CN111463445B - Modified carbon material, all-vanadium redox flow battery, and preparation method and application thereof - Google Patents
Modified carbon material, all-vanadium redox flow battery, and preparation method and application thereof Download PDFInfo
- Publication number
- CN111463445B CN111463445B CN202010222082.XA CN202010222082A CN111463445B CN 111463445 B CN111463445 B CN 111463445B CN 202010222082 A CN202010222082 A CN 202010222082A CN 111463445 B CN111463445 B CN 111463445B
- Authority
- CN
- China
- Prior art keywords
- carbon material
- modified carbon
- reaction
- electrolyte
- producing
- 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
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 85
- 150000001721 carbon Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000002994 raw material Substances 0.000 claims abstract description 52
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000012954 diazonium Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- YYAQOJILQOVUSK-UHFFFAOYSA-N n,n'-diphenylpropanediamide Chemical compound C=1C=CC=CC=1NC(=O)CC(=O)NC1=CC=CC=C1 YYAQOJILQOVUSK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001752 diazonium salt group Chemical group 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 230000007774 longterm Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 14
- 239000011261 inert gas Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- 239000000835 fiber Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- SALQMMXSINGXMI-UHFFFAOYSA-N 4-nitrosoaniline Chemical compound NC1=CC=C(N=O)C=C1 SALQMMXSINGXMI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical group [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
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
- H01M4/96—Carbon-based electrodes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/415—Amides of aromatic carboxylic acids; Acylated aromatic amines
-
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- 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 modified carbon material, an all-vanadium redox flow battery, and a preparation method and application thereof. The preparation method of the modified carbon material comprises the following steps: (1) under the condition of electrification, the oxidized carbon material placed at two poles of the alternating current electrolysis device reacts with sulfuric acid in electrolyte in the alternating current electrolysis device to obtain the acid oxidized carbon material; (2) loading a reaction raw material I on the carbon material subjected to acid oxidation to obtain a material I; (3) reacting a reaction raw material I in the material I with a reaction raw material II; in the step (1), the electrolyte is sulfuric acid-containing electrolyte, wherein the mass percent of the sulfuric acid is 15-60 wt%; the current density of the reaction is 1.0-6.0A/dm2The voltage is 10-40V, the temperature is 0-50 ℃, and the time is 0.1-3 h. The modified carbon material prepared by the preparation method has better electrochemical activity, conductivity and long-term operation stability.
Description
Technical Field
The invention relates to a modified carbon material, an all-vanadium redox flow battery, and a preparation method and application thereof.
Background
In order to improve the hydrophilicity and electrochemical activity of graphite felt or carbon felt, there are roughly two technical routes in the prior art: (1) oxidation methods, including air oxidation, strong acid liquid phase oxidation, plasma oxidation, electrochemical oxidation, and the like; (2) the surface doping or deposition modification method respectively comprises doping elements such as nitrogen, oxygen and boron, modifying metal oxide or noble metal, grafting or vapor depositing graphene, carbon nano tube and other materials with high specific surface area, and the like.
The oxidation method mainly aims to increase the actual surface area of the graphite fiber by forming oxidation etching on the surface of the graphite fiber; meanwhile, the hydrophilicity and the electrochemical activity of the electrode are improved by increasing the content of carbon-oxygen groups on the surface of the graphite fiber after oxidation treatment.
The surface doping or deposition modification method is different from the oxidation method, which not only changes the microstructure of the graphite felt, but also introduces metal active components on the surface of the graphite felt through various methods, and improves the activity of the graphite felt by utilizing the high conductivity and catalytic performance of metal or alloy. However, the adopted metals are mostly transitional elements, which can increase the cost of the battery, so the modification of the graphite felt by the method is limited to a certain extent, and the metal elements can fall off from the graphite felt to pollute the electrolyte.
Chinese patent document, publication No. CN105609796B, discloses a method for modifying an electrode material for an all-vanadium redox flow battery, which comprises the steps of firstly oxidizing a carbon felt or a graphite felt in a mixed solvent of nitric acid and sulfuric acid for several hours, then cleaning the carbon felt or the graphite felt to be neutral, putting the carbon felt or the graphite felt into an oven for drying, and electrodepositing the carbon felt or the graphite felt in a mixed solution of copper sulfate and stannous sulfate after drying, so that the internal resistance of the carbon felt is reduced, the electrochemical activity is improved, and the redox reversibility is improved.
