CN110034305B - Activation method of graphite felt electrode material for iron-chromium flow battery - Google Patents
Activation method of graphite felt electrode material for iron-chromium flow battery Download PDFInfo
- Publication number
- CN110034305B CN110034305B CN201910184697.5A CN201910184697A CN110034305B CN 110034305 B CN110034305 B CN 110034305B CN 201910184697 A CN201910184697 A CN 201910184697A CN 110034305 B CN110034305 B CN 110034305B
- Authority
- CN
- China
- Prior art keywords
- graphite felt
- silica sol
- flow battery
- iron
- graphite
- 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.)
- Active
Links
Images
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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- 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
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8846—Impregnation
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
Landscapes
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
An activation method of graphite felt electrode material for iron-chromium flow battery is provided, which comprises immersing graphite felt in silica sol; and etching the graphite surface by using a thermal reduction method to obtain the graphite felt electrode for the modified iron-chromium redox flow battery, wherein the specific method comprises the following steps: 1) preparing silica sol: dropwise adding hydrochloric acid into sodium silicate, continuously stirring, adjusting the pH value of the solution to 2-4, and then standing for 1-2 hours to obtain uniform transparent sol with viscosity; 2) using deionized water to perform constant volume on the silica sol, and using ultrasonic waves to disperse for 30-50 min; 3) activation of the graphite felt: dipping the graphite felt subjected to cleaning pretreatment into the prepared silica sol, and ultrasonically dispersing for 30-50 min at the frequency of 1-100 kHz by using an ultrasonic cleaner; and (3) carrying out heat treatment for 5-15 h in a muffle furnace at 400-550 ℃ to prepare the activated graphite felt. Compared with the prior art, the invention has the beneficial effects that: the method is used for improving the electrochemical activity of the graphite felt electrode of the iron-chromium redox flow battery.
Description
Technical Field
The invention relates to the field of redox flow batteries, in particular to an activation method of a graphite felt electrode material for an iron-chromium flow battery.
Background
In recent years, wind energy and solar energy are widely developed and utilized, but both wind energy and solar energy are lack of large energy storage batteries with excellent performance to be matched with the wind energy and solar energy, so that the wind energy and solar energy cannot be efficiently utilized and applied. The iron-chromium redox flow battery has the advantages of energy and power separation, high energy efficiency, good safety, high reaction speed, long period and the like, and provides a more promising choice for large-scale energy storage.
The electrode, as a key component of an iron-chromium redox flow battery, plays an important role in determining the performance of the battery, since it not only provides active sites for the redox reaction, but also affects the transport of ions/protons within the porous structure. Graphite felt is commonly used as an electrode material for iron-chromium batteries due to its good electrical conductivity, corrosion resistance, large porosity and low cost. However, the graphite felt electrode has poor dynamic performance on the iron-chromium ion redox reaction, so that the performance of the iron-chromium battery is poor. Therefore, the modification research on the graphite felt electrode is of great significance.
Disclosure of Invention
The invention aims to provide an activation method of a graphite felt electrode material for a ferro-chromium flow battery, which is used for improving the electrochemical activity of the graphite felt electrode of the ferro-chromium redox flow battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
an activation method of graphite felt electrode material for iron-chromium flow battery is provided, which comprises immersing graphite felt in silica sol; and etching the graphite surface by using a thermal reduction method to obtain the graphite felt electrode for the modified iron-chromium redox flow battery, wherein the specific method comprises the following steps:
1) preparing silica sol: dropwise adding hydrochloric acid into sodium silicate, continuously stirring, adjusting the pH value of the solution to 2-4, and then standing for 1-2 hours to obtain uniform transparent sol with viscosity;
2) using deionized water to perform constant volume on the silica sol, and using ultrasonic waves to disperse for 30-50 min;
3) activation of the graphite felt: dipping the graphite felt subjected to cleaning pretreatment into the prepared silica sol, and ultrasonically dispersing for 30-50 min at the frequency of 1-100 kHz by using an ultrasonic cleaner; and (3) carrying out heat treatment for 5-15 h in a muffle furnace at 400-550 ℃ to prepare the activated graphite felt.
