CN102020845B - Preparation method of conductive polyaniline polypyrrole composite membrane - Google Patents
Preparation method of conductive polyaniline polypyrrole composite membrane Download PDFInfo
- Publication number
- CN102020845B CN102020845B CN2010105608903A CN201010560890A CN102020845B CN 102020845 B CN102020845 B CN 102020845B CN 2010105608903 A CN2010105608903 A CN 2010105608903A CN 201010560890 A CN201010560890 A CN 201010560890A CN 102020845 B CN102020845 B CN 102020845B
- Authority
- CN
- China
- Prior art keywords
- preparation
- liquid
- polymerization
- solution
- conductive polyaniline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a conductive polyaniline polypyrrole composite membrane and a preparation method thereof. Aniline and pyrrole monomers are dissolved into an organic solvent, a supporting electrolyte is dissolved into water, thus two solutions are respectively prepared, the two solutions are transferred into a reactor in steps, so as to form a liquid-liquid interface, and a working electrode is directly inserted in the liquid-liquid interface, an auxiliary electrode and a reference electrode are placed into the supporting electrode solution, and electrochemical polymerization is carried out by electrochemical means. The polymer prepared by the method of the invention can spread out and grow on the interface, the polymerization product is proved to have good conductivity, and the polymerization product can be applied to a super capacitor, the anode material and cathode material of a battery, electromagnetic shielding and the like.
Description
Technical field
The present invention relates to a kind of preparation method of conductive polymers, but particularly relate to a kind of method of mass preparation electrically conductive polyaniline composite polypyrrole film, belong to polymeric material field.
Background technology
Conductive polymers is claimed conducting polymer again, is meant through means such as doping the polymkeric substance of specific conductivity in semi-conductor and conductor scope.Contain alternative singly-bound and two keys on this base polymer main chain, thereby formed big conjugated pi system.The mobile possibility that produces conduction of πDian Zi.Common conductive polymers has: polyacetylene, Polythiophene, polyaniline, polyaniline, polyhenylene, polyphenylene ethylene and polyacetylene etc.Conductive polymers not only has higher specific conductivity, and has photoconductivity matter, nonlinear optical property and magnetic property etc., not only has important scientific research value, and has great application prospect.
The polyaniline film good conductivity has monomer low price, unique doping characteristic and high advantages such as electric density, becomes in the conducting polymer composite one of the most potential kind.At present, the preparation method of polyaniline mainly contains two kinds of chemical polymerization and electrochemical polymerizations.Direct Electrochemistry method polymerisate purity is high, good conductivity, but receive the restriction of electrode area, be difficult to scale operation.Patent (patent publication No. CN101740228A) discloses a kind of preparation method who on stainless steel base, prepares polyaniline film, and this method is on stainless steel electrode, adopts the continuous current method to obtain having certain thickness polyaniline film stainless steel electrode.Patent CN200610038602.1 also discloses in a kind of three-electrode system and has had preparation nano polyaniline particulate method under the magnetic field condition, but the restriction that polyaniline nano particle that these methods obtain or film receive electrode area is difficult to real industrial production; It is big that chemical polymerization has output, the preparation characteristic of simple, but product purity is not high, and separate complex.And the liquid-liquid interface electrochemical polymerization method has been taken into account the advantage of chemical method and electrochemical process, simultaneously through monomer and ionogen are dissolved in respectively in immiscible two media such as organic solvent and the water; And the formation liquid-liquid interface; Working electrode directly is inserted into this liquid-liquid interface, and supporting electrode and reference electrode are put in the solution that is dissolved with supporting electrolyte, utilize electrochemical means to carry out electrochemical polymerization; Products therefrom is the self-supported membrane on liquid-liquid interface; So the separation and purification of film is very simple, make this method become a kind of technology of the conducting polymer composite that can be mass-produced, especially to the monomer that is insoluble in water as: effects such as thiophene, pyrroles are splendid.But for hydrophilic monomer aniline poor effect then.Consider that the pyrroles has and protonic acid doping characteristics like the phenyl amines and same high electric density; And the pyrroles can form the very polypyrrole film of the conduction of even compact at water-oil interface; So aniline and pyrrole monomer are mixed; Utilize the characteristics of pyrroles at interface growth, control aniline also generates in film synchronously, thereby can prepare the polyaniline composite polypyrrole film of conduction.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to prior art, and the electrochemical preparation method of a kind of efficient height, eco-friendly electrically conductive polyaniline composite polypyrrole film is provided.
