CN109192528A - A kind of preparation method of the polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure - Google Patents
A kind of preparation method of the polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure Download PDFInfo
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- CN109192528A CN109192528A CN201811026282.7A CN201811026282A CN109192528A CN 109192528 A CN109192528 A CN 109192528A CN 201811026282 A CN201811026282 A CN 201811026282A CN 109192528 A CN109192528 A CN 109192528A
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- polyaniline
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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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
- Y02E60/13—Energy storage using capacitors
Abstract
A kind of preparation method of the polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure of disclosure of the invention.The preparation method makes anilinechloride, crosslinking agent, permanganate react to obtain polyaniline/manganese dioxide electrode material in polyvinyl alcohol water solution.Preparation method of the invention, due to introducing polyvinyl alcohol and crosslinking agent, has obtained the polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure during preparing electrode material.The three-dimensional net structure of this enhancing can not only overcome expansion and contraction of the polyaniline in charge and discharge process, and good protection can also be formed to manganese dioxide, to promote the stability of electrode material；And all raw materials, system and after mixing need to be only sequentially added, stands and reacts.In standing reaction process, polyaniline is formed by oxidation polymerization, and at the same time, oxidant is reduced into manganese dioxide again.Preparation method is simple for this.
Description
Technical field
The present invention relates to electrochemical energy storage technical field more particularly to a kind of polyphenyl with enhancing three-dimensional net structure
Amine/manganese bioxide electrode material preparation method.
Background technique
In recent years, the serious environmental problems due to caused by the huge consumption of non-renewable fossil fuel, people to cleaning and
The demand of sustainable energy is increasingly urgent.Supercapacitor is that the model electrochemical energy storage being concerned nearly ten years is set
Standby, compared with battery and traditional capacitor, it has the features such as high power density, long circulation life and fast charging and discharging.Therefore,
Supercapacitor is widely applied in electric car, mobile electronic product and uninterrupted energy supply field.According to storage
Motor reason, supercapacitor can generally be divided into a point seed type: (1) electric double layer capacitance, and this kind of supercapacitor passes through electrode
Interface between electrolyte stores charge, such as using carbon material as the supercapacitor of electrode material；(2) fake capacitance (faraday
Capacitor), this kind of supercapacitor passes through reversible oxidation-reduction reaction (faraday's charge transmission reaction) then to produce electricl energy,
Such as using transition metal oxide, conducting polymer as the supercapacitor of electrode material.Although the electrode of double conduction capacity types
Material, such as carbon material have excellent cyclical stability, but its specific volume is but significantly lower than fake capacitance electrode material.Therefore, it opens
Send out the hot research content that more novel fake capacitance electrode materials are electrode material for super capacitor fields.
Polyaniline and manganese dioxide are belonging respectively to conducting polymer and transition metal oxide, they all have synthetic method
Simply, the advantages of at low cost, environmental-friendly Fabrication of High Specific Capacitance is most potential two classes fake capacitance electrode material.But they
It is respectively present some intrinsic defects again, for example, manganese dioxide poorly conductive, and cannot stablize in acidic electrolyte bath；Polyphenyl
Amine easily expands in charge and discharge process and shrinks, and cause cycle life short etc..To solve the above-mentioned problems, researcher opens
Send out polyaniline/manganese dioxide composite material various, the preferable electrochemical energy storage characteristic of these composite materials, but it is more complicated
Preparation method can hinder their commodity application to a certain extent.
Summary of the invention
It is an object of the present invention to be directed to the above-mentioned deficiency of the prior art, propose a kind of with enhancing three-dimensional network
The preparation method of the polyaniline/manganese dioxide electrode material of structure.
A kind of preparation method of polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure of the invention,
Anilinechloride, crosslinking agent, permanganate is set to react to obtain polyaniline/manganese dioxide electrode material in polyvinyl alcohol water solution.
It preferably, further include that reaction product is placed in a large amount of deionized water cleaning and balances.