The hydrochloric acid in the step 1) is 2-6 mol/L dilute hydrochloric acid.
The adding amount of the deionized water in the step 2) is 7-8 times of the mass of the graphite felt.
The adding amount of the silica sol in the step 3) is less than or equal to 100% of the mass of the graphite felt.
Compared with the prior art, the invention has the beneficial effects that:
1) the iron-chromium redox flow battery adopting the graphite felt modified by the method of the invention as the electrode has the advantages of improved battery efficiency and reduced capacity loss, thereby improving the electrochemical performance of the iron-chromium redox flow battery and enhancing the stability.
2) The modification method of the graphite felt for the iron-chromium redox flow battery is more stable and cheaper, and the specific surface area of the graphite felt electrode can be increased by etching the graphite felt with the silica sol, so that the aim of improving the electrochemical activity of the graphite felt electrode is fulfilled.
3) At present, the method for modifying the graphite felt electrode of the iron-chromium oxidation flow battery mainly comprises the steps of increasing active functional groups, improving the effective reaction area and adding a surface catalyst. Compared with the prior art, the polyacrylonitrile-based graphite felt is used as a raw material, the active graphite felt electrode with a larger specific surface area is prepared through silica sol heat treatment, and the electrode material has good electrochemical activity and is more likely to be widely applied to iron-chromium redox flow batteries.
Drawings
FIG. 1 is a schematic diagram of the operation of the process for modifying a graphite felt of the present invention.
Detailed Description
The present invention will be described in detail below, but the scope of the present invention is not limited to the following embodiments.
An activation method of graphite felt electrode material for iron-chromium flow battery is provided, which comprises immersing graphite felt after cleaning pretreatment in silica sol; and etching the graphite surface by using a thermal reduction method to obtain the graphite felt electrode for the modified iron-chromium redox flow battery, wherein the specific method comprises the following steps:
firstly, cleaning and pretreating a graphite felt: firstly, putting the graphite felt into deionized water, and ultrasonically oscillating and cleaning the graphite felt for 40min at the frequency of 1-100 kHz by using a microwave cleaning instrument to remove insoluble impurities on the surface of the graphite felt and dissolve soluble impurities in water; and then placing the graphite felt in a 1-2 mol/L NaOH solution for soaking in a 70-90 ℃ water bath for 30-60 min to remove organic impurities, taking out the graphite felt, washing the graphite felt with deionized water for multiple times until the pH value is 6-8, and drying the graphite felt in a forced air drying oven at 70-90 ℃. However, the present invention is not limited thereto, and any method capable of cleaning the graphite felt may be used.
1) Preparing silica sol: dropwise adding hydrochloric acid into sodium silicate, continuously stirring, adjusting the pH value of the solution to 2-4, and then standing for 1-2 hours to obtain uniform transparent sol with viscosity; in order to ensure the pH value of the silica sol, the hydrochloric acid is dripped and then the mixture needs to be fully stirred, and then the pH value is measured;
2) using deionized water to perform constant volume on the silica sol, and using ultrasonic waves to disperse for 30-50 min;
3) activation of the graphite felt: dipping the graphite felt subjected to cleaning pretreatment into the prepared silica sol, and ultrasonically dispersing for 30-50 min at the frequency of 1-100 kHz by using an ultrasonic cleaner; and (3) carrying out heat treatment for 5-15 h in a muffle furnace at 400-550 ℃ to prepare the activated graphite felt.
The hydrochloric acid in the step 1) is 2-6 mol/L dilute hydrochloric acid.
The adding amount of the deionized water in the step 2) is 7-8 times of the mass of the graphite felt.
