal spraying apparatus or plasma spraying equipment with the surface of molten aluminum particle spray coating at activated carbon fiber, just can form a layer thickness on the surface of activated carbon fiber cloth at 150～300 microns after the alumina particles cooling, continuously but comparatively coarse metal aluminium lamination, the distance between control gun slot and the fiber cloth and the translational speed of activated carbon fiber cloth can be controlled the thickness of aluminium lamination, the advantage of spraying coating process is that equipment is simple, metal adheres to bed thickness, metallic particles can infiltrate into the depths of activated carbon fiber cloth, but its shortcoming is metal adhesion layer rough surface, burr is more, causes the micro-short circuit phenomenon between the electrode easily.
Evaporation process passes the evaporation roller with cloth and is wound on the rolling station for activated carbon fiber cloth is contained in unreeling on the station of vacuum evaporation plating machine, vacuumizes with vacuum pump, makes the vacuum degree in the deposited chamber reach 4 * 10
-4More than the mba, the heating evaporation boat melts highly purified aluminium wire and flashes to gaseous aluminum under 1300 ℃～1400 ℃ temperature.Starting reel system makes the gaseous aluminum particulate promptly form the continuous and bright metal aluminium lamination of one deck in the activated carbon fiber cloth surface deposition that moves, cooling, aluminum layer thickness is at 50～200 microns, evaporation rate by the control metallic aluminium, vacuum degree in the translational speed of activated carbon fiber cloth and the deposited chamber waits the thickness of controlling aluminium coated, the advantage of evaporation process is that aluminium coat is even, burr is few, and the aluminium surface oxidation degree is low.
Described conductive adhesive is that 50%～90% silver-colored electroconductive stuffing is filled in the epoxy resin gluing agent system and forms conductive adhesive by silver-colored weight percent content, or be that 10%～60% acetylene black electroconductive stuffing is filled in the epoxy resin gluing agent system and forms conductive adhesive by the acetylene black percentage by weight, adding acetone or N-methyl pyrrolidone diluted after preparation was finished, to adjust the viscosity and the flowability of conductive adhesive, evenly be as the criterion to adopt blade coating or to brush, be coated on the both sides of aluminum foil current collector or the side that activated carbon fiber cloth is attached with the aluminum metal conductive layer, then activated carbon fiber cloth is sticked to aluminum foil current collector both side surface and compacting, so that adhere to more solid between the two, carrying out baking processing then solidifies to impel adhesive, treatment temperature is 140 ℃～160 ℃, stoving time was not less than 2 hours, be no more than 24 hours, these conductive adhesives have formed the molecular structure of conducting resinl after curing, and make conductive filler particles form passage.Thereby effectively reduce the internal resistance that contacts between activated carbon fiber and the aluminum foil current collector, and then can improve the high power discharge characteristic of capacitor.
The invention has the beneficial effects as follows by the preparation active carbon fiber electrode, effectively raise capacitor volume, reduced the internal resistance of capacitor; Adopt new nonaqueous electrolyte of filling a prescription to improve the operating voltage of capacitor, improved the high-temperature working performance of capacitor.This ultracapacitor operating voltage range is 0V～2.8V, and energy storage density can reach 6Wh/kg.Have good high-temperature environmental work characteristic, working life can reach more than 200,000 times under 70 ℃ of conditions.The performance of above-mentioned excellence makes ultracapacitor of the present invention at industrial uninterrupted power supply, motor vehicle, wind power generation, and fields such as high-power military power supply, radio communication are widely used.