The modification method of the above patent document can increase the specific surface area of the graphite felt or the carbon felt to some extent or increase the electrochemical activity thereof. However, the electrochemical activity, conductivity and long-term operation stability of the catalyst are still to be further improved.
Disclosure of Invention
The invention aims to overcome the defects that the electrochemical activity, the conductivity and the long-term operation stability of a modified graphite felt or a modified carbon felt obtained by the conventional graphite felt or carbon felt modification method are still required to be further improved, and provides a modified carbon material, an all-vanadium redox flow battery, and a preparation method and application thereof.
The invention solves the technical problems through the following technical scheme:
the invention provides a preparation method of a modified carbon material, which comprises the following steps:
(1) under electrification, the oxidized carbon material placed at two poles of the alternating current electrolysis device reacts with sulfuric acid in electrolyte in the alternating current electrolysis device to obtain an acid oxidized carbon material;
(2) loading a reaction raw material I on the carbon material subjected to acid oxidation to obtain a material I;
(3) reacting the reaction raw material I in the material I with a reaction raw material II;
in the step (1), the electrolyte is sulfuric acid-containing electrolyte, and the mass percent of sulfuric acid in the electrolyte is 15-60%; the carbon material is graphite felt and/or carbon felt; the oxidized carbon material is a carbon material obtained by oxidizing oxygen-containing gas; the current density of the reaction is 1.0-6.0A/dm2The voltage is 10-40V, the temperature is 0-50 ℃, and the time is 0.1-3 h;
in the step (2), the reaction raw material I is
Wherein X is-H, -NO2or-Cl; y is-Cl, -Br or-I;
in the step (3), the reaction raw material II is
G is-H, -OCH3or-CH3。
In the step (1), preferably, the mass percentage of the sulfuric acid in the electrolyte is 35%.
In the step (1), the current density of the reaction is preferably 3.0A/dm2The voltage is 25V, the temperature is 30 ℃, and the time is 0.5 h.
In the step (1), the electrolyte preferably contains VOSO4And VOSO4The mass fraction in the electrolyte is preferably 2% to 30%, for example 10%.
In the step (1), the electrolyte preferably contains lactic acid, and the mass fraction of lactic acid in the electrolyte is preferably 2% to 20%, for example, 5%.
In the step (1), the electrolyte preferably contains glycerol, and the mass fraction of glycerol in the electrolyte is preferably 1% to 10%, for example, 2%.
In the step (1), the carbon material is preferably a graphite felt.
In step (1), the mass ratio of the oxidized carbon material to the electrolyte is preferably 1:70 to 1:90, for example, 1: 80.
In step (1), the oxidized carbon material is generally referred to as an air-oxidized graphite felt or an air-oxidized carbon felt. The carbon material after air oxidation can be a commercially available carbon material after air oxidation, or can be prepared by a conventional preparation method in the field, and a porous or high-defect surface structure is formed on the surface of the carbon material fiber by the air oxidation method so as to provide a proper micropore space for the subsequent entering of a modifying substance. The preparation process of the carbon material after air oxidation is as follows: and placing the carbon material in a muffle furnace, introducing inert gas, heating, introducing air under the condition of ensuring the flow of the introduced inert gas, preserving heat, stopping introducing the air, continuing to introduce nitrogen, and cooling to room temperature.
The inert gas may be conventional, such as nitrogen and/or argon, among others. The flow rate of the inert gas may be conventional, for example 20-400mL/min, for example 200 mL/min.
Wherein, the end temperature of the temperature rise may be conventional, such as 500-.
Wherein the flow rate of the air can be conventional, for example, the flow rate of the air accounts for 20% -30% of the total flow rate of the inert gas and the air.
Wherein the time of the heat preservation can be conventional, such as 20-30 min.
In step (1), the reaction is preferably carried out under stirring, which may be, for example, mechanical stirring.
In the step (2), preferably, the carbon material after acid oxidation is placed in a solution containing a reaction raw material I until adsorption of the reaction raw material I by the carbon material after acid oxidation reaches a saturated state. More preferably, the carbon material after acid oxidation is placed in a solution containing a reaction raw material I, and is soaked under stirring or ultrasound; wherein, the mass percentage of the reaction raw material I in the solution containing the reaction raw material I is 2-18 percent, such as 5.8-6.5 percent, and the soaking time is 1-3 min.
In step (2), X is preferably para to the diazonium salt.