The adding amount of the silica sol in the step 3) is less than or equal to 100% of the mass of the graphite felt.
In order to ensure the linear relation between the addition amount and the activation effect, the silica sol should be uniformly prepared, and the shape and the size of the used graphite felt should be kept consistent and uniformly immersed in the silica sol.
The modified graphite felt of the invention is applied to an iron-chromium redox flow battery, which comprises: an electrode, a positive electrolyte, a negative electrolyte, a current collector, and an ion exchange membrane (Nafion 115). The electrode was a silica sol activated graphite felt. The positive and negative electrolyte is mixed electrolyte of ferrous chloride, chromium chloride and hydrochloric acid, and 1MFe can be adopted for both the positive and negative electrolytes2++1MCr3 ++3MHCl (where M is molar).
Example 1:
adding 25% of silica sol by mass of the graphite felt, adding deionized water into the silica sol to fix the volume to 50mL, and dispersing for 30min by using ultrasonic waves; dipping a graphite felt (5mm thick, 30mm multiplied by 30mm) after cleaning pretreatment into diluted silica sol, and ultrasonically dispersing for 30min at the frequency of 10kHz by using an ultrasonic cleaner; drying the impregnated graphite felt in a blast drying oven at 80 ℃ for 24h,and then placing the graphite felt electrode in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 5 hours to obtain the 25 wt% silica sol activated graphite felt electrode. Using the treated graphite felt as an electrode of an iron-chromium redox flow battery to assemble a single cell at 60-120mA/cm2The current density of the (A) was 60mA/cm2The charging capacity reaches 1240.9mAh, and is improved by 9.55 percent compared with the charging capacity of a single cell assembled by using the untreated graphite felt.
Example 2:
adding 50% of silica sol by mass of the graphite felt, adding deionized water into the silica sol to fix the volume to 50mL, and dispersing for 30min by using ultrasonic waves; dipping a graphite felt (5mm thick, 30mm multiplied by 30mm) after cleaning pretreatment into diluted silica sol, and ultrasonically dispersing for 30min at the frequency of 10kHz by using an ultrasonic cleaner; and drying the impregnated graphite felt in a blast drying oven at 80 ℃ for 24h, then placing the dried graphite felt in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 5h to obtain the 50 wt% silica sol activated graphite felt electrode. Using the treated graphite felt as an electrode of an iron-chromium redox flow battery to assemble a single cell at 60-120mA/cm2The current density of the graphite felt is 60mA/cm compared with a single cell assembled by untreated graphite felt2The hourly coulombic efficiency is improved by 3.78 percent, the voltage efficiency is improved by 2.97 percent, and the energy efficiency is improved by 6.09 percent; the current density is 120mA/cm2The time-voltage efficiency is improved by 12.55 percent, and the energy efficiency is improved by 11.74 percent.
Example 3:
adding silica sol in an amount of 75% of the mass of the graphite felt, adding deionized water into the silica sol to fix the volume to 50mL, and dispersing for 30min by using ultrasonic waves; dipping a graphite felt (5mm thick, 30mm multiplied by 30mm) after cleaning pretreatment into diluted silica sol, and ultrasonically dispersing for 30min at the frequency of 10kHz by using an ultrasonic cleaner; and (3) drying the impregnated graphite felt in a blast drying oven at 80 ℃ for 24h, then placing the dried graphite felt in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, and preserving heat for 5h to obtain the 75 wt% silica sol activated graphite felt electrode. The treated graphite felt is used as an electrode of an iron-chromium redox flow battery to assemble a single battery at 60-120mA/cm2The capacity retention rate after 20 charge-discharge cycles is 31.37% higher than that of a single cell assembled by using an untreated graphite felt.
