CN115472849A - Preparation method of composite carbon felt electrode of all-vanadium redox flow battery - Google Patents
Preparation method of composite carbon felt electrode of all-vanadium redox flow battery Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
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- 229910017604 nitric acid Inorganic materials 0.000 claims 1
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
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- 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
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Abstract
A preparation method of a composite carbon felt electrode of an all-vanadium redox flow battery comprises the following steps: firstly taking Bi 2 S 3 Chemicals, then adding the Bi 2 S 3 Grinding and drying chemicals for later use; adding Bi 2 S 3 Uniformly coating the powder on a carbon felt electrode; putting the coated carbon felt electrode into a prepared alkaline electrolyte, and performing constant-pressure electrochemical desulfurization on Bi 2 S 3 Converting into a Bi simple substance; taking down the desulfurized carbon felt electrode, firstly carrying out acid washing neutralization, and then washing; and (3) putting the cleaned carbon felt electrode into a vacuum drying box for drying, and obtaining a finished product of the composite carbon felt electrode after vacuum drying. The invention adjusts the light weight of the metal sulfideThe content of the produced metal simple substance is conveniently regulated and controlled, and the composite electrode with low metal catalyst content is prepared. The voltage efficiency and the energy efficiency of the all-vanadium redox flow battery can be effectively improved by adjusting and controlling the interface reaction of the modified electrode. The process method is simple and feasible, and can be popularized and applied to other flow battery systems.
Description
Technical Field
The invention is applied to the technical field of energy storage of flow batteries, and particularly provides a preparation method of a composite carbon felt electrode of an all-vanadium flow battery.
Background
In recent years, with the increasing development of economy, the increasing demand for energy and the shortage of energy form a huge contradiction, and the transformation of an energy structure from thermal power generation to renewable energy sources such as wind energy and solar energy is urgent. Due to the characteristics of intermittency, randomness and the like of power generation of renewable energy sources such as wind energy, solar energy and the like, the power generation system is combined into a power grid on a large scale, and serious impact is brought to the safe and stable operation of the power grid. Therefore, a large-scale energy storage technology, especially an energy storage technology with safe and long-term operation, is urgently needed to realize peak regulation and valley leveling of a power grid, so as to improve the consumption capacity of the power grid for power generation of renewable energy sources, practically and effectively adjust an energy structure, and assist in achieving the goals of carbon peak reaching and carbon neutralization.
The flow battery is considered to be used for large-scale energy storage due to the characteristics of flexible system structure design, independent design of power density and battery capacity, high safety, long service life, large-current operation and the like. The all-vanadium flow battery system is the most mature and commercialized battery system in the flow batteries, and is considered to be used for solving the problems of unstable and uncertain energy production of renewable energy sources such as wind energy, solar energy and the like.
The electrode is one of the most critical components in the flow battery, and plays an important role in providing an oxidation-reduction reaction interface for positive and negative active materials. Based on this, it is required that the electrode has the characteristics of high conductivity, high electrochemical activity, high porosity, corrosion resistance and the like. The electrode material of flow batteries is typically graphite felt because of its relatively low cost, high corrosion resistance, and relatively high electrical conductivity. However, graphite felts produced by manufacturers suffer from low electrochemical activity and poor reaction kinetics, which limit the efficiency of flow batteries and increase the overall battery cost.
Disclosure of Invention
The invention provides a preparation method of a composite carbon felt electrode of an all-vanadium flow battery, aiming at solving the problems of low electrochemical activity and poor reaction kinetics of the electrode in the all-vanadium flow battery. The process method is simple and easy to implement, has low cost, and can be popularized and applied to other flow battery systems.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the preparation method of the composite carbon felt electrode of the all-vanadium redox flow battery is characterized by comprising the following steps of: the method comprises the following steps:
1) Firstly weighing a certain amount of Bi 2 S 3 Chemicals, then adding the Bi 2 S 3 Grinding and drying chemicals for later use;
2) Taking out a certain amount of dried Bi 2 S 3 Uniformly coating the powder on a carbon felt electrode;
3) Preparing an alkaline solution as an electrolyte solution,
4) Placing the coated carbon felt electrode in alkaline electrolyte, and performing constant-pressure electrochemical desulfurization on Bi 2 S 3 Converting into a Bi simple substance;
5) Taking down the desulfurized carbon felt electrode, firstly carrying out acid washing neutralization, and then washing the carbon felt electrode clean by deionized water;
6) And (3) putting the cleaned carbon felt electrode into a vacuum drying box for drying, and obtaining a finished product of the composite carbon felt electrode after vacuum drying.
