CN103996856B - Codope polypyrrole material and its preparation method and application - Google Patents
Codope polypyrrole material and its preparation method and application Download PDFInfo
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- CN103996856B CN103996856B CN201410206867.2A CN201410206867A CN103996856B CN 103996856 B CN103996856 B CN 103996856B CN 201410206867 A CN201410206867 A CN 201410206867A CN 103996856 B CN103996856 B CN 103996856B
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- Prior art keywords
- polypyrrole
- codope
- graphene oxide
- composite material
- anthraquinone
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- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 18
- 238000004070 electrodeposition Methods 0.000 claims abstract description 16
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 230000005611 electricity Effects 0.000 claims description 6
- 239000002019 doping agent Substances 0.000 claims description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- -1 anthracene compounds Chemical class 0.000 claims description 4
- 150000004053 quinones Chemical class 0.000 claims description 4
- 229960004051 menadione sodium bisulfite Drugs 0.000 claims description 2
- XDPFHGWVCTXHDX-UHFFFAOYSA-M menadione sodium sulfonate Chemical compound [Na+].C1=CC=C2C(=O)C(C)(S([O-])(=O)=O)CC(=O)C2=C1 XDPFHGWVCTXHDX-UHFFFAOYSA-M 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 abstract description 7
- 150000004056 anthraquinones Chemical class 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 229920001940 conductive polymer Polymers 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000010757 Reduction Activity Effects 0.000 description 5
- 239000002322 conducting polymer Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of codope polypyrrole material and its preparation method and application.Method for using electrochemical deposition method to obtain polypyrrole/anthraquinone/graphene oxide composite material being dissolved with in pyrrole monomer, anthraquinone-2-sodium, graphene oxide solution, then is carried out electrochemical reduction and is obtained polypyrrole/anthraquinone/graphene oxide composite material.Method of the present invention can be carried out at normal temperatures, and equipment is simple, processing ease and the codope system range of choice used is wide.Porous prepared by the present invention, the Pt/Polypyrrole composite material of micro nano structure is a kind of electrode material with superior electrical conductivity energy and chemical property, can be used as in flexible energy storage device.
Description
Technical field
The present invention relates to a kind of codope polypyrrole material and its preparation method and application, particularly a kind of method preparing biocompatibility battery polypyrrole combination electrode material.
Background technology
Existing Implantable Medical Device power supply used based on lithium battery, as Li/I
2, Li/V
2o
5, Li/MnO
2, Li/Ag
2v
4o
11andLi/CFx.The toxicity of electrode material and electrolyte itself makes battery need battery case and human body to keep completely cutting off to ensure safety, and this considerably increases the volume of battery and Implantable Medical Device virtually, is unfavorable for that it is microminiaturized.The Implantable Medical Device power supply of research microminiaturization has become current research topic popular and extremely urgent in the world.
Biocompatibility battery structure is comparatively simple, and principle is a kind of metal-air batteries.It utilizes human body fluid as electrolyte, utilizes the oxygen in body fluid to react simultaneously, consumes negative pole and provides power supply.Usual negative pole is zinc or the magnesium alloy of bio-compatible, and positive pole is bio-compatible and has the noble metal platinum of oxygen reduction activity.This battery, due to the bio-compatible of both positive and negative polarity and product and human body, can be eliminated electrolyte and battery case use in the battery, substantially increase the possibility of battery microminiaturization.
In above-mentioned biocompatibility battery, platinum becomes the preferred material of air cathode due to the oxygen reduction activity of excellence and bio-compatible, but as noble metal, due to fancy price, limits it and apply on a large scale.By large quantity research, scientists points out that conducting polymer is (as polypyrrole (PPy), poly-3,4-ethylenedioxy thiophene (PEDOT)) because good oxygen reduction activity and bio-compatible, can be applied in bio-compatible battery.Meanwhile, conducting polymer has that conductivity is high, raw material is easy to get, synthesize the features such as easy, is the ideal material as positive pole.But relative to metal platinum, the oxygen reduction activity of conducting polymer limits battery performance, particularly the voltage platform of battery.In addition, because conducting polymer is easy to the reduction-state changing self in heavy-current discharge process, and the conducting polymer of reduction-state is insulation, this considerably increases the internal resistance of battery, thus causes cell voltage to decline fast, affect battery performance.The high rate capability improving battery also becomes conductive polymers based biocompatibility battery practical application matter of utmost importance urgently to be resolved hurrily.
