CN1753116A - A kind of carbon back multi-hole electrode film that is used for ultracapacitor and preparation method thereof - Google Patents
A kind of carbon back multi-hole electrode film that is used for ultracapacitor and preparation method thereof Download PDFInfo
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Abstract
A kind of carbon back multi-hole electrode film that is used for ultracapacitor and preparation method thereof.Each constituent content of film is: active carbon content is 72mass%～99mass%, conductive carbon black or content of graphite are 0.1mass%～20mass%, the content of nm-class powder of zirconium oxide is 0.1mass%～5mass%, and the nano metal nickel powder content is 0.1mass%～3mass%; Voidage is 45%～75%, and further preferred voidage is 55%～65%.Preparing film of the present invention at first mixes deionized water, organic monomer and crosslinking agent; Then dispersant being added solution stirs and obtains premixed solution; Material powder is added, ball milling mixes, and makes slurry again; The gained slurry is added defrother and carries out froth in vacuum; Slurry with after initator and the catalyst adding de-bubble after stirring, is obtaining green compact on the casting machine behind moulding, curing and demoulding, again through the weak oxide atmosphere heat treatment, obtain the target multi-hole electrode film.Moulding process of the present invention is simple, molding time weak point, easy to operate, and the film thickness controllability is good, mesopore is flourishing.
Description
Technical field
A kind of composite carbon of the present invention Quito pore electrod film and preparation method thereof relates in particular to composite carbon Quito pore electrod film that is used for ultracapacitor and preparation method thereof.
Technical background
The energy more and more is subjected to people's great attention as one of pillar industry of human modern civilization.Meanwhile, the various exhaust gas discharging that the energy produced, the environmental problem that the greenhouse effect that cause cause have become the focus that the whole world is paid close attention to the most, also are deep day by day socialization problems.Rugged environment pollutes, and has brought serious threat not only for the mankind and biological existence space, and can stay infinite hidden danger to the generation after generation of descendants.Global scientist and knowledgeable people call upon States one after another government and branch of industry are researching and developing new forms of energy energetically, when accelerating to solve energy crisis, and the environment of must preserving our planet, protection human existence space.At this urgent problem; beginning western developed country from the eighties, to take the lead in seeking with efficient, energy-conservation, low public hazards be final goal; research and development cleanings, novel power supply efficiently; wherein the ultracapacitor energy storage system unifies " green technology " with the energy mutually with environmental protection; carry out the research and development of ultracapacitor energy storage device; is a positive feasible strategy to air conservation, greenhouse effect with environmental protection, relates to the human society significant problem and has strategic importance for the solution energy, these two of environment.
Ultracapacitor (Super capacitor) is a kind of novel energy device that occurs in recent years, it is a kind of a kind of novel energy device between rechargeable battery and capacitor, have the dual-use function of electric capacity and battery concurrently, its power density is far above common batteries (10 times～100 times), energy density is far above conventional physical electric capacity (＞100 times), compare with battery with ordinary capacitor, it is little that ultracapacitor has a volume, capacity is big, charging rate is fast, have extended cycle life, the discharge power height, working temperature wide (40 ℃～85 ℃), good reliability and advantage such as with low cost, therefore can develop into a kind of novel, efficiently, practical energy accumulating device, thereby at the energy, communication, power electronics, all there is very wide application prospect in fields such as national defence, as: portable instrument equipment, the data accumulating storage system, electric car power supply, aspects such as emergent back-up source.
In recent years, ultracapacitor is as a kind of energy storage device of excellent performance, becomes the U.S., Japan, Russia and European developed country at one of focus of material, electric power, electronics, physics, chemical multidisciplinary crossing domain research.Main goal in research is the required low-cost electrode material of the fine and close energy of preparation high-energy-density and high power density, and the electrolyte body based material of operating voltage height, stable electrochemical property, conductivity height and long service life, and prepare the ultracapacitor that can be used for dynamical system (comprising back-up source and electric motor car etc.) renewable energy system of high power density, high capacity density and stable performance on this basis.
Electrode is the core part of capacitor, and its structure, character play decisive influence to the performance of double electric layer capacitor.Electrode material can be divided three classes: metal oxide, high molecular polymer and carbon-based electrode material.Wherein cost an arm and a leg and the high molecular polymer less stable, thereby be difficult to large-scale industrial production and application owing to metal oxide.Carbon-based material because have porous, big specific area, porosity height, chemical stability is good, with low cost and characteristics such as long service life, electrode material as double electric layer capacitor, can obtain high energy density and power density, therefore at present mostly with active carbon as polarizing electrode.But carbon-based material itself exists capacity density and the lower shortcoming of conductivity, has limited ultracapacitor in many application that require the high-energy-density field.The factor of capacity density that influences ultracapacitor carbon-based electrode material is a lot, and wherein pore-size distribution is one of most important factor of its capacity density of decision.Therefore the porous carbon base electrode that how to prepare the mesopore prosperity becomes present urgency key issue to be solved.