In step (2), X is preferably-H or-NO2。
In the step (2), the reaction raw material I is preferably
And/or
In the step (3), preferably, the material I is placed in a solution containing the reaction raw material II until the reaction raw material I completely reacts. Preferably, the material I is placed in a solution containing a reaction raw material II, and is soaked under stirring or ultrasonic waves; wherein, the mass percent of the reaction raw material II in the solution containing the reaction raw material II is 10-50 percent, for example 40 percent, and the soaking time is 5-10 min.
In the step (3), the reaction raw material II is preferably N, N '-diphenyl malonamide and/or N, N' -di-p-methoxyphenyl malonamide.
The invention also provides a modified carbon material prepared by the preparation method of the modified carbon material.
The invention also provides an all-vanadium redox flow battery containing the modified carbon material.
The invention also provides an application of the modified carbon material as an electrode in an all-vanadium redox flow battery.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. compared with the preparation method in the prior art, the modified carbon material prepared by the preparation method has better electrochemical activity and conductivity.
2. According to the preparation method of the modified carbon material, the carbon material which is subjected to acid oxidation and has uniform aperture and proper size can be prepared in the step (1), then in the step (2), the reaction raw material I can be well infiltrated into micropores of the carbon material to form firm anchor groups, and then the reaction raw material I and the reaction raw material II react to form a multi-functional-group macromolecular structure, so that the macromolecular structure can be firmly adsorbed on the surface of carbon material fibers and is not easy to wash away, and the long-term operation stability of the obtained modified carbon material in a flow battery can be favorably maintained.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Examples 1 to 2
A method for producing a modified carbon material, comprising the steps of:
(1) under electrification, placing the oxidized carbon material at two poles of an alternating current electrolysis device, and reacting to obtain an acid oxidized carbon material;
(2) placing the carbon material subjected to acid oxidation in a solution containing a reaction raw material I to obtain a material I;
(3) putting the material I into a solution containing a reaction raw material II;
the electrolyte in the alternating current electrolysis device is sulfuric acid-containing electrolyte; the current density, voltage, temperature and time of the reaction, reaction material I and reaction material II are shown in Table 1.
Step (1)In the electrolyte, VOSO is also contained4Lactic acid and glycerol, the mass fractions of which in the electrolyte are shown in table 1.
In the step (1), the oxidized carbon material is an air-oxidized carbon material, and the preparation process is as follows: and (3) placing the carbon material in a muffle furnace, introducing inert gas, heating, introducing air under the condition of ensuring the flow of the introduced inert gas, preserving the heat, stopping introducing the air, continuing to introduce nitrogen, and cooling to room temperature. The type and flow rate of the inert gas, the temperature rise end point temperature, the flow rate of the air, the percentage of the flow rate of the air to the total flow rate of the inert gas and the air, and the heat preservation time are shown in table 1.
In the step (2), the carbon material after acid oxidation is placed in a solution containing the reaction raw material I until the adsorption of the carbon material after acid oxidation on the reaction raw material I reaches a saturated state. Specifically, the carbon material after acid oxidation is placed in a solution containing a reaction raw material I, and is soaked under stirring or ultrasound; wherein, the mass percentage and the soaking time of the reaction raw material I in the solution containing the reaction raw material I are shown in the table 1.
And (3) putting the material I into a solution containing a reaction raw material II until the reaction raw material I completely reacts. Specifically, the material I is placed in a solution containing a reaction raw material II, and is soaked under stirring or ultrasound; wherein, the mass percent and the soaking time of the reaction raw material II in the solution containing the reaction raw material II are shown in the table 1.
In the step (2), the reaction raw material I is obtained by the following preparation method: mixing p-nitrosoaniline, hydrochloric acid and water according to the mass ratio of 1:2.5:2.5 to obtain a mixed solution, adding 10 wt% of sodium nitrite aqueous solution, stirring, reacting for 10min at the temperature of 0-5 ℃, and reacting according to the following equation to obtain the sodium nitrite aqueous solution.
In the step (3), the reaction raw material II is obtained by the following preparation method: adding aniline and xylene in a mass ratio of 1:1.25 into a flask, dropwise adding ethyl malonate while heating and stirring, controlling the temperature at 100 ℃, reacting according to the following equation, and distilling to extract ethanol to obtain the product.
In the step (3), the reaction of the reaction raw material I and the reaction raw material II is as follows:
example 3
The method for producing a modified carbon material is different from example 1 in the temperature of the reaction in step (1), the kind of the reaction material I in step (2), the soaking time, and the kind of the reaction material II in step (3), and is specifically shown in table 1, and the rest is the same as example 1.
In the step (2), the reaction raw material I is obtained by the following preparation method: mixing p-nitrosoaniline, hydrochloric acid and water according to the mass ratio of 1:2.5:2.5 to obtain a mixed solution, adding 10 wt% of sodium nitrite aqueous solution, stirring, reacting for 10min at the temperature of 0-5 ℃, and reacting according to the following equation to obtain the sodium nitrite aqueous solution.
In the step (3), the reaction raw material II is obtained by the following preparation method: adding methylaniline and xylene in a mass ratio of 1:1.25 into a flask, dropwise adding ethyl malonate while heating and stirring, controlling the temperature at 100 ℃, reacting according to the following equation, and distilling to extract ethanol to obtain the product.
In the step (3), the reaction of the reaction raw material I and the reaction raw material II is as follows:
effect examples 1 to 3
The method for testing the charging and discharging of the single battery is adopted to compare the electrical property improvement effect before and after the treatment of the graphite felt, the method refers to NB/T42081-2016, P7 appendix A, and the energy efficiency and the internal resistance of the specific test can be directly given by the sampling software of the commercially available charging and discharging integrated test equipment. And (3) testing conditions are as follows: the area of the graphite felt electrode is 50cm2Current density 100mA/cm2The voltage range is 1.0V-1.65V. The test results are shown in the following table.
Compared with graphite felts which are not treated and graphite felts which are oxidized by air, the modified carbon material prepared by the preparation method of the embodiment 1-3 has better energy efficiency and further has better electrochemical activity; the modified carbon material prepared by the preparation method of the embodiment 1-3 of the invention has lower internal resistance, and further has better conductivity.
In addition, after the modified carbon material is circulated for 100 times, the modified carbon material still has energy efficiency and internal resistance which are 3 times of circulation, namely the modified carbon material prepared by the preparation method has better long-term operation stability. The reason is as follows: step (1) can make the carbon material after the aperture is even, the suitable acid oxidation of size, and then in step (2), just can form firm anchor base with the micropore that reaction raw materials I permeates the carbon material well, rethread reaction raw materials I and reaction raw materials II's reaction forms the macromolecular structure of polyfunctional group, and then just can make this macromolecular structure firmly adsorb on carbon material fibre surface, is difficult for being washed away, is favorable to keeping the long-term operation stability of gained modified carbon material in redox flow battery.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (15)
1. A preparation method of a modified carbon material is characterized by comprising the following steps:
(1) under electrification, the oxidized carbon material placed at two poles of the alternating current electrolysis device reacts with sulfuric acid in electrolyte in the alternating current electrolysis device to obtain an acid oxidized carbon material;
(2) loading a reaction raw material I on the carbon material subjected to acid oxidation to obtain a material I;
(3) putting the material I into a solution containing a reaction raw material II, and reacting the reaction raw material I with the reaction raw material II;
in the step (1), the electrolyte is sulfuric acid-containing electrolyte, and the mass percent of sulfuric acid in the electrolyte is 15-60%; the carbon material is graphite felt and/or carbon felt; the oxidized carbon material is a carbon material obtained by oxidizing oxygen-containing gas; the current density of the reaction is 1.0-6.0A/dm2The voltage is 10-40V, the temperature is 0-50 ℃, and the time is 0.1-3 h;
in the step (2), the reaction raw material I is
Wherein X is-H, -NO2or-Cl; y is-Cl, -Br or-I;
in the step (3), the reaction raw material II is
G is-H, -OCH3or-CH3。
2. The method for producing a modified carbon material according to claim 1, wherein in the step (1), the electrolyte contains VOSO4And VOSO4The mass fraction of the electrolyte is 2-30%;
and/or in the step (1), the electrolyte contains lactic acid, and the mass fraction of the lactic acid in the electrolyte is 2-20%;
and/or, in the step (1), the electrolyte contains glycerol, and the mass fraction of the glycerol in the electrolyte is 1-10%;
and/or, in the step (1), the carbon material is graphite felt.
3. The method for producing a modified carbon material according to claim 1, wherein in the step (1), the mass ratio of the oxidized carbon material to the electrolyte is 1:70 to 1: 90.
4. The method for producing a modified carbon material according to claim 1, wherein in the step (2), the acid-oxidized carbon material is immersed in a solution containing the reaction material I under stirring or ultrasonic waves.
5. The method for producing a modified carbon material according to claim 4, wherein the mass percentage of the reaction material I in the solution containing the reaction material I is 2% to 18%.
6. The method for producing a modified carbon material according to claim 4, wherein the mass percentage of the reaction material I in the solution containing the reaction material I is 5.8% to 6.5%.
7. The method for producing a modified carbon material according to claim 4, wherein the soaking time is 1 to 3 min.
8. The method for producing a modified carbon material according to claim 1, wherein in the step (2), X is in the para position of the diazonium salt; andor, in the step (2), X is-H or-NO2。
9. The method for producing a modified carbon material according to claim 1, wherein in the step (2), the reaction material I is
And/or
10. The method for producing a modified carbon material according to claim 1, wherein in the step (3), the material I is immersed in a solution containing the reaction material II under stirring or ultrasonic waves.
11. The method for producing a modified carbon material according to claim 10, wherein the mass percentage of the reaction material II in the solution containing the reaction material II is 10% to 50%; the soaking time is 5-10 min.
12. The method for producing a modified carbon material according to claim 10, wherein the reaction material II is N, N '-diphenylmalonamide and/or N, N' -di-p-methoxyphenyl malonamide.
13. A modified carbon material produced by the method for producing a modified carbon material according to any one of claims 1 to 12.
14. An all vanadium flow battery comprising the modified carbon material of claim 13.
15. The application of the modified carbon material as an electrode in an all-vanadium flow battery, wherein the modified carbon material is the modified carbon material as claimed in claim 13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010222082.XA CN111463445B (en) | 2020-03-26 | 2020-03-26 | Modified carbon material, all-vanadium redox flow battery, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010222082.XA CN111463445B (en) | 2020-03-26 | 2020-03-26 | Modified carbon material, all-vanadium redox flow battery, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111463445A CN111463445A (en) | 2020-07-28 |
| CN111463445B true CN111463445B (en) | 2022-05-06 |
Family
ID=71680179
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010222082.XA Active CN111463445B (en) | 2020-03-26 | 2020-03-26 | Modified carbon material, all-vanadium redox flow battery, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111463445B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848438B (en) * | 2020-07-29 | 2023-05-23 | 浙江鼎龙科技股份有限公司 | Process for preparing 4, 6-diphenyl azo resorcinol and 4, 6-diamino resorcinol |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2000267249A1 (en) * | 2000-08-16 | 2002-02-25 | Squirrel Holdings Ltd. | Vanadium electrolyte preparation using asymmetric vanadium reduction cells and use of an asymmetric vanadium reduction cell for rebalancing the state of charge of the electrolytes of an operating vanadium redox battery |
| CN101182678A (en) * | 2007-11-05 | 2008-05-21 | 攀钢集团攀枝花钢铁研究院 | Graphite felt watch surface modified method and modified mineral carbon felt |
| AU2011246147B9 (en) * | 2010-04-27 | 2015-01-29 | Sumitomo Electric Industries, Ltd. | Redox flow battery |
| CN105609796A (en) * | 2016-01-21 | 2016-05-25 | 湖南农业大学 | Modification method of electrode material for all-vanadium redox flow battery |
| CN105742658A (en) * | 2016-01-21 | 2016-07-06 | 湖南农业大学 | Preparation method of electrode material for all-vanadium flow battery |
| CN106410219A (en) * | 2016-11-11 | 2017-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | All-vanadium-redox-flow-battery electrode material and preparing method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160359186A1 (en) * | 2015-06-08 | 2016-12-08 | Institute of Nuclear Energy Research, Atomic Energy Council, Executive Yuan, R.O.C. | Method of Direct Electrochemical Oxidation For Modifying Carbon Felts of Flow Battery |
| US10017897B1 (en) * | 2017-01-03 | 2018-07-10 | Institute of Nuclear Energy Research, Atomic Energy Council, Executive Yuan, R.O.C. | Method of enhancing efficiency of carbon felts in flow battery through sonication |
-
2020
- 2020-03-26 CN CN202010222082.XA patent/CN111463445B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2000267249A1 (en) * | 2000-08-16 | 2002-02-25 | Squirrel Holdings Ltd. | Vanadium electrolyte preparation using asymmetric vanadium reduction cells and use of an asymmetric vanadium reduction cell for rebalancing the state of charge of the electrolytes of an operating vanadium redox battery |
| CN101182678A (en) * | 2007-11-05 | 2008-05-21 | 攀钢集团攀枝花钢铁研究院 | Graphite felt watch surface modified method and modified mineral carbon felt |
| AU2011246147B9 (en) * | 2010-04-27 | 2015-01-29 | Sumitomo Electric Industries, Ltd. | Redox flow battery |
| CN105609796A (en) * | 2016-01-21 | 2016-05-25 | 湖南农业大学 | Modification method of electrode material for all-vanadium redox flow battery |
| CN105742658A (en) * | 2016-01-21 | 2016-07-06 | 湖南农业大学 | Preparation method of electrode material for all-vanadium flow battery |
| CN106410219A (en) * | 2016-11-11 | 2017-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | All-vanadium-redox-flow-battery electrode material and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Electrolyte transfer mechanism and optimization strategy for vanadium flow batteries adopting a Nafion membrane;Yuxi Song，et al.;《Journal of power sources》;20191205;全文 * |
| Review of material research and development for vanadium redox flow battery applications;Aishwarya Parasuraman，et al.;《Electrochimica Acta》;20120928;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111463445A (en) | 2020-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102709573B (en) | Fuel cell air electrode catalyst and manufacture method thereof | |
| CN103227334B (en) | Carbon-containing metal catalyst, preparation method and application thereof | |
| CN106040277B (en) | A kind of " vesica string " structural carbon fiber composite material and preparation method of supporting Pt | |
| US9997788B2 (en) | Methods of producing porous platinum-based catalysts for oxygen reduction | |
| CN102088091A (en) | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof | |
| CN105734725B (en) | One kind " vesica string " structure pure carbon fiber material and preparation method thereof | |
| EP2866287A1 (en) | Catalyst for solid polymer fuel cell and method for producing same | |
| CN111463445B (en) | Modified carbon material, all-vanadium redox flow battery, and preparation method and application thereof | |
| DE102008023781A1 (en) | Preparing porous, carbon and titanium oxide containing particles, useful in carrier catalyst for fuel cells, comprises forming dispersion from carbonizable polymer, surfactant and titanium alkoxide in fluid medium; evaporating; and heating | |
| CN106268798A (en) | Pd/WO for formic acid oxidation3rGO catalyst and preparation method thereof | |
| CN103915633A (en) | Composite carbon fiber-loaded metal catalyst as well as preparation method and application thereof | |
| CN101249435B (en) | Surface treating method of carbon nano-tube and loading type catalyst of carbon nano-tube | |
| CN111244484A (en) | Preparation method of sub-nano platinum-based ordered alloy | |
| TWI639271B (en) | Catalyst for polymer electrolyte fuel cell and method for producing the same | |
| CN103706375B (en) | Preparation method for the PtFe/C catalyst of Proton Exchange Membrane Fuel Cells | |
| Wang et al. | A novel multi-porous and hydrophilic anode diffusion layer for DMFC | |
| JP5728364B2 (en) | Method for producing metal supported catalyst and catalyst layer of fuel cell | |
| CN105836855A (en) | Preparation method and application of graphene gas diffusion electrode | |
| KR101609913B1 (en) | Carbon felt electrode for redox flow battery and method for preparing the same | |
| CN113506885A (en) | Graphitized carbon carrier for hydrogen fuel cell, preparation method and cell catalyst thereof | |
| CN112103515A (en) | Fuel cell gas diffusion layer and preparation method thereof | |
| CN114907566B (en) | Polyimide-metal monoatomic composite material and preparation method and application thereof | |
| CN109244486B (en) | Method for preparing iron carbide/graphene composite | |
| CN113604816B (en) | Preparation method and application of high-entropy alloy fiber electrocatalyst | |
| CN106757142B (en) | Preparation method and application of carbon fiber loaded nanoscale bimetal PtCo catalytic electrode |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231208 Address after: No. 8 Qianchuan Road, Chaohu Economic Development Zone, Hefei City, Anhui Province, 238014 Patentee after: Shanghai Electric (Anhui) energy storage technology Co.,Ltd. Address before: 30th Floor, No. 8 Xingyi Road, Changning District, Shanghai, 2003 Patentee before: Shanghai Electric Group Co.,Ltd. |
|
| TR01 | Transfer of patent right |