CN106384831A - All-vanadium redox flow battery composite electrode and preparation method thereof - Google Patents
All-vanadium redox flow battery composite electrode and preparation method thereof Download PDFInfo
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- CN106384831A CN106384831A CN201610994009.8A CN201610994009A CN106384831A CN 106384831 A CN106384831 A CN 106384831A CN 201610994009 A CN201610994009 A CN 201610994009A CN 106384831 A CN106384831 A CN 106384831A
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- carbon fiber
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Engineering & Computer Science (AREA)
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Abstract
The invention provides an all-vanadium redox flow battery composite electrode and a preparation method thereof. The all-vanadium redox flow battery composite electrode comprises a carbon fiber felt substrate and carbon nanotubes, wherein the carbon nanotubes are combined on the surface of the carbon fiber felt substrate; the carbon nanotubes carbon nanotubes with double bonds of carbon to oxygen and/or single bond of carbon to oxygen. The preparation method comprises the following steps of: introducing pyrrole, dispersing the carbon nanotubes and grafting the carbon nanotubes. As the content-controllable carbon nanotubes with the single bond of carbon to oxygen or double bonds of carbon to oxygen are grafted on carbon fiber felt, active groups can be introduced, and meanwhile original properties of the carbon fiber felt are not damaged; in addition, due to introduction of the carbon nanotubes, the conductivity and the specific surface area of the carbon fiber felt can be correspondingly increased, power charge and discharge reactions can be facilitated, and the all-vanadium redox flow battery composite electrode has the advantages of being low in energy consumption, gentle in reaction, easy to operate, possible in industrial production, and the like.
Description
Technical field
A kind of the invention belongs to vanadium redox flow battery electrode field of material technology, it relates in particular to all-vanadium flow battery
Combination electrode and preparation method thereof.
Background technology
All-vanadium flow battery is a kind of Novel pollution-free chemical energy storage power supply, is flow battery, does not have solid-state reaction, do not send out
The change of living beings structure, and low price, therefore exploitation all-vanadium flow battery can alleviate energy shortage situation.Carbon fiber felt
Because it is cheap, good conductivity, porosity be big, good chemical stability and become electrode material for all-vanadium flow battery
First-selection, but the electro-chemical activity of carbon fiber felt and hydrophily can't fully meet the requirement of flow battery, be therefore directed to carbon
The study on the modification of felt is just particularly important.
At present, found according to research, the invertibity of carbon fiber felt is poor, and electro-chemical activity is not high and hydrophily is poor, therefore
Need modified to it using suitable method, hydrophobic simultaneously in reduction, improve the activity of reaction, to improve electrode performance.
In prior art, some can improve the method for modifying of carbon fiber felt activity, and such as thermal oxidation, wet heating process, concentrated acid is processed
It is that the part of not reaction completely during carbon fiber and graphite on carbon fiber felt is carried out Strong oxdiative reaction etc. processing method；However,
So fierce reaction will necessarily destroy the structure of carbon fiber felt, so that the mechanical performance of felt is reduced or destroy graphitic layers, also can
The electric conductivity of carbon fiber felt is made to reduce.
Content of the invention
An object of the present invention is to solve one or more problems present in above-mentioned prior art.For example, this
One of bright purpose is to provide the all-vanadium flow battery combination electrode that a kind of electro-chemical activity is good and electric conductivity is excellent.
To achieve these goals, an aspect of of the present present invention provides a kind of preparation side of all-vanadium flow battery combination electrode
Method, comprises the following steps：Carbon fiber felt is immersed pyrroles-acetone mixture, obtains the carbon fiber felt after pyrroles is processed, described pyrrole
Coughing up with the volume ratio of acetone is 1:1～4:1；CNT is put in distilled water, carries out decentralized processing, obtain CNT
Liquid；Under the conditions of sonic oscillation, in carbon fiber felt after pyrroles is processed immersion CNT liquid, dropping hydrogen peroxide is to reacting knot
Bundle, dries, obtains all-vanadium flow battery combination electrode.
Another aspect provides a kind of all-vanadium flow battery combination electrode, described all-vanadium flow battery compound electric
Pole includes the carbon fiber felt matrix and combination CNT in carbon fiber felt matrix surface, and it is fine that described CNT accounts for described carbon
The 3%～10% of dimension felt quality, described CNT is the CNT containing C=O bond and/or carbon oxygen singly-bound.
All-vanadium flow battery combination electrode according to an exemplary embodiment of the present invention, described carbon fiber felt and CNT
Intermediate connector can be pyrroles.
Compared with prior art, beneficial effects of the present invention include：Containing of controlled content can be grafted on carbon fiber felt
Carbon oxygen singly-bound or the CNT of C=O bond；And while introducing active group, carbon fiber felt script will not be destroyed
Energy；The content introducing active group and species can be controlled, so that the performance of carbon fiber felt is improved；Have energy consumption low, reaction
Gently, easy to operate and can industrialized production the advantages of.
Specific embodiment
Hereinafter, the all-vanadium flow battery combination electrode according to the present invention will be described in detail with reference to exemplary embodiment
And preparation method thereof.
In the present invention, using the CNT containing carbon oxygen singly-bound or C=O bond functional group for the grafting on carbon fiber felt
Method is improving electro-chemical activity and the hydrophily of carbon fiber felt.Specifically, carbon oxygen singly-bound or C=O bond are that impact carbon is fine
Dimension felt electro-chemical activity and hydrophilic essential groups.The double containing carbon oxygen singly-bound or carbon oxygen of controlled content are formed on carbon fiber felt
The CNT of key, while introducing active group, will not destroy the performance of carbon fiber felt script, and due to CNT
Introducing, enhance electric conductivity and the specific surface area of combination electrode, be more beneficial for battery charging and discharging reaction carrying out.
In one exemplary embodiment of the present invention, the preparation method of all-vanadium flow battery combination electrode includes following step
Suddenly：
1) cleaning pretreatment of carbon fiber felt
The purpose that carbon fiber felt is cleaned with pre-process is to remove carbon fiber felt surface impurity.For example, can be using super
The mode of sound cleaning is cleaned to carbon fiber felt processing.However, the invention is not restricted to this, other can remove carbon fiber felt table
The cleaning way of face impurity also may be used.Preferably, carbon fiber felt is cleaned by ultrasonic 15 minutes～30 minutes with distilled water, cleaning completes
Afterwards, put in baking oven and dry, obtain pretreated carbon fiber felt.
2) introducing of pyrroles
It is 1 that pretreated carbon fiber felt is completely immersed in pyrroles with acetone volume:1～1:In 4 mixed solution, then
Carbon fiber felt is taken out, places 4 hours～8 hours under greenhouse.
3) dispersion of CNT
Weigh the CNT accounting for carbon fiber felt quality 3%～10%, it is handled for then CNT being added volume
Ultrasonically treated 15～30 minutes in the distilled water that 3～5 times of carbon fiber felt volume, obtain CNT liquid；
4) grafting of CNT
While ultrasonic, in the carbon fiber felt immersion CNT liquid after pyrroles is processed, dropping concentration is more than 30%,
Volume is the hydrogen peroxide of pyrroles-acetone mixture volume 3%～6%, after completion of dropping, reacts 15～30 points while ultrasonic
Clock, then takes out carbon fiber felt, with distillation water washing 3～5 times, dries.
In another exemplary embodiment of the present invention, all-vanadium flow battery combination electrode include carbon fiber felt matrix with
And combination is in the CNT of carbon fiber felt matrix surface, described CNT accounts for the 3%～10% of described carbon fiber felt quality,
Described CNT is the CNT containing C=O bond and/or carbon oxygen singly-bound.
In the present example embodiment, described carbon fiber felt and the intermediate connector of CNT are pyrroles.
To further describe the exemplary embodiment of the present invention below in conjunction with specific example.
Embodiment 1
The 10g carbon fiber felt of the 2cm × 2cm after cleaning treatment × 0.1cm is completely immersed in 40ml pyrroles and 10ml acetone
Mixed liquor in, place at normal temperatures after taking-up 7 hours.Configuration 5g CNT and the mixed liquor of 20ml distilled water, Ran Houjing
Cross ultrasonication and obtain CNT liquid in 30 minutes.In carbon fiber felt immersion CNT liquid after processing through pyrroles, so
Drip 5ml afterwards, mass concentration is 30% hydrogen peroxide, after continuing ultrasonic 30 minutes, take out carbon fiber felt, with distillation water washing 4 times
Post-drying.The carbon fiber felt obtaining is assembled into monocell, compares the battery with the assembling of untreated carbon fiber felt, its coulomb is imitated
Rate improves 12.1%, and energy efficiency improves 9.8%.
Embodiment 2
10g carbon fiber felt after cleaning treatment is completely immersed in the mixed liquor that 60ml pyrroles is with 20ml acetone, after taking-up
Place 6 hours at normal temperatures.Configuration 0.8g CNT and the mixed liquor of 20ml distilled water, are then passed through 25 points of ultrasonication
Clock obtains CNT liquid.In carbon fiber felt immersion CNT liquid after processing through pyrroles, then drip 10ml, concentration is
75% hydrogen peroxide, takes out carbon fiber felt, with distilling 4 post-dryings of water washing after continuing ultrasonic 30 minutes.The carbon obtaining is fine
Dimension felt is assembled into monocell, compares the battery with the assembling of untreated carbon fiber felt, and its coulombic efficiency improves 13.4%, can dose-effect
Rate improves 11.5%.
Embodiment 3
5g carbon fiber felt after cleaning treatment is completely immersed in the mixed liquor of 30ml pyrroles and 30ml acetone, after taking-up
Place 5 hours under normal temperature.Configuration 0.5g CNT and the mixed liquor of 20ml distilled water, are then passed through ultrasonication 20 minutes
Obtain CNT liquid.In carbon fiber felt immersion CNT liquid after processing through pyrroles, then drip 10ml, concentration is
50% hydrogen peroxide, takes out carbon fiber felt, with distilling 4 post-dryings of water washing after continuing ultrasonic 20 minutes.The carbon obtaining is fine
Dimension felt is assembled into monocell, compares the battery with the assembling of untreated carbon fiber felt, and its coulombic efficiency improves 10.4%, can dose-effect
Rate improves 8.8%.
In sum, for the method for the Treatment of Carbon felt of the present invention is compared to oxidative treatment carbon fiber felt, have
Energy consumption is low, reaction is gentle, easy to operate and the advantages of be suitable to industrial production.Meanwhile, with thermal oxidation, wet heating process, concentrated acid
The processing method such as process the part of not reaction completely during carbon fiber and graphite on carbon fiber felt carried out Strong oxdiative reaction and compare,
While the inventive method introduces carbon oxygen groups, structure and the graphitic layers of carbon fiber felt itself will not be destroyed, carbon will not be reduced
The mechanical performance of fibrofelt.
Although above by describing the present invention with reference to exemplary embodiment, those skilled in the art should be clear
Chu, in the case of the spirit and scope being limited without departing from claim, can be carried out respectively to the exemplary embodiment of the present invention
Plant modifications and changes.
Claims (6)
1. a kind of preparation method of all-vanadium flow battery combination electrode is it is characterised in that described preparation method comprises the following steps：
Carbon fiber felt is immersed pyrroles-acetone mixture, obtains the carbon fiber felt after pyrroles is processed, the body of described pyrroles and acetone
Long-pending ratio is 1:1～4:1；
CNT is put in distilled water, carries out decentralized processing, obtain CNT liquid；
Under the conditions of sonic oscillation, in the carbon fiber felt immersion CNT liquid after pyrroles is processed, dropping hydrogen peroxide is to reaction
Terminate, dry, obtain all-vanadium flow battery combination electrode.
2. the preparation method of all-vanadium flow battery combination electrode according to claim 1 is it is characterised in that described preparation side
Before method is additionally included in carbon fiber felt immersion pyrroles-acetone mixture, carbon fiber felt is cleaned pre-process, with except carbon elimination fibre
Dimension felt surface impurity.
3. the preparation method of all-vanadium flow battery combination electrode according to claim 1 is it is characterised in that described carbon nanometer
Pipe accounts for the 3%～10% of carbon fiber felt quality.
4. the preparation method of all-vanadium flow battery combination electrode according to claim 1 is it is characterised in that described hydrogen peroxide
Addition is the 3%～6% of pyrroles-acetone mixture volume.
5. a kind of all-vanadium flow battery combination electrode is it is characterised in that described all-vanadium flow battery combination electrode includes carbon fiber
Felt matrix and combine CNT in carbon fiber felt matrix surface, described CNT accounts for described carbon fiber felt quality
3%～10%, described CNT is the CNT containing C=O bond and/or carbon oxygen singly-bound.
6. all-vanadium flow battery combination electrode according to claim 5 is it is characterised in that described carbon fiber felt and carbon nanometer
The intermediate connector of pipe is pyrroles.
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| CN201610994009.8A CN106384831A (en) | 2016-11-11 | 2016-11-11 | All-vanadium redox flow battery composite electrode and preparation method thereof |
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| CN201610994009.8A CN106384831A (en) | 2016-11-11 | 2016-11-11 | All-vanadium redox flow battery composite electrode and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598513A (en) * | 2018-04-04 | 2018-09-28 | 苏州舒广袖新能源科技有限公司 | A kind of technology for preparing electrode used for all-vanadium redox flow battery based on high-performance |
| CN110890552A (en) * | 2018-09-07 | 2020-03-17 | 赛高创新株式会社 | Method for producing battery electrode, and battery electrode |
| CN114068959A (en) * | 2021-11-23 | 2022-02-18 | 成都先进金属材料产业技术研究院股份有限公司 | Method for improving activity of carbon fiber felt for vanadium battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101651201A (en) * | 2009-08-19 | 2010-02-17 | 湖南维邦新能源有限公司 | Electrode materials and all-vanadium redox flow battery containing electrode materials |
| CN102468492A (en) * | 2010-11-09 | 2012-05-23 | 中国科学院金属研究所 | Surface modification treatment method for increasing activity of vanadium battery electrode materials |
| CN103706387A (en) * | 2013-12-09 | 2014-04-09 | 吉林大学 | Non-noble metal doped carbon felt, and application in catalyzing oxygen reduction |
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2016
- 2016-11-11 CN CN201610994009.8A patent/CN106384831A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101651201A (en) * | 2009-08-19 | 2010-02-17 | 湖南维邦新能源有限公司 | Electrode materials and all-vanadium redox flow battery containing electrode materials |
| CN102468492A (en) * | 2010-11-09 | 2012-05-23 | 中国科学院金属研究所 | Surface modification treatment method for increasing activity of vanadium battery electrode materials |
| CN103706387A (en) * | 2013-12-09 | 2014-04-09 | 吉林大学 | Non-noble metal doped carbon felt, and application in catalyzing oxygen reduction |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598513A (en) * | 2018-04-04 | 2018-09-28 | 苏州舒广袖新能源科技有限公司 | A kind of technology for preparing electrode used for all-vanadium redox flow battery based on high-performance |
| CN110890552A (en) * | 2018-09-07 | 2020-03-17 | 赛高创新株式会社 | Method for producing battery electrode, and battery electrode |
| CN114068959A (en) * | 2021-11-23 | 2022-02-18 | 成都先进金属材料产业技术研究院股份有限公司 | Method for improving activity of carbon fiber felt for vanadium battery |
| CN114068959B (en) * | 2021-11-23 | 2023-10-27 | 成都先进金属材料产业技术研究院股份有限公司 | Method for improving activity of carbon fiber felt for vanadium battery |
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