CN112160156A - Preparation method of all-vanadium battery modified carbon felt electrode material - Google Patents
Preparation method of all-vanadium battery modified carbon felt electrode material Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 69
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 36
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
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- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- 238000002791 soaking Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000006172 buffering agent Substances 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
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- 238000000034 method Methods 0.000 claims description 16
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- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 6
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- 239000000872 buffer Substances 0.000 claims description 3
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- 238000010304 firing Methods 0.000 claims 1
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- 238000011068 loading method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of a modified carbon felt electrode material of an all-vanadium battery, which comprises the steps of respectively carrying out ultrasonic treatment on a polyacrylonitrile-based graphite felt in an absolute ethyl alcohol solution and deionized water, then placing the polyacrylonitrile-based graphite felt in a muffle furnace for drying, then heating to a certain temperature, carrying out heat treatment under the air condition, and soaking the polyacrylonitrile-based graphite felt in bismuth trioxide (Bi)2O3) Taking out the solution, placing in an oven, heating and drying under air condition, soaking in dopamine solution, addingAnd adding a buffering agent to start polymerization of dopamine, stirring and reacting for a period of time, washing with deionized water, placing in a tubular furnace, and baking and carbonizing in a nitrogen atmosphere to obtain the modified carbon felt electrode. The carbon felt electrode material has excellent electrochemical performance and conductivity.
Description
Technical Field
The invention belongs to the field of all-vanadium redox flow battery electrodes, and particularly relates to a preparation method of a modified carbon felt electrode material of an all-vanadium battery.
Background
Polyacrylonitrile-based graphite felt (carbon felt) is the most commonly used electrode material in all-vanadium flow batteries at present. The carbon felt is a three-dimensional porous material, does not generate large pressure on the flowing of the electrolyte, and is beneficial to the conduction of active substances. But the poor hydrophilic and electrochemical properties of the carbon felt restrict the large-scale commercial use of the untreated carbon felt. Therefore, since the carbon felt is widely used as an electrode material of the all-vanadium flow battery, research on modification methods of the carbon felt is continuously carried out, wherein the modification methods include a heat treatment method, an acid treatment method, an electrochemical oxidation method, metal ion doping modification, non-metal element doping modification, carbon-carbon composite modification, high polymer doping modification and the like.
Chinese patent 201610159140.2 discloses a method for preparing an electrode material for a flow battery, and particularly relates to a method for preparing an electrode material for an all-vanadium flow battery. The method comprises the following implementation processes: immersing a carbon material into a nitrogen-containing raw material with a certain concentration, carrying out ultrasonic treatment and drying treatment to obtain a precursor of the target electrode, and then carbonizing the precursor at high temperature to obtain the target electrode. The modified electrode material has the advantages that the nitrogen-containing functional groups on the surface of the modified electrode material are greatly improved, the electrochemical activity and the conductivity of the modified electrode material are improved, the reaction internal resistance of the electrode for the all-vanadium redox flow battery is reduced, and the reaction active sites of the electrode and electrolyte are increased.
Disclosure of Invention
The invention aims to provide a preparation method of a modified carbon felt electrode material of an all-vanadium battery, which comprises the following steps:
s1: respectively carrying out ultrasonic treatment on the polyacrylonitrile-based graphite felt in an absolute ethyl alcohol solution and deionized water for 30min, then placing the polyacrylonitrile-based graphite felt in a muffle furnace, drying the polyacrylonitrile-based graphite felt for 4h under the air condition of 120 ℃, then heating the polyacrylonitrile-based graphite felt to 500-600 ℃ at the heating rate of 2 ℃/min, and carrying out heat treatment for 6h under the air condition.
S2: soaking the product obtained in step S1 in bismuth trioxide (Bi)2O3) And (3) soaking the carbon-doped felt in the solution for 10-20 hours, taking out the carbon-doped felt, placing the carbon-doped felt in an oven, and heating and drying the carbon-doped felt for 4-12 hours at 90-120 ℃ in air.
S3: dissolving dopamine in deionized water, then soaking the doped carbon felt obtained in the step S2 in a dopamine solution for 4-6 hours in a vacuum and room-temperature environment, then adding 60-80 mu L of buffering agent to enable dopamine to start polymerization, stirring and reacting for 5 hours, washing with the deionized water, then placing in a tubular furnace, and baking and carbonizing at 600-900 ℃ for 2-6 hours in a nitrogen atmosphere to obtain the modified carbon felt electrode.
Preferably, Bi in the step S22O3Is alpha-type Bi2O3Beta form of Bi2O3Sigma type Bi2O3Any one of them.
Preferably, the bismuth trioxide solution in step S2 is any one of a bismuth trioxide hydrochloric acid solution and a sulfuric acid solution.
Preferably, the heating temperature in the step S2 is 90 to 110 ℃.
Preferably, the heating time in the step S2 is 4 to 8 hours.
Preferably, the weight ratio of the dopamine to the deionized water in the step S3 is 1: 0.5-1.6.
Preferably, the buffer described in step S3 is tris- (hydroxymethyl) -aminomethane.
Preferably, the temperature of the calcination and carbonization in the step S3 is 600-800 ℃.
The invention has the following beneficial effects:
(1) the all-vanadium battery modified carbon felt electrode material prepared by the invention adopts bismuth trioxide doped polyacrylonitrile-based graphite felt, and Bi is used in the doping process2O3Utilize Bi2O3Insoluble in water and alkaline solution, and soluble in acidic solution, so that the graphite felt is soaked in Bi2O3When in acid solution, the acid solution oxidizes and etches the graphite felt, and the specific surface area of the carbon felt is increased to increase Bi content2O3The carbon felt is loaded on the surface of the carbon felt, and meanwhile, the acid solution increases oxygen-containing functional groups on the surface of the carbon felt, so that the conductivity of the electrochemical performance of the carbon felt is improved from two aspects.
(2) The all-vanadium battery prepared by the inventionModified carbon felt electrode material in the presence of Bi2O3Bi loaded by soaking in acidic solution2O3Then polymerizing dopamine and loading the dopamine on the surface of the carbon felt, and using Bi in the loading process2O3Soaking the carbon felt loaded by the acid solution in dopamine aqueous solution, and Bi2O3Is insoluble in water so that Bi is not further influenced2O3Loading on carbon felt, and polymerizing the dopamine after further adding buffer solution to obtain Bi2O3Coating on the surface of carbon felt to ensure that Bi2O3The load is more firm.
(3) The all-vanadium battery modified carbon felt electrode material prepared by the invention is prepared by Bi2O3Bi loaded by soaking in acidic solution2O3And then, dopamine is loaded on the graphite felt in a polymerization manner, and after high-temperature baking carbonization, the dopamine is used as a carbon source and a nitrogen source to be doped into the carbon felt, so that the graphite felt is further modified, the gas electrochemical performance and the conductivity are improved, and the process is simple and environment-friendly.
Drawings
FIG. 1 is a process diagram of the present invention for preparing a modified carbon felt electrode material;
FIG. 2 is a graph of a CV curve of a modified carbon felt electrode material prepared in example 1 of the present invention;
Detailed Description
The following describes embodiments of the present invention in detail, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are provided, but the scope of the present invention is not limited to the following embodiments.
Example 1
An all-vanadium battery modified carbon felt electrode material comprises the following specific preparation steps:
s1: respectively carrying out ultrasonic treatment on the polyacrylonitrile-based graphite felt in an absolute ethyl alcohol solution and deionized water for 30min, then placing the polyacrylonitrile-based graphite felt in a muffle furnace, drying the polyacrylonitrile-based graphite felt for 4h under the air condition of 120 ℃, then heating the polyacrylonitrile-based graphite felt to 500 ℃ at the heating rate of 2 ℃/min, and carrying out heat treatment for 6h under the air condition.
S2: will be described in detailImmersion of the product obtained in S1 in alpha-form Bi2O3And (3) soaking in sulfuric acid solution for 10 hours, taking out the solution, placing the solution in an oven, and heating and drying the solution at 90 ℃ in the air for 4 hours to obtain the doped carbon felt.
S3: dissolving dopamine in deionized water, wherein the weight ratio of the dopamine to the deionized water is 1:0.5, then soaking the doped carbon felt obtained in the step S2 in a dopamine solution for 4 hours in a vacuum room-temperature environment, then adding 60 mu L of tris- (hydroxymethyl) -aminomethane buffering agent to start polymerization of the dopamine, stirring and reacting for 5 hours, washing with the deionized water, then placing in a tubular furnace, and baking and carbonizing at 600 ℃ for 2 hours in a nitrogen atmosphere to obtain the modified carbon felt electrode.
Example 2
An all-vanadium battery modified carbon felt electrode material comprises the following specific preparation steps:
s1: respectively carrying out ultrasonic treatment on the polyacrylonitrile-based graphite felt in an absolute ethyl alcohol solution and deionized water for 30min, then placing the polyacrylonitrile-based graphite felt in a muffle furnace, drying the polyacrylonitrile-based graphite felt for 4h under the air condition of 120 ℃, then heating the polyacrylonitrile-based graphite felt to 600 ℃ at the heating rate of 2 ℃/min, and carrying out heat treatment for 6h under the air condition.
S2: immersing the product obtained in the step S1 in alpha-type Bi2O3And (3) soaking in a sulfuric acid solution for 20 hours, taking out the solution, placing the solution in an oven, and heating and drying the solution at 120 ℃ in the air for 12 hours to obtain the doped carbon felt.
S3: dissolving dopamine in deionized water, wherein the weight ratio of the dopamine to the deionized water is 1:1.6, then soaking the doped carbon felt obtained in the step S2 in a dopamine solution for 6 hours in a vacuum room-temperature environment, then adding 80 mu L of tris- (hydroxymethyl) -aminomethane buffering agent to start polymerization of the dopamine, stirring and reacting for 5 hours, washing with the deionized water, then placing in a tubular furnace, and baking and carbonizing at 900 ℃ for 6 hours in a nitrogen atmosphere to obtain the modified carbon felt electrode.
Example 3
An all-vanadium battery modified carbon felt electrode material comprises the following specific preparation steps:
s1: respectively carrying out ultrasonic treatment on the polyacrylonitrile-based graphite felt in an absolute ethyl alcohol solution and deionized water for 30min, then placing the polyacrylonitrile-based graphite felt in a muffle furnace, drying the polyacrylonitrile-based graphite felt for 4h under the air condition of 120 ℃, then heating the polyacrylonitrile-based graphite felt to 500 ℃ at the heating rate of 2 ℃/min, and carrying out heat treatment for 6h under the air condition.
S2: immersing the product obtained in the step S1 in beta-type Bi2O3And (3) soaking in sulfuric acid solution for 12h, taking out, placing in an oven, and heating and drying at 110 ℃ for 6h in the air to obtain the doped carbon felt.
S3: dissolving dopamine in deionized water, wherein the weight ratio of the dopamine to the deionized water is 1:0.6, then soaking the doped carbon felt obtained in the step S2 in a dopamine solution for 5 hours in a vacuum room-temperature environment, then adding 75 mu L of tris- (hydroxymethyl) -aminomethane buffering agent to start polymerization of the dopamine, stirring and reacting for 5 hours, washing with the deionized water, then placing in a tubular furnace, and baking and carbonizing at 800 ℃ for 3 hours in a nitrogen atmosphere to obtain the modified carbon felt electrode.
Example 4
An all-vanadium battery modified carbon felt electrode material comprises the following specific preparation steps:
s1: respectively carrying out ultrasonic treatment on the polyacrylonitrile-based graphite felt in an absolute ethyl alcohol solution and deionized water for 30min, then placing the polyacrylonitrile-based graphite felt in a muffle furnace, drying the polyacrylonitrile-based graphite felt for 4h under the air condition of 120 ℃, then heating the polyacrylonitrile-based graphite felt to 500 ℃ at the heating rate of 2 ℃/min, and carrying out heat treatment for 6h under the air condition.
S2: immersing the product obtained in the step S1 in sigma type Bi2O3And (3) soaking in sulfuric acid solution for 12h, taking out, placing in an oven, and heating and drying at 110 ℃ for 6h in the air to obtain the doped carbon felt.
S3: dissolving dopamine in deionized water, wherein the weight ratio of the dopamine to the deionized water is 1:0.6, then soaking the doped carbon felt obtained in the step S2 in a dopamine solution for 5 hours in a vacuum room-temperature environment, then adding 75 mu L of tris- (hydroxymethyl) -aminomethane buffering agent to start polymerization of the dopamine, stirring and reacting for 5 hours, washing with the deionized water, then placing in a tubular furnace, and baking and carbonizing at 800 ℃ for 3 hours in a nitrogen atmosphere to obtain the modified carbon felt electrode.
Performance test experiments:
the modified carbon felt electrode material prepared in example 1 is tested by an electrochemical workstation, a three-level system is used as a testing device, a saturated calomel electrode is selected as a reference electrode, and the scanning rate is 1mV s-1As shown in fig. 2, the electrode is always stable and has stable electrochemical activity after continuously scanning for 15 times;
the carbon felt prepared in the example 1 is used as the cathode of the battery anode, the Nafion115 type ion exchange membrane is used as the diaphragm, and the all-vanadium redox flow battery is assembled, wherein the anode electrolyte is 20mL1.5mol/L VO2++3mol/L H2SO4The solution and the negative electrode electrolyte are 20mL1.5mol/LVO3++3mol/L H2SO4The electrode materials were then tested for coulombic efficiency, voltage efficiency, and energy efficiency, with the results shown in table 1,
TABLE 1 test results
The electrode material has a current density of 60mA/cm2The coulomb efficiency reaches 95.21 percent, and the current density is increased to 150mA/cm2In the process, the coulombic efficiency can also reach 92.13 percent, and the coulombic efficiency is not greatly reduced along with the increase of the current density; the current density is 60mA/cm2The voltage efficiency at this time was 93.67%, and the current density increased to 150mA/cm2In time, the voltage efficiency is still kept above 90%; at a current density of 60mA/cm2The energy efficiency is 92.03 percent and the current density is 150mA/cm2The lower energy efficiency is still kept above 86%, and the comprehensive performance of the electrode material is better than that of other electrode materials in the same field.
It should be noted that the carbon felt materials prepared in the other examples have the same or similar performance as the material prepared in example 1, and are not described in detail herein.
Claims (9)
1. A preparation method of a modified carbon felt electrode material of an all-vanadium battery is characterized in that the carbon felt electrode material is a polyacrylonitrile-based graphite felt, and the preparation method is characterized in that the polyacrylonitrile-based graphite felt is pretreated by the carbon felt electrode material under a high-temperature environment, then the pretreated polyacrylonitrile-based graphite felt is modified by bismuth trioxide, dopamine and a buffer, and the modified carbon felt electrode material is obtained by baking.
2. The preparation method of the all-vanadium battery modified carbon felt electrode material as claimed in claim 1, wherein the preparation method comprises the following steps:
s1: respectively carrying out ultrasonic treatment on a polyacrylonitrile-based graphite felt in an absolute ethyl alcohol solution and deionized water for 30min, then placing the polyacrylonitrile-based graphite felt in a muffle furnace, drying the polyacrylonitrile-based graphite felt for 4h under the air condition of 120 ℃, then heating the polyacrylonitrile-based graphite felt to 500-600 ℃ at a heating rate of 2 ℃/min, and carrying out heat treatment for 6h under the air condition;
s2: soaking the product obtained in step S1 in bismuth trioxide (Bi)2O3) Putting the solution in an oven after being fished out for 10-20 h, and heating and drying the solution for 4-12 h at the temperature of 90-120 ℃ in the air to obtain a doped carbon felt;
s3: dissolving dopamine in deionized water, then soaking the doped carbon felt obtained in the step S2 in a dopamine solution for 4-6 hours in a vacuum and room-temperature environment, then adding 60-80 mu L of buffering agent to enable dopamine to start polymerization, stirring and reacting for 5 hours, washing with the deionized water, then placing in a tubular furnace, and baking and carbonizing at 600-900 ℃ for 2-6 hours in a nitrogen atmosphere to obtain the modified carbon felt electrode.
3. The method for preparing the all-vanadium battery modified carbon felt electrode material as claimed in claim 2, wherein the Bi in step S22O3Is alpha-type Bi2O3Beta form of Bi2O3Sigma type Bi2O3Any one of them.
4. The method for preparing the all-vanadium battery modified carbon felt electrode material as claimed in claim 2, wherein the bismuth trioxide solution in step S2 is any one of a bismuth trioxide hydrochloric acid solution or a sulfuric acid solution.
5. The preparation method of the all-vanadium battery modified carbon felt electrode material as claimed in claim 2, wherein the heating temperature in the step S2 is 90-110 ℃.
6. The preparation method of the all-vanadium battery modified carbon felt electrode material as claimed in claim 2, wherein the heating time in the step S2 is 4-8 h.
7. The preparation method of the all-vanadium battery modified carbon felt electrode material as claimed in claim 2, wherein the weight ratio of the dopamine to the deionized water in the step S3 is 1: 0.5-1.6.
8. The method for preparing the all-vanadium battery modified carbon felt electrode material as claimed in claim 2, wherein the buffer in the step S3 is tris- (hydroxymethyl) -aminomethane.
9. The preparation method of the all-vanadium battery modified carbon felt electrode material as claimed in claim 2, wherein the firing and carbonization temperature in the step S3 is 600-800 ℃.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112897581A (en) * | 2021-03-04 | 2021-06-04 | 太原蒲公英科技有限公司 | Preparation method of all-vanadium redox battery electrode material |
CN113809338A (en) * | 2021-09-22 | 2021-12-17 | 广州市上万科技有限公司 | Preparation method of electrode material for all-vanadium redox flow battery |
CN116154197A (en) * | 2023-04-24 | 2023-05-23 | 西子清洁能源装备制造股份有限公司 | Biomass modified all-vanadium redox flow battery electrode and preparation method and application thereof |
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2020
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112897581A (en) * | 2021-03-04 | 2021-06-04 | 太原蒲公英科技有限公司 | Preparation method of all-vanadium redox battery electrode material |
CN112897581B (en) * | 2021-03-04 | 2023-01-10 | 林源电力(南京)有限公司 | Preparation method of all-vanadium redox battery electrode material |
CN113809338A (en) * | 2021-09-22 | 2021-12-17 | 广州市上万科技有限公司 | Preparation method of electrode material for all-vanadium redox flow battery |
CN113809338B (en) * | 2021-09-22 | 2023-09-08 | 贵州志喜科技有限公司 | Preparation method of electrode material for all-vanadium redox flow battery |
CN116154197A (en) * | 2023-04-24 | 2023-05-23 | 西子清洁能源装备制造股份有限公司 | Biomass modified all-vanadium redox flow battery electrode and preparation method and application thereof |
CN116154197B (en) * | 2023-04-24 | 2023-08-11 | 西子清洁能源装备制造股份有限公司 | Biomass modified all-vanadium redox flow battery electrode and preparation method and application thereof |
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