Description of drawings
Fig. 1 is an activated carbon fiber loose structure schematic diagram
Fig. 2 is the activated carbon fiber electron scanning micrograph
Fig. 3 detects (energy spectrum method) figure for the activated carbon fiber elemental composition
Fig. 4 is the activated carbon fiber structural representation that has adhered to the aluminum metal conductive layer
Fig. 5 is the activated carbon fiber scanning electron micro that has adhered to the aluminum metal conductive layer
Fig. 6 is a cylindrical electrode cored structure schematic diagram
Fig. 7 is the cylindrical capacitor structural representation
Fig. 8 is a square electrode cores structural representation
Fig. 9 is a square capacitor arrangement schematic diagram
Embodiment
The present invention proposes the manufacture method of a kind of active carbon fiber electrode super capacitor and electrode, the structure of described ultracapacitor is after superposition is wound into electrode cores successively by anode, barrier film and negative electrode, the perfusion nonaqueous electrolyte, be sealed in and constitute column type or square structure in stainless steel or the aluminium shell, assembling becomes the full seal type ultracapacitor, and described anode and negative electrode are made attached to anode aluminium foil collector and cathode aluminum foil collector two sides respectively by active-carbon fibre material; Described perfusion nonaqueous electrolyte is by electrolyte triethyl group monomethyl tetrafluoro boric acid ammonium salt, solvent is gamma-butyrolacton and 6: 3 by ratio of weight and the number of copies mixed solution of propene carbonate, the additive sulfolane is formed, three's ratio of weight and number is 6: 3: 1, wherein the concentration of tetrafluoro boric acid ammonium salt for O.5mol/L～1mol/L.
Described electrode is for being prepared from sticking on the aluminum foil current collector by conductive adhesive behind the activated carbon fiber surface attachment aluminum metal conductive layer.The ultracapacitor energy density of manufacturing of the present invention reaches 6Wh/kg, is expected to obtain extensive use in multiple field such as electronics, automobile, space flight, military affairs.
Activated carbon fiber, the detailed process of active carbon fiber electrode preparation and ultracapacitor assembling is:
1. the detailed preparation technology of active-carbon fibre material: described active-carbon fibre material is to adopt viscose rayon cloth 1 as raw material (adopting shown in the activated carbon fiber cloth constituent content contrast schematic diagram that energy spectrum method detects as Fig. 2 activated carbon fiber cloth pattern stereoscan photograph and Fig. 3), adopt diammonium hydrogen phosphate as impregnating agent, finish by five step such as dipping, oven dry, carbonization, activation, reprocessing operation.Choose viscose rayon as raw material, viscose rayon cloth proportion is at 100～200g/m
2Between, desirable proportion is 180g/m
2Select for use diammonium hydrogen phosphate to be dissolved in and be mixed with the impregnating agent that concentration range is 25wt% ~ 40wt% in the deionized water, optimum concentration range is 35wt%.Viscose rayon is positioned over fully immersion in the impregnating agent, and soak time was controlled at 55 minutes.Take out the back and dries under sunshine and draughty situation, the airing time should be no more than 72 hours, after the airing in the cloth moisture be no more than 5wt%.Viscose rayon after the airing is carried out the carbonization preliminary treatment under steam air mixed atmosphere, carburizing temperature is controlled between 250～400 ℃, and maximum temperature should not surpass 420 ℃, and best carburizing temperature is at 320 ℃.The material that carbonization treatment is crossed further carries out activation processing in steam nitrogen mixed in equal amounts atmosphere, activation temperature is controlled at 920 ℃, soak time is answered proper extension, and the re-activation that fall flat can be carried out the activation processing product under the same terms once more after finishing as an activation processing is handled until thorough activation.The activated carbon fiber that activation processing is finished is immersed in 5% aqueous sulfuric acid and cleans to remove residual tar by the method for supersound washing, cleans repeatedly with a large amount of deionized waters at last and with its thorough oven dry.The activated carbon fiber loose structure feature of above-mentioned prepared as shown in Figure 1, Fig. 1 is an activated carbon fiber loose structure schematic diagram, 1 is activated carbon fiber cloth among the figure, 2 is microcellular structure.The material microscopic appearance as shown in Figure 2.The distinguishing feature of the prepared fiber material of above-mentioned technology is that impurity content is few, and its phosphorus content is up to 95wt% as shown in Figure 3, and its phosphorus impurities content is lower than 1wt%, and oxygen impurities content is lower than 4wt%, and specific area is greater than 1500m
2/ g is suitable as the electrode material of ultracapacitor very much.
