CN102443167A - Composite material for super capacitor, super capacitor and preparation method thereof - Google Patents
Composite material for super capacitor, super capacitor and preparation method thereof Download PDFInfo
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- CN102443167A CN102443167A CN201010506404XA CN201010506404A CN102443167A CN 102443167 A CN102443167 A CN 102443167A CN 201010506404X A CN201010506404X A CN 201010506404XA CN 201010506404 A CN201010506404 A CN 201010506404A CN 102443167 A CN102443167 A CN 102443167A
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Abstract
The invention relates to a composite material for a super capacitor, the super capacitor and a preparation method thereof. The preparation method for the composite material comprises the following steps of: providing a porous inorganic compound, wherein the specific surface area of the porous inorganic compound is 1000-3000 m<2>/g; uniformly mixing the porous inorganic compound with a monomer solution of a conductive polymer, and making the monomer solution fill into pores of the porous inorganic compound; and making in-situ polymerization for monomers of the conductive polymer. The composite material of the porous inorganic compound/conductive polymer can be used as electrodes and is additionally provided with an insulating film to directly manufacture the super capacitor. According to the composite material prepared by using the method, the porous inorganic compound with high specific surface area is used, and the monomers of the conductive polymer are polymerized in-situ, and the more uniform compounding effect of the conductive polymer and the porous inorganic compound can be achieved. Thereby, the super capacitor prepared by using the composite material has the features of high capability, light weight and long cycle life.
Description
Technical field
The present invention relates to a kind of preparation method of matrix material, matrix material and super capacitor that comprises this matrix material and its preparation method of using this method to prepare.
Background technology
In recent years, most of portable unit all used lithium cell as power supply.Lithium cell can provide higher voltage and stable electric current to supply power to portable unit.But the capacity of lithium cell is not high enough.So, have to charge the battery continually, and process of charging is generally wanted several hrs consuming time.For example, some move ultrasonic equipment and need charge about 2.5 hours, but its battery only can provide 1 hour electric power.Another technical problem of portable unit be the battery that uses now not only capacity is low, and volume is bigger, can occupy certain space.In addition, the cycle life of lithium cell also needs to improve: lithium cell only can present superperformance in thousand charge and discharge cycles at present.So, need a kind of efficient power to reach the desirable combination of heavy body, charging quickly and long circulation life.
At present, commercially available super capacitor can provide the characteristic of rapid charge, but its capacity only can reach the 5-10% of similar volume lithium battery capacity.So the capacity of super capacitor need be greatly improved and just can meet the demands.Present business-like super capacitor uses the micron order carbon dust as electrode materials, and its specific surface area is lower, and its effective surface area is about 100-1000m usually
2/ g, its specific storage is about 30-100F/g.Electrode materials is one of most important composition of super capacitor, also is the key factor that influences the super capacitor capacity.In sum, press at present and develop high surface area material or matrix material prepares the efficient power with heavy body.
Summary of the invention
In order to address the above problem; The invention provides a kind of preparation method of matrix material; This method has been utilized the porous, inorganic compound of high-specific surface area; And the method through in-situ polymerization obtains more evenly compound material, utilizes the super capacitor of the Composite Preparation that this preparation method obtains to have electrical capacity height, in light weight, characteristics that cycle life is longer.The present invention also provides the material of this preparing method's preparation and with the super capacitor of this material prepn.
An embodiment of the invention provide a kind of preparation method of matrix material, comprise the steps:
The porous, inorganic compound is provided, and the specific surface area of wherein said porous, inorganic compound is at 1000-3000m
2In/g the scope;
Said porous, inorganic compound is mixed with the monomer solution of conductive polymers, said monomer solution is filled in the hole of said porous, inorganic compound;
Make the monomer in-situ polymerization of said conductive polymers.
Wherein, said porous, inorganic compound comprises at least a in carbide, nitride and the boride.Said conductive polymers comprises at least a in polyaniline, Polythiophene and polypyrrole and the verivate thereof.The mass ratio of said conductive polymers and said porous, inorganic compound is 10: 90-99: in 1 scope, preferably 20: 80-95: in 5 scopes, more preferably 40: 60-95: in 5 scopes.
Preferably, said porous, inorganic compound is a carbide, and carbide comprises at least a in carbon nanotube, thomel and the order mesoporous carbonization thing, more preferably thomel and order mesoporous carbonization thing.
Said thomel comprises carbon fiber nonwoven fabric and carbon fibre fabric.Itself can form the successive network carbon fibre fabric and carbon fiber nonwoven fabric, can not need molded process directly as the super capacitor electrode.
Said porous, inorganic compound can make through acid activation, and activation method comprises: the mineral compound that will be used for preparing said porous, inorganic compound joins in the acid catalyst aqueous solution, reflux, or direct oxidized activating in High Temperature Furnaces Heating Apparatus.In this reactivation process, make this mineral compound form vesicular structure.
Preferably, above-mentioned order mesoporous carbonization thing can prepare through following method:
Nonionogenic tenside is dissolved in the acid catalyst solutions, preferably uses the aqueous solution of acid catalyst;
The silicon source is scattered in the acid catalyst aqueous solution of said nonionogenic tenside;
Ageing, and separate the throw out obtain;
With throw out high temperature cabonization in nitrogen atmosphere;
Remove the silica composition in the carbonized product with hydrofluoric acid.
This order mesoporous carbonization thing has high porosity, specific surface area is big, pore size distribution is concentrated and the characteristic of good conductivity.
Nonionogenic tenside described in the above-mentioned preparation method is polyethylene oxide-polypropyleneoxide, polyethylene oxide-polybutylene oxide, alkane-polyethylene oxide type diblock or triblock copolymer tensio-active agent.Said acid catalyst is selected from C
1-C
3Organic acid, phenylformic acid or mineral acid at least a.For example, acid catalyst can be selected from one or more in formic acid, acetate, oxalic acid, propionic acid, phenylformic acid, sulfuric acid, hydrochloric acid, nitric acid, the phosphoric acid.Said silicon source can be organoalkoxysilane, preferred tetraethyl silicane acid esters (TEOS).
In another embodiment, the present invention also provides the matrix material with method for preparing.This matrix material since be by the monomer of conductive polymers with porous, inorganic compound uniform mixing after the in-situ polymerization preparation, so can reach the two compound more equably and purpose of contact more fully, thereby improve the specific storage of matrix material.
In another embodiment of the present invention; A kind of matrix material that is used for super capacitor is provided; This matrix material comprises conductive polymers and porous, inorganic compound, and wherein, said conductive polymers is packed in the hole of said porous, inorganic compound; And contact with said porous, inorganic compound, and the specific surface area of said porous, inorganic compound is at 1000-3000m
2In/g the scope, preferred 2000-3000m
2In/g the scope.
The said specific storage that is used for the matrix material of super capacitor can reach 100-900F/g, preferred 200-900F/g, more preferably 600-900F/g.The high-specific surface area of said porous, inorganic compound has directly caused the increase of electric capacity electrolyte interface area; Simultaneously, the uniform mixing of said conductive polymers and said porous, inorganic compound and the filling of said conductive polymers in the hole of said porous, inorganic compound fully contact the two, thereby make the specific storage of this matrix material be increased.
The mass ratio of said conductive polymers and said porous, inorganic compound is 10: 90-99: in 1 scope, preferably 20: 80-95: in 5 scopes, more preferably 40: 60-95: in 5 scopes.The content of said porous, inorganic compound is high more, and its specific surface area is big more, and the specific storage of matrix material is big more.But conductive polymers content is crossed the low defective that can cause composite formed property aspect.The contriver draws the matrix material of mass ratio in above-mentioned preferable range of said conductive polymers and said porous, inorganic compound through repeatedly screening, balance the relation between composite formed property and the specific storage, can access optimum effect.
Said porous, inorganic compound can be carbide, nitride, boride etc. all can be used for the material of super capacitor electrode.Preferred carbide, carbide can comprise at least a in carbon nanotube, thomel and the order mesoporous carbonization thing, more preferably thomel and order mesoporous carbonization thing.Said thomel comprises at least a in carbon fiber nonwoven fabric and the carbon fibre fabric.All have vesicular structure after these carbide activation, therefore specific surface area can increase the specific storage of matrix material greater than micron order carbon dust commonly used at present.And it is in light weight, can reduce the overall weight of the super capacitor of processing at last, to meet the demand of portable unit.
Said conductive polymers comprises at least a in polyaniline, polypyrrole and Polythiophene and the verivate thereof.Said verivate comprises all verivates with conduction property that can be used in super capacitor, and those skilled in the art can select as required voluntarily.These polymkeric substance all can form by the in-situ polymerization through monomer whose in the Composite Preparation process.The conductive polymers that forms through situ aggregation method closely contacts with the network of above-mentioned porous, inorganic compound, evenly compound, further improved the performance of super capacitor.
In another embodiment, the present invention also provides a kind of super capacitor, comprises above-mentioned matrix material or the matrix material for preparing according to above-mentioned preparation method.This super capacitor can prepare with the preparation method of routine: be distributed in the aqueous solution with above-mentioned matrix material or according to the matrix material of method for preparing, the suspension-s that obtains is mixed with binder solution, the formation slurry.Tackiness agent can include but not limited to tetrafluoroethylene and PVDF for this area tackiness agent commonly used.Be coated on slurry and make the super capacitor electrode on the conductive matrices.The electrode coil package is formed super capacitor.
Perhaps, in another embodiment, the present invention also provides a kind of preparation method of super capacitor, utilizes matrix material of the present invention as electrode, between above-mentioned composite electrode, adds the permeable insulating film of electrolytic solution, is wound into super capacitor.Because matrix material of the present invention itself can form the conductive network structure, therefore need not carry out molding process, can directly be used as electrode, thereby simplify the preparation process of super capacitor.For example; Activatory carbon fiber nonwoven fabric or carbon fibre fabric are immersed in the conductive polymers monomer solution; Make the absorption of conductive polymers monomer, be filled in the hole of carbon fiber nonwoven fabric or carbon fibre fabric, carry out in-situ polymerization then, be prepared into the electrochemical capacitance electrode.Between two this electrochemical capacitance electrodes, add the permeable insulating film of electrolytic solution, directly reel, form super capacitor.Because carbon fiber nonwoven fabric or carbon fibre fabric itself can form network structure, so do not need molding process promptly to can be made into the electrochemical capacitance electrode.
In another embodiment, the invention provides a kind of super capacitor that comprises matrix material of the present invention.Because matrix material of the present invention has height ratio capacity and advantage such as in light weight; When using super capacitor of the present invention in the power-supply system as the alternative power source of portable unit; Compare with the power supply that uses lithium cell; This super capacitor power supply has following advantage: 1, charging is fast: super capacitor just can charge in less than 10 minutes fully, and the charging of lithium cell needs several hrs usually; 2, heavy body and volume are little: can access higher specific storage with matrix material of the present invention; That is to say, the material of same weight, the specific storage of matrix material of the present invention can be bigger; Therefore under the situation that satisfies the electrical capacity demand, it is compact more that power supply can design; 3, in light weight: super capacitor of the present invention is by the Composite Preparation with high-specific surface area, and for example activatory carbon nanotube, thomel and order mesoporous carbonization thing are so compared with the lithium cell of same volume, its weight is lighter; 4, have extended cycle life: the cycle life of super capacitor can reach tens thousand of circulations, and is almost high 10 times than lithium cell.
Description of drawings
Fig. 1 is the circuit diagram that comprises the power supply of super capacitor of the present invention;
Fig. 2 is the electromicroscopic photograph of carbon fibre fabric;
Fig. 3 is the synoptic diagram of embodiment 1 said composite material and preparation method thereof.
Embodiment
In order to solve shortcomings such as the lithium battery capacity that is used for portable unit in the prior art is not high enough, the duration of charging is long and volume is big, weight is big, the invention provides matrix material of a kind of height ratio capacity and preparation method thereof.The present invention also provides super capacitor that uses said height ratio capacity Composite Preparation and preparation method thereof.Super capacitor of the present invention has that heavy body, volume are little, in light weight, advantage such as have extended cycle life.
According to an embodiment; The invention provides a kind of super capacitor and use matrix material; This matrix material comprises conductive polymers and porous, inorganic compound, and wherein, said conductive polymers is packed in the hole of said porous, inorganic compound; And contact with said porous, inorganic compound, and the specific surface area of said porous, inorganic compound is at 1000-3000m
2In/g the scope, preferably at 2000-3000m
2In/g the scope, more preferably at 2500-3000m
2In/g the scope.
The structure of said matrix material can form through the in-situ polymerization of said conductive polymers and said porous, inorganic compound: at first, prepare above-mentioned porous, inorganic compound; This porous, inorganic compound is mixed with the monomer solution of said conductive polymers, said monomer solution is filled in the hole of said porous, inorganic compound; Make the monomer in-situ polymerization of said conductive polymers.Through this in-situ polymerization, make said conductive polymers can contact fully with said porous, inorganic compound, compound more equably.The character of monomer solution has determined it can more easily get in the hole of said porous, inorganic compound, passes through after the in-situ polymerization again, in the hole of said porous, inorganic compound, has formed conductive polymers.This and conductive polymers and the direct mixed phase ratio of porous, inorganic compound can have more conductive polymers to arrive the hole wall of porous, inorganic compound, have strengthened its compound and effect that contacts, thereby have obtained higher specific storage.
Said porous, inorganic compound can comprise at least a in carbide, nitride or the boride, and these mineral compound are handled through overactivation etc. and produced the porous structure, and its specific surface area is at 1000-3000m
2In/g the scope, preferably at 2000-3000m
2In/g the scope, more preferably at 2500-3000m
2In/g the scope.The preferred carbide of mineral compound, carbide preferably include at least a in carbon nanotube, thomel and the order mesoporous carbonization thing.Carbon nanotube and thomel can be through joining in the acid catalyst aqueous solution, reflux, or directly in High Temperature Furnaces Heating Apparatus the method for oxidized activating carry out activation, in this reactivation process, form vesicular structure.
Said thomel preferably includes at least a in carbon fiber nonwoven fabric and the carbon fibre fabric.Referring to Fig. 2,,, and do not need the electrode molding process so carbon fiber nonwoven fabric and carbon fibre fabric can directly be used as the super capacitor electrode because carbon fiber nonwoven fabric and carbon fibre fabric have from the conductive network structure.In the present invention; Form vesicular structure after carbon fiber nonwoven fabric and the carbon fibre fabric activation; Then the conductive polymers monomer solution is adsorbed, floods or is packed in the hole of said vesicular structure, form matrix material as the super capacitor electrode after the monomer in-situ polymerization of conductive polymers.Between this matrix material super capacitor electrode, add the permeable insulating film of electrolytic solution, can directly be wound into super capacitor without molding process.
The acid catalyst that uses in the above-mentioned reactivation process can be C
1-C
3Organic acid, phenylformic acid or mineral acid in one or more.For example, can be in formic acid, acetate, oxalic acid, propionic acid, phenylformic acid, sulfuric acid, hydrochloric acid, nitric acid, the phosphoric acid one or more.
Said order mesoporous carbonization thing specific surface area is at 1000-3000m
2In/g the scope, preferably at 2000-3000m
2In/g the scope, more preferably at 2500-3000m
2In/g the scope.This order mesoporous carbonization thing can be used following method preparation: nonionogenic tenside is dissolved in the acid catalyst solutions, preferably uses the aqueous solution of acid catalyst; The silicon source is scattered in the acid catalyst aqueous solution of said nonionogenic tenside; Ageing, and separate the throw out obtain; With throw out high temperature cabonization in nitrogen atmosphere; Remove the silica composition in the carbonized product with hydrofluoric acid.The order mesoporous carbonization thing of this activatory has high porosity, specific surface area is big, pore size distribution is concentrated and the advantage of good conductivity.
Particularly, said order mesoporous carbonization thing can prepare through following method: (1) is dissolved in nonionogenic tenside and acid catalyst in the water, is stirred to and obtains settled solution; (2) under agitation in said settled solution, add the silicon source, and silicon source molecule is well-dispersed in the said settled solution; (3) solution that obtains in the step of ageing (2), and filter, washing and the dry throw out that obtains; (4) with throw out high temperature cabonization in nitrogen atmosphere; (5) carbonized product is immersed the silica composition of removing in the hydrofluoric acid wherein.Wherein, nonionogenic tenside can be polyethylene oxide-polypropyleneoxide, polyethylene oxide-polybutylene oxide, alkane-polyethylene oxide type diblock or triblock copolymer tensio-active agent, for example triblock copolymer P123 (Aldrich).Acid catalyst can be C
1-C
3Organic acid, phenylformic acid or mineral acid in one or more.For example, acid catalyst can be one or more in formic acid, acetate, oxalic acid, propionic acid, phenylformic acid, sulfuric acid, hydrochloric acid, nitric acid, the phosphoric acid.The silicon source can be organoalkoxysilane, preferred tetraethyl orthosilicate ester (TEOS).Wherein (mole) ratio in nonionogenic tenside and silicon source is 100: 1 to 1: 1 scopes, preferably in 10: 1 to 1: 1 scopes.Because pore-forming material has mainly been played in the silicon source in the method, so the porosity and the specific surface area of product had direct influence.Nonionogenic tenside and the molar ratio, particularly molar ratio in silicon source of use in above-mentioned preferable range is 5: 1 o'clock, can obtain higher porosity and specific surface area.
In the above-mentioned reaction process, it is fixed that the condition of each step of dissolving, ageing, carbonization, removal silicon-dioxide is come according to the reactant of selecting, and those skilled in the art are according to the reactant of selecting selective reaction condition suitably.In general, the ageing temperature is in the 273-373K scope, and digestion time is in 1-24 hour scope.Can ageing 1-3 time, the ageing temperature raises one by one.Carbonization temperature can be in about 873-1673K scope, and carbonization time can change in 1-100 hour, and those skilled in the art can decide according to the carbonization effect.
After making the porous, inorganic compound of above-mentioned high-specific surface area, with the monomer thorough mixing of itself and conductive polymers, let the monomer in-situ polymerization of mixed conductive polymers, form even compound conductive polymers-porous, inorganic compound composite material.Said conductive polymers includes but not limited to polyaniline, polypyrrole and Polythiophene and verivate thereof etc., and all can be used as the electrolytical polymkeric substance of electric capacity.Said verivate comprises all verivates with conduction property that can be used in super capacitor, and those skilled in the art can select as required voluntarily.These polymkeric substance all can form by the in-situ polymerization through monomer whose in the Composite Preparation process.The conductive polymers that forms through situ aggregation method closely contacts with the network of above-mentioned porous, inorganic compound, evenly compound, further improved the performance of super capacitor.
After obtaining above-mentioned matrix material; Utilize this matrix material; Can super capacitor method well known in the art prepare super capacitor of the present invention: matrix material of the present invention is distributed in the aqueous solution, the suspension-s that obtains is mixed with binder solution, form slurry.Tackiness agent can include but not limited to tetrafluoroethylene and PVDF for this area tackiness agent commonly used.Be coated on slurry and make the super capacitor electrode on the conductive matrices.The electrode coil package is formed super capacitor.
Perhaps; Can utilize the method for preparing super capacitor provided by the invention; Prepare super capacitor more quickly and easily: utilize matrix material of the present invention as electrode; Between above-mentioned composite electrode, add the permeable insulating film of electrolytic solution,, directly be wound into super capacitor without molding process.For example; Prepare above-mentioned matrix material with carbon fiber nonwoven fabric or carbon fibre fabric, need not pass through molding process: earlier polymer monomer is adsorbed in carbon fiber nonwoven fabric or the carbon fibre fabric, then in-situ polymerization; Directly prepare combined electrode; Add an insulating film between two combined electrodes, need not molding process, and the packing of directly reeling forms super capacitor.
In addition, in order super capacitor of the present invention to be used for the power supply of portable unit, referring to Fig. 1, can design the circuit that is used for controlling voltage and current as required, this circuit is used as two purposes: the first, and the charging of monitoring and control capacitance; The second, as power supply changeover device, under the situation that output voltage changes when super capacitor discharges, keep constant voltage output.Can this circuit be used for the power supply of portable unit with super capacitor of the present invention; When keeping constant voltage output, ensureing the normal use of portable unit; Can also overcome the above-mentioned defective of lithium cell; Have the advantage that charging is quick, volume is little, in light weight, have extended cycle life, further strengthened the characteristic portable, easy to use of portable unit.
Hereinafter will combine specific embodiment and accompanying drawing further to explain the present invention, but the present invention is not limited to each listed embodiment, its protection domain is as the criterion with what limit in claims.
Embodiment 1: use the order mesoporous carbonization thing of activatory to prepare super capacitor
Adopt the order mesoporous carbonization thing of activatory, polyaniline to prepare matrix material, and with this Composite Preparation super capacitor electrode, and then the preparation super capacitor, preparation flow figure is referring to Fig. 3.
Preparation super capacitor electrode method comprises the steps: the preparation of A, the order mesoporous carbonization thing of activatory; B, composite porous preparation; C, utilize this Composite Preparation super capacitor electrode.
The preparation of A, the order mesoporous carbonization thing of activatory
The mesoporous carbide material of high-sequential prepares with the following step: (1) is dissolved in 100g triblock copolymer P123 in 20% concentrated sulfuric acid aqueous solution.After stirring 5 hours, under agitation in this solution, dropwise add tetraethyl orthosilicate ester (TEOS, 98%).(2) with the solution that obtains ageing 24 hours under 313K, further ageing 24 hours under 373K then.The throw out that filtration obtains, washing is also at room temperature dry; (3) the dun material that obtains is 1123K carbonization 2 hours under the purity nitrogen atmosphere in horizontalchamber oven, then carbon/the silicon composite that obtains at room temperature is immersed in the hydrofluoric acid of 48wt% 48 hours, to remove the silicon template, obtains ordered mesoporous material.This ordered mesoporous material presents 1000-3000m
2The high-specific surface area of/g.
The preparation of the conductive polymers of B, heavy body/order mesoporous carbonization thing matrix material
The order mesoporous carbonization thing of the activatory for preparing in the above-mentioned A step is immersed in the aqueous hydrochloric acid that contains aniline monomer.After stirring 60 minutes, under 273K, dropwise add ammonium persulfate solution, continue to stir 3 hours.The product that filtration obtains is also with acetone, HCl and deionized water repeated washing successively.Vacuum-drying there are under 373K 24 hours most.The specific storage that obtains matrix material through this in-situ polymerization has reached 800F/g to 900F/g; Show that situ aggregation method has improved the dispersity of polymkeric substance in porous carbon matrix; Strengthen contacting between polymkeric substance and the porous carbon fiber, and made the more electrolyte ion can to lead to polymkeric substance.This provides more polymer active site for the induction reaction, and has caused bigger specific storage.
In this step, can regulate the ratio of order mesoporous carbonization thing of activatory and polyaniline, to obtain the matrix material (table 1) of different carbide contents.
The preparation of C, super capacitor
With the composite sample of above-mentioned different carbide contents, be distributed to respectively in the aqueous solution, mix with the tackiness agent tetrafluoroethylene then, form slurry.This slurry is coated on makes the super capacitor electrode on the conductive matrices.The electrode coil package is formed super capacitor.
The electrical capacity of each super capacitor that contains different carbide contents that detection obtains, the result is as shown in table 1 below:
Table 1: the relation of carbide content and electrical capacity
| Sample number | Carbide content | Electrical capacity |
| 1 | 8.5％ | 210F |
| 2 | 9.5％ | 206F |
| 3 | 12.5％ | 190F |
Embodiment 2: use carbon fiber nonwoven fabric conduct mineral compound wherein, the preparation super capacitor
With carbon fiber nonwoven fabric with sulfuric acid (10%) under 80 ℃, reflux, activation 24 hours makes the porous carbon fiber non-woven fabrics.
This activatory porous carbon fiber non-woven fabrics is mixed with thiophene monomer, after mixing,, obtain porous carbon fiber non-woven fabrics-polythiophene composite material the thiophene monomer in-situ polymerization.
Adopt and this Composite Preparation is become super capacitor with embodiment 1 said identical method.
Embodiment 3:
Adopt to prepare super capacitor, just change carbon fiber nonwoven fabric into carbon nanotube, change Polythiophene into polypyrrole, the corresponding change of polymerization method with embodiment 2 identical methods.
Embodiment 4:
Adopt to prepare super capacitor with embodiment 2 identical methods, just change carbon fiber nonwoven fabric into carbon fibre fabric, change Polythiophene into polyaniline, polymerization method is identical with embodiment 1.
The super capacitor for preparing in the foregoing description all can reach the technique effect that improves electrical capacity, weight reduction, compares with traditional lithium cell, also has the advantage that charging is fast, volume is little.When the porous, inorganic compounds content below 60%, preferred 20% when following, its specific storage even discharge and recharge after 40 circulations, still can keep the specific storage of about 600F/g up to more than the 600-800F/g.
Claims (21)
1. the preparation method of a matrix material comprises the steps:
The porous, inorganic compound is provided, and the specific surface area of wherein said porous, inorganic compound is at 1000-3000m
2In/g the scope;
Said porous, inorganic compound is mixed with the monomer solution of conductive polymers, said monomer solution is filled in the hole of said porous, inorganic compound;
Make the monomer in-situ polymerization of said conductive polymers.
2. the method for claim 1, wherein said porous, inorganic compound comprises at least a in carbide, nitride and the boride.
3. the method for claim 1, wherein said conductive polymers comprises at least a in polyaniline, Polythiophene and polypyrrole and the verivate thereof.
4. the mass ratio of the method for claim 1, wherein said conductive polymers and said porous, inorganic compound is 10: 90-99: in 1 scope.
5. according to claim 1 or claim 2 method; Wherein, The said step of porous, inorganic compound that provides comprises: the mineral compound that will be used for preparing said porous, inorganic compound joins in the acid catalyst aqueous solution, reflux, or direct oxidized activating in High Temperature Furnaces Heating Apparatus.
6. method as claimed in claim 2, wherein, said carbide comprises at least a in carbon nanotube, thomel and the order mesoporous carbonization thing.
7. method as claimed in claim 6, wherein, said thomel comprises at least a in carbon fiber nonwoven fabric and the carbon fibre fabric.
8. method as claimed in claim 6, wherein, said order mesoporous carbonization thing prepares through following method:
Nonionogenic tenside is dissolved in the acid catalyst aqueous solution;
The silicon source is scattered in the acid catalyst aqueous solution of said nonionogenic tenside;
Ageing, and separate the throw out obtain;
With said throw out high temperature cabonization in nitrogen atmosphere;
Remove the silica composition in the carbonized product with hydrofluoric acid.
