CN103996856A - Co-doping polypyrrole material as well as preparation method and application thereof - Google Patents
Co-doping polypyrrole material as well as preparation method and application thereof Download PDFInfo
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- CN103996856A CN103996856A CN201410206867.2A CN201410206867A CN103996856A CN 103996856 A CN103996856 A CN 103996856A CN 201410206867 A CN201410206867 A CN 201410206867A CN 103996856 A CN103996856 A CN 103996856A
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- polypyrrole
- preparation
- graphene oxide
- codope
- anthraquinone
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- 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
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- 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
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- 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
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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
Abstract
The invention relates to a co-doping polypyrrole material as well as a preparation method and an application thereof. The preparation method is characterized by comprising the steps: obtaining a polypyrrole/anthraquinone/graphene oxide composite material in a liquid which is formed from pyrrole monomer, anthraquinone-2-sodium sulfonate and graphene oxide by utilizing an electrochemical deposition method, and then electrochemically reducing the polypyrrole/anthraquinone/graphene oxide composite material to obtain the polypyrrole/anthraquinone/graphene oxide composite material. The preparation method can be carried out under the normal temperature, equipment is simple and easy to operate, and the selection range of the used co-doping system is wide. The porous micro-nano polypyrrole material prepared through the preparation method is excellent in conductivity and electrochemical performance and can be applied to a 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 of preparing biocompatibility battery use polypyrrole combination electrode material.
Background technology
Existing Implantable Medical Device power supply used be take lithium battery as main, as Li/I
2, Li/V
2o
5, Li/MnO
2, Li/Ag
2v
4o
11and Li/CFx.The toxicity of electrode material and electrolyte itself makes battery need battery case and human body to keep isolated to guarantee safety, and this has increased the volume of battery and Implantable Medical Device virtually greatly, is unfavorable for its microminiaturization.Study microminiaturized Implantable Medical Device power supply and become current popular and extremely urgent research topic 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 power supply is provided.Conventionally negative pole is zinc or the magnesium alloy of bio-compatible, and positive pole is noble metal platinum bio-compatible and that have hydrogen reduction activity.This battery, due to the bio-compatible of both positive and negative polarity and product and human body, can be eliminated the use in battery of electrolyte and battery case, has greatly improved the possibility of battery microminiaturization.
In above-mentioned biocompatibility battery, platinum, because excellent hydrogen reduction is active and bio-compatible becomes the preferred material of air positive pole, still as noble metal, due to fancy price, has limited it and has applied on a large scale.Scientists points out that by large quantity research conducting polymer (as polypyrrole (PPy), poly-3,4-ethylenedioxy thiophene (PEDOT)), because good hydrogen reduction is active and bio-compatible, can be applied in bio-compatible battery.Meanwhile, conducting polymer has the features such as conductivity is high, raw material is easy to get, synthetic easy, is as anodal ideal material.But with respect to metal platinum, the hydrogen reduction activity of conducting polymer has limited battery performance, particularly the voltage platform of battery.In addition, because conducting polymer is easy to change into the reduction-state of self in heavy-current discharge process, and the conducting polymer of reduction-state insulate, and this has increased the internal resistance of battery greatly, thereby causes cell voltage fast-descending, affects battery performance.The high rate capability that improves 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 introducing has the hydrogen reduction catalytic capability that the dopant of hydrogen reduction activity contributes to improve polypyrrole.In prior art, people's electrochemical depositions such as Zhang Guoquan obtain polypyrrole/anthraquinone composite material, and this material list reveals good hydrogen reduction catalytic activity.But this material can not overcome the problem that solves 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, form electro-deposition polypyrrole with two kinds of dissimilar dopants with codope, it is characterized in that, in being dissolved with 0.05-0.2 M pyrrole monomer, the water-soluble quinones of 0.0005-0.002 M, 0.5-2.0 mg/ml graphene oxide solution, use electrochemical deposition method to obtain polypyrrole/anthracene compounds/graphene oxide composite material, applying electric current is 0.1-2 mA cm
-2, the electric weight 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 a kind of or its combination in anthraquinone-2-sodium, sulfonation phenanthrenequione, menadione sodium bisulfite.
A 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 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, in polypyrrole structure, introduce conductivity that the Graphene with superior electrical conductivity improved polymer with and reducing condition under conductivity.
Beneficial effect:
(1) the collaborative effect of anthraquinone and Graphene has not only strengthened the oxygen reducing ability of electrode, and electrical conductance also obtains considerable raising, has significantly improved the performance of polypyrrole base bio-compatible battery.
(2) anthraquinone and Graphene show ' competitive relation ' as pyrroles's dopant, thereby make material surface occur loose structure, are beneficial to the conduction of material intermediate ion and oxygen.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment mono-prepared PPy/AQS/r-GO.
Fig. 2 is the cyclic voltammogram of embodiment mono-prepared PPy/AQS/r-GO, and sweeping speed is 5 mV s
-1.
Fig. 3 is the discharge curve of the prepared PPy/AQS/r-GO electrode of embodiment mono-on bio-battery.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, following examples do not produce restriction to the present invention.
Embodiment mono-:
Configuration, containing pyrrole monomer, 0.0005 M AQS sulfate, 1.0 mg/ml graphene oxide (GO) aqueous solution of 0.1 M, is led to N
2after 30min, adopt three-electrode system to carry out constant current electro-deposition, applying electric current is 0.5 mA cm
-2, the electric weight of electro-deposition is 1.2 coulombs; After resulting PPy/AQS/GO composite material is cleaned, carry out electrochemical reduction in being placed on three-electrode system, applying voltage is 1.1 V, and electrolyte is PBS cushioning liquid, and after reaction, water repeatedly cleans and can obtain PPy/AQS/r-GO electrode material.