This polymerization method is realized through following technical scheme:
Aniline and pyrrole monomer are dissolved in the organic solvent; Supporting electrolyte is soluble in water, and wiring solution-forming moves into reactor drum step by step with two kinds of solution respectively; Form liquid-liquid interface; And working electrode directly is inserted into this liquid-liquid interface, supporting electrode and reference electrode are put in the solution that is dissolved with supporting electrolyte, utilize electrochemical means to carry out electrochemical polymerization.
The Traditional electrochemical polyreaction is in homogeneous system, to carry out, and poly-unit is not had special requirement, and interfacial polymerization method of the present invention relates to two immiscible phases, so its poly-unit needs special design.
When the density of the solution that is dissolved with supporting electrolyte " sol1 " during, adopt the single port slot device, shown in accompanying drawing 1 less than aniline and pyrroles's mixing solutions " sol2 ".Otherwise,, adopt three mouthfuls of slot devices when the density of the solution that is dissolved with supporting electrolyte " sol1 " during greater than aniline and pyrroles's mixing solutions " sol2 "; Shown in accompanying drawing 2; By reference groove (A), work nest (B), auxiliary tank (C) is formed; Reference groove (A) and work nest (B) are through Shandong gold bend pipe (D) conducting and point to water-oil interface, and auxiliary tank (C) is through a diameter thicker bend pipe (E) and work nest (B) conducting.The poly-unit that so designs during polymerization can guarantee that reference electrode and supporting electrode can the coverlet body pollutions.
Interfacial polymerization of the present invention requires working electrode to insert at the liquid-liquid interface place, all contacts with two kinds of solution, and supporting electrode and reference electrode all are put in the solution that is dissolved with supporting electrolyte.Polyreaction starts from working electrode and the liquid/solid-liquid three-phase intersection that neither dissolves each other mutually, and product is for being the black-and-blue film at center with the working electrode.Polymerisate is insoluble to any phase; And sprawl growth along liquid-liquid interface; The conductive polymers that has generated plays the effect of electronics collector in late phase reaction; The polymkeric substance that has promptly generated has served as working electrode again, and this has fundamentally overcome the obstacle that receives the working electrode area constraints in the Traditional electrochemical reaction, and the potentiality that realize scale operation are arranged.
Described working electrode can be thread, bar-shaped, sheet, also can be by many pencils that bundle etc.There is electric field to exist between working electrode and the supporting electrode; And this strength of electric field is different with size, shape and the placement location of two electrodes with the meeting that distributes; Therefore can regulate and control the speed of growth of conductive polymers through size, shape and the placement location of regulating and control two electrodes, prepare difform conducting polymer thin film at this two dimensional surface different directions of liquid-liquid interface.
About the selection of the inventive method two-phase solvent, the most basic criterion is that two phases are not dissolved each other or solvability is very low each other, and wherein a relative monomer has strong dissolving power, and another relative supporting electrolyte has strong dissolving power; Secondly consider from the angle of environmental safety; Select hypotoxic free of contamination solvent system as far as possible; It can be the liquid-liquid interface that halohydrocarbon/water or long chain alkane/water forms; Promptly dissolving monomeric organic solvent can be methylene dichloride, trichloromethane, 1,2-ethylene dichloride, hexanaphthene, octane, n-hexadecane etc.
Said monomer aniline and the concentration of pyrroles in solution all can from 0.01-0.5mol/L.
Said supporting electrolyte concentration of aqueous solution is 0.5-2mol/L.
The concentration ratio of said aniline and pyrroles's solution and supporting electrolyte solution is 1: 1～1: 20.
Said supporting electrolyte can be mineral acid, and like perchloric acid, sulfuric acid, phosphoric acid, organic acid is like p-methyl benzenesulfonic acid, inorganic salt, like lithium perchlorate etc.