Though it is a lot of to prepare the method for electrode film, as The tape casting, plasma spraying method, pressing, rolling formation method, extrinsion pressing etc.Wherein plasma spraying method and pressing etc. exist the higher and process cycle length of cost to be unfavorable for that industrialization produces continuously, pressing is unsuitable for preparing large area film, and roll film and extrusion because the higher production cost that causes of content of organics is higher and seriously polluted, but therefore The tape casting because of have equipment simply, process stabilizing continued operation and production efficiency advantages of higher, be fit to industrialization and produce continuously, but have organic substance consumption height simultaneously, problem such as green density is low and pliability is poor, the environmental pollution of organic substance strong toxicity is serious.
People such as Fujioka Mikio propose a kind of preparation method who adopts plasma spraying method to prepare indefiniteness carbon electrode film in patent WO2004072322 and JP20030033859, this method is fit to the above electrode films of the several microns of preparation, but exist complex technical process, parameter wayward, be unsuitable for shortcoming such as serialization production.
Fujii Takas hi and Some Yamasao propose a kind of method for preparing carbon nano-tube film in patent US2004166235 and JP2001331509, be on supporter, to adopt binding agent to make carbon nano-tube film carbon nano-tube, this method need adopt supporter to be used as the carrier of carbon nano-tube film, while binding agent large usage quantity, increased cost on the one hand, reduce the content of active material in electrode film on the other hand relatively, thereby be unsuitable for preparing the electrode of super capacitor film.
People such as Nis h iyama Tos hi h iko are at patent EP0987775, a kind of method for preparing electrode film is proposed among JP2000082467 and the US6686089, mainly be powdered carbon to be added contain in the acetate of polypyridine, and it is coated on the active material dry back forms collector body, itself and active material constitute electrode, this method is simple to operate, but there is uneven thickness after the coating drying in it, solvent has certain toxicity, and solid content of slurry is low to cause forming problems such as aperture in the film is excessive owing to apply, thereby is unsuitable for preparing the controlled thin-film material of pore-size distribution.
People such as Avarbz Robert Gustavoviti propose a kind of method for preparing porous electrode in patent EP0864167 and CN1203694A, mainly be to adopt die pressing to make required porous thin slice with binding agent active material, this method is suitable for preparing the base sheet of thickness greater than 300 μ m, has simultaneously that the binding agent consumption is higher, technology is complicated, cost is higher and is not suitable for shortcoming such as serialization production.
From above analysis as can be known, remain in the preparation process for the carbon-based electrode film long in complex process, organic substance consumption height, manufacturing cycle, the environmental pollution of solvent tool toxicity is serious or the more high urgency of cost problem to be solved, therefore develop the low-cost quick shaping process of multi-hole electrode film, becoming the new approaches of present raising carbon-based electrode material energy density, is to realize its effective way in the widespread commercial application in fields such as automobile, telecommunications, portable electric appts and Aero-Space.
At above problem, the present invention proposes a kind of porous nano composite carbon base electrode film that is used for ultracapacitor and preparation method thereof, the technology of quick easy manufacture electrode film is provided on the one hand, adopt this method can obtain the controlled porous nano composite carbon base film electrode of target thickness and size and pore-size distribution on the other hand, help improving the capacity density of ultracapacitor by control of process parameters such as solid content, heat treatment temperature, atmosphere.
Summary of the invention
The present invention seeks to propose a kind of nano combined carbon back multi-hole electrode film that is used for ultracapacitor and preparation method thereof.Each component of carbon back multi-hole electrode film of the present invention and content thereof are: active carbon content is 72mass%～99mass%, conductive carbon black or content of graphite are 0.1mass%～20mass%, the content of nm-class powder of zirconium oxide is 0.1mass%～5mass%, and the nano metal nickel powder content is 0.1mass%～3mass%.
The preparation method that the present invention is used for the nano combined carbon back multi-hole electrode film of ultracapacitor has that technology is simple, the cycle short, with low cost, pollute little, can produce continuously, advantage such as electrode aperture is controlled, be easy to commercial the application.
The present invention is achieved through the following technical solutions: utilize organic monomer to aggregate into macromolecule with the powder granule fixed aggregate together, form the base substrate with definite shape and intensity.Technical process is fairly simple: by static and sterically hindered stabilization, powder granule is scattered in the monomer solution that contains organic monomer, crosslinking agent and dispersant uniformly with higher solid volume content, makes the high solids content stable slurry of low viscosity and high fluidity; Water and other additive, stir, behind flow casting molding, under certain condition, the monomer in-situ solidifying, behind certain hour, the base that will wet is dry at a certain temperature, forms to have the machinable base substrate of certain intensity, again through Overheating Treatment, remove moisture and partial organic substances in the base substrate, can obtain the multi-hole electrode film of different pore-size distributions by the control heat treatment process parameter.
The compound porous electrode film preparation method of carbon back of the present invention may further comprise the steps:
(1) at first with material powder and absolute ethyl alcohol according to (1～10): the ratio of (1～30) joins in the agate jar that agate ball is housed, and material ball ratio is 1: (1～6), ball milling 4 hours～24 hours;
(2) with ball milling gained compound, under 70 ℃～120 ℃ conditions, 300 order nylon mesh are crossed in vacuumize 6 hours～20 hours then, obtain uniform blended stock powder;
(3) with organic monomer and crosslinking agent according to mass ratio (15～90): 1 ratio, dissolve in the deionized water, make concentration and be 1～25% solution;
(4) consumption of dispersant being pressed the 0.1mass%～3mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution;
(5) the mixed material powder is added premixed solution, place the agate jar that agate ball is housed to carry out ball milling and stir, the time is 24 hours～72 hours, makes the stable slurry that solid concentration is higher than 50vol%;
(6) in the stable slurry of preparation, adding consumption is the defrother of the 0.005vol%～0.05vol% of stable slurry volume, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble;
(7) with consumption be slurry after the catalyst of the initator of 0.005vol%～0.5vol% of stable slurry volume and 0.05vol%～0.2vol% adds de-bubble, stir, promptly obtain plastic slurry;
(8) with gained slurry curtain coating on the flow casting molding machine, by control edge of a knife height, can obtain thickness is the green compact of 30 μ m～500 μ m;
(9) green compact are placed under inert gas shielding or the vacuum state, in 35 ℃～70 ℃ temperature ranges, heat 10min～60min simultaneously, green compact are solidified into the base sheet;
(10) the base sheet can be cut into different size as required, under the weak oxide atmospheric condition, 300 ℃～800 ℃ heat treatment 10min～200min promptly obtain porous carbon base electrode film then.
Above-mentioned raw materials used powder is the mixture of active carbon, conductive carbon black or graphite, nm-class powder of zirconium oxide, metal nickel nano powder; Wherein active carbon content is 72mass%～99mass%, and conductive carbon black or content of graphite are 0.1mass%～20mass%, and the content of nm-class powder of zirconium oxide is 0.1mass%～5mass%, and the nano metal nickel powder content is 0.1mass%～3mass%.
Above-mentioned organic monomer is a kind of in acrylamide or the first class acrylamide.
Above-mentioned crosslinking agent is N, a kind of in the two propylene olefin(e) acids of N '-methylene level bisacrylamide or polyethylene.
Above-mentioned dispersant is one or more in polyethylene glycol, polyvinyl alcohol, poly amic acid or the ammonium citrate.
Above-mentioned defrother is a tbp.
Above-mentioned initator is a kind of in fine of ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide or azo two isobutyls.
Above-mentioned catalyst is N, N, N ', N '-tetramethylethylenediamine.
Above-mentioned inert atmosphere is high pure nitrogen or argon shield.
The above-mentioned ultracapacitor of gained of the present invention with each component of carbon back multi-hole electrode film and content thereof is: wherein active carbon content is 72mass%～99mass%, conductive carbon black or content of graphite are 0.1mass%～20mass%, the content of nm-class powder of zirconium oxide is 0.1mass%～5mass%, and the nano metal nickel powder content is 0.1mass%～3mass%; Through detecting with the BET method, voidage is 45%～75%, and further preferred voidage is 55%～65%.
The advantage that the present invention compared with prior art has is: there are problems such as cost is higher, organic substance consumption height, manufacturing cycle is long, the environmental pollution of solvent tool toxicity is serious or cost is higher, electrode film pore-size distribution control difficulty in the method that is used to prepare electrode film in the prior art more, advantages such as that method of the present invention by comparison has is with low cost, non-environmental-pollution, the organic substance consumption is low, technology is simple and the cycle short, the electrode film pore-size distribution is controlled.
Gained porous composite electrode film of the present invention can be used as electrode and is used for secondary cells such as ultracapacitor, lithium ion battery.