Embodiment bis-:
Configuration, containing pyrrole monomer, 0.0005 M AQS sulfate, 1.0 mg/ml graphene oxide (GO) aqueous solution of 0.2 M, is led to N
2after 30min, adopt three-electrode system to carry out constant current electro-deposition, applying electric current is 2 mA cm
-2, the electric weight of electro-deposition is 2.0 coulombs; After resulting PPy/AQS/GO composite material is cleaned, carry out electrochemical reduction in being placed on three-electrode system, applying voltage is 1.2 V, and electrolyte is PBS cushioning liquid, and after reaction, water repeatedly cleans and can obtain PPy/AQS/r-GO electrode material.
Embodiment tri-:
Configuration, containing pyrrole monomer, 0.1 M AQS sulfate, 1 mg/ml graphene oxide (GO) aqueous solution of 0.05 M, is led to N
2after 30min, adopt three-electrode system to carry out constant current electro-deposition, applying electric current is 1 mA cm
-2, the electric weight of electro-deposition is 1.6 coulombs; After resulting PPy/AQS/GO composite material is cleaned, carry out electrochemical reduction in being placed on three-electrode system, applying voltage is 1.0 V, and electrolyte is PBS cushioning liquid, and after reaction, water repeatedly cleans and can obtain PPy/AQS/r-GO electrode material.
Embodiment tetra-:
Configuration, containing pyrrole monomer, 0.1 M AQS sulfate, 0.5 mg/ml graphene oxide (GO) aqueous solution of 0.05 M, is led to N
2after 30min, adopt three-electrode system to carry out constant current electro-deposition, applying electric current is 0.5 mA cm
-2, the electric weight of electro-deposition is 1.8 coulombs; After resulting PPy/AQS/GO composite material is cleaned, carry out electrochemical reduction in being placed on three-electrode system, applying voltage is 1.1 V, and electrolyte is PBS cushioning liquid, and after reaction, water repeatedly cleans and can obtain PPy/AQS/r-GO electrode material.
Claims (4)
1. the preparation method of a codope polypyrrole material, form electro-deposition polypyrrole with two kinds of dissimilar dopants with codope, it is characterized in that, in being dissolved with 0.05-0.2 M pyrrole monomer, the water-soluble quinones of 0.0005-0.002 M, 0.5-2.0 mg/ml graphene oxide solution, use electrochemical deposition method to obtain polypyrrole/anthracene compounds/graphene oxide composite material, applying electric current is 0.1-2 mA cm
-2, the electric weight of electro-deposition is 0.5-4 coulomb, then is carried out electrochemical reduction and obtain polypyrrole/anthracene compounds/graphene oxide composite material.
2. according to the preparation method of codope polypyrrole material claimed in claim 1, it is characterized in that, described water-soluble quinones is a kind of or its combination in anthraquinone-2-sodium, sulfonation phenanthrenequione, menadione sodium bisulfite.
3. a codope polypyrrole material, is characterized in that, by method described in above-mentioned arbitrary claim, is prepared.
According to codope polypyrrole material described in claim 3 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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| CN103996856B CN103996856B (en) | 2016-04-27 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104022263A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Codoped conducting polymer, preparation method and application thereof |
| 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 |
| CN104900889A (en) * | 2015-04-30 | 2015-09-09 | 广东工业大学 | Preparation method of polypyrrole-carbon nanotube-manganese-AQDS composite electrode material |
| CN104934605A (en) * | 2015-04-22 | 2015-09-23 | 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 |
| CN109603906A (en) * | 2019-01-15 | 2019-04-12 | 安徽大学 | A kind of anthraquinone-2-sodium/graphene oxide composite photo-catalysis bactericide and its preparation method and application |
| CN114784249A (en) * | 2022-04-29 | 2022-07-22 | 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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| CN102509806A (en) * | 2011-10-28 | 2012-06-20 | 四川大学 | Novel sufficient metal air battery oxygen electrode and preparation method thereof |
| 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 |
| 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 |
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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 |
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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 |
| 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 |
| 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 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104022263A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Codoped conducting polymer, preparation method and application thereof |
| 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 |
| CN104934605A (en) * | 2015-04-22 | 2015-09-23 | 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 |
| 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 |
| CN104900889A (en) * | 2015-04-30 | 2015-09-09 | 广东工业大学 | Preparation method of polypyrrole-carbon nanotube-manganese-AQDS composite electrode material |
| CN104900889B (en) * | 2015-04-30 | 2017-12-08 | 广东工业大学 | Polypyrrole CNT manganese AQDS combination electrode material preparation methods |
| CN109603906A (en) * | 2019-01-15 | 2019-04-12 | 安徽大学 | A kind of anthraquinone-2-sodium/graphene oxide composite photo-catalysis bactericide and its preparation method and application |
| CN109603906B (en) * | 2019-01-15 | 2021-10-01 | 安徽大学 | Anthraquinone-2-sodium sulfonate/graphene oxide composite photocatalytic bactericide and preparation method and application thereof |
| CN114784249A (en) * | 2022-04-29 | 2022-07-22 | 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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| CN103996856B (en) | 2016-04-27 |
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