2. the preparation method of described active carbon fiber electrode comprises that employing evaporation or spraying method adhere to the layer of aluminum conductive layer in a side of activated carbon fiber cloth.Evaporation process passes chill roll (evaporation roller) with cloth and is wound on the rolling station for activated carbon fiber cloth is contained in unreeling on the station of vacuum evaporation plating machine, vacuumizes with vacuum pump, makes the vacuum degree in the deposited chamber reach 4 * 10
-4More than the mba, the heating evaporation boat melts highly purified aluminium wire and flashes to gaseous aluminum under 1300 ℃～1400 ℃ temperature.Start reel system and make the gaseous aluminum particulate promptly form the continuous and bright metal aluminium lamination of one deck in the activated carbon fiber cloth surface deposition that moves, cooling, its structure as shown in Figure 4.Evaporation rate by the control metallic aluminium, vacuum degree in the translational speed of activated carbon fiber cloth and the deposited chamber waits the thickness of controlling aluminium coated, general aluminum layer thickness is at 50～200 microns, optimum thickness is 160～180 microns, and the advantage of evaporation process is that aluminium coat is very even, and burr is few, and the aluminium surface oxidation degree is low, it is less than normal that but shortcoming is a thickness of coating, and the evaporation time is longer, and the technology cost is higher.
Spraying coating process is for to be contained in unreeling on the station of flush coater with activated carbon fiber cloth, be wound on the rolling station after cloth passed coldplate (spray coating plate), start thermal spraying apparatus or plasma spraying equipment with the surface of molten aluminum particle spray coating at activated carbon fiber, just can form one deck after the alumina particles cooling on the surface of activated carbon fiber cloth continuously but comparatively coarse metal aluminium lamination, its structure as shown in Figure 4,3 is the activated carbon fiber bundle among the figure, and 4 is the aluminum metal conductive layer of carbon cloth surface attachment.The distance between control gun slot and the fiber cloth and the translational speed of activated carbon fiber cloth can be controlled the thickness of aluminium lamination, general spraying aluminum layer thickness is at 150～300 microns, because the spraying aluminum layer thickness is bigger, therefore its optimum thickness is 200～240 microns, the advantage of spraying coating process is that equipment is simple, metal adheres to bed thickness, metallic particles can infiltrate into the depths of activated carbon fiber cloth, but its shortcoming is metal adhesion layer rough surface, burr is more, cause the micro-short circuit phenomenon between the electrode easily, and the spray process process is to finish under air atmosphere, metal adhesion layer degree of oxidation is bigger.The surface microscopic topographic electron scanning micrograph of spray metal adhesion layer as shown in Figure 5.
3. the detailed preparation technology of active carbon fiber electrode: after finishing the activated carbon fiber cloth surface metal and adhering to processing, need be with its surface attached to the serialization aluminum foil current collector.The patented technology of Maxwell house journal technology and Sino Power Star Co., Ltd. (SPSCAP) all is that activated carbon fiber cloth is simply contacted with aluminum foil current collector.This patent proposes to pass through the bonding new technology of conductive adhesive between a kind of activated carbon fiber cloth and the aluminium foil both side surface, can significantly reduce activated carbon fiber cloth and the direct contact resistance of aluminium foil, and be convenient to the automated production of capacitor.To be that silver powder or conductive acetylene are black wait conductive filler to be dissolved in agent of thermosetting gluing such as the epoxy resin gluing agent system fully shear agitation to prepare and become conductive adhesive concrete technology.As select silver as electroconductive stuffing, and then its weight percent content is no more than 90%, is not less than 50%, and the present invention selects 75%; As to select acetylene black be electroconductive stuffing, and then its percentage by weight is no more than 60%, is not less than 10%, and the present invention selects 45%; Can add diluents such as proper amount of acetone, N-methyl pyrrolidone after preparation is finished to adjust the viscosity and the flowability of adhesive, these diluents can vapor away when follow-up hot setting was handled.After finishing, the conductive adhesive preparation adopt modes such as blade coating, brushing to be uniformly coated on the both sides of aluminium foil or the side that activated carbon fiber cloth is attached with the aluminum metal conductive layer, then activated carbon fiber cloth is sticked to aluminium foil both side surface and compacting so that adhere to more solid between the two, electrode is carried out baking processing to be solidified to impel adhesive, treatment temperature is 120 ℃～180 ℃, optimum treatmenting temperature is 160 ℃, stoving time was not less than 2 hours, was no more than 24 hours.After finishing dealing with electrode being cut becomes the electrode cores preparation of definite shape in order to next step.