Embodiment
Further specify the present invention with specific embodiment below.But the present invention is not limited to embodiment.In following examples raw materials used purity be chemical pure or analyze pure more than.
Embodiment 1
At first the content according to 72mass% and 20mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 5mass% and the nano metal nickel powder of 3mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 30 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 1, ball milling 4 hours; With ball milling gained compound, under 80 ℃ of conditions, 300 order nylon mesh are crossed in vacuumize 10 hours then, obtain uniform blended stock powder again; With acrylamide and N, N '-methylene level bisacrylamide dissolves in the deionized water according to 15: 1 ratio of mass ratio, makes the solution that concentration is 18mass% then; Then ammonium polyacrylate and polyethylene glycol are pressed the 1.0mass% of mixed material powder quality and the consumption adding premixed solution of 0.5mass% respectively, stir, obtain premixed solution; Again with the mixed material powder according to target the consumption of the 60mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 60mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.005vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the N of the warm and fine 0.15vol% of azo two isobutyls of the 0.10vol% of stable slurry volume again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 30 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 35 ℃ of temperature ranges, heat 50min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 800 ℃ of heat treatment 10min promptly obtain target porous composite carbon base electrode film at last.Adopt the BET method to detect, voidage is 75%.
Embodiment 2
At first the content according to 95mass% and 4.8mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 0.1mass% and the nano metal nickel powder of 0.1mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 1 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 1, ball milling 4 hours; With ball milling gained compound, under 120 ℃ of conditions, 300 order nylon mesh are crossed in vacuumize 6 hours then, obtain uniform blended stock powder again; With acrylamide and N, N '-methylene level bisacrylamide dissolves in the deionized water according to 15: 1 ratio of mass ratio, makes the solution that concentration is 15mass% then; The consumption of then polyvinyl alcohol being pressed the 0.1mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 80mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 80mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.01vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the ammonium persulfate of 0.5vol% of stable slurry volume and the N of 0.2vol% again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 100 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 45 ℃ of temperature ranges, heat 30min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 300 ℃ of heat treatment 200min promptly obtain target porous composite carbon base electrode film at last.Adopt the BET method to detect, voidage is 45%.
Embodiment 3
At first the content according to 85mass% and 10mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 2.0mass% and the nano metal nickel powder of 3.0mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 5 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 3, ball milling 4 hours; With ball milling gained compound, under 80 ℃ of conditions, drying 20 hours is crossed 300 order nylon mesh then, obtains uniform blended stock powder again; With acrylamide and N, N '-methylene level bisacrylamide dissolves in the deionized water according to 15: 1 ratio of mass ratio, makes the solution that concentration is 1mass% then; The consumption of then poly amic acid being pressed the 0.1mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 60mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 60mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.005vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the ammonium persulfate of 0.005vol% of stable slurry volume and the N of 0.05vol% again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 50 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 35 ℃ of temperature ranges, heat 60min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 500 ℃ of heat treatment 150min promptly obtain target porous composite carbon base electrode film at last.Adopt the BET method to detect, voidage is 60%.
Embodiment 4
At first the content according to 80mass% and 14mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 5.0mass% and the nano metal nickel powder of 1.0mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 1 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 3, ball milling 4 hours; With ball milling gained compound, under 110 ℃ of conditions, 300 order nylon mesh are crossed in vacuumize 10 hours then, obtain uniform blended stock powder again; Then with the two acrylic acid of methacryl ammonium and polyethylene according to 60: 1 ratio of mass ratio, dissolve in the deionized water, make the solution that concentration is 25mass%; The consumption of then ammonium citrate being pressed the 3mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 75mass% of slurry add premixed solution, carry out ball milling and stir, the time is 72 hours, makes the stable slurry that solid concentration is 75mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.05vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the potassium peroxydisulfate of 0.25vol% of stable slurry volume and the N of 0.10vol% again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 100 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 65 ℃ of temperature ranges, heat 20min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 700 ℃ of heat treatment 30min promptly obtain target porous composite carbon base electrode film at last.Adopt the BET method to detect, voidage is 70%.
Embodiment 5
At first the content according to 95mass% and 0.1mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 1.9mass% and the nano metal nickel powder of 3.0mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 3 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 1, ball milling 4 hours; With ball milling gained compound, under 90 ℃ of conditions, 300 order nylon mesh are crossed in vacuumize 6 hours then, obtain uniform blended stock powder again; Then with the two acrylic acid of acrylamide and polyethylene according to 90: 1 ratio of mass ratio, dissolve in the deionized water, make the solution that concentration is 25mass%; The consumption of then polyethylene glycol being pressed the 3mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 75mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 75mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.01vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the ammonium persulfate of 0.5vol% of stable slurry volume and the N of 0.05vol% again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 30 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 70 ℃ of temperature ranges, heat 10min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 400 ℃ of heat treatment 180min promptly obtain target porous composite carbon base electrode film at last.Adopt the BET method to detect, voidage is 50%.
Embodiment 6
At first the content according to 85mass% and 10mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 3.0mass% and the nano metal nickel powder of 2.0mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 5 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 6, ball milling 4 hours; With ball milling gained compound, under 110 ℃ of conditions, 300 order nylon mesh are crossed in vacuumize 6 hours then, obtain uniform blended stock powder again; Then with the two acrylic acid of acryloyl ammonium and polyethylene according to 10: 1 ratio of mass ratio, dissolve in the deionized water, make the solution that concentration is 15mass%; The consumption of then polyvinyl alcohol being pressed the 0.1mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 70mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 70mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.01vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the potassium peroxydisulfate of 0.25vol% of stable slurry volume and the N of 0.15vol% again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 300 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 45 ℃ of temperature ranges, heat 30min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 600 ℃ of heat treatment 50min promptly obtain target porous composite carbon base electrode film at last.Adopt the BET method to detect, voidage is 65%.
Embodiment 7
At first the content according to 99mass% and 0.1mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 0.1mass% and the nano metal nickel powder of 0.8mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 30 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 6, ball milling 4 hours; With ball milling gained compound, under 80 ℃ of conditions, 300 order nylon mesh are crossed in vacuumize 20 hours then, obtain uniform blended stock powder again; Then with the two acrylic acid of methacryl ammonium and polyethylene according to 90: 1 ratio of mass ratio, dissolve in the deionized water, make the solution that concentration is 25mass%; Then ammonium citrate and polyethylene glycol are pressed the 0.5mass% of mixed material powder quality and the consumption adding premixed solution of 0.8mass% respectively, stir, obtain premixed solution; Again with the mixed material powder according to target the consumption of the 70mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 70mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.01vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the N of the warm and fine 0.15vol% of azo two isobutyls of the 0.10vol% of stable slurry volume again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 50 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 45 ℃ of temperature ranges, heat 30min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 600 ℃ of heat treatment 80min promptly obtain target porous composite carbon base electrode film at last.
Embodiment 8
At first the content according to 85mass% and 11.9mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 0.1mass% and the nano metal nickel powder of 3.0mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 3 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 3, ball milling 4 hours; With ball milling gained compound, under 110 ℃ of conditions, 300 order nylon mesh are crossed in vacuumize 6 hours then, obtain uniform blended stock powder again; Then with the two acrylic acid of acrylamide and polyethylene according to 15: 1 ratio of mass ratio, dissolve in the deionized water, make the solution that concentration is 15mass%; The consumption of then polyvinyl alcohol being pressed the 0.1mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 80mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 80mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.01vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the ammonium persulfate of 0.05vol% of stable slurry volume and the N of 0.1vol% again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 200 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 45 ℃ of temperature ranges, heat 30min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 550 ℃ of heat treatment 100min promptly obtain target porous composite carbon base electrode film at last.Adopt the BET method to detect, voidage is 55%.
Embodiment 9
At first the content according to 90mass% and 4.9mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 5mass% and the nano metal nickel powder of 0.1mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 3 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 6, ball milling 4 hours; With ball milling gained compound, under 80 ℃ of conditions, 300 order nylon mesh are crossed in vacuumize 20 hours then, obtain uniform blended stock powder again; With methacryl ammonium and N, N '-methylene level bisacrylamide dissolves in the deionized water according to 45: 1 ratio of mass ratio, makes the solution that concentration is 25mass% then; The consumption of then ammonium polyacrylate being pressed the 0.5mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 75mass% of slurry add premixed solution, carry out ball milling and stir, the time is 72 hours, makes the stable slurry that solid concentration is 75mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.05vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the potassium peroxydisulfate of 0.25vol% of stable slurry volume and the N of 0.10vol% again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 100 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 65 ℃ of temperature ranges, heat 20min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 700 ℃ of heat treatment 30min promptly obtain target porous composite carbon base electrode film at last.