Preferably, crosslinking agent is boric acid, borax, glutaraldehyde or epoxychloropropane.
Preferably, the mass concentration of the polyvinyl alcohol is 0.5~10wt%.
Preferably, the substance withdrawl syndrome of the anilinechloride is 0.02~2mol/L.
Preferably, the mass ratio of the crosslinking agent and polyvinyl alcohol is 0~0.5.
Preferably, the permanganate is potassium permanganate, sodium permanganate or ammonium permanganate.
It preferably, further include oxidant, the oxidant is ammonium persulfate, iron chloride, ferric nitrate or hydrogen peroxide.
Preferably, the amount of substance of oxidant and anilinechloride ratio is 0.01~2.
Preferably, the time of the reaction is 2~48h.
There is kind of the invention the preparation method of the polyaniline/manganese dioxide electrode material of enhancing three-dimensional net structure to make
During standby electrode material, due to introducing polyvinyl alcohol and crosslinking agent, the polyphenyl with enhancing three-dimensional net structure has been obtained
Amine/manganese bioxide electrode material.The three-dimensional net structure of this enhancing can not only overcome polyaniline in charge and discharge process
Expansion and contraction, can also form good protection, to promote the stability of electrode material to manganese dioxide；And it is all
Raw material, such as polyvinyl alcohol, anilinechloride, crosslinking agent and oxidant need to only sequentially add system and after mixing, standing
Reaction.In standing reaction process, polyaniline is formed by oxidation polymerization, and at the same time, oxidant is reduced into again
Manganese dioxide.Preparation method is simple for this.
Detailed description of the invention
Fig. 1 is the stereoscan photograph for the polyaniline/manganese dioxide electrode material that embodiment 1 is prepared.
Specific embodiment
Following is a specific embodiment of the present invention in conjunction with the accompanying drawings, technical scheme of the present invention will be further described,
However, the present invention is not limited to these examples.
Embodiment 1
1.0g polyvinyl alcohol is dissolved completely in a heated condition in 20mL deionized water, after natural cooling, for use.It will prepare
Good polyvinyl alcohol water solution, which is placed in ice-water bath, to be stirred, and 2.07g anilinechloride, 0.05g boric acid, 1.27g high are sequentially added
Potassium manganate is stored at room temperature reaction certain time after mixing evenly.Reaction product is placed in a large amount of deionized water cleaning and balances, with
Oligomer and inorganic matter are removed, polyaniline/manganese dioxide electrode material can be obtained.
Embodiment 2
1.0g polyvinyl alcohol is dissolved completely in 20mL deionized water at 90 DEG C, after natural cooling, for use.It will be prepared
Polyvinyl alcohol water solution is placed in ice-water bath and stirs, and sequentially adds 1.65g anilinechloride, 0.05g boric acid, 1.27g permanganic acid
Potassium is stored at room temperature reaction certain time after mixing evenly.Reaction product is placed in a large amount of deionized water cleaning and balances, to remove
Polyaniline/manganese dioxide electrode material can be obtained in oligomer and inorganic matter.
Embodiment 3
1.0g polyvinyl alcohol is dissolved completely in 20mL deionized water at 90 DEG C, after natural cooling, for use.It will be prepared
Polyvinyl alcohol water solution is placed in ice-water bath and stirs, and sequentially adds 2.07g anilinechloride, 0.05g boric acid, 1.27g permanganic acid
Potassium, 1.82g ammonium persulfate are stored at room temperature reaction certain time after mixing evenly.It is net that reaction product is placed in a large amount of deionized waters
Change balance, to remove oligomer and inorganic matter, polyaniline/manganese dioxide electrode material can be obtained.
Embodiment 4
1.0g polyvinyl alcohol is dissolved completely in 20mL deionized water at 90 DEG C, after natural cooling, for use.It will be prepared
Polyvinyl alcohol water solution is placed in ice-water bath and stirs, and sequentially adds 2.07g anilinechloride, 0.05g boric acid, 1.27g permanganic acid
Potassium, 1.29g iron chloride are stored at room temperature reaction certain time after mixing evenly.Reaction product is placed in a large amount of deionized water purifications
Balance, to remove oligomer and inorganic matter, can be obtained polyaniline/manganese dioxide electrode material.
Embodiment 5
1.0g polyvinyl alcohol is dissolved completely in 20mL deionized water at 90 DEG C, after natural cooling, for use.It will be prepared
Polyvinyl alcohol water solution is placed in ice-water bath and stirs, and sequentially adds 2.07g anilinechloride, 0.05g boric acid, 1.27g permanganic acid
Potassium, 1.93g ferric nitrate are stored at room temperature reaction certain time after mixing evenly.Reaction product is placed in a large amount of deionized water purifications
Balance, to remove oligomer and inorganic matter, can be obtained polyaniline/manganese dioxide electrode material.
Embodiment 6
0.5g polyvinyl alcohol is dissolved completely in 20mL deionized water at 85 DEG C, after natural cooling, for use.It will be prepared
Polyvinyl alcohol water solution is placed in ice-water bath and stirs, and sequentially adds 2.07g anilinechloride, 0.025g boric acid, 1.27g permanganic acid
Potassium, 1.82g ammonium persulfate are stored at room temperature reaction certain time after mixing evenly.It is net that reaction product is placed in a large amount of deionized waters
Change balance, to remove oligomer and inorganic matter, polyaniline/manganese dioxide electrode material can be obtained.
Embodiment 7
1.0g polyvinyl alcohol is dissolved completely in 20mL deionized water at 85 DEG C, after natural cooling, for use.It will be prepared
Polyvinyl alcohol water solution is placed in ice-water bath and stirs, and sequentially adds 2.07g anilinechloride, 0.05g borax, 1.27g permanganic acid
Potassium is stored at room temperature reaction certain time after mixing evenly.Reaction product is placed in a large amount of deionized water cleaning and balances, to remove
Polyaniline/manganese dioxide electrode material can be obtained in oligomer and inorganic matter.
Referring to attached drawing, Fig. 1 is the stereoscan photograph for the polyaniline/manganese dioxide electrode material that embodiment 1 is prepared:
(a) low magnification, (b) high-amplification-factor.By in figure it is obvious that prepared electrode material have it is typical three-dimensional
The network structure of intertexture, polyaniline, manganese dioxide active material are equably carried in network structure.Preparation method of the invention
The polyaniline/manganese dioxide electrode material of preparation has many advantages, such as the three dimensional network structure structure of enhancing, and preparation method is simple,
There is great application prospect in high-performance super capacitor electrode material field.
It is not directed to place above, is suitable for the prior art.
Although some specific embodiments of the invention are described in detail by example, the skill of this field
Art personnel it should be understood that above example merely to be illustrated, the range being not intended to be limiting of the invention, belonging to the present invention
Those skilled in the art can make various modifications or additions to described specific embodiment or using class
As mode substitute, but without departing from direction of the invention or beyond the scope of the appended claims.Ability
Domain it is to be understood by the skilled artisans that according to the technical essence of the invention to made by embodiment of above it is any modification, etc.
With replacement, improvement etc., protection scope of the present invention should be included in.
Claims (10)
1. a kind of preparation method of the polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure, it is characterised in that:
Anilinechloride, crosslinking agent, permanganate is set to react to obtain polyaniline/manganese dioxide electrode material in polyvinyl alcohol water solution.
2. a kind of system of polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure as described in claim 1
Preparation Method, it is characterised in that: further include that reaction product is placed in a large amount of deionized water cleaning and balances.
3. a kind of system of polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure as described in claim 1
Preparation Method, it is characterised in that: crosslinking agent is boric acid, borax, glutaraldehyde or epoxychloropropane.
4. a kind of system of polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure as described in claim 1
Preparation Method, it is characterised in that: the mass concentration of the polyvinyl alcohol is 0.5~10wt%.