4. the assembling detailed process of the preparation of electrode cores and capacitor: electrode cores mainly comprises cylindrical and two kinds of structures of square, wherein the cylindrical electrode cored structure as shown in Figure 6,3 is the activated carbon fiber bundle among the figure, 4 is the aluminum metal conductive layer of carbon cloth surface attachment.
Its preparation basic craft course is by the thorn riveting on anode aluminium foil collector 7 and cathode aluminum foil collector 8, mode such as cold welding and ultra-sonic welded connects strip or needle-like drainage body 6, then according to shown in Fig. 7 with anode aluminium foil collector 7, the positive activated carbon fiber 9 of its surface adhesion, cathode aluminum foil collector 8, the cathode activity carbon fiber 10 of its surface adhesion, barrier film 11 assemblies such as grade are by method for winding preparation becoming cylindrical electrode core body, with the drainage body of electrode cores respectively with top cover 13 on positive terminal 14 and negative terminal 15 put into cylindrical housings 12 after adopting the mode of riveted joint or welding to connect, the mode that adopts press seal or welding then is connected housing 12 and finishes and confirm sealing with top cover 13, then the semi-finished product that process are placed on dry 120 ℃ of vacuum conditions under standby more than 72 hours.
Square electrode cores structure as shown in Figure 8, its preparation basic craft course is electrode cores for connecting strip or needle-like drainage body 6 by ultra-sonic welded or the mode that directly cuts on aluminum foil current collector, by the lamination mode structural group such as anode and negative electrode and barrier film being dressed up then.The structure of square capacitor as shown in Figure 9, with electrode cores drainage body respectively with end cap 13 on positive terminal 14, negative terminal 15 be positioned in the housing 12 after connecting by welding manner, by welding manner end cap 13 and housing 12 connected and to finish and confirms sealing, then the semi-finished product that process are placed on dry under 120 ℃ of vacuum conditions standby more than 72 hours.
5. the fluid injection of ultracapacitor and sealing: with packaged but as yet not the capacitor of fluid injection inject nonaqueous electrolytes and tighten the liquid injection port bolt and finish sealing from liquid injection port 16 then in the down oven dry more than 72 hours of 120 ℃ of vacuum conditions.Described nonaqueous electrolyte is by electrolyte and solvent composition, electrolyte is a triethyl group monomethyl tetrafluoro boric acid ammonium salt, solvent is gamma-butyrolacton and 6: 3 by ratio of weight and the number of copies mixed solution of propene carbonate, the additive sulfolane is formed, above-mentioned three kinds of solvents all have good temperature resistance energy and higher decomposition voltage, mixed electrolytic solution can effectively improve capacitor improves capacitor in the operating characteristic under the hot environment operating voltage, and three's best proportioning is 6: 3: 1.The concentration of tetrafluoro boric acid ammonium salt is 0.5mol/L～1mol/L in the electrolyte, and the big more then electrolyte of concentration conductance is high more, and the stability of the low more then electrolyte of concentration is good more, and it is 0.8mol/L that the present invention adopts concentration; Adopt the capacitor working pressure of above-mentioned electrolyte to reach 2.8V, energy storage density reaches 6Wh/kg, have good high-temperature environmental work characteristic, working life can reach more than 200,000 times under 70 ℃ of conditions, after the electrolyte perfusion finishes liquid injection port 16 sealings is finished the assembling of capacitor.
Above-mentioned ultracapacitor cell operating voltage based on novel active carbon electrode and organic electrolyte reaches 2.8V, the performance of above-mentioned excellence makes ultracapacitor that the present invention proposes at industrial uninterrupted power supply, motor vehicle, wind power generation, and fields such as high-power military power supply, radio communication are widely used.