Said electrochemical means is constant potential polymerization, continuous current polymerization or volt-ampere scanning polymerization etc.
Current potential is with respect to saturated calomel current potential 0.6-1.2V during the constant potential polymerization; Perhaps volt-ampere scanning polymerization, polymerization potential is interval: with respect to saturated calomel current potential-0.2V～1.6V, sweep velocity: 20-100mV/s.
The polyaniline polypyrrole film of the inventive method preparation, but self-supporting has physical strength preferably in liquid-liquid interface.
Polypyrrole pattern and the polymerization potential relation of the inventive method preparation are remarkable, and low potential time can prepare densification, polyaniline polypyrrole film that physical strength is high; Improve polymerization potential, can prepare porous-film.Thereby, can control the product form according to demand.
The polymkeric substance of the inventive method preparation can be sprawled growth at the interface, confirms that polymerisate has good electrical conductivity, can be used for the aspects such as positive and negative pole material, electromagnetic shielding of ultracapacitor, battery.
The present invention also provides a kind of electrically conductive polyaniline polypyrrole film, and this film is aniline and pyrroles's a polymkeric substance, and wherein monomer aniline and pyrroles change between the ratio of film was from 1: 9 to 9: 1.
Beneficial effect of the present invention is:
1, the reaction system of the inventive method comprises two phases; Like this through selecting suitable solvent; Can realize the regulation and control significantly of polymerization single polymerization monomer and supporting electrolyte concentration; Even can directly select for use polymerization single polymerization monomer as a phase, so polymerization efficiency improves greatly, and polymerization velocity can conveniently regulating and controlling.
2, the polymkeric substance of the inventive method preparation is insoluble to any phase; But be to have certain physical strength and self-supporting in the film of liquid-liquid interface; This just is easy to realize the separation and the purifying of product, and the size of film and thickness also can pass through the fine control of experiment condition.
3, conducting polymer product pattern and the polymerization potential relation of the inventive method preparation are remarkable, and low potential time can prepare densification, polyaniline polypyrrole film that physical strength is high; Improve polymerization potential, can prepare porous-film.Thereby, can control the product form according to demand.
Description of drawings
Fig. 1 single port reactor assembly synoptic diagram
Three mouthfuls of reactor assembly synoptic diagram of Fig. 2
Current-time curvel among Fig. 3 embodiment 2 during the constant potential polymerization
The composite package of preparation is at 0.5mol/L H among Fig. 4 embodiment 2
2SO
4In the volt-ampere scanning curve
Embodiment
Can better elaboration be arranged to the present invention through following embodiment and Comparative Examples, but these embodiment can not be interpreted as the qualification to the scope of the invention.
Get earlier a certain amount of polymerization single polymerization monomer aniline (AN), pyrroles (PY) and supporting electrolyte perchloric acid (HClO respectively
4) be dissolved in respectively in organic solvent dichloromethane and the water, be made into 0.01mol/L AN and 0.01mol/L the PY dichloromethane solution and 0.2mol/L HClO
4The aqueous solution; Get successively and be dissolved with AN and monomeric dichloromethane solution of PY and HClO
4The aqueous solution is put in the single port poly-unit shown in Figure 1, forms liquid-liquid interface clearly; Platinum filament working electrode (diameter is 0.5mm) with certain-length vertically slowly is inserted into liquid-liquid interface then, and guarantees that platinum filament slightly surpasses liquid-liquid interface, gos deep into the about 0.5mm of oil phase, and platinized platinum supporting electrode and saturated calomel (SCE) reference electrode are inserted into the LiClO on upper strata
4In the aqueous solution; Adopt the cyclic voltammetry polymerization, potential region: 0.2V～1.2V, sweep velocity: 20mV/s.
Get earlier a certain amount of polymerization single polymerization monomer aniline (AN) and pyrroles (PY) and supporting electrolyte sulfuric acid (H respectively
2SO
4) be dissolved in respectively in organic solvent trichloromethane and the water, be made into 0.5mol/L AN and 0.5mol/L the PY chloroform soln and 2mol/LH
2SO
4The aqueous solution; Get the AN of certain volume and chloroform soln and the H of PY successively
2SO
4The aqueous solution is put in the single port poly-unit shown in Figure 1, forms liquid-liquid interface clearly; Platinum filament working electrode (diameter is 0.5mm) with certain-length vertically slowly is inserted into liquid-liquid interface then, and guarantees that platinum filament slightly surpasses liquid-liquid interface, gos deep into the about 0.5mm of oil phase,, platinized platinum supporting electrode and saturated calomel (SCE) reference electrode are inserted into the H on upper strata
2SO
4In the aqueous solution; Adopt constant potential 0.7V (vs SCE) polymerization, but promptly can be made into the polyaniline composite polypyrrole film of the conduction of self-supporting, the polymerization process current-time curvel is seen Fig. 3.With the polyaniline composite polypyrrole film for preparing and acetylene black and tetrafluoroethylene emulsion by 90: 5: 5 mass ratio mixing press mold after, at 0.5mol/LH
2SO
4Carry out cyclic voltammetry scan in the solution, sweep velocity is 20mV/s, and the gained volt-ampere curve is seen Fig. 4, and curve approximation is square, demonstrates the favorable charge-discharge characteristic, and the capacitance that is calculated this composite package by this figure is 158.7F/g.
Embodiment 3
Get a certain amount of polymerization single polymerization monomer aniline (AN) and pyrroles (PY) and supporting electrolyte lithium perchlorate (LiClO respectively
4) be dissolved in respectively in organic solvent trichloromethane and the water, be made into 0.05mol/L AN and 0.5mol/L pyrroles's chloroform soln and 0.5mol/L LiClO
4The aqueous solution; Get AN and the PY chloroform soln and the LiClO of certain volume successively
4The aqueous solution is put in the single port poly-unit shown in Figure 1, forms liquid-liquid interface clearly; Platinum filament working electrode (diameter is 0.5mm) with certain-length vertically slowly is inserted into liquid-liquid interface then, and guarantees that platinum filament slightly surpasses liquid-liquid interface, gos deep into another 0.5mm that makes an appointment, and platinized platinum supporting electrode and saturated calomel (SCE) reference electrode are inserted into the LiClO on upper strata
4In the aqueous solution; Adopt constant potential 1.2V (vs SCE) polymerization.But promptly can be made into the polyaniline composite polypyrrole film of the conduction of self-supporting.
Embodiment 4
Prepare earlier AN and the pyrrole ring hexane solution of 0.1mol/L and the LiClO of 0.4mol/L of 0.5mol/L respectively
4The aqueous solution; Poly-unit is taked three mouthfuls of groove poly-units shown in Figure 2; Inject the LiClO of 10mL earlier to work nest A
4The aqueous solution, and make two side channels be full of 0.4mol/L LiClO
4The aqueous solution; Injection 30mL AN and PY hexanaphthene dissolve in work nest A again, form liquid-liquid interface clearly.Platinum filament working electrode (diameter is 0.5mm) with certain-length vertically slowly is inserted into the liquid-liquid interface among the major trough A then, and saturated calomel (SCE) reference electrode platinized platinum and supporting electrode are inserted into respectively among side channel B and the C; Adopt the cyclic voltammetry polymerization, potential region: 0.2V～1.2V, sweep velocity: 20mV/s.But promptly can be made into the polyaniline composite polypyrrole film of the conduction of self-supporting.
Claims (5)
1. the preparation method of an electrically conductive polyaniline composite polypyrrole film is characterized in that: aniline and pyrrole monomer is dissolved in the organic solvent, and supporting electrolyte is soluble in water; The difference wiring solution-forming; Two kinds of solution are moved into reactor drum step by step, form liquid-liquid interface, and working electrode directly is inserted into this liquid-liquid interface; Supporting electrode and reference electrode are put in the solution of supporting electrolyte, utilize electrochemical means to carry out electrochemical polymerization;
The organic solvent of dissolved monomer is methylene dichloride, trichloromethane, 1,2-ethylene dichloride, hexanaphthene, octane or n-hexadecane, and monomer aniline and pyrroles are fluctuateed from 0.01 to 0.5mol/L in the concentration of solution;
Said supporting electrolyte is perchloric acid, sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid or lithium perchlorate, and the supporting electrolyte concentration of aqueous solution is 0.5-2mol/L.
2. the preparation method of electrically conductive polyaniline composite polypyrrole film as claimed in claim 1 is characterized in that: the concentration ratio of said aniline and pyrrole monomer solution and supporting electrolyte solution is 1: 1～1: 20.
3. according to claim 1 or claim 2 the preparation method of electrically conductive polyaniline composite polypyrrole film, it is characterized in that: said electrochemical means is constant potential, volt-ampere scanning, square wave current potential or streaming current polymerization.
4. the preparation method of electrically conductive polyaniline composite polypyrrole film as claimed in claim 3 is characterized in that: said constant potential polymeric current potential is for being 0.6-1.2V with respect to saturated calomel current potential.
5. the preparation method of electrically conductive polyaniline composite polypyrrole film as claimed in claim 3 is characterized in that: said volt-ampere scanning polymeric polymerization potential is interval: with respect to saturated calomel current potential-0.2V～1.6V, sweep velocity: 20-100mV/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105608903A CN102020845B (en) | 2010-11-25 | 2010-11-25 | Preparation method of conductive polyaniline polypyrrole composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105608903A CN102020845B (en) | 2010-11-25 | 2010-11-25 | Preparation method of conductive polyaniline polypyrrole composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102020845A CN102020845A (en) | 2011-04-20 |
| CN102020845B true CN102020845B (en) | 2012-05-23 |
Family
ID=43862646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105608903A Expired - Fee Related CN102020845B (en) | 2010-11-25 | 2010-11-25 | Preparation method of conductive polyaniline polypyrrole composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102020845B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532892B (en) * | 2012-01-20 | 2013-07-24 | 北京师范大学 | Conductive polymer film and preparation method thereof |
| CN104157875B (en) * | 2014-06-10 | 2017-05-17 | 西北师范大学 | Method for preparing nanometer silicon conductive polymer composite material for lithium ion batteries |
| CN104140674B (en) * | 2014-07-22 | 2016-08-31 | 中国海洋大学 | A kind of poly-(pyrroles-aniline)/Fe3O4 complex and preparation method thereof |
| CN106290510B (en) * | 2016-08-05 | 2018-09-07 | 武汉科技大学 | A kind of pH sensitivities polyaniline/polypyrrole laminated film and preparation method thereof |
| CN106474546B (en) * | 2016-09-09 | 2019-10-18 | 华南理工大学 | A kind of electric polypyrrole/poly-dopamine nanofiber and the preparation method and application thereof |
| CN106400048B (en) * | 2016-09-10 | 2018-07-20 | 华南理工大学 | A kind of electric Fenton cathode material and preparation method thereof based on lignin |
| CN107799327A (en) * | 2017-10-19 | 2018-03-13 | 沈阳师范大学 | The method that transiting metal oxidation vanadium regulates and controls polyaniline one-dimensional growth |
| CN109031834A (en) * | 2018-07-23 | 2018-12-18 | 上海第二工业大学 | A kind of self-charging polypyrrole discoloration battery and preparation method thereof |
| CN108970414B (en) * | 2018-07-31 | 2019-12-24 | 西安理工大学 | High-molecular composite conductive ultrafiltration membrane based on stainless steel mesh and preparation method of ultrafiltration membrane |
| CN109827898B (en) * | 2019-03-29 | 2021-09-17 | 河海大学 | Metal corrosion test device |
| CN110060816B (en) * | 2019-04-23 | 2021-04-20 | 西北工业大学深圳研究院 | Method for local in-situ electropolymerization of conductive polymer by 3D printing |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1770521A (en) * | 2004-11-03 | 2006-05-10 | 中国科学院大连化学物理研究所 | Method for modifying proton exchange membrane fuel cell metal dual-polarity board |
| CN1995143A (en) * | 2006-12-26 | 2007-07-11 | 西安交通大学 | Method for preparing composite electrode material for super capacitor |
| CN1995132A (en) * | 2006-12-26 | 2007-07-11 | 西安交通大学 | Preparation method of conductive high polymer and carbon nanotube composite electrode material |