The physical-chemical property of polypyrrole easily changes along with the change of dopant, so introduce the hydrogen reduction catalytic capability that the dopant with oxygen reduction activity contributes to improving polypyrrole.In prior art, people's electrochemical depositions such as Zhang Guoquan obtain polypyrrole/anthraquinone composite material, and this material list reveals excellent oxygen reduction catalytic activity.But this material can not overcome the problem solving polypyrrole high impedance under reduction-state.
Summary of the invention
For overcoming the shortcoming of prior art, the invention provides a kind of codope polypyrrole material and its preparation method and application.
A kind of preparation method of codope polypyrrole material, with two kinds of dissimilar dopants with the form electro-deposition polypyrrole of codope, it is characterized in that, be dissolved with in 0.05-0.2M pyrrole monomer, the water-soluble quinones of 0.0005-0.002M, 0.5-2.0mg/ml graphene oxide solution use electrochemical deposition method obtain polypyrrole/anthracene compounds/graphene oxide composite material, applying electric current is 0.1-2mAcm
-2, the electricity of electro-deposition is 0.5-4 coulomb, then is carried out electrochemical reduction and obtain polypyrrole/anthracene compounds/graphene oxide composite material.
Described water-soluble quinones is one in anthraquinone-2-sodium, sulfonation phenanthrenequione, menadione sodium bisulfite or its combination.
A kind of codope polypyrrole material, is prepared by above-mentioned arbitrary described method.
Codope polypyrrole material is as the application of the combination electrode of biocompatibility battery.
A kind of bio-compatible battery, positive pole is the stainless (steel) wire that surface electrical deposits polypyrrole (PPy)/anthraquinone (AQS)/Graphene (r-GO) composite material; Negative pole is AZ61 magnesium alloy; Electrolyte is PBS cushioning liquid.
The present invention adopts electropolymerization-electroreduction technology to prepare polypyrrole (PPy)/anthraquinone (AQS)/Graphene (r-GO) composite electrode, introduce in polypyrrole structure the Graphene with superior electrical conductivity improve the conductivity of polymer and its reducing condition under conductivity.
Beneficial effect:
(1) the collaborative validity of anthraquinone and Graphene not only increases the oxygen reducing ability of electrode, and electrical conductance also obtains considerable raising, significantly improves the performance of polypyrrole base bio-compatible battery.
(2) anthraquinone and Graphene show ' competitive relation ' as pyrroles's dopant, thus material surface is occurred loose structure, be beneficial to the conduction of material intermediate ion and oxygen.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of PPy/AQS/r-GO prepared by embodiment one.
Fig. 2 is the cyclic voltammogram of PPy/AQS/r-GO prepared by embodiment one, sweeps speed for 5mVs
-1.
Fig. 3 is the discharge curve of PPy/AQS/r-GO electrode on bio-battery prepared by embodiment one.
Embodiment
Be described further technical scheme of the present invention below in conjunction with embodiment, following examples do not produce restriction to the present invention.
Embodiment one:
Configuration, containing pyrrole monomer, 0.0005MAQS sulfate, 1.0mg/ml graphene oxide (GO) aqueous solution of 0.1M, leads to N
2after 30min, adopt three-electrode system to carry out constant current electro-deposition, applying electric current is 0.5mAcm
-2, the electricity of electro-deposition is 1.2 coulombs; Carry out electrochemical reduction being placed in three-electrode system after being cleaned by obtained PPy/AQS/GO composite material, applying voltage is 1.1V, and electrolyte is PBS cushioning liquid, repeatedly cleans can obtain PPy/AQS/r-GO electrode material after reaction with water.
Embodiment two:
Configuration, containing pyrrole monomer, 0.0005MAQS sulfate, 1.0mg/ml graphene oxide (GO) aqueous solution of 0.2M, leads to N
2after 30min, adopt three-electrode system to carry out constant current electro-deposition, applying electric current is 2mAcm
-2, the electricity of electro-deposition is 2.0 coulombs; Carry out electrochemical reduction being placed in three-electrode system after being cleaned by obtained PPy/AQS/GO composite material, applying voltage is 1.2V, and electrolyte is PBS cushioning liquid, repeatedly cleans can obtain PPy/AQS/r-GO electrode material after reaction with water.
Embodiment three:
Configuration, containing pyrrole monomer, 0.1MAQS sulfate, 1mg/ml graphene oxide (GO) aqueous solution of 0.05M, leads to N
2after 30min, adopt three-electrode system to carry out constant current electro-deposition, applying electric current is 1mAcm
-2, the electricity of electro-deposition is 1.6 coulombs; Carry out electrochemical reduction being placed in three-electrode system after being cleaned by obtained PPy/AQS/GO composite material, applying voltage is 1.0V, and electrolyte is PBS cushioning liquid, repeatedly cleans can obtain PPy/AQS/r-GO electrode material after reaction with water.