Claims (2)
1. the electrode preparation method of an active carbon fiber electrode super capacitor is characterized in that, the preparation method of described active carbon fiber electrode comprises the preparation of activated carbon fiber cloth and active carbon fiber electrode,
(1) activated carbon fiber cloth is that employing proportion is 100～200g/m
2Viscose rayon cloth adopts diammonium hydrogen phosphate as impregnating agent as raw material, finishes by dipping, oven dry, carbonization, activation and five step of reprocessing operation;
A) impregnation technology is dissolved in for raw material are adopted that to be mixed with concentration in the deionized water be that the diammonium hydrogen phosphate of 25wt%～40wt% soaks, and soak time was controlled at 40 minutes～60 minutes;
B) stoving process dries under sunshine and draughty situation for the raw material that immersion is finished, and the airing time should be no more than 72 hours, and after the airing, moisture is no more than 5wt% in the cloth;
C) carbonization technique carries out carbonization treatment for the raw material after will drying are controlled between 250～420 ℃ in carburizing temperature under water vapour-air mixed in equal amounts atmosphere protection;
D) activating process for raw material that carbonization treatment is crossed in 900～920 ℃ of temperature ranges, activating pore-creating under water vapour-nitrogen mixed in equal amounts atmosphere protection handled 40～60 minutes, if fall flat after an activation processing is finished is then carried out twice above same process and is handled until thorough activation;
E) aftertreatment technology is immersed in the 5wt% aqueous sulfuric acid for the activated carbon fiber cloth that activation processing is crossed, and residual tar is removed in supersound washing, cleans repeatedly with a large amount of deionized waters at last and thoroughly oven dry;
Activated carbon fiber phosphorus impurities content by above-mentioned prepared is lower than 1wt%, and oxygen impurities content is lower than 4wt%, and specific area is greater than 1500m
2/ g is suitable as the electrode material of ultracapacitor very much;
(2) active carbon fiber electrode is to adopt the method for spraying or evaporation to adhere to one deck minute metallic alumina particles as conductive layer in a side of activated carbon fiber cloth, the inside that the minute metallic alumina particles penetrates into activated carbon fiber cloth constitutes the conductive network structure, above-mentioned activated carbon fiber cloth is adhered to the both sides preparation of the side of conductive layer adopting conductive adhesive to stick to the serialization aluminum foil current collector becomes active carbon fiber electrode, and wherein aluminum foil current collector is anode aluminium foil collector or cathode aluminum foil collector; The method of described employing spraying or evaporation is
A) spraying coating process is for to be contained in unreeling on the station of flush coater with activated carbon fiber cloth, be wound on the rolling station after cloth passed coldplate, start thermal spraying apparatus or plasma spraying equipment with the surface of molten aluminum particle spray coating at activated carbon fiber, just can form a layer thickness on the surface of activated carbon fiber cloth at 150～300 microns after the alumina particles cooling, continuously but comparatively coarse aluminium lamination, the distance between control gun slot and the fiber cloth and the translational speed of activated carbon fiber cloth can be controlled the thickness of aluminium lamination, the advantage of spraying coating process is that equipment is simple, aluminium lamination is thick, metallic particles can infiltrate into the depths of activated carbon fiber cloth, but its shortcoming is the aluminium lamination rough surface, burr is more, causes the micro-short circuit phenomenon between the electrode easily;
B) evaporation process passes the evaporation roller with activated carbon fiber cloth and is wound on the rolling station for activated carbon fiber cloth is contained in unreeling on the station of vacuum evaporation plating machine, vacuumizes with vacuum pump, makes the vacuum degree in the deposited chamber reach 4 * 10
-4More than the mba, the heating evaporation boat melts highly purified aluminium wire and flashes to gaseous aluminum under 1300 ℃～1400 ℃ temperature, starting reel system makes the gaseous aluminum particulate promptly form the continuous and bright aluminium lamination of one deck in the activated carbon fiber cloth surface deposition that moves, cooling, aluminum layer thickness is at 50～200 microns, evaporation rate by the control metallic aluminium, vacuum degree in the translational speed of activated carbon fiber cloth and the deposited chamber is controlled the thickness of aluminium lamination, the advantage of evaporation process is that aluminium lamination is even, burr is few, and the aluminium surface oxidation degree is low.
2. according to the electrode preparation method of the described active carbon fiber electrode super capacitor of claim 1, it is characterized in that, described conductive adhesive is that 50%～90% silver-colored electroconductive stuffing is filled in the epoxy resin gluing agent system and forms conductive adhesive by silver-colored weight percent content, or be that 10%～60% acetylene black electroconductive stuffing is filled in the epoxy resin gluing agent system and forms conductive adhesive by the acetylene black percentage by weight, adding acetone or N-methyl pyrrolidone diluted after preparation was finished, to adjust the viscosity and the flowability of conductive adhesive, evenly be as the criterion to adopt blade coating or to brush, be coated on the both sides of aluminum foil current collector or the side that activated carbon fiber cloth is attached with the aluminum metal conductive layer, then activated carbon fiber cloth is sticked to aluminum foil current collector both side surface and compacting, so that adhere to more solid between the two, carrying out baking processing then solidifies to impel adhesive, treatment temperature is 140 ℃～160 ℃, stoving time is 2 hours～24 hours, these conductive adhesives have formed the molecular structure of conducting resinl after curing, mechanical property and adhesive property guarantee are provided, and have made the electroconductive stuffing particle form passage; Thereby effectively reduce the internal resistance that contacts between activated carbon fiber and the aluminum foil current collector, and then can improve the high power discharge characteristic of capacitor.
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| CN103210123B (en) * | 2010-11-11 | 2016-03-16 | 日立金属株式会社 | The manufacture method of aluminium foil |
| CN102496482B (en) * | 2011-12-26 | 2016-01-20 | 东莞新能源科技有限公司 | A kind of super-capacitor pole piece and preparation method thereof |
| CN103400968A (en) * | 2013-08-09 | 2013-11-20 | 天津巴莫科技股份有限公司 | Lithium manganese phosphate-capacitance carbon composite material, preparation method thereof, and lithium ion capacitance battery |
| CN104694977B (en) * | 2014-11-28 | 2018-04-06 | 昆明理工大学科技产业经营管理有限公司 | A kind of highly conductive carbon fiber electrode material and preparation method |
| CN107112511B (en) * | 2014-12-11 | 2020-10-02 | 阿克爱科蒂夫有限公司 | Method and machine for manufacturing fibre electrodes |
| CN105780364B (en) * | 2016-02-26 | 2018-03-16 | 浙江大学 | A kind of method for preparing ultramicropore flexibility carbon cloth and products thereof and application |
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| CN109346725B (en) * | 2018-10-18 | 2021-08-03 | 深圳中科瑞能实业有限公司 | Energy storage device aluminum cathode, energy storage device and preparation method thereof |
| CN109317125A (en) * | 2018-11-03 | 2019-02-12 | 北京卡林新能源技术有限公司 | A kind of preparation method of activated carbon fiber electro-thermal regeneration unit |
| CN110372067B (en) * | 2019-06-05 | 2020-08-21 | 清华大学 | Flowing electrode and application thereof |
| CN112216518B (en) * | 2020-09-15 | 2022-08-30 | 暨南大学 | Flexible zinc ion hybrid capacitor and preparation method and application thereof |
| CN113237816A (en) * | 2021-04-19 | 2021-08-10 | 山东鲁北国际新材料研究院有限公司 | Method for preliminarily detecting morphology of ternary cathode material precursor particles |
| CN114094210A (en) * | 2021-10-19 | 2022-02-25 | 陈璞 | Three-dimensional positive electrode and aqueous zinc-manganese battery |
| CN115122714B (en) * | 2022-05-30 | 2023-09-22 | 安徽天富环保科技材料有限公司 | Preparation process of activated carbon fiber cloth for electrode preparation |
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