CN102709056A - Current collector of energy storage device, and preparation method of current collector - Google Patents
Current collector of energy storage device, and preparation method of current collector Download PDFInfo
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- CN102709056A CN102709056A CN2012101320949A CN201210132094A CN102709056A CN 102709056 A CN102709056 A CN 102709056A CN 2012101320949 A CN2012101320949 A CN 2012101320949A CN 201210132094 A CN201210132094 A CN 201210132094A CN 102709056 A CN102709056 A CN 102709056A
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
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- 238000011065 in-situ storage Methods 0.000 claims description 5
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
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- 239000013543 active substance Substances 0.000 abstract 1
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a current collector of an energy storage device, and a preparation method of the current collector. Specifically, a composite material used for the current collector of the energy storage device comprises the following components in parts by weight: 0.001-20 parts of metal nanowire, 10-99 parts of energy storage active substance and 10-20 parts of adhesive, wherein the metal nanowire is used as the nano current collector.
Description
Technical field
The present invention relates to energy nanometer technology association area, the collector that relates in particular to energy storage devices such as being used for ultra-capacitor, battery with and manufacturing approach.
Background technology
In the preparation of energy storage devices such as ultra-capacitor, battery, for bringing into play the effect of energy storage active component better, reduce the internal resistance of energy storage device, often need wire netting or metal foaming material as the electronics collector, for example: to use stainless (steel) wire, nickel foam etc.This type conventional electrical collector is in energy storage devices such as battery, ultra-capacitor; For the memory capacity that improves device; Reduce the internal resistance of device, the use power that improves device all plays a part very important, be all kinds of energy storage devices can not obtain scarce, important part.
Aspect energy storage device, CNT than traditional collector clear superiority, can significantly improve the effective rate of utilization of electrode material as the nanometer collector, reduces the internal resistance of electrode, improves the power density of energy storage device.The compound capacity that can improve lithium battery significantly of Graphene and metal oxide.Nano-Ag particles is carbon nano-tube modified, metal oxide (like manganese dioxide, cobaltosic oxide) etc., can be used for the electrode material of lithium battery, ultra-capacitor.
But the electric conductivity of CNT and Graphene is far below metal nanometer line, and its effect as the energy storage device collector is limited; Although metal nanoparticle can improve the electric conductivity between energy storage active material and metal collector, in general, the raising degree is limited.
In view of this, truly have need provide a kind of novel high-performance nano collector that is used for energy storage device that can solve above-mentioned deficiency with and preparation technology.
Summary of the invention
The object of the invention is intended to solve the problems referred to above of existing in the prior art and at least one aspect of defective.
One of the object of the invention provides a kind of composite material that is used for the collector of energy storage device; Wherein, Said composite material comprises metal nanometer line, energy storage active material and binding agent; Said metal nanometer line is used as the nanometer collector, and the proportioning of said metal nanometer line, energy storage active material and each component of binding agent by mass parts is:
Metal nanometer line: 0.001-20 part,
The energy storage active material: 10-99 part,
Binding agent: 0-20 part.
Preferably, said metal nanometer line comprises any in the corresponding alloy nano-wire of nano silver wire, nanowires of gold, copper nano-wire, aluminium nano wire, nickel nano wire, titanium nano wire and above-mentioned metal.
Preferably, the diameter of said metal nanometer line is 5nm-500nm, and length is 0.5 μ m-2000 μ m.
Preferably, said energy storage active material is a kind of in Graphene, active carbon, mesoporous charcoal, CNT or their combination in any, perhaps is a kind of in polyaniline, polypyrrole, polythiophene, its derivative or their combination in any.
Preferably, said binding agent is the polytetrafluoroethylene aqueous emulsion that does not react with said energy storage active material or its electrolyte.
Preferably, said binding agent is any in carboxymethyl cellulose, CMS or their combination.
Preferably, said energy storage device is ultra-capacitor or battery.
According to a further aspect in the invention, a kind of preparation method who makes the composite material of the above-mentioned collector that is used for energy storage device is provided, has said method comprising the steps of:
(1) the energy storage active material is dispersed in first solvent to obtain energy storage active material dispersion liquid and metal nanometer line is dispersed in second solvent to obtain the metal nanometer line dispersion liquid;
(2) the metal nanometer line dispersion liquid is joined in the energy storage active material dispersion liquid to obtain a mixed solution;
(3) filtration, washing, dry said mixed solution, and after adding an amount of binding agent, form energy storage active material and metal nanometer line composite material.
Preferably, said preparation method also comprises said energy storage active material and metal nanometer line composite material is carried out the compressing tablet processed steps.
Preferably, said step (1) and step (2) are carried out under sonic oscillation or churned mechanically situation.
Preferably, said first solvent and second solvent are water, alcohol, ether, alkane, acetone, oxolane, chloroform, benzene,toluene,xylene or their combination in any.
According to a further aspect in the invention, a kind of preparation method who makes like the composite material of the above-mentioned collector that is used for energy storage device is provided, has said method comprising the steps of:
(1) dispersion liquid of adding metal nanometer line or metal nanometer line in the reaction of preparation energy storage active material is to obtain comprising a mixed solution of energy storage active material and metal nanometer line in-situ composite;
(2) filtration, washing, dry said mixed solution, and after adding an amount of binding agent, form energy storage active material and metal nanometer line composite material.
Preferably, said step (1) be earlier metal nanometer line and first reactant of energy storage active material are mixed and add afterwards the energy storage active material second reactant through back flow reaction to obtain said mixed solution.
Preferably, said preparation method also comprises said energy storage active material and metal nanometer line composite material is carried out the compressing tablet processed steps.
Preferably, said step (1) is carried out under sonic oscillation or churned mechanically situation.
Preferably, said metal nanometer line is disperseed by water, alcohol, ether, alkane, acetone, oxolane, chloroform, benzene,toluene,xylene or their combination in any.
Description of drawings
These and/or other aspect of the present invention and advantage are from obviously with easily understanding below in conjunction with becoming the accompanying drawing description of preferred embodiments, wherein:
Fig. 1 is the sem photograph according to the nano silver wire/Graphene in the embodiments of the invention 1, and has demonstrated the part nano silver wire; With
Fig. 2 is according to the sem photograph that is in the nano silver wire/Graphene under another multiplication factor of the present invention, and has demonstrated the part nano silver wire.
Embodiment
Pass through embodiment below, and combine accompanying drawing 1-2, do further bright specifically technical scheme of the present invention.In specification, same or analogous drawing reference numeral is indicated same or analogous parts.Following explanation to embodiment of the present invention is intended to present general inventive concept of the present invention is made an explanation with reference to accompanying drawing, and is not to be understood that to a kind of restriction of the present invention.
With reference to accompanying drawing 1-2 the composite material that is used for the collector of energy storage device according to the present invention is described below.
In one embodiment of the invention; A kind of composite material that is used for the collector of energy storage device is provided; Wherein, Said composite material comprises metal nanometer line, energy storage active material and binding agent, and said metal nanometer line is used as the nanometer collector, and the proportioning of said metal nanometer line, energy storage active material and each component of binding agent by mass parts is:
Metal nanometer line: 0.001-20 part,
The energy storage active material: 10-99 part,
Binding agent: 0-20 part.
The composite material of the said collector of being made by metal nanometer line preferably is used for ultra-capacitor or battery.
Particularly, said metal nanometer line comprises any in the corresponding alloy nano-wire of nano silver wire, nanowires of gold, copper nano-wire, aluminium nano wire, nickel nano wire, titanium nano wire and above-mentioned metal.Preferably, said metal nanometer line is a nano silver wire.The diameter of said metal nanometer line is 5nm-500nm, and length is 0.5 μ m-2000 μ m.
Said energy storage active material is a kind of in Graphene, active carbon, mesoporous charcoal, CNT or their combination in any, perhaps is a kind of in polyaniline, polypyrrole, polythiophene, its derivative or their combination in any.
Said binding agent is the polytetrafluoroethylene aqueous emulsion that does not react with said energy storage active material or its electrolyte.In addition; In view of known metal nanometer line is reunited owing to its higher surface energy easily; Need at first it to be dispersed in the solvent, but, need to select a kind of suitable binding agent again in order to keep its electric conductivity in the composite material of the collector of final preparation; Said binding agent can play dispersed metal nano wire to a certain extent, but can keep their the connection degree that is fit to.Such binding agent can be any in carboxymethyl cellulose, CMS or their combination.
In another aspect of this invention, a kind of preparation method who makes the composite material of the above-mentioned collector that is used for energy storage device is provided, has said method comprising the steps of:
(1) the energy storage active material is dispersed in first solvent to obtain energy storage active material dispersion liquid and metal nanometer line is dispersed in second solvent to obtain the metal nanometer line dispersion liquid;
(2) the metal nanometer line dispersion liquid is joined in the energy storage active material dispersion liquid to obtain a mixed solution;
(3) filtration, washing, dry said mixed solution, and after adding an amount of binding agent, form energy storage active material and metal nanometer line composite material.
Said preparation method also comprises said energy storage active material and metal nanometer line composite material is carried out the compressing tablet processed steps.Particularly, said step (1) and step (2) are carried out under sonic oscillation or churned mechanically situation.Said first solvent and second solvent are water, alcohol, ether, alkane, acetone, oxolane, chloroform, benzene,toluene,xylene or their combination in any.
In embodiment 1, demonstrate above-mentioned manufacturing approach, specific as follows.
Embodiment 1
At first, the preparation 1mg/mL graphite oxide ethanolic solution 100mL, and with its sonic oscillation to steady suspension.Afterwards, in said suspension, add the dimethyl formamide reducing agent, refluxing is heated to boiling, and reduction 6h with the filtration of the Graphene after the reduction, washing repeatedly, 60 ℃ of dryings, obtains the black graphene powder.
The nano silver wire ethanolic solution is added drop-wise in this graphene powder; And adding acetylene black, three's mass ratio is 15: 70: 15, adds 5mL ethanol and disperses; Sonic oscillation 3h; Obtain compound uniform Graphene of machinery and nano silver wire composite material, add 0.1g binding agent carboxymethyl cellulose, continue ultrasonic 3h.Scattered mixture compressing tablet is processed electrode, for electro-chemical test subsequent use.This electrode composite material in the 1mol/L sulfuric acid electrolyte specific capacity be 600F/g.
As illustrated in fig. 1 and 2, the sem photograph of the nano silver wire in the collector composite material of embodiment 1 manufacturing.Visible from Fig. 1 and 2, nano silver wire is scattered therein, but has kept certain connection degree.
In addition, the preparation method of the composite material of the collector that is used for energy storage device of the present invention can also be may further comprise the steps:
(1) dispersion liquid of adding metal nanometer line or metal nanometer line in the reaction of preparation energy storage active material is to obtain comprising a mixed solution of energy storage active material and metal nanometer line in-situ composite;
(2) filtration, washing, dry said mixed solution, and after adding an amount of binding agent, form energy storage active material and metal nanometer line composite material.Wherein, said step (1) be earlier metal nanometer line and first reactant of energy storage active material are mixed and add afterwards the energy storage active material second reactant through back flow reaction to obtain said mixed solution.Said preparation method also comprises said energy storage active material and metal nanometer line composite material is carried out the compressing tablet processed steps.Said step (1) is carried out under sonic oscillation or churned mechanically situation.Said metal nanometer line is disperseed by water, alcohol, ether, alkane, acetone, oxolane, chloroform, benzene,toluene,xylene or their combination in any.
Above-mentioned another preparation method of the present invention is particularly shown in embodiment 2.
At first, prepare the graphite oxide aqueous solution 100mL of 1mg/mL, drip the ethanolic solution of nano silver wire therein, both mass ratioes are 4.7: 1, to obtain comprising the solution of graphite oxide and nano silver wire.Afterwards, to this solution sonic oscillation 6h, and add the dimethyl formamide reducing agent, obtain a mixture solution, it is heated to boiling by backflow, reduction 6h, Graphene that obtains and nano silver wire in-situ composite.This Graphene and nano silver wire in-situ composite are filtered, wash repeatedly, and carry out 60 ℃ of dryings, and the black powder that obtains Graphene and nano silver wire composite material is subsequent use.A certain amount of Graphene of weighing and nano silver wire original position compound, acetylene black, both mass ratioes are 85: 15, disperse with an amount of ethanol, add 0.lg binding agent carboxymethyl cellulose, carry out compressing tablet and prepare electrode, for electro-chemical test subsequent use.The specific capacity of this electrode composite material in the 1mol/L sulfuric acid electrolyte is 980F/g.
In addition, the present invention also provides following examples.
Embodiment 3
The 5g active carbon is dispersed in the 40ml ethanol, and sonic oscillation 3h is added drop-wise to the nano silver wire alcohol dispersion liquid 1ml of 0.1g/ml in the above-mentioned active carbon dispersion liquid; Continue ultrasonic 3h, filter drying; Add an amount of binding agent carboxymethyl cellulose, compressing tablet is processed electrode, for electro-chemical test subsequent use.The specific capacity of this electrode composite material in the 1mol/L sulfuric acid electrolyte is 192F/g.
Embodiment 4
The 5g polyaniline is dispersed in the 50ml methyl alcohol, and sonic oscillation 3h is added drop-wise to the nano silver wire alcohol dispersion liquid 1ml of 0.1g/ml in the above-mentioned polyaniline dispersion liquid; Continue ultrasonic 3h, filter drying; Add an amount of binding agent carboxymethyl cellulose, compressing tablet is processed electrode, and the power backup test chemical is used.The specific capacity of this electrode composite material in sulfuric acid electrolyte is 500F/g.
Should be noted that in embodiments of the invention 1-4 for the ease of contrast, wherein binding agent is defined as carboxymethyl cellulose.Should be appreciated that binding agent except being the carboxymethyl cellulose, can also be in polytetrafluoroethylene aqueous emulsion, carboxymethyl cellulose, CMS or their combination that does not react with said energy storage active material or its electrolyte any.
Comparative example 1
At first, the preparation 1mg/mL graphite oxide aqueous solution 100mL, and with its sonic oscillation to steady suspension.Afterwards, in said suspension, add the dimethyl formamide reducing agent, refluxing is heated to boiling, and reduction 6h with the filtration of the Graphene after the reduction, washing repeatedly, 60 ℃ of dryings, obtains the black graphene powder.
This graphene powder is mixed with acetylene black, and both mass ratioes are 70: 30, add 5mL ethanol and disperse, and sonic oscillation 3h obtains compound uniform Graphene of machinery and silver composite material, add 0.1g binding agent carboxymethyl cellulose, continue ultrasonic 3h.Scattered mixture compressing tablet is processed electrode, for electro-chemical test subsequent use.This electrode composite material in the 1mol/L sulfuric acid electrolyte specific capacity be 300F/g.
This comparative example 1 only is not add nano silver wire with the difference of embodiment 1; Contrast through them can know that the specific capacity of the electrode material among the embodiment 1 is approximately 1 times of comparative example 1, and obviously, the electrode material of embodiment 1 provides more performance.
Comparative example 2
The 5g active carbon is dispersed in the 40ml ethanol, and sonic oscillation 3h is added to 0.5g acetylene black in the above-mentioned active carbon dispersion liquid, continues ultrasonic 3h, filters, and drying adds an amount of binding agent carboxymethyl cellulose, and compressing tablet is processed electrode, for electro-chemical test subsequent use.The specific capacity of this electrode composite material in the 1mol/L sulfuric acid electrolyte is 140F/g.
Comparative example 2 and embodiment 3 different are to have added acetylene black in the comparative example and embodiment 3 has added nano silver wire, and other part is all identical.Can know that through contrast the electrode material of embodiment 3 provides than comparative example 2 more performance, for example specific capacity.
Should be noted that those skilled in the art can know, binding agent can join in the mixture of metal nanometer line and energy storage active material at arbitrary preparatory phase of preparation method of the present invention.Each preparatory phase of preparation method of the present invention can be synthesis under normal pressure or reaction under high pressure; Also can be normal-temperature reaction or pyroreaction.Notice that each stage of reaction among embodiments of the invention 1-4 and the comparative example 1-2 is all reacted at normal temperatures and pressures.
Can know through above-mentioned analysis, the composite material of collector of the present invention improved energy storage active material in the energy storage devices such as all kinds of ultra-capacitors, battery effective rate of utilization, reduce the device internal resistance, improve the capacity of active material.In addition, the present invention has improved a kind of easy, efficient, feasible method.Adopt metal nanometer line, as: nano silver wire, copper nano-wire, nanowires of gold, nickel nano wires etc. play the afflux effect for the nanometer collector adds in the energy storage active material.
Though some embodiment of this present general inventive concept are shown and explain; Those skilled in the art will appreciate that; Under the situation of principle that does not deviate from this present general inventive concept and spirit, can make a change these embodiment, scope of the present invention limits with claim and their equivalent.
Claims (16)
1. composite material that is used for the collector of energy storage device; Wherein, Said composite material comprises metal nanometer line, energy storage active material and binding agent; Said metal nanometer line is used as the nanometer collector, and the proportioning of said metal nanometer line, energy storage active material and each component of binding agent by mass parts is:
Metal nanometer line: 0.001-20 part,
The energy storage active material: 10-99 part,
Binding agent: 0-20 part.
2. the composite material that is used for the collector of energy storage device according to claim 1; Wherein, said metal nanometer line comprises any in the corresponding alloy nano-wire of nano silver wire, nanowires of gold, copper nano-wire, aluminium nano wire, nickel nano wire, titanium nano wire and above-mentioned metal.
3. the composite material that is used for the collector of energy storage device according to claim 2, wherein, the diameter of said metal nanometer line is 5nm-500nm, length is 0.5 μ m-2000 μ m.
4. the composite material that is used for the collector of energy storage device according to claim 1; Wherein, Said energy storage active material is a kind of in Graphene, active carbon, mesoporous charcoal, CNT or their combination in any, perhaps is a kind of in polyaniline, polypyrrole, polythiophene, its derivative or their combination in any.
5. the composite material that is used for the collector of energy storage device according to claim 1, wherein, said binding agent is the polytetrafluoroethylene aqueous emulsion that does not react with said energy storage active material or its electrolyte.
6. the composite material that is used for the collector of energy storage device according to claim 1, wherein, said binding agent is any in carboxymethyl cellulose, CMS or their combination.
7. the composite material that is used for the collector of energy storage device according to claim 1, wherein, said energy storage device is ultra-capacitor or battery.
8. preparation method like the composite material of each described collector that is used for energy storage device among the claim 1-7 said method comprising the steps of:
(1) the energy storage active material is dispersed in first solvent to obtain energy storage active material dispersion liquid and metal nanometer line is dispersed in second solvent to obtain the metal nanometer line dispersion liquid;
(2) the metal nanometer line dispersion liquid is joined in the energy storage active material dispersion liquid to obtain a mixed solution;
(3) filtration, washing, dry said mixed solution, and after adding an amount of binding agent, form energy storage active material and metal nanometer line composite material.
9. preparation method according to claim 8, wherein, said preparation method also comprises said energy storage active material and metal nanometer line composite material is carried out the compressing tablet processed steps.
10. preparation method according to claim 8, wherein, said step (1) and step (2) are carried out under sonic oscillation or churned mechanically situation.
11. preparation method according to claim 8, wherein, said first solvent and second solvent are water, alcohol, ether, alkane, acetone, oxolane, chloroform, benzene,toluene,xylene or their combination in any.
12. the preparation method like the composite material of each described collector that is used for energy storage device among the claim 1-7 said method comprising the steps of:
(1) dispersion liquid of adding metal nanometer line or metal nanometer line in the reaction of preparation energy storage active material is to obtain comprising a mixed solution of energy storage active material and metal nanometer line in-situ composite;
(2) filtration, washing, dry said mixed solution, and after adding an amount of binding agent, form energy storage active material and metal nanometer line composite material.
13. preparation method according to claim 12, wherein, said step (1) be earlier metal nanometer line and first reactant of energy storage active material are mixed and add afterwards the energy storage active material second reactant through back flow reaction to obtain said mixed solution.
14. preparation method according to claim 13, wherein, said preparation method also comprises said energy storage active material and metal nanometer line composite material is carried out the compressing tablet processed steps.
15. preparation method according to claim 12, wherein, said step (1) is carried out under sonic oscillation or churned mechanically situation.
16. preparation method according to claim 12, wherein, said metal nanometer line is disperseed by water, alcohol, ether, alkane, acetone, oxolane, chloroform, benzene,toluene,xylene or their combination in any.
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