5. a kind of system of polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure as described in claim 1
Preparation Method, it is characterised in that: the substance withdrawl syndrome of the anilinechloride is 0.02~2mol/L.
6. a kind of system of polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure as described in claim 1
Preparation Method, it is characterised in that: the mass ratio of the crosslinking agent and polyvinyl alcohol is 0~0.5.
7. a kind of system of polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure as described in claim 1
Preparation Method, it is characterised in that: the permanganate is potassium permanganate, sodium permanganate or ammonium permanganate.
8. a kind of system of polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure as described in claim 1
Preparation Method, it is characterised in that: further include oxidant, the oxidant is ammonium persulfate, iron chloride, ferric nitrate or hydrogen peroxide.
9. a kind of system of polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure as described in claim 1
Preparation Method, it is characterised in that: the amount of substance of oxidant and anilinechloride ratio is 0.01~2.
10. a kind of system of polyaniline/manganese dioxide electrode material with enhancing three-dimensional net structure as described in claim 1
Preparation Method, it is characterised in that: the time of the reaction is 2~48h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811026282.7A CN109192528B (en) | 2018-09-04 | 2018-09-04 | Preparation method of polyaniline/manganese dioxide electrode material with three-dimensional network structure |
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| CN201811026282.7A CN109192528B (en) | 2018-09-04 | 2018-09-04 | Preparation method of polyaniline/manganese dioxide electrode material with three-dimensional network structure |
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| CN109192528B CN109192528B (en) | 2021-01-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110280191A (en) * | 2019-05-24 | 2019-09-27 | 江苏大学 | The manganese dioxide nanowire aeroge and its preparation method and application of acid and alkali-resistance self assembly laminated construction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225165A (en) * | 2008-01-31 | 2008-07-23 | 上海交通大学 | Ball-milling force-chemical synthesis method of polyaniline |
| CN101696323A (en) * | 2009-10-30 | 2010-04-21 | 华南师范大学 | Method for preparing polyaniline/manganese dioxide composite material for super capacitor |
| CN103413689A (en) * | 2013-07-19 | 2013-11-27 | 北京科技大学 | Method for preparing graphene aerogel and graphene/ metallic oxide aerogel |
| CN106067385A (en) * | 2016-07-06 | 2016-11-02 | 清华大学 | Preparation method as the manganese dioxide/conductive polymer nanometer network structure electrode material of ultracapacitor |
-
2018
- 2018-09-04 CN CN201811026282.7A patent/CN109192528B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225165A (en) * | 2008-01-31 | 2008-07-23 | 上海交通大学 | Ball-milling force-chemical synthesis method of polyaniline |
| CN101696323A (en) * | 2009-10-30 | 2010-04-21 | 华南师范大学 | Method for preparing polyaniline/manganese dioxide composite material for super capacitor |
| CN103413689A (en) * | 2013-07-19 | 2013-11-27 | 北京科技大学 | Method for preparing graphene aerogel and graphene/ metallic oxide aerogel |
| CN106067385A (en) * | 2016-07-06 | 2016-11-02 | 清华大学 | Preparation method as the manganese dioxide/conductive polymer nanometer network structure electrode material of ultracapacitor |
Non-Patent Citations (1)
| Title |
|---|
| XIANJUN WEI, ET AL: "Chemical crosslinking engineered nitrogen-doped carbon aerogels from polyaniline-boric acid-polyvinyl alcohol gels for high-performance electrochemical capacitors", 《CARBON》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110280191A (en) * | 2019-05-24 | 2019-09-27 | 江苏大学 | The manganese dioxide nanowire aeroge and its preparation method and application of acid and alkali-resistance self assembly laminated construction |
| CN110280191B (en) * | 2019-05-24 | 2022-02-15 | 江苏大学 | Manganese dioxide nanowire aerogel with acid-base-resistant self-assembled laminated structure and preparation method and application thereof |
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| CN109192528B (en) | 2021-01-08 |
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