Embodiment 10
At first the content according to 79.8mass% and 20mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 0.1mass% and the nano metal nickel powder of 0.1mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 3 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 3, ball milling 4 hours; With ball milling gained compound, under 80 ℃ of conditions, 300 order nylon mesh are crossed in vacuumize 20 hours then, obtain uniform blended stock powder again; Then with the two acrylic acid of methacryl ammonium and polyethylene according to 30: 1 ratio of mass ratio, dissolve in the deionized water, make the solution that concentration is 25mass%; The consumption of then ammonium citrate being pressed the 0.1mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 70mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 70mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.01vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the N of the warm and fine 0.20vol% of azo two isobutyls of the 0.15vol% of stable slurry volume again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 100 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 45 ℃ of temperature ranges, heat 30min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 600 ℃ of heat treatment 100min promptly obtain target porous composite carbon base electrode film at last.
Embodiment 11
At first the content according to 85mass% and 12mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 2.0mass% and the nano metal nickel powder of 1.0mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 5 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 5, ball milling 4 hours; With ball milling gained compound, under 110 ℃ of conditions, 200 order nylon mesh are crossed in vacuumize 10 hours then, obtain uniform blended stock powder again; Then with the two acrylic acid of methacryl ammonium and polyethylene according to 60: 1 ratio of mass ratio, dissolve in the deionized water, make the solution that concentration is 25mass%; The consumption of then ammonium citrate being pressed the 3mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 70mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 70mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.005vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the N of the warm and fine 0.20vol% of azo two isobutyls of the 0.15vol% of stable slurry volume again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 100 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 45 ℃ of temperature ranges, heat 30min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 800 ℃ of heat treatment 10min promptly obtain target porous composite carbon base electrode film at last.
Embodiment 12
At first the content according to 95mass% and 1.0mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 1.0mass% and the nano metal nickel powder of 3.0mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 30 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 1, ball milling 4 hours; With ball milling gained compound, under 120 ℃ of conditions, drying 4 hours is crossed 200 order nylon mesh then, obtains uniform blended stock powder again; With methacryl ammonium and N, N '-methylene level bisacrylamide dissolves in the deionized water according to 30: 1 ratio of mass ratio, makes the solution that concentration is 1mass% then; The consumption of then poly amic acid being pressed the 1mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 70mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 70mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.01vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the ammonium persulfate of 0.15vol% of stable slurry volume and the N of 0.20vol% again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 30 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 35 ℃ of temperature ranges, heat 60min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 800 ℃ of heat treatment 10min promptly obtain target porous composite carbon base electrode film at last.
Embodiment 13
At first the content according to 85mass% and 12mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 2.0mass% and the nano metal nickel powder of 1.0mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 5 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 5, ball milling 4 hours; With ball milling gained compound, under 80 ℃ of conditions, drying 20 hours is crossed 300 order nylon mesh then, obtains uniform blended stock powder again; With acrylamide and N, N '-methylene level bisacrylamide dissolves in the deionized water according to 15: 1 ratio of mass ratio, makes the solution that concentration is 1mass% then; The consumption of then poly amic acid being pressed the 0.1mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 60mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 60mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.005vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the ammonium persulfate of 0.005vol% of stable slurry volume and the N of 0.05vol% again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 500 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 35 ℃ of temperature ranges, heat 60min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 500 ℃ of heat treatment 150min promptly obtain target porous composite carbon base electrode film at last.
Embodiment 14
At first the content according to 90mass% and 4.9mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 5mass% and the nano metal nickel powder of 0.1mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 3 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 6, ball milling 4 hours; With ball milling gained compound, under 80 ℃ of conditions, 300 order nylon mesh are crossed in vacuumize 20 hours then, obtain uniform blended stock powder again; Then with the two acrylic acid of methacryl ammonium and polyethylene according to 30: 1 ratio of mass ratio, dissolve in the deionized water, make the solution that concentration is 25mass%; The consumption of then ammonium citrate being pressed the 0.1mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 70mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 70mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.01vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the N of the warm and fine 0.20vol% of azo two isobutyls of the 0.15vol% of stable slurry volume again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 100 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 45 ℃ of temperature ranges, heat 30min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 600 ℃ of heat treatment 60min promptly obtain target porous composite carbon base electrode film at last.