9. method as claimed in claim 8, wherein, said nonionogenic tenside is polyethylene oxide-polypropyleneoxide, polyethylene oxide-polybutylene oxide, alkane-polyethylene oxide type diblock or triblock copolymer tensio-active agent.
10. method as claimed in claim 8, wherein, said acid catalyst is selected from C
1-C
3Organic acid, phenylformic acid or mineral acid at least a.
11. method as claimed in claim 8, wherein, said silicon source is an organoalkoxysilane.
12. matrix material according to each described method preparation among the claim 1-11.
13. matrix material that is used for super capacitor; Said matrix material comprises conductive polymers and porous, inorganic compound; Wherein, Said conductive polymers is packed in the hole of said porous, inorganic compound, and contacts with said porous, inorganic compound, and the specific surface area of said porous, inorganic compound is at 1000-3000m
2In/g the scope.
14. matrix material as claimed in claim 13, wherein, the specific storage of said matrix material is in the 100-900F/g scope.
15. matrix material as claimed in claim 13, wherein, the mass ratio of said conductive polymers and said porous, inorganic compound is 10: 90-99: in 1 scope.
16. matrix material as claimed in claim 1, wherein, said porous, inorganic compound comprises at least a in carbide, nitride and the boride.
17. matrix material as claimed in claim 16, wherein, said carbide comprises carbon nanotube, thomel and order mesoporous carbonization thing.
18. matrix material as claimed in claim 17, wherein, said thomel comprises at least a in carbon fiber nonwoven fabric and the carbon fibre fabric.
19. matrix material as claimed in claim 13, wherein, said conductive polymers comprises at least a in polyaniline, Polythiophene and polypyrrole and the verivate thereof.
20. the preparation method of a super capacitor, comprise with like each described matrix material among the claim 12-19 as electrode, between said electrode, add the permeable insulating film of electrolytic solution, be wound into super capacitor.
21. a super capacitor comprises like each described matrix material among the claim 12-19.
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| CN103044680A (en) * | 2012-12-21 | 2013-04-17 | 郑州大学 | Synthetic method of polyaniline/carbon fiber composite material with nano-ordered structure |
| CN104124073A (en) * | 2014-07-03 | 2014-10-29 | 湖南工业大学 | Preparation method for phenolic resin carbon/polythiophene composite electrode |
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| CN109524653A (en) * | 2018-11-21 | 2019-03-26 | 湖南中车特种电气装备有限公司 | A method of lithium-ion capacitor specific capacity is promoted using conducting polymer |
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| CN102794200A (en) * | 2012-08-31 | 2012-11-28 | 华南师范大学 | Preparation method of anode catalyst used for microbial fuel cells and application thereof |
| CN102794200B (en) * | 2012-08-31 | 2014-11-05 | 华南师范大学 | Preparation method of anode catalyst used for microbial fuel cells and application thereof |
| CN103044680A (en) * | 2012-12-21 | 2013-04-17 | 郑州大学 | Synthetic method of polyaniline/carbon fiber composite material with nano-ordered structure |
| CN103044680B (en) * | 2012-12-21 | 2015-04-15 | 郑州大学 | Synthetic method of polyaniline/carbon fiber composite material with nano-ordered structure |
| CN104124073A (en) * | 2014-07-03 | 2014-10-29 | 湖南工业大学 | Preparation method for phenolic resin carbon/polythiophene composite electrode |
| CN108538613A (en) * | 2018-03-30 | 2018-09-14 | 徐州工业职业技术学院 | A kind of preparation method of the controllable porous polyaniline electrode material of network interworking and duct |
| CN109524653A (en) * | 2018-11-21 | 2019-03-26 | 湖南中车特种电气装备有限公司 | A method of lithium-ion capacitor specific capacity is promoted using conducting polymer |
| CN109545566A (en) * | 2018-11-21 | 2019-03-29 | 湖南中车特种电气装备有限公司 | A kind of high specific energy lithium-ion capacitor |
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