Embodiment four:
Configuration, containing pyrrole monomer, 0.1MAQS sulfate, 0.5mg/ml graphene oxide (GO) aqueous solution of 0.05M, leads to N
2after 30min, adopt three-electrode system to carry out constant current electro-deposition, applying electric current is 0.5mAcm
-2, the electricity of electro-deposition is 1.8 coulombs; Carry out electrochemical reduction being placed in three-electrode system after being cleaned by obtained PPy/AQS/GO composite material, applying voltage is 1.1V, and electrolyte is PBS cushioning liquid, repeatedly cleans can obtain PPy/AQS/r-GO electrode material after reaction with water.
Claims (3)
1. the preparation method of a codope polypyrrole material, with two kinds of dissimilar dopants with the form electro-deposition polypyrrole of codope, it is characterized in that, be dissolved with in 0.05-0.2M pyrrole monomer, the water-soluble quinones of 0.0005-0.002M, 0.5-2.0mg/ml graphene oxide solution use electrochemical deposition method obtain polypyrrole/anthracene compounds/graphene oxide composite material, applying electric current is 0.1-2mAcm
-2, the electricity of electro-deposition is 0.5-4 coulomb, then is carried out electrochemical reduction and obtain polypyrrole/anthracene compounds/graphene oxide composite material;
Described water-soluble quinones is one in anthraquinone-2-sodium, sulfonation phenanthrenequione, menadione sodium bisulfite or its combination.
2. a codope polypyrrole material, is characterized in that, is prepared by method described in above-mentioned arbitrary claim.
3. by codope polypyrrole material described in claim 2 as the application of the combination electrode of biocompatibility battery.
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| CN201410206867.2A CN103996856B (en) | 2014-05-16 | 2014-05-16 | Codope polypyrrole material and its preparation method and application |
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|---|---|---|---|
| CN201410206867.2A CN103996856B (en) | 2014-05-16 | 2014-05-16 | Codope polypyrrole material and its preparation method and application |
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| CN103996856A CN103996856A (en) | 2014-08-20 |
| CN103996856B true CN103996856B (en) | 2016-04-27 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104022263B (en) * | 2014-05-28 | 2016-08-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Codope conducting polymer and its preparation method and application |
| CN104332639A (en) * | 2014-11-05 | 2015-02-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of co-doped conductive polymer electrode material |
| CN104934605B (en) * | 2015-04-22 | 2017-05-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for N-(pendant nitroxide radical group) polypyrrole derivant electrode |
| CN104900889B (en) * | 2015-04-30 | 2017-12-08 | 广东工业大学 | Polypyrrole CNT manganese AQDS combination electrode material preparation methods |
| CN109603906B (en) * | 2019-01-15 | 2021-10-01 | 安徽大学 | A kind of anthraquinone-2-sodium sulfonate/graphene oxide composite photocatalytic bactericide and preparation method and application thereof |
| CN114784249B (en) * | 2022-04-29 | 2023-06-16 | 楚能新能源股份有限公司 | Lithium iron phosphate composite positive electrode material and preparation method thereof |
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| CN101645515A (en) * | 2009-08-20 | 2010-02-10 | 华南理工大学 | Microbiological fuel cell as well as preparation method and applications thereof |
| CN102509806A (en) * | 2011-10-28 | 2012-06-20 | 四川大学 | Novel sufficient metal air battery oxygen electrode and preparation method thereof |
| CN103399051A (en) * | 2013-07-31 | 2013-11-20 | 华南理工大学 | Water body toxicity detecting method and portable device based on microbial electrochemical signals |
| CN103401008A (en) * | 2013-07-31 | 2013-11-20 | 华南理工大学 | Method and device for storing bioelectrical energy by virtue of capacitive anode |
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2014
- 2014-05-16 CN CN201410206867.2A patent/CN103996856B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101645515A (en) * | 2009-08-20 | 2010-02-10 | 华南理工大学 | Microbiological fuel cell as well as preparation method and applications thereof |
| CN102509806A (en) * | 2011-10-28 | 2012-06-20 | 四川大学 | Novel sufficient metal air battery oxygen electrode and preparation method thereof |
| CN103399051A (en) * | 2013-07-31 | 2013-11-20 | 华南理工大学 | Water body toxicity detecting method and portable device based on microbial electrochemical signals |
| CN103401008A (en) * | 2013-07-31 | 2013-11-20 | 华南理工大学 | Method and device for storing bioelectrical energy by virtue of capacitive anode |
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