Embodiment 15
At first the content according to 99mass% and 0.1mass% takes by weighing active carbon and conductive carbon black respectively, takes by weighing the nano zirconium oxide powder of 0.1mass% and the nano metal nickel powder of 0.8mass% more respectively, mixes to obtain the mixed material powder; This mixture and the absolute ethyl alcohol ratio according to 1: 30 is joined in the agate jar that agate ball is housed, and material ball ratio is 1: 6, ball milling 4 hours; With ball milling gained compound, under 110 ℃ of conditions, 200 order nylon mesh are crossed in vacuumize 10 hours then, obtain uniform blended stock powder again; Then with the two acrylic acid of methacryl ammonium and polyethylene according to 60: 1 ratio of mass ratio, dissolve in the deionized water, make the solution that concentration is 25mass%; The consumption of then ammonium citrate being pressed the 3mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution; Again with the mixed material powder according to target the consumption of the 70mass% of slurry add premixed solution, carry out ball milling and stir, the time is 24 hours, makes the stable slurry that solid concentration is 70mass%; In the stable slurry of preparation, adding consumption is the tbp of the 0.005vol% of stable slurry volume then, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble; Be the N of the warm and fine 0.20vol% of azo two isobutyls of the 0.15vol% of stable slurry volume again with consumption, N, N ', N '-tetramethylethylenediamine adds the slurry after the de-bubble, stirs, and promptly obtains plastic slurry; With gained slurry curtain coating on the flow casting molding machine,, can obtain the green compact that thickness is 500 μ m then by control edge of a knife height; Green compact are placed under inert gas shielding or the vacuum state again, in 40 ℃ of temperature ranges, heat 30min simultaneously, green compact are solidified into the base sheet; Then the base sheet can be cut into different size as required; With the base sheet of cutting out, under the weak oxide atmospheric condition, 700 ℃ of heat treatment 30min promptly obtain target porous composite carbon base electrode film at last.
Claims (10)
1, a kind of carbon back multi-hole electrode film that is used for ultracapacitor is characterized in that its component is active carbon active carbon, conductive carbon black or graphite, nm-class powder of zirconium oxide and nano metal nickel powder; Each constituent content is: active carbon content is 72mass%～99mass%, conductive carbon black or content of graphite are 0.1mass%～20mass%, the content of nm-class powder of zirconium oxide is 0.1mass%～5mass%, and the nano metal nickel powder content is 0.1mass%～3mass%.
2, the preparation method who is used for the carbon back multi-hole electrode film of ultracapacitor according to claim 1 is characterized in that may further comprise the steps:
(1) at first with material powder and absolute ethyl alcohol according to (1～10): the ratio of (1～30) joins in the agate jar that agate ball is housed, and material ball ratio is 1: (1～6), ball milling 4 hours～24 hours;
(2) with ball milling gained compound, under 70 ℃～120 ℃ conditions, 300 order nylon mesh are crossed in vacuumize 6 hours～20 hours then, obtain uniform blended stock powder;
(3) with organic monomer and crosslinking agent according to mass ratio (15～90): 1 ratio, dissolve in the deionized water, make the solution that concentration is 1mass%～25mass%;
(4) consumption of dispersant being pressed the 0.1mass%～3mass% of mixed material powder quality adds premixed solution, stirs, and obtains premixed solution;
(5) the mixed material powder is added premixed solution, place the agate jar that agate ball is housed to carry out ball milling and stir, the time is 24 hours～72 hours, makes the stable slurry that solid concentration is higher than 50vol%;
(6) in the stable slurry of preparation, adding consumption is the defrother of the 0.005vol%～0.05vol% of stable slurry volume, and under the vacuum condition of-0.1MPa, stirs or the vibration de-bubble;
(7) with consumption be slurry after the catalyst of the initator of 0.005vol%～0.5vol% of stable slurry volume and 0.05vol%～0.2vol% adds de-bubble, stir, promptly obtain plastic slurry;
(8) with gained slurry curtain coating on the flow casting molding machine, by control edge of a knife height, can obtain thickness is the green compact of 30 μ m～500 μ m;
(9) green compact are placed under inert gas shielding or the vacuum state, in 35 ℃～70 ℃ temperature ranges, heat 10min～60min simultaneously, green compact are solidified into the base sheet;
(10) the base sheet can be cut into different size as required, under the weak oxide atmospheric condition, 300 ℃～800 ℃ heat treatment 10min～200min promptly obtain porous carbon base electrode film then.
3, the compound porous electrode film preparation method of carbon back that is used for ultracapacitor according to claim 2 is characterized in that described material powder is the mixture of active carbon, conductive carbon black or graphite, nm-class powder of zirconium oxide, metal nickel nano powder; Wherein active carbon content is 72mass%～99mass%, and conductive carbon black or content of graphite are 0.1mass%～20mass%, and the content of nm-class powder of zirconium oxide is 0.1mass%～5mass%, and the nano metal nickel powder content is 0.1mass%～3mass%.
4, the preparation method who is used for the compound porous electrode film of carbon back of ultracapacitor according to claim 2 is characterized in that: described organic monomer is a kind of in acrylamide or the first class acrylamide.