Preferably, step 1) is specifically: weighing a certain amount of Bi by using a weighing balance 2 S 3 Chemical compound of Bi 2 S 3 Grinding and drying chemicals: the Bi 2 S 3 The purity of the chemical is more than or equal to 99 percent, and the Bi 2 S 3 Grinding the chemicals to 1000-3000 meshes; then grinding the Bi 2 S 3 Drying the chemical at room temperatureDrying for 3-6 hours at 100-120 ℃.
Preferably, step 2) is specifically: taking out the dried Bi 2 S 3 Uniformly coating the powder on a carbon felt electrode: bi 2 S 3 The amount of the chemicals is 0.1-0.2 weight part of the carbon felt electrode;
preferably, step 3) is specifically: preparing an alkaline solution as an electrolyte; preparing alkaline solution with pH value of 10-14 and alkaline electrolyte with KOH or NaOH as ion source;
preferably, step 4) is specifically: the coated electrode is put in electrolyte, and Bi is removed by a constant-pressure electrochemical desulfurization method 2 S 3 Conversion to elemental Bi: the method adopts a double-electrode system, takes untreated carbon felt as a working electrode, a Pt electrode as a counter electrode and KOH solution (PH is 10-14) as supporting electrolyte, and carries out electrochemical reduction by using an electrochemical desulfurization method, wherein the voltage is set as constant voltage.
Preferably, step 5) is specifically: taking down the carbon felt electrode after the electric desulfurization, firstly carrying out acid washing, and then washing with deionized water: and (3) washing KOH residues on the carbon felt electrode by using 1-3 mol/L hydrochloric acid, and then washing the whole carbon felt by using water.
Preferably, step 6) is specifically: putting the cleaned carbon felt electrode into a vacuum drying box for drying: setting the vacuum degree of a drying oven at-0.1-0 Kpa, setting the temperature at 90-110 ℃, and putting the carbon felt into the drying oven to dry for 3-5 hours to obtain the modified composite carbon felt electrode.
The invention has the beneficial effects that: the surface of the carbon felt electrode is coated with a layer of metal sulfide powder, and a constant voltage is applied to break the chemical bond between metal and sulfur by utilizing electrons, so that the process of converting solid-phase metal sulfide into solid-phase simple substance is realized. The method can easily and conveniently regulate the content of the produced metal simple substance by regulating the amount of the metal sulfide, and prepare the composite electrode with low metal catalyst content. The voltage efficiency and the energy efficiency of the all-vanadium redox flow battery can be effectively improved by regulating and controlling the interface reaction of the modified electrode. The process method is simple and feasible, and can be popularized and applied to other flow battery systems.
Drawings
FIG. 1 is a schematic diagram of an all-vanadium redox flow battery according to the present invention; this figure 1 mainly comprises: the device comprises a positive electrolyte storage tank 1, a negative electrolyte storage tank 2, a flow battery diaphragm 3, a positive electrode 4, a negative electrode 5, a positive end plate 6, a negative end plate 7, a positive pump 8 and a negative pump 9.
FIG. 2 (a) is a carbon felt contact angle test chart before process treatment; fig. 2 (b) is a contact angle test chart after bismuth is added.
FIG. 3 (a) is an electron microscope image of a carbon felt before process treatment; fig. 3 (b) is a microscopic electron microscope image of the modified carbon felt.
Fig. 4 is a schematic diagram of energy efficiency in rate performance tests with current densities from 200-400 after assembly of an all vanadium flow battery with electrodes modified by examples of the invention.
Fig. 5 is a schematic diagram of voltage efficiency in rate capability tests at current densities from 200-400 after assembly of an all vanadium flow battery with electrodes modified by examples of the invention.
Detailed Description
As shown in fig. 1, the all-vanadium redox flow battery of the present invention mainly comprises: the structure of the liquid storage tank comprises an anode electrolyte storage tank 1, a cathode electrolyte storage tank 2, a flow battery diaphragm 3, an anode electrode 4, a cathode electrode 5, an anode end plate 6, a cathode end plate 7, an anode pump 8 and a cathode pump 9, and the liquid storage tank is as follows:
the bottom of the positive electrolyte storage tank 1 is connected with the lower part of the positive electrode 4 through a positive pump 8 on the pipeline, the top of the positive electrolyte storage tank 1 is connected with the upper part of the positive electrode 4 through the pipeline, and a positive end plate 6 is arranged on the outer side of the positive electrode 4 to form the positive part of the flow battery. The bottom of the negative electrolyte storage tank 2 is connected with the lower part of the negative electrode 5 through a negative pump 9 on the pipeline, the top of the negative electrolyte storage tank 2 is connected with the upper part of the negative electrode 5 through the pipeline, and a negative end plate 7 is arranged on the outer side of the negative electrode 5 to form the positive part of the flow battery. The positive electrode 4 and the negative electrode 5 are vertically arranged in parallel relatively, and the positive electrode 4 and the negative electrode 5 are separated by the flow battery diaphragm 3. The invention is arranged in the cathode 4 of the redox flow battery and is used in the all-vanadium redox flow batteryThe modified electrode and the positive electrode still use untreated raw felt as the electrode. The carbon felt electrode has a very large active area, and the areas of the carbon felt electrodes used in the all-vanadium flow battery are all 2 multiplied by 2 cm 2 The battery diaphragm adopts a commercial Nafion proton exchange membrane commonly used for the flow battery, and the area of the proton exchange membrane is 2 multiplied by 2 cm 2 And clamping each component by using aluminum alloy end plates (a positive end plate 6 and a negative end plate 7), wherein the reaction equations of the positive and negative electrodes during charging are shown as the following (1) and (2);
and (3) positive electrode:
(1)
negative electrode:
(2)
other advantages and capabilities of the present invention will be apparent to those skilled in the art from the present disclosure by describing the embodiments of the present invention with specific examples. The invention is capable of other and different embodiments and of being practiced or of being utilized, and various details within the specification may be modified or changed in various respects, all without departing from the spirit of the invention.
Example 1
The embodiment provides a preparation method of a composite carbon felt electrode of an all-vanadium redox flow battery, which comprises the following steps:
1) Weighing a large amount of Bi by a weighing balance 2 S 3 A pharmaceutical preparation comprising Bi 2 S 3 Grinding and drying the medicines; wherein the weighed medicine is ground to 1000 meshes, and the ground Bi is 2 S 3 Drying the chemical at 100 deg.c for 6 hr;
2) Taking out a certain amount of dried Bi 2 S 3 Uniformly coating the medicines on the carbon felt electrode; bi 2 S 3 The chemical consumption is 0.015 g, the length and width of the carbon felt are 1.5 multiplied by 1.5 cm 2 A thickness of 4 mm;
3) Preparing an alkaline solution as an electrolyte; preparing an alkaline solution with the pH value of 10;
4) The coated carbon felt electrode is put into electrolyte, and Bi is removed by a constant-pressure electrochemical desulfurization method 2 S 3 Converting into a Bi simple substance; adopting a double-electrode system, taking an untreated carbon felt as a working electrode, a Pt electrode as a counter electrode, taking a potassium hydroxide solution with the pH =10 as a supporting electrolyte, and carrying out electrochemical reduction by using an electrochemical desulfurization method, wherein the voltage is set to be a constant voltage value of 1.6V;
5) Taking down the carbon felt electrode after electric desulfurization, firstly carrying out acid cleaning, and then washing with deionized water; wherein the concentration of hydrochloric acid is 1 mol/L
6) Cleaning, and vacuum drying in a drying oven; the vacuum degree is minus 0.1Kpa, the temperature is set to 90 ℃, and the modified composite carbon felt electrode is obtained after drying for 3 hours.
Example 2
The embodiment provides a preparation method of a composite carbon felt electrode of an all-vanadium redox flow battery, which comprises the following steps:
1) Weighing a large amount of Bi by a weighing balance 2 S 3 A pharmaceutical preparation comprising Bi 2 S 3 Grinding and drying the medicines; wherein the weighed medicine is ground to 2000 meshes, and the ground Bi is 2 S 3 Drying the chemical at 110 ℃ for 4.5 hours;
2) Taking out a certain amount of dried Bi 2 S 3 Uniformly coating the medicines on the carbon felt electrode; bi 2 S 3 The chemical consumption is 0.02 g, the length and width of the carbon felt are 2 multiplied by 2 cm 2 A thickness of 4 mm;
3) Preparing an alkaline solution as an electrolyte; preparing an alkaline solution with the pH value of 12;
4) The coated carbon felt electrode is put into electrolyte, and Bi is removed by a constant-pressure electrochemical desulfurization method 2 S 3 Transforming into a Bi simple substance; adopting a double-electrode system, taking an untreated carbon felt as a working electrode, a Pt electrode as a counter electrode, taking a potassium hydroxide solution with PH =12 as a supporting electrolyte, and carrying out electrochemical reduction by using an electrochemical desulfurization method, wherein the voltage is set to be a constant voltage value of 1.6V;
5) Taking down the carbon felt electrode after electric desulfurization, firstly carrying out acid cleaning, and then washing with deionized water; wherein the concentration of hydrochloric acid is 2 mol/L
6) Cleaning, and vacuum drying in a drying oven; the vacuum degree is minus 0.05Kpa, the temperature is set as 100 ℃, and the modified composite carbon felt electrode is obtained after drying for 4 hours.
Example 3
The embodiment provides a preparation method of a composite carbon felt electrode of an all-vanadium redox flow battery, which comprises the following steps:
1) Weighing a large amount of Bi by a weighing balance 2 S 3 A pharmaceutical preparation comprising Bi 2 S 3 Grinding and drying the medicines; wherein the weighed medicine is ground to 3000 meshes, and the ground Bi is treated 2 S 3 Drying the chemical at 120 deg.C for 3 hr;
2) Taking out a certain amount of dried Bi 2 S 3 Uniformly coating the medicines on the carbon felt electrode; bi 2 S 3 The chemical consumption is 0.025 g, and the length and width of the carbon felt are 2.5 multiplied by 2.5 cm 2 A thickness of 4 mm;
3) Preparing an alkaline solution as an electrolyte; preparing an alkaline solution with the pH value of 13.5;
4) The coated carbon felt electrode is put into electrolyte, and Bi is removed by a constant-pressure electrochemical desulfurization method 2 S 3 Converting into a Bi simple substance; adopting a double-electrode system, taking an untreated carbon felt as a working electrode, a Pt electrode as a counter electrode, taking a potassium hydroxide solution with the pH =13.5 as a supporting electrolyte, and carrying out electrochemical reduction by using an electrochemical desulfurization method, wherein the voltage is set to be a constant voltage value of 1.6V;
5) Taking down the carbon felt electrode after electric desulfurization, firstly carrying out acid washing, and then washing with deionized water; wherein the concentration of the hydrochloric acid is 3 mol/L;
6) Cleaning, and vacuum drying in a drying oven; and (3) setting the vacuum degree to be 0Kpa and the temperature to be 110 ℃, and drying for 5 hours to obtain the modified composite carbon felt electrode.
Performance test experiments:
the composite carbon felt electrode material prepared in example 1 was subjected to a contact angle test, and the test results are shown in fig. 2. As can be seen from fig. 2, the contact angle of the modified carbon felt is changed to 0 degree which is much smaller than 115 degrees of the original felt, which indicates that the addition of the elemental bismuth can improve the hydrophilicity of the carbon felt, which is beneficial to the diffusion of vanadium ions on the surface of the carbon felt, thereby enhancing the electrochemical reaction process.
The modified composite carbon felt electrode material prepared in example 1 was subjected to electron microscope scanning, and the result after 5000-fold magnification is shown in fig. 3. As can be seen from fig. 3, the bismuth attached to the modified carbon felt in this embodiment is dense and uniform, and the particle diameter of the bismuth is between 300 nanometers and 1 micrometer, which can effectively promote the reversibility and reaction kinetics of the vanadium negative electrode, thereby further explaining the maturity and stability of the process selected by us.
The composite carbon felt electrode prepared in the example 1 is used as a battery cathode, an original carbon felt electrode is used as a positive electrode, a perfluorinated sulfonic acid ion exchange membrane is used as a diaphragm, and the all-vanadium redox flow battery is assembled, wherein the positive electrode electrolyte is 15 mL of VO (volatile organic solvent) 1 mol/L 2+ +3 mol/L H 2 SO 4 The solution is 15 mL of 1 mol/L V as the negative electrode electrolyte 3+ +3 mol/L H 2 SO 4 And (3) solution. Fig. 4 shows the energy efficiency of the battery test result, the energy efficiency of the battery using the modified composite carbon felt electrode is significantly improved, and the energy efficiency is improved by 7% at 400 d, which indicates that the addition of bismuth promotes the reaction kinetics of the vanadium negative electrode. And the energy efficiency of the battery is 80% under 200 electric density, 70.6% under 400 electric density, and the comprehensive performance of the battery is better compared with other electrode materials in the same field.
Fig. 5 shows the voltage efficiency of the cell test results, which is significantly improved by using the modified composite carbon felt electrode. The energy efficiency is improved by 7.6% under 400 electrical density, the voltage efficiency of the battery is 86% under 200 electrical density, 73.4% under 400 electrical density, and the comprehensive performance of the battery is better compared with other electrode materials in the same field, so that the overall cost of the all-vanadium redox flow battery is reduced. The process is simple and stable, obviously improves the performance of the battery, and can be completely popularized to the field of other flow batteries.
It should be noted that the composite carbon felt electrode material prepared in the other examples has the same or similar performance as the material prepared in example 1, and is not described in detail herein.
The above embodiments are merely illustrative and modifications or variations may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A preparation method of a composite carbon felt electrode of an all-vanadium redox flow battery is characterized by comprising the following steps: the method comprises the following steps:
1) Firstly weighing a certain amount of Bi 2 S 3 Chemicals, then adding the Bi 2 S 3 Grinding and drying chemicals for later use;
2) Taking out a certain amount of dried Bi 2 S 3 Uniformly coating the powder on a carbon felt electrode;
3) Preparing an alkaline solution as an electrolyte solution,
4) Placing the coated carbon felt electrode in alkaline electrolyte, and performing constant-pressure electrochemical desulfurization on Bi 2 S 3 Converting into a Bi simple substance;
5) Taking down the desulfurized carbon felt electrode, firstly carrying out acid washing neutralization, and then washing the carbon felt electrode clean by deionized water;
6) And (3) putting the cleaned carbon felt electrode into a vacuum drying box for drying, and obtaining a finished product of the composite carbon felt electrode after vacuum drying.
2. The preparation method of the composite carbon felt electrode of the all-vanadium flow battery according to claim 1, which is characterized by comprising the following steps of: the Bi 2 S 3 The purity of the chemical is more than or equal to 99 percent, and the Bi 2 S 3 Grinding the chemical to 1000-3000 mesh.
3. The preparation method of the composite carbon felt electrode of the all-vanadium flow battery according to claim 1 or 2, which is characterized by comprising the following steps of: the Bi 2 S 3 The purity of the chemical product is more than or equal to 99 percent, and the chemical product is dried for 3 to 6 hours at the drying temperature of between 100 and 120 ℃.
4. The preparation method of the composite carbon felt electrode of the all-vanadium flow battery according to claim 1, which is characterized by comprising the following steps of: the Bi 2 S 3 The coating amount of the chemicals is 0.1-0.2 weight part of the carbon felt electrode.
5. The preparation method of the composite carbon felt electrode of the all-vanadium flow battery according to claim 1, which is characterized by comprising the following steps of: the pH value of the prepared alkaline solution is 10-14, and the ion source of the prepared alkaline solution is alkaline electrolyte of KOH or NaOH.
6. The preparation method of the composite carbon felt electrode of the all-vanadium flow battery according to claim 1, which is characterized by comprising the following steps of: the carbon felt electrode selected was a three-dimensional carbon felt with a conductivity of 1000S/m, 25 ℃, and resistance to corrosion by sulfuric acid, hydrochloric acid, or/and nitric acid as the carbon felt electrode.
7. The preparation method of the composite carbon felt electrode of the all-vanadium flow battery according to claim 1, wherein the step 4) is specifically as follows: putting the coated carbon felt electrode in electrolyte, and performing constant-pressure electrochemical desulfurization on Bi on the carbon felt electrode 2 S 3 Powder conversion to elemental Bi: adopting a double-electrode system, taking an untreated carbon felt electrode as a working electrode, a Pt electrode as a counter electrode, taking KOH solution with the pH value of 10-14 as supporting electrolyte, carrying out electrochemical reduction by using an electrochemical desulfurization method, and setting the voltage as constant voltage.
8. The preparation method of the composite carbon felt electrode of the all-vanadium flow battery according to claim 1, wherein the step 5) is specifically as follows: and taking down the carbon felt electrode after the electric desulfurization, pickling, and washing with deionized water, wherein the concentration of hydrochloric acid is 1-3 mol.
9. The preparation method of the composite carbon felt electrode of the all-vanadium flow battery according to claim 1, wherein the step 6) is specifically as follows: and (3) putting the cleaned carbon felt electrode into a vacuum drying oven for drying, setting the vacuum degree to be minus 0.1-0.0 Kpa and the temperature to be about 90-110 ℃, putting the carbon felt into the drying oven for drying for 3-5 hours, and taking out the carbon felt electrode to obtain the modified composite carbon felt electrode.
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| CN108054390A (en) * | 2017-11-29 | 2018-05-18 | 辽宁科技大学 | A kind of method of modifying of efficiently and effectively graphite felt for vanadium cell |
| CN109338406A (en) * | 2018-12-05 | 2019-02-15 | 昆明理工大学 | A kind of electroreduction metal sulfide method and device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108054390A (en) * | 2017-11-29 | 2018-05-18 | 辽宁科技大学 | A kind of method of modifying of efficiently and effectively graphite felt for vanadium cell |
| CN109338406A (en) * | 2018-12-05 | 2019-02-15 | 昆明理工大学 | A kind of electroreduction metal sulfide method and device |
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| JIAKANG QU等: "Electrochemical desulfurization of solid copper sulfides in strongly alkaline solutions" * |
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