CN117154105B - Preparation method and application of modified graphite felt for vanadium redox flow galvanic pile - Google Patents
Preparation method and application of modified graphite felt for vanadium redox flow galvanic pile Download PDFInfo
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- CN117154105B CN117154105B CN202311414213.4A CN202311414213A CN117154105B CN 117154105 B CN117154105 B CN 117154105B CN 202311414213 A CN202311414213 A CN 202311414213A CN 117154105 B CN117154105 B CN 117154105B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 44
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 61
- 239000010439 graphite Substances 0.000 claims abstract description 61
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 10
- 239000006228 supernatant Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 6
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 6
- 229960001231 choline Drugs 0.000 claims description 6
- DWTYPCUOWWOADE-UHFFFAOYSA-M hydron;tetramethylazanium;sulfate Chemical compound C[N+](C)(C)C.OS([O-])(=O)=O DWTYPCUOWWOADE-UHFFFAOYSA-M 0.000 claims description 6
- KJFVITRRNTVAPC-UHFFFAOYSA-L tetramethylazanium;sulfate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.[O-]S([O-])(=O)=O KJFVITRRNTVAPC-UHFFFAOYSA-L 0.000 claims description 6
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 26
- 238000012360 testing method Methods 0.000 description 11
- 229920002239 polyacrylonitrile Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000000713 high-energy ball milling Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002096 quantum dot Substances 0.000 description 6
- 229910001456 vanadium ion Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 4
- 238000006479 redox reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012546 transfer Methods 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The application relates to the technical field of vanadium redox flow pile electrode materials, and particularly discloses a preparation method and application of a modified graphite felt for a vanadium redox flow pile. The preparation method comprises the following specific steps: step 1, weighing MAX phase compound and strong alkali solution in a vacuum ball milling tank, performing ball milling reaction on a ball milling instrument for 12-24h, and performing vacuum drying at 60-80 ℃ to obtain MXene powder; step 2, mixing MXene powder with a quaternary ammonium compound solution, carrying out ultrasonic water bath, and centrifuging to obtain a supernatant to obtain MXene QDs dispersion; and 3, immersing the graphite felt in MXene QDs dispersion liquid, performing hydrothermal reaction, cooling, washing the graphite felt with deionized water, and freeze-drying to obtain the modified graphite felt modified by MXene QDs. The modified graphite felt prepared by the method can effectively increase the specific surface area of the graphite felt, enhance hydrophilicity, improve conductivity and increase electrochemical activity, and is applied to a vanadium redox flow battery stack to be beneficial to improving the performance of the vanadium redox flow battery.
Description
Technical Field
The application relates to the technical field of vanadium redox flow pile electrode materials, in particular to a preparation method and application of a modified graphite felt for a vanadium redox flow pile.
Background
The all-vanadium redox flow battery is a redox battery taking vanadium as an active material and in a circulating flowing liquid state. The electric energy of the vanadium battery is stored in sulfuric acid electrolyte of vanadium ions in different valence states in a chemical energy mode, the electrolyte is hydraulically pressed into the battery stack body through an external pump, the electrolyte circularly flows in closed loops of different liquid storage tanks and half batteries under the action of mechanical power, a proton exchange membrane is adopted as a diaphragm of the battery pack, the electrolyte solution flows through the electrode surfaces in parallel and generates electrochemical reaction, and electric current is collected and conducted through double electrode plates, so that the chemical energy stored in the solution is converted into electric energy.
In recent years, the energy storage technology of the all-vanadium redox flow battery gradually becomes a focus of the large-scale energy storage field due to the advantages of high safety, long service life, simplicity in maintenance, no pollution and the like. The electrode is used as a main place for oxidation-reduction reaction in the all-vanadium redox flow battery and is one of key materials of a galvanic pile. Vanadium battery electrode materials are mainly classified into three types: metals such as Pb, ti, etc.; carbon such as graphite, carbon cloth, carbon felt, etc.; composite materials such as conductive polymers, polymeric composites, and the like. Compared with a metal electrode, the carbon material has the advantages of good corrosion resistance, high electrochemical stability, low preparation cost and the like, and is widely used as an electrode material of an all-vanadium redox flow pile.
The carbon electrode material suitable for all-vanadium redox flow pile mainly comprises glass carbon, carbon cloth, graphite plate, graphite felt and the like. The polyacrylonitrile-based graphite felt has the characteristics of large specific surface area, higher conductivity, good chemical stability, convenient processing and the like, and is an all-vanadium redox flow battery electrode material with the best comprehensive performance, so that the polyacrylonitrile-based graphite felt is widely used in a redox flow battery. However, untreated polyacrylonitrile-based graphite felt has weak electrochemical activity and poor wettability, so that active sites on an electrode are fewer, and the power performance and energy efficiency of the all-vanadium redox flow battery are limited.
Disclosure of Invention
In order to solve the problems of low electrochemical activity and poor hydrophilicity of graphite felt used as an electrode material, the application provides a preparation method and application of a modified graphite felt for a vanadium redox flow galvanic pile.
In order to achieve the technical purpose, the preparation method of the modified graphite felt for the vanadium redox flow battery provided by the application adopts the following technical scheme:
a preparation method of a modified graphite felt for a vanadium redox flow battery comprises the following steps:
step 1, weighing 1g of MAX phase compound and 30mL of strong alkali solution in a vacuum ball milling tank, performing ball milling reaction on a ball milling instrument for 12-24h, and performing vacuum drying at 60-80 ℃ to obtain MXene powder;
step 2, mixing the MXene powder obtained in the step 1 with 200ml of quaternary ammonium compound solution, carrying out ultrasonic water bath, and centrifuging to obtain supernatant fluid to obtain MXene QDs dispersion;
step 3, immersing the graphite felt in MXene QDs dispersion liquid, carrying out hydrothermal reaction, cooling, washing the graphite felt with deionized water, and freeze-drying to obtain the modified graphite felt modified by MXene QDs;
the MAX phase compound is selected from Ti 3 AlC 2 、Ti 2 AlC、Nb 2 AlC、V 2 AlC and Mo 2 One of AlC;
the quaternary ammonium compound solution is selected from one of tetramethyl ammonium hydroxide, tetramethyl ammonium chloride, tetramethyl ammonium bisulfate and tetramethyl ammonium sulfate;
the concentration of the quaternary ammonium compound is 25-60 wt%;
the concentration of the strong alkali solution is 7wt% to 50wt%.
By adopting the technical scheme, the MXene material has excellent conductivity, and the sheet layer is connected with a large amount of-OH, oxygen-containing groups and the like, so that good hydrophilicity is provided; the method adopts MXene to modify the graphite felt, so that the conductivity of the graphite felt can be effectively improved, the specific surface area of the graphite felt is increased, and more reaction interfaces are provided for redox reaction of the vanadium redox flow battery; and greatly increasing the number of oxygen-containing functional groups of the graphite felt electrode, enhancing the hydrophilicity and improving the wettability, thereby being beneficial to accelerating the transmission rate of vanadium ions and improving the battery efficiency.
Step 1 of the application provides a method for preparing MXene quantum dots by alkali liquor etching, which etches amphoteric element Al in MAX phase by alkali liquor, prepares MXene quantum dots without F ions by virtue of corrosiveness of alkaline solution and intercalation of cations, and is beneficial to grafting of subsequent quaternary ammonium compounds.
The quaternary ammonium compound and the MXene surface are grafted and intercalated, interlayer spacing is enlarged, and then ultrasonic treatment is matched, so that two-dimensional MXene can be sheared into MXene quantum dots. The MXene quantum dot obtained by the method not only maintains the characteristics of high specific surface area, high hydrophilicity and excellent conductivity of MXene, but also increases the number of hydrophilic groups on the surface of the MXene material, and the MXene quantum dot cannot easily fall off after being compounded with a graphite felt, and the grafted quaternary ammonium compound introduces a nitrogen source, can realize nitrogen doping after being compounded with the graphite felt, and is beneficial to further improving the electrochemical activity of a graphite felt electrode.
PreferablyThe MAX phase compound is selected from Ti 3 AlC 2 、Ti 2 AlC、Nb 2 AlC、V 2 AlC and Mo 2 One of AlC.
Preferably, the MXene is selected from Ti 3 C 2 T x 、Ti 2 CT x 、Nb 2 CT x 、V 2 CT x And Mo (Mo) 2 CT x One of them.
Preferably, in the step 1, the ball-milling reaction has a ball-to-material ratio of (15-20): 1 and a rotational speed of 400-800rpm.
Preferably, in the step 2, the centrifugation condition is that the rotation speed is 3000-8000rpm and the time is 15-30min.
Preferably, in the step 3, the hydrothermal reaction condition is that the temperature is 60-180 ℃ and the time is 2-15h.
Preferably, the quaternary ammonium compound solution is selected from one of 25wt% tetramethylammonium hydroxide solution, 60wt% tetramethylammonium chloride solution, 40wt% tetramethylammonium bisulfate solution, 35% tetramethylammonium sulfate solution.
Preferably, the strong base is selected from one of sodium hydroxide, potassium hydroxide, tetrabutylammonium hydroxide and choline.
Preferably, the strong base solution is selected from one of 7.39wt% sodium hydroxide solution, 10wt% potassium hydroxide solution, 40wt% tetrabutylammonium hydroxide solution, 48wt% choline solution.
The application also provides a modified graphite felt prepared by the preparation method and application of the modified graphite felt in the all-vanadium redox flow battery.
In summary, the present application has the following beneficial effects:
(1) According to the preparation method of the modified graphite felt, the specific surface area of the graphite felt modified by MXene QDs is greatly improved, and more reaction interfaces are provided for redox reactions of the vanadium redox flow battery; the number of oxygen-containing functional groups of the graphite felt electrode is greatly increased, the hydrophilicity is enhanced, the wettability is improved, the transmission rate of vanadium ions is accelerated, and the battery efficiency is improved;
(2) The MXene QDs introduced by the modified graphite felt have excellent electronic conductivity, and are beneficial to improving the conductivity of the graphite felt, so that the internal ohmic resistance and the reaction polarization resistance of the battery are reduced; meanwhile, the nitrogen source introduced by the quaternary ammonium compound in the preparation process can realize nitrogen atom doping of the graphite felt, so that the electrochemical activity of the graphite felt electrode is improved;
(3) The preparation method of the modified graphite felt provided by the application has high repeatability and simple preparation method, and is suitable for industrial mass production.
Drawings
FIG. 1 is a flow chart of a preparation process of a modified graphite felt for a vanadium redox flow battery of the present application;
fig. 2 is an ac impedance characteristic graph of the modified graphite felt electrode obtained in example 1 of the present application and the original graphite felt electrode.
Detailed Description
The present application is described in further detail below with reference to the drawings and examples.
Referring to fig. 1, a preparation method of a modified graphite felt for a vanadium redox flow battery comprises the following steps:
step 1, weighing MAX phase compound and strong alkali solution in a vacuum ball milling tank, performing ball milling reaction on a ball milling instrument for 12-24 hours, wherein the ball-material ratio is (15-20): 1, the rotating speed is 400-800rpm, and vacuum drying is performed at 60-80 ℃ to obtain MXene powder; wherein the MAX phase compound is selected from Ti 3 AlC 2 、Ti 2 AlC、Nb 2 AlC、V 2 AlC and Mo 2 One of AlC; correspondingly, MXene is Ti 3 C 2 T x 、Ti 2 CT x 、Nb 2 CT x 、V 2 CT x And Mo (Mo) 2 CT x One of the following; the strong base is selected from one of sodium hydroxide, potassium hydroxide, tetrabutylammonium hydroxide and choline.
Step 2, mixing MXene powder with a quaternary ammonium compound solution, and centrifuging at 3000-8000rpm for 15-30min after ultrasonic water bath to obtain supernatant, namely MXene QDs dispersion; wherein the quaternary ammonium compound is selected from one or more of tetramethyl ammonium hydroxide, tetramethyl ammonium chloride, tetramethyl ammonium bisulfate and tetramethyl ammonium sulfate.
And 3, immersing the graphite felt in MXene QDs dispersion liquid, carrying out hydrothermal reaction for 2-15h at 60-180 ℃, cooling, washing the graphite felt with deionized water, and freeze-drying to obtain the modified graphite felt modified by MXene QDs.
Examples
Example 1
The preparation method of the modified graphite felt for the vanadium redox flow galvanic pile specifically comprises the following steps:
step 1, weighing Ti 3 AlC 2 Powder 1g, 2mol/L (7.39 wt%) sodium hydroxide solution 30ml are placed in a vacuum ball-milling tank, and high-energy ball-milling reaction is carried out for 12h on a planetary ball-milling instrument, the ball-material ratio is controlled to be 15:1, the rotating speed is controlled to be 800rpm, and vacuum drying is carried out at 60 ℃ to obtain Ti 3 C 2 T x And (3) powder.
Step 2, ti obtained in the step 1 is processed 3 C 2 T x Mixing the powder with 200mL of 25wt% tetramethylammonium hydroxide aqueous solution, performing water bath ultrasonic treatment in 40KHz ultrasonic machine for 36 hr, centrifuging at 6000rpm for 20min, and collecting supernatant to obtain Ti 3 C 2 T x QDs dispersion.
Step 3, immersing a polyacrylonitrile-based graphite felt (10 cm. Times.10 cm. Times.6 mm) in 100mL of Ti 3 C 2 T x Placing the QDs dispersion liquid into a reaction kettle to perform a hydrothermal reaction under the conditions of 120 ℃ for 10 hours, cooling to 25 ℃, washing the graphite felt with deionized water, and freeze-drying for 18 hours to obtain Ti 3 C 2 T x QDs modified graphite felt.
Example 2
The preparation method of the modified graphite felt for the vanadium redox flow galvanic pile specifically comprises the following steps:
step 1, weighing Ti 2 AlC powder 1g and 40wt% tetrabutylammonium hydroxide solution 30ml are put in a vacuum ball milling tank, high-energy ball milling reaction is carried out for 15 hours on a planetary ball mill, the ball-material ratio is controlled to be 16:1, the rotating speed is controlled to be 700rpm, and Ti is obtained by vacuum drying at 60 ℃ 2 CT x And (3) powder.
Step 2, ti obtained in the step 1 is processed 2 CT x Powder with 200mL, 60wt% tetramethyl chlorideMixing ammonium solution, performing water bath ultrasonic treatment in 40KHz ultrasonic machine for 48 hr, centrifuging at 8000rpm for 15min, and collecting supernatant to obtain Ti 2 CT x QDs dispersion.
Step 3, immersing a polyacrylonitrile-based graphite felt (10 cm. Times.10 cm. Times.6 mm) in 100mL of Ti 2 CT x Placing the QDs dispersion liquid into a reaction kettle to perform a hydrothermal reaction under the condition of 150 ℃ for 8 hours, cooling to 25 ℃, washing the graphite felt with deionized water, and freeze-drying for 18 hours to obtain Ti 2 CT x QDs modified graphite felt.
Example 3
The preparation method of the modified graphite felt for the vanadium redox flow galvanic pile specifically comprises the following steps:
step 1, weighing Nb 2 1g AlC powder, 30ml 2mol/L (10 wt%) potassium hydroxide solution are placed in a vacuum ball-milling tank, high-energy ball-milling reaction is carried out for 18h on a planetary ball-milling instrument, the ball-material ratio is controlled to be 17:1, the rotating speed is controlled to be 600rpm, and vacuum drying is carried out at 80 ℃ to obtain Nb 2 CT x And (3) powder.
Step 2, nb obtained in the step 1 is obtained 2 CT x Mixing the powder with 200mL of 25wt% tetramethylammonium hydroxide solution, performing water bath ultrasonic treatment in 40KHz ultrasonic machine for 48 hr, centrifuging at 8000rpm for 15min, and collecting supernatant to obtain Nb 2 CT x QDs dispersion.
Step 3, immersing a polyacrylonitrile-based graphite felt (10 cm. Times.10 cm. Times.6 mm) in 100mL Nb 2 CT x Placing the QDs dispersion liquid into a reaction kettle for hydrothermal reaction under the conditions of 100 ℃ for 15 hours, cooling to 25 ℃, washing graphite felt with deionized water, and freeze-drying for 18 hours to obtain Nb 2 CT x QDs modified graphite felt.
Example 4
The preparation method of the modified graphite felt for the vanadium redox flow galvanic pile specifically comprises the following steps:
step 1, weighing V 2 1g of AlC powder and 30ml of 48wt% choline solution are put in a vacuum ball milling tank, high-energy ball milling reaction is carried out for 15 hours on a planetary ball mill, the ball-to-material ratio is controlled to be 18:1, the rotating speed is controlled to be 500rpm, and the rotating speed is controlled to be 60Vacuum drying at a temperature of V 2 CT x And (3) powder.
Step 2, V obtained in the step 1 2 CT x Mixing the powder with 200mL of 40wt% tetramethyl ammonium bisulfate solution, performing water bath ultrasonic treatment in 40KHz ultrasonic machine for 48 hr, centrifuging at 8000rpm for 15min, and collecting supernatant to obtain V 2 CT x QDs dispersion.
Step 3, immersing a polyacrylonitrile-based graphite felt (10 cm. Times.10 cm. Times.6 mm) in 100mL V 2 CT x Placing the QDs dispersion liquid into a reaction kettle for hydrothermal reaction under the condition of 150 ℃ for 8 hours, cooling to 25 ℃, washing graphite felt with deionized water, and freeze-drying for 18 hours to obtain V 2 CT x QDs modified graphite felt.
Example 5
The preparation method of the modified graphite felt for the vanadium redox flow galvanic pile specifically comprises the following steps:
step 1, weighing Mo 2 AlC powder 1g, 40wt% tetrabutylammonium hydroxide solution 30ml are put in a vacuum ball milling tank, high-energy ball milling reaction is carried out for 24 hours on a planetary ball mill, the ball-material ratio is controlled to be 20:1, the rotating speed is controlled to be 400rpm, and Mo is obtained by vacuum drying at 60 ℃ 2 CT x And (3) powder.
Step 2, mo obtained in the step 1 is processed 2 CT x Mixing the powder with 200mL of 35wt% tetramethyl ammonium sulfate solution, performing water bath ultrasonic treatment in 40KHz ultrasonic machine for 36h, centrifuging at 5000rpm for 30min, and collecting supernatant to obtain Mo 2 CT x QDs dispersion.
Step 3, immersing a polyacrylonitrile-based graphite felt (10 cm. Times.10 cm. Times.6 mm) in 100mL of Mo 2 CT x Placing the QDs dispersion liquid into a reaction kettle for hydrothermal reaction under the conditions of 180 ℃ for 6 hours, cooling to 25 ℃, washing the graphite felt with deionized water, and freeze-drying for 12 hours to obtain Mo 2 CT x QDs modified graphite felt.
Comparative example
Comparative example 1
The polyacrylonitrile-based graphite felt is the original graphite felt without any modification treatment.
Comparative example 2
The preparation method of the MXene/graphite felt composite material specifically comprises the following steps:
step 1: weigh Ti 3 AlC 2 Carrying out high-energy ball milling reaction for 12 hours on 1g of powder and 30ml of 2mol/L sodium hydroxide solution in a vacuum ball milling tank on a planetary ball mill, controlling the ball-material ratio to be 15:1, controlling the rotating speed to be 800rpm, and carrying out vacuum drying at 60 ℃ to obtain Ti 3 C 2 T x And (3) powder.
Step 2: ti obtained in step 1 3 C 2 T x Dispersing the powder in 200ml distilled water, performing water bath ultrasonic treatment in 40KHz ultrasonic machine for 36 hr, centrifuging at 6000rpm for 20min, collecting supernatant to obtain Ti 3 C 2 T x And (3) a dispersion.
Step 3: polyacrylonitrile-based graphite felt (10 cm. Times.10 cm. Times.6 mm) was immersed in 100ml of Ti 3 C 2 T x Placing the dispersion liquid into a reaction kettle to perform hydrothermal reaction under the condition of 120 ℃ for 10 hours, cooling to room temperature, washing the graphite felt with deionized water, and freeze-drying for 18 hours to obtain Ti 3 C 2 T x Graphite felt composite material.
Performance test
The products prepared in the examples and the comparative examples are subjected to electrochemical tests, and the specific test method is as follows: the end plate, the copper current collecting plate, the bipolar plate, the graphite felt electrode, the liquid flow frame, the Nafion-212 ion membrane, the liquid flow frame, the graphite felt electrode, the bipolar plate, the copper current collector and the end plate are sequentially stacked, sealed by gaskets, and fastened by bolts and nuts to form the galvanic pile. The initial valence state of the positive and negative electrolyte is 1.5M V 3.5+ + 2M H 2 SO 4 The volume of the mixed solution is 100mL, peristaltic pumps are used for providing power, the electrolyte circularly flows in the battery, and the flow rate is unified to be 80mL/min. And on a blue electric battery test system, completing constant-current charge and discharge test on the assembled all-vanadium redox flow battery, wherein the charge and discharge cut-off voltage is 1.65-0.90V, and the effective area of a graphite felt is 10cm multiplied by 10cm. Voltage efficiency, energy efficiency were tested and recorded under the same test conditions. The test results are recorded inTable 1.
The element content of the products prepared in example 1 and comparative example 1 is measured, and the specific measuring method is as follows: energy Dispersive Spectrometry (EDS), cutting graphite felt to 0.3 cm x 0.3 cm sheets, adhesively securing to a sample stage using conductive adhesive, incubating for 10h in a vacuum oven at 60 ℃ and sufficiently drying to ensure no residual moisture effects on the test results. And testing the sample by using an energy dispersion spectrometer after drying to obtain the content of the surface elements of the graphite felt electrode. The measurement results are shown in Table 2 below.
TABLE 1 vanadium redox flow pile Performance test results
Table 2 determination of surface element content of graphite felt electrode obtained in example 1 and comparative example 1
From the above test results, it can be seen that the test results of examples 1 to 5 have smaller phase difference amplitude under the same current density, and the test results are more stable and have good reproducibility, which indicates that the preparation method of the modified graphite felt of the present application is more stable.
The method has the advantages that the method is difficult to directly prepare the MXene quantum dots without adding quaternary ammonium compounds, the MXene is large in size, the MXene is not easy to compound with the graphite felt, the forced compounding is easy to cause uneven compounding, the electrochemical performance is not obviously improved, and the MXene is easy to fall off from the graphite felt, so that the MXene/graphite felt composite material is directly prepared, namely the comparative example 2.
Comparing the test results of example 1 with those of comparative examples 1 and 2, it can be seen that: whether at 200mA/cm 2 Is also under the current density test condition of 250mA/cm 2 In comparison with comparative examples 1 and 2, example 1 shows higher voltage efficiency and energy efficiency, which shows that the graphite felt can be effectively enlarged by modifying the graphite felt after grafting intercalation of quaternary ammonium compound and MXene surfaceThe specific surface area of the vanadium redox flow battery is increased, hydrophilicity is enhanced, more reaction interfaces are improved for redox reaction of the vanadium redox flow battery, and therefore the transmission efficiency of vanadium ions is accelerated, and the battery efficiency is improved.
Referring to fig. 2, which is an ac impedance characteristic graph of the modified graphite felt and the original graphite felt electrode obtained in example 1 of the present application, it can be seen that: the semi-circle diameter of the modified graphite felt electrode in the high frequency area is smaller, and the slope of the straight line in the low frequency area is larger, so that the modified graphite felt electrode has smaller charge transfer resistance and faster vanadium ion transmission rate. The modified graphite felt is beneficial to improving the conductivity of the graphite felt, accelerating the transmission rate of vanadium ions and improving the electrochemical activity of a graphite felt electrode.
As can be seen from the measurement results of the above Table 2, the nitrogen source introduced by the quaternary ammonium compound can realize nitrogen atom doping of the graphite felt in the preparation process, and the electrochemical activity of the graphite felt electrode is improved.
The above description is only a preferred embodiment of the present application, and the protection scope of the present application is not limited to the above examples, and all technical solutions belonging to the concept of the present application belong to the protection scope of the present application. It should be noted that modifications and adaptations to those skilled in the art without departing from the principles of the present application are intended to be comprehended within the scope of the present application.
Claims (10)
1. The preparation method of the modified graphite felt for the vanadium redox flow galvanic pile is characterized by comprising the following steps of:
step 1, weighing 1g of MAX phase compound and 30mL of strong alkali solution in a vacuum ball milling tank, performing ball milling reaction on a ball milling instrument for 12-24h, and performing vacuum drying at 60-80 ℃ to obtain MXene powder;
step 2, mixing the MXene powder obtained in the step 1 with 200mL of quaternary ammonium compound solution, carrying out ultrasonic water bath, and centrifuging to obtain supernatant fluid to obtain MXene QDs dispersion;
step 3, immersing the graphite felt in MXene QDs dispersion liquid, carrying out hydrothermal reaction, cooling, washing the graphite felt with deionized water, and freeze-drying to obtain the modified graphite felt modified by MXene QDs;
the MAX phase compound is selected from Ti 3 AlC 2 、Ti 2 AlC、Nb 2 AlC、V 2 AlC and Mo 2 One of AlC;
the quaternary ammonium compound is selected from one or more of tetramethyl ammonium hydroxide, tetramethyl ammonium chloride, tetramethyl ammonium bisulfate and tetramethyl ammonium sulfate;
the concentration of the quaternary ammonium compound solution ranges from 25wt% to 60wt%;
the concentration of the strong base solution ranges from 7wt% to 50wt%.
2. The method for preparing a modified graphite felt for a vanadium redox flow battery according to claim 1, wherein the MXene is selected from Ti 3 C 2 T x 、Ti 2 CT x 、Nb 2 CT x 、V 2 CT x And Mo (Mo) 2 CT x One of them.
3. The method for preparing a modified graphite felt for a vanadium redox flow battery according to claim 1, wherein in the step 1, the ball-milling reaction has a ball-to-material ratio of (15-20): 1 and a rotational speed of 400-800rpm.
4. The method for preparing a modified graphite felt for a vanadium redox flow battery according to claim 1, wherein in the step 2, the centrifugation condition is a rotation speed of 3000-8000rpm for 15-30min.
5. The method for preparing a modified graphite felt for a vanadium redox flow battery according to claim 1, wherein in the step 3, the hydrothermal reaction condition is that the temperature is 60-180 ℃ and the time is 2-15h.
6. The method for preparing a modified graphite felt for a vanadium redox flow battery according to claim 1, wherein the quaternary ammonium compound solution is one selected from a 25wt% tetramethylammonium hydroxide solution, a 60wt% tetramethylammonium chloride solution, a 40wt% tetramethylammonium bisulfate solution, and a 35% tetramethylammonium sulfate solution.
7. The method for preparing a modified graphite felt for a vanadium redox flow battery according to claim 1, wherein the strong base is one selected from sodium hydroxide, potassium hydroxide, tetrabutylammonium hydroxide, and choline.
8. The method for preparing a modified graphite felt for a vanadium redox flow battery according to claim 7, wherein the strong base solution is one selected from 7.39wt% sodium hydroxide solution, 10wt% potassium hydroxide solution, 40wt% tetrabutylammonium hydroxide solution, 48wt% choline solution.
9. A modified graphite felt characterized in that it is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the modified graphite felt of claim 9 in a vanadium redox flow battery.
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