| CN101302341A (en) * | 2007-05-09 | 2008-11-12 | 郑州泰达电子材料科技有限公司 | Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode |
-
2010
- 2010-11-25 CN CN2010105608903A patent/CN102020845B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1770521A (en) * | 2004-11-03 | 2006-05-10 | 中国科学院大连化学物理研究所 | Method for modifying proton exchange membrane fuel cell metal dual-polarity board |
| CN1995143A (en) * | 2006-12-26 | 2007-07-11 | 西安交通大学 | Method for preparing composite electrode material for super capacitor |
| CN1995132A (en) * | 2006-12-26 | 2007-07-11 | 西安交通大学 | Preparation method of conductive high polymer and carbon nanotube composite electrode material |
| CN101302341A (en) * | 2007-05-09 | 2008-11-12 | 郑州泰达电子材料科技有限公司 | Conductive composite material, composite electrode, and super large capacitor and lithium battery using the composite electrode |
Non-Patent Citations (1)
| Title |
|---|
| ZHIQIANG GAO等.ELECTROCHEMICAL STUDY ON THE POLYPYRROLE-POLYANILINE BILAYERS.《Synthetic Metals》.1993,第55-57卷第1477-1482页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102020845A (en) | 2011-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102020845B (en) | Preparation method of conductive polyaniline polypyrrole composite membrane | |
| CN101979438B (en) | Preparation method of conductive polypyrrole | |
| CN102020832B (en) | Conductive poly 3,4-ethylene dioxy thiophene film and preparation method thereof | |
| CN102817042B (en) | A kind of preparation method of electroactive polypyrrole film | |
| CN102071433B (en) | Interface polymerization method for conductive polymers | |
| CN106981374B (en) | Functional graphene oxide modified polymer gel electrolyte and its preparation method and application | |
| CN106898492A (en) | A kind of preparation method and applications for being conjugated microporous polymer film | |
| CN101012309A (en) | Method of preparing conductive macromolecule electrode material for super capacitor | |
| CN103854875A (en) | Polyaniline/MnO2 compound modified three-dimensional graphene composite material, preparation method and application of composite material | |
| CN108298588A (en) | It is a kind of to prepare δ-MnO2The method of nanometer sheet | |
| CN104361999B (en) | Carbon nano-tube @ nickel manganese core-shell heterostructure material, and preparation method and application thereof | |
| KR20150016943A (en) | Devices and methods including polyacetylenes | |
| CN105820358A (en) | Method for preparing organic/inorganic hybrid electroactivity ion exchange membrane in microgravity environment | |
| CN106024094B (en) | A kind of compliant conductive polyaniline nano fiber bumps electrode material and preparation method thereof | |
| CN101710541B (en) | Preparation method of polyaniline nano-fiber electrode material for super capacitor | |
| CN103871754A (en) | Polypyrrole/MnO2 compound modified three-dimensional graphene composite and preparation method and application thereof | |
| CN106298264A (en) | A kind of preparation method of the molybdenum trioxide of super capacitor material molybdenum trioxide and hydrogen doping | |
| CN102898669B (en) | Preparation method and device of conducting polypyrrole film | |
| CN107394159A (en) | A kind of composite fibre negative material and preparation method thereof | |
| CN108831749A (en) | A kind of electrochemical energy storage composite material and preparation method | |
| CN102592837B (en) | Method for preparing tetrachloride metal quaternary ammonium salt doped polyaniline electrode for super capacitor | |
| CN102157266B (en) | Flexible film super capacitor and preparation method thereof | |
| CN109280178A (en) | A kind of transition metal ions coordination conducting polymer and its preparation method and application | |
| CN106328386B (en) | The preparation method and application of combination electrode material, combination electrode | |
| CN111115769B (en) | One-step electrosynthesis graphene composite electrode by using electrochemical method and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20181125 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |