CN103268946A - Flow battery graphite felt electrode sintering modification treatment method - Google Patents
Flow battery graphite felt electrode sintering modification treatment method Download PDFInfo
- Publication number
- CN103268946A CN103268946A CN2013102162805A CN201310216280A CN103268946A CN 103268946 A CN103268946 A CN 103268946A CN 2013102162805 A CN2013102162805 A CN 2013102162805A CN 201310216280 A CN201310216280 A CN 201310216280A CN 103268946 A CN103268946 A CN 103268946A
- Authority
- CN
- China
- Prior art keywords
- graphite felt
- felt electrode
- microwave
- flow battery
- electrode
- 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.)
- Pending
Links
Images
Classifications
-
- 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
Abstract
The invention discloses a flow battery graphite felt electrode sintering modification treatment method. After the surface of a graphite felt electrode is cleaned, the graphite felt electrode is put in a microwave center in a microwave sintering oven and is subjected to microwave heating treatment. The treatment temperature is 300-500 DEG C, and the heating treatment time is 5-30 minutes. The flow battery graphite felt electrode sintering modification treatment method has the beneficial effects that the electrochemical activity of the graphite felt electrode can be improved, the treatment time can be greatly shortened, and the cost is reduced. The invention is a novel surface modification method for improving the electrochemical activity of the graphite felt electrode.
Description
Technical field
The invention belongs to the battery technology field, relate in particular to hydrogen-oxidation-reduction pair flow battery.
Background technology
Hydrogen-oxidation-reduction pair flow battery is a kind of novel flow battery, different as both positive and negative polarity electrode reaction active material by the metal ion that is dissolved in the different valence state in the finite concentration sulfuric acid solution with traditional flow battery, hydrogen-oxidation-reduction pair flow battery negative pole is the platinum carbon electrode, and the hydrogen in the platinum carbon electrode Catalytic Layer under catalyst action electrode reaction takes place.Be separated into two Room (side of the positive electrode and negative side) that are mutually independent with amberplex between the battery plus-negative plate, anodal electrolyte is forced to circulate by reative cell by liquid-feeding pump when battery operated, participates in electrochemical reaction.The reaction that takes place on the electrode is as follows:
Anodal: M
O N++ xe
-→ M
R M+
Negative pole: H
2→ 2H
++ 2e
-
Positive active material M is fluid liquid oxidation-reduction pair such as VO
2+/ VO
2 +, Fe
3+/ Fe
2+, Ce
4+/ Ce
3+Deng sulfuric acid solution.This novel flow battery is except having, and traditional flow battery self discharge efficient is low, long service life, be convenient to safeguard, the characteristics such as but the no cross pollution degree of depth is put, because both positive and negative polarity all adopts reversible electrode, the right energy-storage battery of hydrogen-metal electricity can discharge and recharge near under the thermodynamical equilibrium current potential, solved traditional electrode of liquid flow cell irreversible bring exceed potential loss, be expected to solve the deficiency that present energy storage technology exists.
Though hydrogen-oxidation-reduction pair flow battery has significant advantage than traditional flow battery, but its anodal reaction is identical with traditional flow battery, still equally with traditional flow battery face many problems that wait to solve, such as, how to screen the barrier film with good selection permeability, and how to obtain good stability, resistivity is low, electro-chemical activity is good electrode etc.Wherein, electrode still is the key that determines whole hydrogen-oxidation-reduction pair flow battery performance quality.
In the prior art, best flow battery anode electrode is graphite felt.Graphite felt need increase it by suitable pre-treatment to the redox reaction catalytic action of flow battery.Method commonly used is: heat treatment, concentrated sulfuric acid processing, chemical oxidation treatment etc.The deficiencies in the prior art are:
Though conventional heat treating process technology is simple, operating flexibility is less, and energy consumption is big, and oxidation reaction is wayward.And traditional carbonization, the heating mode in the activation method are that heat passes to inside by the surface by heat conduction heating.This heat transfer type reaches heat balance needs the long time, and thermal loss is big, and power consumption is high;
It is the concentrated sulfuric acid that the concentrated sulfuric acid is handled the inorganic agent that is to use, and very dangerous, the suitability for industrialized production difficulty is big; The time that electrochemical oxidation method for treating is handled is long, during consumption energy consumption.
Summary of the invention
The purpose of this invention is to provide a kind of energy-conservation flow battery anode electrode graphite felt pre-treating method, overcome the deficiencies in the prior art.
Basic ideas of the present invention are: utilize microwave heating to come treatment fluid galvanic battery anode electrode graphite felt, it is approximate instant that the microwave heating energy changes the required time, can reach the purpose of Fast Heating, the heat leakage of having avoided long-time heating to cause is a kind of energy-conservation mode of heating.
Technical scheme of the present invention is: a kind of flow battery graphite felt electrode sintering modification processing method, comprise heat treatment method, it is characterized in that: described heat treatment method is to be placed on after the graphite felt electrode surface is cleaned out to use microwave heating treatment in the microwave agglomerating furnace.
A kind of flow battery graphite felt electrode sintering modification processing method of the present invention, it is characterized in that: described being placed on after the graphite felt electrode surface is cleaned out used microwave heating treatment in the microwave agglomerating furnace, be the microwave center heat treated that the graphite felt electrode centers is placed microwave agglomerating furnace.
A kind of flow battery graphite felt electrode sintering modification processing method of the present invention, it is characterized in that: the described microwave center that the graphite felt electrode centers is placed microwave agglomerating furnace, be that the graphite felt electrode is placed silicon carbide crucible in the microwave agglomerating furnace, silicon carbide crucible external application heat-preservation cotton parcel, silicon carbide crucible places the microwave center heat treated of microwave agglomerating furnace.
A kind of flow battery graphite felt electrode sintering modification processing method of the present invention, it is characterized in that: the temperature of described microwave heating treatment is 300 ℃-500 ℃, and the heat treated time is 5-30min.
In the microwave heating process, the oxidative degradation of graphite felt fiber surface generation decarboxylic reaction and aliphatic chain, make the graphite felt fiber produce the decomposition oxygen evolution reaction of spot corrosion and water, produce " oxidation is peeled off " effect and make the graphite felt fiber surface sheet occur to degrade, the sheet of graphite felt fiber surface is degraded phenomenon and is aggravated with prolonging heating time.After the microwave heating treatment, the content of the functional group that is of value to electrochemical reaction on graphite felt surface increases to some extent, can improve graphite felt electrode electro Chemical activity.
The invention has the beneficial effects as follows: graphite felt electrode processing method of the present invention, can improve graphite felt electrode electro Chemical activity, can shorten the processing time greatly, reduce cost, be the surface modifying method that a kind of novel graphite felt electrode improves electro-chemical activity.
Description of drawings
Fig. 1 is the graphite felt surface SEM scintigram that conventional heat treatment method is handled
Fig. 2 is the graphite felt surface SEM scintigram of microwave thermal disposal methods
Fig. 3 is the cyclic voltammetric comparison diagram of conventional heat treatment process method the graphite felt electrode of handling and the graphite felt electrode of using the microwave thermal disposal methods
Fig. 4 is the charge-discharge performance comparison diagram of the graphite felt electrode of the graphite felt electrode handled of conventional heat treatment method and microwave thermal disposal methods
Among Fig. 3, solid line is represented the cyclic voltammetry curve with the graphite felt electrode of conventional heat treatment method processing, dotted line is represented the cyclic voltammetry curve with the graphite felt electrode of microwave thermal disposal methods of the present invention, among Fig. 4, the square dot curve is the discharge performance curve with the graphite felt electrode of microwave thermal disposal methods, the Diamond spot curve is the charging performance curve with the graphite felt electrode of microwave thermal disposal methods, the equilateral triangle point curve is the discharge performance curve of the graphite felt electrode of conventional heat treatment method processing, and the del point curve is the discharge performance curve of the graphite felt electrode of conventional heat treatment method processing.
Embodiment
Below in conjunction with embodiment the present invention will be further described book.
After the graphite felt removing surface of the thick 4*7 square centimeter of 3mm is clean, put into the silicon carbide crucible of microwave agglomerating furnace, silicon carbide crucible external application heat-preservation cotton parcel, silicon carbide crucible is in the microwave center of microwave agglomerating furnace; Close fire door, and make oven door sealing, prevent microwave leakage; Setting microwave heating temperature is 400 ℃, and be 15min heating time, connects the power supply heat treated, takes out by setting heating-up temperature and the intact back of heat treated heating time, obtains the graphite felt through the microwave heating modification.
The graphite felt that this Microwave Treatment is crossed is cut into each a slice of graphite felt electrode of 0.3*1*7 cubic centimetre and 0.3*3*4 cubic centimetre, and the same graphite felt electrode that other gets conventional heat treatment 30 hours carries out the performance comparison test:
Do the cyclic voltammetric test with 0.3*1*7 cubic centimetre electrode, with 0.3*1*7 cubic centimetre electrode paraffin approved sample, be of a size of the 0.3*1*1 cubic centimetre, classical three-electrode system is adopted in the cyclic voltammetric test, with the Pt sheet as to electrode, saturated calomel electrode is as reference electrode, and the graphite felt behind the approved sample connects reference electrode and work electrode as work electrode with the salt bridge that has Luggin capillary.Cyclic voltammetry scan speed is 2mV/s, and the scanning voltage scope is 0～1.6V.Test result such as Fig. 3, test result shows that oxidation peak, the reduction peak current density of conventional heat treatment graphite felt electrode are respectively 62mA/cm
2, 46mA/cm
2Graphite felt anodizing peak, reduction peak current density that heated by microwave is handled are 120mA/cm
2, 82mA/cm
2, all handle the graphite felt electrode greater than conventional heat treating process, data analysis as can be known: the electrochemical reaction rates of the graphite felt electrode that heated by microwave is handled is faster, compares with conventional heat treatment graphite felt and has embodied better dynamic performance.
To the flow battery monocell, carry out the charge-discharge performance test with 0.3*3*4 cubic centimetre graphite felt electrode assembling hydrogen-metal electricity at ambient temperature, electrolyte is 0.5mol/LVOSO
4With 3mol/LH
2SO
4Mixed solution, adopt Nafion212 film separate batteries positive and negative polarities, relatively the charge-discharge performance of two kinds of electrodes.Test result shows: under same current density, the graphite felt electrode discharge voltage that the graphite felt electrode that the microwave heating treatment method is handled is handled than conventional heat treatment method is higher, charging voltage is lower, and the graphite felt electrode performance that the microwave heating treatment method is handled obviously is better than the graphite felt electrode performance that conventional heat treatment method is handled.
By in the SEM scintigram of conventional heat treatment graphite felt and microwave heating treatment graphite felt surface as can be seen: have through the heat treated graphite felt of routine surface that some are tiny, be parallel to fiber axis to defectives such as etching, groove.And the aggravation of the graphite felt surface etch of microwave heating treatment, groove deepens.
Claims (4)
1. a flow battery graphite felt electrode sintering modification processing method comprises heat treatment method, it is characterized in that: described heat treatment method is to be placed on after the graphite felt electrode surface is cleaned out to use microwave heating treatment in the microwave agglomerating furnace.
2. according to the described a kind of flow battery graphite felt electrode sintering modification processing method of claim 1, it is characterized in that: described being placed on after the graphite felt electrode surface is cleaned out used microwave heating treatment in the microwave agglomerating furnace, be the microwave center heat treated that the graphite felt electrode centers is placed microwave agglomerating furnace.
3. according to the described a kind of flow battery graphite felt electrode sintering modification processing method of claim 2, it is characterized in that: the described microwave center heat treated that the graphite felt electrode centers is placed microwave agglomerating furnace, be that the graphite felt electrode is placed silicon carbide crucible in the microwave agglomerating furnace, silicon carbide crucible external application heat-preservation cotton parcel, silicon carbide crucible places the microwave center heat treated of microwave agglomerating furnace.
4. according to the described a kind of flow battery graphite felt electrode sintering modification processing method of claim 3, it is characterized in that: the temperature of described microwave heating treatment is 300 ℃-500 ℃, and the heat treated time is 5-30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102162805A CN103268946A (en) | 2013-06-03 | 2013-06-03 | Flow battery graphite felt electrode sintering modification treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102162805A CN103268946A (en) | 2013-06-03 | 2013-06-03 | Flow battery graphite felt electrode sintering modification treatment method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103268946A true CN103268946A (en) | 2013-08-28 |
Family
ID=49012563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013102162805A Pending CN103268946A (en) | 2013-06-03 | 2013-06-03 | Flow battery graphite felt electrode sintering modification treatment method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103268946A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108432022A (en) * | 2016-01-07 | 2018-08-21 | 住友电气工业株式会社 | Redox flow batteries, the electrode of redox flow batteries and electrode characteristic appraisal procedure |
| CN108615885A (en) * | 2018-04-03 | 2018-10-02 | 华东师范大学 | A kind of graphite felt treatment process |
| CN109921036A (en) * | 2019-02-26 | 2019-06-21 | 天津大学 | A kind of pre-treating method of TEMPO/MV flow battery combination electrode |
| CN116742018A (en) * | 2023-08-14 | 2023-09-12 | 保定市数果信息技术有限公司 | Graphite felt electrode modification treatment device of flow battery and implementation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005001965A1 (en) * | 2003-06-30 | 2005-01-06 | Tdk Corporation | Carbon material for electrode and method for producing same, battery electrode and method for producing same, and battery and method for producing same |
| CN102136579A (en) * | 2011-01-30 | 2011-07-27 | 国网电力科学研究院武汉南瑞有限责任公司 | Modified method of graphite felt used for full-vanadium fluid flow battery electrode |
| CN102270761A (en) * | 2010-06-03 | 2011-12-07 | 上海空间电源研究所 | Method for making integrated flexible organic free radical electrode |
| CN102723502A (en) * | 2011-06-01 | 2012-10-10 | 中国科学院金属研究所 | Surface modification method for raising activity of electrode material of vanadium cell |
-
2013
- 2013-06-03 CN CN2013102162805A patent/CN103268946A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005001965A1 (en) * | 2003-06-30 | 2005-01-06 | Tdk Corporation | Carbon material for electrode and method for producing same, battery electrode and method for producing same, and battery and method for producing same |
| CN102270761A (en) * | 2010-06-03 | 2011-12-07 | 上海空间电源研究所 | Method for making integrated flexible organic free radical electrode |
| CN102136579A (en) * | 2011-01-30 | 2011-07-27 | 国网电力科学研究院武汉南瑞有限责任公司 | Modified method of graphite felt used for full-vanadium fluid flow battery electrode |
| CN102723502A (en) * | 2011-06-01 | 2012-10-10 | 中国科学院金属研究所 | Surface modification method for raising activity of electrode material of vanadium cell |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108432022A (en) * | 2016-01-07 | 2018-08-21 | 住友电气工业株式会社 | Redox flow batteries, the electrode of redox flow batteries and electrode characteristic appraisal procedure |
| CN108615885A (en) * | 2018-04-03 | 2018-10-02 | 华东师范大学 | A kind of graphite felt treatment process |
| CN109921036A (en) * | 2019-02-26 | 2019-06-21 | 天津大学 | A kind of pre-treating method of TEMPO/MV flow battery combination electrode |
| CN109921036B (en) * | 2019-02-26 | 2021-11-23 | 天津大学 | Pretreatment method of composite electrode for TEMPO/MV flow battery |
| CN116742018A (en) * | 2023-08-14 | 2023-09-12 | 保定市数果信息技术有限公司 | Graphite felt electrode modification treatment device of flow battery and implementation method thereof |
| CN116742018B (en) * | 2023-08-14 | 2024-04-09 | 保定市数果信息技术有限公司 | Graphite felt electrode modification treatment device of flow battery and implementation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Agar et al. | Identification of performance limiting electrode using asymmetric cell configuration in vanadium redox flow batteries | |
| Zhipeng et al. | Cerium-zinc redox flow battery: Positive half-cell electrolyte studies | |
| Men et al. | Carbon felts electrode treated in different weak acid solutions through electrochemical oxidation method for all vanadium redox flow battery | |
| CN103887524A (en) | Modified treatment method of positive electrode graphite felt electrode of all-vanadium redox flow battery | |
| CN101465417A (en) | Electrochemical treatment method for improving vanadium cell electrode material activity | |
| CN111244489B (en) | Application of electrode material in zinc-bromine single flow battery | |
| CN104716392A (en) | Flow cell structure | |
| CN103268946A (en) | Flow battery graphite felt electrode sintering modification treatment method | |
| CN107967997A (en) | A kind of three-dimensional high heat-conductivity conducting composite material, its preparation method and application | |
| CN108054390A (en) | A kind of method of modifying of efficiently and effectively graphite felt for vanadium cell | |
| CN111244485B (en) | Preparation method of high-energy-density low-cost zinc-iron flow battery | |
| CN105609796A (en) | Modification method of electrode material for all-vanadium redox flow battery | |
| CN103296285A (en) | Lead dioxide modified graphite felt electrode of all-vanadium redox flow battery and preparation method thereof | |
| CN104716338B (en) | Processing method of electrode used for liquid flow cell | |
| CN105322186B (en) | A kind of method for reducing all-vanadium flow battery activation polarization | |
| CN113258114A (en) | Stable and high-capacity neutral aqueous liquid flow lithium battery based on redox targeting reaction | |
| Zarei-Jelyani et al. | Investigation of hydroxylated carbon felt electrode in vanadium redox flow battery by using optimized supporting electrolyte | |
| CN101859903B (en) | Carbon electrode material treating agent and method for treating electrode materials by using same | |
| CN110034305B (en) | Activation method of graphite felt electrode material for iron-chromium flow battery | |
| CN105322207A (en) | Phosphorous heteropoly acid all-vanadium redox flow battery positive electrolyte and application thereof | |
| CN110938856A (en) | Novel anodic oxidation process of nickel-based thin film energy storage material | |
| CN110556560A (en) | Catechol positive electrode electrolyte and application thereof in flow battery | |
| Hung et al. | Effects of current scan rate on the polarization curve of vanadium redox flow batteries | |
| CN109904468B (en) | Preparation method of bacteria modified carbon electrode | |
| CN105322194A (en) | Multifunctional negative material and application thereof in all-vanadium redox flow battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130828 |