5, the preparation method who is used for the compound porous electrode film of carbon back of ultracapacitor according to claim 2 is characterized in that described crosslinking agent is N, a kind of in the two propylene olefin(e) acids of N '-methylene level bisacrylamide or polyethylene.
6, the preparation method who is used for the compound porous electrode film of carbon back of ultracapacitor according to claim 2 is characterized in that described dispersant is one or more in polyethylene glycol, polyvinyl alcohol, poly amic acid or the ammonium citrate.
7, the preparation method who is used for the compound porous electrode film of carbon back of ultracapacitor according to claim 2, it is characterized in that: described defrother is a tbp.
8, the preparation method who is used for the compound porous electrode film of carbon back of ultracapacitor according to claim 2 is characterized in that described initator is a kind of in fine of ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide or azo two isobutyls.
9, the preparation method who is used for the compound porous electrode film of carbon back of ultracapacitor according to claim 2 is characterized in that described catalyst is N, N, N ', N '-tetramethylethylenediamine.
10, the preparation method who is used for the compound porous electrode film of carbon back of ultracapacitor according to claim 2 is characterized in that described inert atmosphere is high pure nitrogen or argon shield.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101595541B (en) * | 2006-10-17 | 2012-02-15 | 麦斯韦尔技术股份有限公司 | Electrode for energy storage device and its preparation method |
| CN101757875B (en) * | 2008-12-25 | 2012-10-17 | 比亚迪股份有限公司 | Composite dispersing agent, positive pole material composition and positive pole thereof, and lithium-ion secondary battery |
| CN102964825A (en) * | 2012-10-31 | 2013-03-13 | 安徽省易达电子有限公司 | Capacitor film with nylon PA66 as substrate and preparation method thereof |
| CN103943380A (en) * | 2014-04-24 | 2014-07-23 | 陆艾珍 | Carbon porous electrode preparing method |
| CN104064374A (en) * | 2014-07-02 | 2014-09-24 | 长沙国容新能源有限公司 | Slurry mixing method during manufacture process of capacitor electrode and use method of manufactured slurry |
| CN104064371A (en) * | 2014-06-20 | 2014-09-24 | 四川能宝电源制造有限公司 | Preparation method of Ni/C positive pole slurry and piece for super-capacitor battery |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2084036C1 (en) * | 1995-11-30 | 1997-07-10 | Альфар Интернешнл Лтд. | Capacitor with double electric layer |
| CN1171782C (en) * | 2002-08-19 | 2004-10-20 | 中国科学院山西煤炭化学研究所 | Method of increasing mesopore actire carbon specific capacitance by mixing with cheap metal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101595541B (en) * | 2006-10-17 | 2012-02-15 | 麦斯韦尔技术股份有限公司 | Electrode for energy storage device and its preparation method |
| CN101757875B (en) * | 2008-12-25 | 2012-10-17 | 比亚迪股份有限公司 | Composite dispersing agent, positive pole material composition and positive pole thereof, and lithium-ion secondary battery |
| CN102964825A (en) * | 2012-10-31 | 2013-03-13 | 安徽省易达电子有限公司 | Capacitor film with nylon PA66 as substrate and preparation method thereof |
| CN103943380A (en) * | 2014-04-24 | 2014-07-23 | 陆艾珍 | Carbon porous electrode preparing method |
| CN103943380B (en) * | 2014-04-24 | 2018-09-04 | 陆艾珍 | The preparation method of carbon porous electrode |
| CN104064371A (en) * | 2014-06-20 | 2014-09-24 | 四川能宝电源制造有限公司 | Preparation method of Ni/C positive pole slurry and piece for super-capacitor battery |
| CN104064374A (en) * | 2014-07-02 | 2014-09-24 | 长沙国容新能源有限公司 | Slurry mixing method during manufacture process of capacitor electrode and use method of manufactured slurry |
| CN106498465A (en) * | 2016-11-18 | 2017-03-15 | 珠海特普力高精细化工有限公司 | A kind of water-soluble conducting carbon nano-metal slurry and electrical-conductive nanometer metal carbon film bushing pipe |
| CN106498465B (en) * | 2016-11-18 | 2019-02-01 | 珠海特普力高精细化工有限公司 | A kind of water-soluble conducting carbon nano-metal slurry and electrical-conductive nanometer metal carbon film bushing pipe |
| CN106531470A (en) * | 2016-11-24 | 2017-03-22 | 华南理工大学 | Preparation method of flexible self-supporting carbon paper supercapacitor electrode material and application |
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| CN1753116B (en) | 2010-04-28 |
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