Example 4:
adding the silica sol into the graphite felt in an amount of 100% by mass, adding deionized water into the silica sol to fix the volume to 50mL, and dispersing for 30min by using ultrasonic waves; dipping a graphite felt (5mm thick, 30mm multiplied by 30mm) after cleaning pretreatment into diluted silica sol, and ultrasonically dispersing for 30min at the frequency of 10kHz by using an ultrasonic cleaner; and (3) drying the impregnated graphite felt in a blast drying oven at 80 ℃ for 24h, then placing the dried graphite felt in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min, and preserving heat for 5h to obtain the 100 wt% silica sol activated graphite felt electrode. Using the treated graphite felt as an electrode of an iron-chromium redox flow battery to assemble a single cell at 60-120mA/cm2The current density of the graphite felt is 60mA/cm compared with a single cell assembled by untreated graphite felt2The hourly coulomb efficiency is improved by 5.16 percent, and the energy efficiency is improved by 2.25 percent.
In conclusion, the modified graphite felt electrode for the iron-chromium redox flow battery prepared by the method has the advantages of improved electrochemical activity and reduced electrochemical polarization, and the coulombic efficiency, the voltage efficiency and the energy efficiency of the iron-chromium redox flow battery are highest when the addition amount of the silica sol is 50% of the mass of the graphite felt.
While the present invention has been described above in connection with exemplary embodiments, it will be apparent to those of ordinary skill in the art that various modifications may be made to the above-described embodiments without departing from the spirit and scope of the claims.
Claims (2)
1. A method for activating a graphite felt electrode material for an iron-chromium flow battery is characterized in that the method comprises the steps of immersing a graphite felt in silica sol; and etching the graphite surface by using a thermal reduction method to obtain the graphite felt electrode for the modified iron-chromium redox flow battery, wherein the specific method comprises the following steps:
1) preparing silica sol: dropwise adding hydrochloric acid into sodium silicate, continuously stirring, adjusting the pH value of the solution to 2-4, and then standing for 1-2 hours to obtain uniform transparent sol with viscosity;
2) using deionized water to perform constant volume on the silica sol, and using ultrasonic waves to disperse for 30-50 min;
3) activation of the graphite felt: dipping the graphite felt subjected to cleaning pretreatment into the prepared silica sol, and ultrasonically dispersing for 30-50 min at the frequency of 1-100 kHz by using an ultrasonic cleaner; carrying out heat treatment for 5-15 h in a muffle furnace at 400-550 ℃ to prepare an active graphite felt;
the hydrochloric acid in the step 1) is 2-6 mol/L dilute hydrochloric acid;
the adding amount of the deionized water in the step 2) is 7-8 times of the mass of the graphite felt.
2. The method for activating the graphite felt electrode material for the ferrochrome flow battery as claimed in claim 1, wherein the amount of the silica sol added in the step 3) is not more than 100% by mass of the graphite felt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910184697.5A CN110034305B (en) | 2019-03-12 | 2019-03-12 | Activation method of graphite felt electrode material for iron-chromium flow battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910184697.5A CN110034305B (en) | 2019-03-12 | 2019-03-12 | Activation method of graphite felt electrode material for iron-chromium flow battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110034305A CN110034305A (en) | 2019-07-19 |
| CN110034305B true CN110034305B (en) | 2022-03-04 |
Family
ID=67235899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910184697.5A Active CN110034305B (en) | 2019-03-12 | 2019-03-12 | Activation method of graphite felt electrode material for iron-chromium flow battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110034305B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111740121A (en) * | 2020-07-03 | 2020-10-02 | 朱义奎 | Silicon doping modification method for graphite felt electrode material of vanadium battery |
| CN114744223B (en) * | 2022-05-06 | 2024-01-26 | 湖北理工学院 | Iron-chromium redox flow battery electrode material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102024954A (en) * | 2009-09-16 | 2011-04-20 | 比亚迪股份有限公司 | Graphite felt electrode of vanadium battery and preparation method thereof and vanadium battery comprising the electrode |
| CN104179002A (en) * | 2014-08-14 | 2014-12-03 | 陕西科技大学 | Preparation method of carbon cloth with nanoparticle modified surface |
| CN104987100A (en) * | 2015-07-08 | 2015-10-21 | 赵丽丽 | Infrared reflecting heat-preservation carbon felt manufactured through sol-gel method and application thereof |
| CN107221681A (en) * | 2017-06-14 | 2017-09-29 | 北京航空航天大学 | It is a kind of applied to modified electrode of all-vanadium flow battery and preparation method thereof |
-
2019
- 2019-03-12 CN CN201910184697.5A patent/CN110034305B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102024954A (en) * | 2009-09-16 | 2011-04-20 | 比亚迪股份有限公司 | Graphite felt electrode of vanadium battery and preparation method thereof and vanadium battery comprising the electrode |
| CN104179002A (en) * | 2014-08-14 | 2014-12-03 | 陕西科技大学 | Preparation method of carbon cloth with nanoparticle modified surface |
| CN104987100A (en) * | 2015-07-08 | 2015-10-21 | 赵丽丽 | Infrared reflecting heat-preservation carbon felt manufactured through sol-gel method and application thereof |
| CN107221681A (en) * | 2017-06-14 | 2017-09-29 | 北京航空航天大学 | It is a kind of applied to modified electrode of all-vanadium flow battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 钒电池电极材料和复合电极的研究进展;许茜等;《电源技术》;20081220;第32卷(第12期);第824页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110034305A (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742658B (en) | The preparation method of electrode material for all-vanadium flow battery | |
| CN109546163B (en) | Modification method of graphite felt electrode for organic flow battery | |
| CN105529471A (en) | Treatment method for all-vanadium redox flow battery electrode | |
| CN111244485B (en) | Preparation method of high-energy-density low-cost zinc-iron flow battery | |
| CN111244489B (en) | Application of electrode material in zinc-bromine single flow battery | |
| CN103441246A (en) | Preparation method and application of three-dimensional nitrogen-doped graphene base tin dioxide composite material | |
| CN101465417A (en) | Electrochemical treatment method for improving vanadium cell electrode material activity | |
| CN110034305B (en) | Activation method of graphite felt electrode material for iron-chromium flow battery | |
| CN111740126A (en) | Chemical doping modification method for graphite felt electrode material of vanadium battery | |
| CN116435567A (en) | Alkaline all-iron flow battery and preparation method of electrode material | |
| CN114497660B (en) | Application of complexing agent in zinc-bromine storage battery electrolyte | |
| TWI635648B (en) | Method of optimizing flow battery with carbon electrode | |
| CN112768705A (en) | Sectional type electrode for liquid-liquid type eutectic solvent electrolyte flow battery | |
| CN117080462A (en) | Graphite felt negative electrode of iron-chromium flow battery and modification method thereof | |
| CN116759589A (en) | Preparation method of high-activity electrode for iron-chromium flow battery | |
| CN114744223B (en) | Iron-chromium redox flow battery electrode material and preparation method thereof | |
| CN105702977A (en) | Bromine electrode for bromine hydride energy storage battery and preparation method of bromine electrode | |
| CN109256561A (en) | Hard carbon cathode material and preparation method thereof and the method for making battery using it | |
| CN108365189A (en) | A kind of preparation method of metal sulfide@carbon fibre composite anode material of lithium-ion batteries | |
| CN111180774B (en) | Preparation method of neutral iron-sulfur double-flow battery | |
| CN108539211B (en) | Preparation method of fluoride salt modified multifunctional electrode material for vanadium battery | |
| CN113054204A (en) | Graphite felt electrode for alkaline organic flow battery and modification method | |
| CN104485461A (en) | Low-cost functionalized carbon felt preparation method | |
| CN110718708A (en) | Variable porosity electrode structure flow battery capable of improving battery efficiency | |
| CN117913301B (en) | Method for modifying battery carbon cloth electrode by metal carbide nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |