CN116043531B - Modified graphite felt for high density of vanadium battery and preparation method and application thereof - Google Patents
Modified graphite felt for high density of vanadium battery and preparation method and application thereof Download PDFInfo
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- CN116043531B CN116043531B CN202310203396.9A CN202310203396A CN116043531B CN 116043531 B CN116043531 B CN 116043531B CN 202310203396 A CN202310203396 A CN 202310203396A CN 116043531 B CN116043531 B CN 116043531B
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- titanium dioxide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 26
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 71
- 239000010439 graphite Substances 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012153 distilled water Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 16
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 16
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims abstract description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 238000010000 carbonizing Methods 0.000 claims abstract description 13
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 150
- 239000004408 titanium dioxide Substances 0.000 claims description 75
- 238000010438 heat treatment Methods 0.000 claims description 49
- 238000005576 amination reaction Methods 0.000 claims description 21
- 239000002105 nanoparticle Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 claims description 8
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 8
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- 239000012989 trithiocarbonate Substances 0.000 claims description 3
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 239000000835 fiber Substances 0.000 abstract description 11
- 239000002077 nanosphere Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 22
- 229920006243 acrylic copolymer Polymers 0.000 description 22
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DEKVAWHRMRNKMI-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1OOC(C)(C)C DEKVAWHRMRNKMI-UHFFFAOYSA-N 0.000 description 1
- 229910003088 Ti−O−Ti Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
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- 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
- H01M4/8803—Supports for the deposition of the catalytic active composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
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- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
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Abstract
The invention discloses a modified graphite felt for high density of a vanadium battery, and a preparation method and application thereof, and at least comprises the following steps: step S1: obtaining a first precursor; step S2: obtaining a second precursor; step S3: sequentially adding acrylic acid, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, a cross-linking agent and a chain transfer agent into distilled water, stirring fully, and neutralizing by using alkali liquor to obtain a dispersion liquid; step S4: immersing the second precursor in the dispersion liquid, adding an initiator, cooling and drying to obtain a dispersion liquid coated second precursor; step S5: carbonizing the dispersion liquid to coat the second precursor, and obtaining the modified graphite felt. The invention can effectively improve the specific surface area of the graphite felt fiber, and the carbonized carbon layer not only plays a role in fixing the nanospheres to ensure the carbon sphere structure, but also has good conductivity and more defect sites, can provide more oxygen-containing functional groups, and provides enough active sites for oxidation-reduction reaction.
Description
Technical Field
The invention relates to the technical field of graphite felt for an all-vanadium redox flow battery (VRB), in particular to a modified graphite felt for high electric density of a vanadium battery, and a preparation method and application thereof.
Background
Since the proposal of the concept of the flow battery in the 70 th century of the 20 th century, great efforts have been made in the national government, academia and industry to promote the development of the flow battery technology, i.e. industrialization. The full vanadium redox flow battery technology is initially verified in safety, long service life, environment protection and reliability along with basic research and development, industrialization, technical application and other aspects in more than ten years, becomes the most widely used redox flow battery energy storage technology in commercialization, and along with rapid development of green new energy, the full vanadium redox flow battery technology industry will come to market and industry burst period.
The active material in the vanadium battery electrolyte receives or gives out electrons at the electrode-electrolyte interface to complete electrochemical reaction, so as to realize conversion between electric energy and chemical energy, and further complete energy storage and release. The graphite felt electrode is a key part of the all-vanadium redox flow battery, and the quality of the material directly influences the electrochemical reaction speed, the internal resistance of the battery and the uniformity of electrolyte distribution.
In the present stage, the design of the high-power density electric pile can greatly reduce the manufacturing cost of the all-vanadium redox flow battery, and becomes an important direction of research and development of the all-vanadium redox flow battery. However, the high power density requires that the electrode has higher electrochemical catalytic activity and electrochemical reversibility under high working current density, so that the active area and hydrophilicity of the graphite felt electrode need to be increased, and further, the activation polarization is reduced.
Disclosure of Invention
The invention aims to provide a modified graphite felt for high density of a vanadium battery, and a preparation method and application thereof, and the prepared modified graphite felt has high specific surface area and rich active sites, and can be suitable for high working current density, so that a high-power vanadium battery pile has high energy efficiency.
The technical scheme adopted by the invention is as follows:
the preparation method of the modified graphite felt for high density of the vanadium battery at least comprises the following steps:
step S1: mixing an aqueous solution containing a template agent with an amination reagent, heating, stirring, cooling, centrifuging and cleaning to obtain a first precursor;
step S2: immersing graphite felt in the aqueous solution of the first precursor, and drying to obtain a second precursor;
step S3: sequentially adding acrylic acid, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, a cross-linking agent and a chain transfer agent into distilled water, stirring fully, and neutralizing by using alkali liquor to obtain a dispersion liquid;
step S4: immersing the second precursor in the dispersion liquid, adding an initiator, cooling and drying to obtain a dispersion liquid coated second precursor;
step S5: carbonizing the dispersion liquid to coat the second precursor, and obtaining the modified graphite felt.
Preferably, the modified graphite felt comprises the following components in parts by weight: 30-60 parts of template agent, 40-70 parts of amination reagent, 30-50 parts of acrylic acid, 20-40 parts of acrylamide, 5-10 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1-2 parts of cross-linking agent, 0.2-0.5 part of chain transfer agent and 0.5-1.5 parts of initiator.
Preferably, the template agent is titanium dioxide nano particles;
preferably, the amination reagent is at least one selected from aminopropyl triethoxysilane and polydiallyl dimethylamine hydrochloride.
Preferably, the crosslinking agent is at least one selected from N, N' -methylenebisacrylamide, epichlorohydrin, divinylbenzene and bis-tert-butylperoxyisopropyl benzene.
Preferably, the chain transfer agent is at least one selected from dodecyl mercaptan, sodium bisulphite, sodium hypophosphite and trithiocarbonate.
Preferably, the initiator is at least one selected from ammonium persulfate, sodium persulfate, potassium persulfate, azobisisobutyronitrile, diisopropyl peroxydicarbonate and dilauroyl peroxide.
Preferably, in step S1,
the conditions of heating, stirring, cooling and centrifuging are as follows:
heating at 65-80deg.C;
further preferably, the heating temperature is any value or a range of values between two values of 65 ℃, 70 ℃, 75 ℃, 80 ℃.
Stirring for 6-12h;
further preferably, the stirring time is any value or a range of values between two values of 6h, 7h, 8h, 9h, 10h, 11h, 12h.
Ultrasonic oscillation for 20-40min;
further preferably, the ultrasonic oscillation is performed for any value or a range of values between two values of 20min, 25min, 30min, 35min, 40 min.
Ball milling for 10-12h.
Further preferably, any value or range of values between two values of 10h, 10.5h, 11h, 11.5h, 12h are ball milled.
Preferably, in step S4,
the carbonization conditions are as follows:
the temperature rising rate is 3-10 ℃/min;
further preferably, the temperature rise rate is any value or a range of values between two values of 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min.
Heating to 300-500 ℃;
further preferably, the heating temperature is any value or a range of values between two values in the range of 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃.
The heat preservation time is 4-8h.
Further preferably, the incubation time is any value or range of values between two values of 4h, 5h, 6h, 7h, 8h.
The invention also provides a modified graphite felt for high-density vanadium battery, which is prepared by the preparation method according to any one of the above.
The invention also provides an electrode which contains the modified graphite felt for high density of the vanadium battery.
The beneficial effects of the invention at least comprise:
1. the invention can effectively improve the specific surface area of the graphite felt fiber, and the carbonized carbon layer not only plays a role in fixing the nanospheres to ensure the carbon sphere structure, but also has good conductivity and more defect sites, can provide more oxygen-containing functional groups, and provides enough active sites for oxidation-reduction reaction.
2. The modified graphite felt for the high-density vanadium battery, which is prepared by the invention, controls the carbonization degree of acrylic acid through a sintering process, enhances the conductivity and realizes better activation performance.
3. The modified graphite felt electrode has small polarization and small load transfer resistance, can greatly improve the voltage efficiency and the energy efficiency of a galvanic pile, and has more remarkable advantages especially under the condition of high current working density.
Drawings
FIG. 1 is a mechanism diagram of a preparation method of a modified graphite felt for high density of a vanadium battery;
FIG. 2 is an infrared spectrum of an aminated titanium dioxide of example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the product of each stage of example 1 of the present invention.
Detailed Description
The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, the mechanism of the present invention is: firstly, amination is carried out on the surface of a template agent titanium dioxide nanoparticle to ensure that the surface of the nanoparticle is positively charged, and the surface of a graphite felt fiber is negatively charged, so that the nanoparticle can be uniformly adsorbed on the surface of the graphite felt fiber (GF) to obtain TiO 2 GF, then adding acrylic acid, acrylamide and 2-acrylamide-2-methylpropanesulfonic acid, and making free radical copolymerization reaction to obtain copolymer/TiO 2 and/GF, finally sintering and carbonizing at high temperature to obtain a carbonized layer/TiO 2 GF modified graphite felt.
Example 1
Step S1: 45 parts of template titanium dioxide nano particles are dissolved in 500 parts of distilled water,mixing with 55 parts of aminopropyl triethoxysilane, heating to 70deg.C, stirring for 10 hr, cooling, centrifuging, ultrasonically oscillating for 30min, cleaning with distilled water for several times, and ball milling for 10 hr to obtain aminated titanium dioxide (TiO) 2 -NH 2 ) The method comprises the steps of carrying out a first treatment on the surface of the Referring to FIG. 2, it can be found that 3432cm was observed by comparing the infrared spectra before and after amination of titanium dioxide -1 The place is the-OH telescopic vibration absorption peak of 2920cm -1 The stretching vibration peak of C-H. 1625cm -1 The O-H bending vibration peak of the water adsorbed between titanium dioxide layers. 604cm -1 Is the absorption peak of Ti-O-Ti. As can be seen from the figure, the number of new peaks of the amino modified nanoparticle is 1096cm -1 Is C-N telescopic vibration peak 964cm -1 The adsorption peak of Si-O-Ti is the adsorption peak, and the amino group exists on the modified nano particles in the titanium dioxide amination reaction process, which indicates that the amino group grafting is successful.
Step S2: immersing a graphite felt in the aqueous solution of the aminated titanium dioxide, and drying to obtain a titanium dioxide/graphite felt; since the surface of the aminated titanium dioxide is strongly electropositive and the surface of the micron-sized graphite felt fiber is negatively charged to a certain extent, the aminated titanium dioxide can be adsorbed on the graphite felt fiber, as shown in (a) of fig. 3, the graphite felt fiber; as in (b) of fig. 3, which is a titanium dioxide/graphite felt, it can be seen that titanium dioxide is uniformly attached to the graphite felt fibers.
Step S3: sequentially adding 45 parts of acrylic acid, 37 parts of acrylamide, 10 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1.5 parts of cross-linking agent N, N' -methylene bisacrylamide and 0.2 part of chain transfer agent dodecyl mercaptan into 900 parts of distilled water, stirring fully, and neutralizing by using alkali liquor to obtain an acrylic copolymer;
step S4: immersing the titanium dioxide/graphite felt in the acrylic acid copolymer, adding 1.3 parts of initiator ammonium persulfate, cooling and drying to obtain an acrylic acid copolymer coated titanium dioxide/graphite felt; as shown in FIG. 3 (c) is an acrylic copolymer coated titanium dioxide/graphite felt, after which the acrylic copolymer is coated, the graphite felt fibers and TiO are replicated 2 The morphology of the nanospheres and the size of the nanospheres are increased. At the same time due to the acrylic copolymerThe structure of the carbon sphere is not easy to damage, and the stability of the electrode structure is ensured.
Step S5: heating at a heating rate of 5 ℃/min, heating at a temperature of 450 ℃ and preserving heat for 4 hours, and carbonizing the acrylic copolymer coated titanium dioxide/graphite felt to obtain the modified graphite felt. As shown in fig. 3 (d) which is a modified graphite felt, the acrylic copolymer is converted into a carbon layer at high temperature, and other structural integrity is maintained without any damage except for the thickness variation. TiO is also evident from the enlarged view 2 The nanospheres and the fibers are completely coated by the carbon layer, so that the carbon layer with uniformly dispersed carbon spheres is formed.
Example 2
Step S1: dissolving 35 parts of template agent titanium dioxide nano particles in 800 parts of distilled water, mixing with 65 parts of amination reagent polydiallyl dimethylamine hydrochloride, heating to 65 ℃, stirring for 6 hours, cooling, centrifuging, ultrasonically oscillating for 20 minutes, adopting distilled water for cleaning for many times, and ball-milling for 11 hours to obtain aminated titanium dioxide (TiO) 2 -NH 2 ）；
Step S2: immersing a graphite felt in the aqueous solution of the aminated titanium dioxide, and drying to obtain a titanium dioxide/graphite felt;
step S3: sequentially adding 30 parts of acrylic acid, 40 parts of acrylamide, 10 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1 part of cross-linking agent divinylbenzene and 0.5 part of chain transfer agent sodium bisulphite into 1000 parts of distilled water, stirring fully, and neutralizing by using alkali liquor to obtain an acrylic copolymer;
step S4: immersing the titanium dioxide/graphite felt in the acrylic acid copolymer, adding 1 part of initiator sodium persulfate, cooling and drying to obtain an acrylic acid copolymer coated titanium dioxide/graphite felt;
step S5: heating at a heating rate of 3 ℃/min, heating at 350 ℃ and preserving heat for 6 hours, and carbonizing the acrylic copolymer coated titanium dioxide/graphite felt to obtain the modified graphite felt.
Example 3
Step S1: 30 parts of template titanium dioxide nanoparticles were dissolved in 400 parts of distilled water and aminated with 70 partsMixing the reagent polydiallyl dimethylamine hydrochloride, heating to 80 ℃, stirring for 8 hours, cooling, centrifuging, ultrasonically oscillating for 25 minutes, washing for many times by distilled water, and ball milling for 11 hours to obtain the aminated titanium dioxide (TiO) 2 -NH 2 ）；
Step S2: immersing a graphite felt in the aqueous solution of the aminated titanium dioxide, and drying to obtain a titanium dioxide/graphite felt;
step S3: sequentially adding 35 parts of acrylic acid, 25 parts of acrylamide, 8 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1.5 parts of cross-linking agent divinylbenzene and 0.3 part of chain transfer agent sodium hypophosphite into 1500 parts of distilled water, stirring fully, and neutralizing by using alkali liquor to obtain an acrylic copolymer;
step S4: immersing the titanium dioxide/graphite felt in the acrylic acid copolymer, adding 1.5 parts of initiator potassium persulfate, cooling and drying to obtain an acrylic acid copolymer coated titanium dioxide/graphite felt;
step S5: heating at a heating rate of 6 ℃/min, heating at 500 ℃, and preserving heat for 8 hours, carbonizing the acrylic copolymer coated titanium dioxide/graphite felt, thereby obtaining the modified graphite felt.
Example 4
Step S1: 45 parts of template titanium dioxide nano particles are dissolved in 600 parts of distilled water and mixed with 55 parts of amination reagent aminopropyl triethoxysilane, the heating temperature is 75 ℃, the mixture is stirred for 12 hours, the mixture is cooled, centrifuged and ultrasonically oscillated for 30 minutes, distilled water is adopted for multiple cleaning, and the amination titanium dioxide (TiO) is obtained after ball milling for 10 hours 2 -NH 2 ）；
Step S2: immersing a graphite felt in the aqueous solution of the aminated titanium dioxide, and drying to obtain a titanium dioxide/graphite felt;
step S3: sequentially adding 40 parts of acrylic acid, 30 parts of acrylamide, 8 parts of 2-acrylamide-2-methylpropanesulfonic acid, 2 parts of cross-linking agent epichlorohydrin and 0.4 part of chain transfer agent dodecyl mercaptan into 1700 parts of distilled water, stirring fully, and neutralizing by using alkali liquor to obtain an acrylic copolymer;
step S4: immersing the titanium dioxide/graphite felt in the acrylic acid copolymer, adding 1 part of initiator azodiisobutyronitrile, cooling and drying to obtain an acrylic acid copolymer coated titanium dioxide/graphite felt;
step S5: heating at a heating rate of 8 ℃/min, heating at 300 ℃ and preserving heat for 5 hours, and carbonizing the acrylic copolymer coated titanium dioxide/graphite felt to obtain the modified graphite felt.
Example 5
Step S1: dissolving 50 parts of template titanium dioxide nano particles in 900 parts of distilled water, mixing with 50 parts of amination reagent polydiallyl dimethylamine hydrochloride, heating to 65 ℃, stirring for 10 hours, cooling, centrifuging, ultrasonically oscillating for 40 minutes, adopting distilled water for cleaning for many times, and ball-milling for 12 hours to obtain aminated titanium dioxide (TiO) 2 -NH 2 ）；
Step S2: immersing a graphite felt in the aqueous solution of the aminated titanium dioxide, and drying to obtain a titanium dioxide/graphite felt;
step S3: sequentially adding 50 parts of acrylic acid, 20 parts of acrylamide, 6 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1 part of cross-linking agent di-tert-butyl peroxy isopropyl benzene and 0.5 part of chain transfer agent dodecyl mercaptan into 1400 parts of distilled water, stirring fully, and neutralizing by using alkali liquor to obtain an acrylic acid copolymer;
step S4: immersing the titanium dioxide/graphite felt in the acrylic acid copolymer, adding 0.8 part of initiator diisopropyl peroxydicarbonate, cooling and drying to obtain an acrylic acid copolymer coated titanium dioxide/graphite felt;
step S5: heating at a heating rate of 10 ℃/min, heating at a temperature of 450 ℃ and preserving heat for 7 hours, and carbonizing the acrylic copolymer coated titanium dioxide/graphite felt to obtain the modified graphite felt.
Example 6
Step S1: 60 parts of template agent titanium dioxide nano particles are dissolved in 700 parts of distilled water and mixed with 40 parts of amination reagent polydiallyl dimethylamine hydrochloride, the heating temperature is 70 ℃, the mixture is stirred for 8 hours, the mixture is cooled, centrifuged and ultrasonically oscillated for 35 minutes, distilled water is adopted for multiple cleaning, and the mixture is ball-milled for 11 hours to obtain the amination titanium dioxide (TiO) 2 -NH 2 ）；
Step S2: immersing a graphite felt in the aqueous solution of the aminated titanium dioxide, and drying to obtain a titanium dioxide/graphite felt;
step S3: sequentially adding 45 parts of acrylic acid, 30 parts of acrylamide, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1.5 parts of cross-linking agent N, N' -methylene bisacrylamide and 0.2 part of chain transfer agent sodium bisulphite into 1200 parts of distilled water, stirring fully, and neutralizing by using alkali liquor to obtain an acrylic copolymer;
step S4: immersing the titanium dioxide/graphite felt in the acrylic acid copolymer, adding 0.5 part of initiator dilauroyl peroxide, cooling and drying to obtain the acrylic acid copolymer coated titanium dioxide/graphite felt;
step S5: heating at a heating rate of 5 ℃/min, heating at 400 ℃ and preserving heat for 5 hours, and carbonizing the acrylic copolymer coated titanium dioxide/graphite felt to obtain the modified graphite felt.
Example 7
Step S1: dissolving 55 parts of template titanium dioxide nano particles in 600 parts of distilled water, mixing with 45 parts of amination reagent polydiallyl dimethylamine hydrochloride, heating to 75 ℃, stirring for 6 hours, cooling, centrifuging, ultrasonically oscillating for 25 minutes, adopting distilled water for multiple cleaning, and ball milling for 10 hours to obtain the amination titanium dioxide (TiO 2 -NH 2 ）；
Step S2: immersing a graphite felt in the aqueous solution of the aminated titanium dioxide, and drying to obtain a titanium dioxide/graphite felt;
step S3: sequentially adding 40 parts of acrylic acid, 35 parts of acrylamide, 8 parts of 2-acrylamide-2-methylpropanesulfonic acid, 2 parts of cross-linking agent N, N' -methylenebisacrylamide and 0.4 part of chain transfer agent dodecyl mercaptan into 1900 parts of distilled water, stirring fully, and neutralizing by using alkali liquor to obtain an acrylic copolymer;
step S4: immersing the titanium dioxide/graphite felt in the acrylic acid copolymer, adding 1 part of initiator ammonium persulfate, cooling and drying to obtain an acrylic acid copolymer coated titanium dioxide/graphite felt;
step S5: heating at a heating rate of 3 ℃/min, heating at a temperature of 450 ℃ and preserving heat for 6 hours, and carbonizing the acrylic copolymer coated titanium dioxide/graphite felt to obtain the modified graphite felt.
Example 8
Step S1: dissolving 40 parts of template titanium dioxide nano particles in 800 parts of distilled water, mixing with 60 parts of amination reagent aminopropyl triethoxysilane, heating to 70 ℃, stirring for 8 hours, cooling, centrifuging, ultrasonically oscillating for 30 minutes, adopting distilled water for cleaning for many times, and ball-milling for 12 hours to obtain the amination titanium dioxide (TiO 2 -NH 2 ）；
Step S2: immersing a graphite felt in the aqueous solution of the aminated titanium dioxide, and drying to obtain a titanium dioxide/graphite felt;
step S3: sequentially adding 35 parts of acrylic acid, 30 parts of acrylamide, 7 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1 part of cross-linking agent divinylbenzene and 0.3 part of chain transfer agent trithiocarbonate into 1600 parts of distilled water, stirring fully, and neutralizing by using alkali liquor to obtain an acrylic copolymer;
step S4: immersing the titanium dioxide/graphite felt in the acrylic acid copolymer, adding 1.2 parts of initiator sodium persulfate, cooling and drying to obtain an acrylic acid copolymer coated titanium dioxide/graphite felt;
step S5: heating at a heating rate of 4 ℃/min, heating at 300 ℃ and preserving heat for 4 hours, and carbonizing the acrylic copolymer coated titanium dioxide/graphite felt to obtain the modified graphite felt.
Example 9
Step S1: 45 parts of template titanium dioxide nano particles are dissolved in 900 parts of distilled water and mixed with 55 parts of amination reagent aminopropyl triethoxysilane, the heating temperature is 65 ℃, the mixture is stirred for 7 hours, the mixture is cooled, centrifuged and ultrasonically oscillated for 30 minutes, distilled water is adopted for multiple cleaning, and the mixture is ball-milled for 10 hours to obtain the amination titanium dioxide (TiO) 2 -NH 2 ）；
Step S2: immersing a graphite felt in the aqueous solution of the aminated titanium dioxide, and drying to obtain a titanium dioxide/graphite felt;
step S3: sequentially adding 40 parts of acrylic acid, 25 parts of acrylamide, 9 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1.5 parts of cross-linking agent divinylbenzene and 0.3 part of chain transfer agent dodecyl mercaptan into 1200 parts of distilled water, stirring fully, and neutralizing by using alkali liquor to obtain an acrylic copolymer;
step S4: immersing the titanium dioxide/graphite felt in the acrylic acid copolymer, adding 1.5 parts of initiator azodiisobutyronitrile, cooling and drying to obtain an acrylic acid copolymer coated titanium dioxide/graphite felt;
step S5: heating at a heating rate of 7 ℃/min, heating at 350 ℃ and preserving heat for 4 hours, and carbonizing the acrylic copolymer coated titanium dioxide/graphite felt to obtain the modified graphite felt.
Example 10
Step S1: dissolving 50 parts of template titanium dioxide nano particles in 900 parts of distilled water, mixing with 50 parts of amination reagent polydiallyl dimethylamine hydrochloride, heating to 70 ℃, stirring for 9 hours, cooling, centrifuging, ultrasonically oscillating for 35 minutes, washing for many times by using distilled water, and ball-milling for 11 hours to obtain aminated titanium dioxide (TiO) 2 -NH 2 ）；
Step S2: immersing a graphite felt in the aqueous solution of the aminated titanium dioxide, and drying to obtain a titanium dioxide/graphite felt;
step S3: sequentially adding 40 parts of acrylic acid, 30 parts of acrylamide, 10 parts of 2-acrylamide-2-methylpropanesulfonic acid, 2 parts of cross-linking agent di-tert-butyl peroxy isopropyl benzene and 0.5 part of chain transfer agent dodecyl mercaptan into 1300 parts of distilled water, stirring fully, and neutralizing by using alkali liquor to obtain an acrylic acid copolymer;
step S4: immersing the titanium dioxide/graphite felt in the acrylic acid copolymer, adding 1.4 parts of initiator diisopropyl peroxydicarbonate, cooling and drying to obtain an acrylic acid copolymer coated titanium dioxide/graphite felt;
step S5: heating rate is 9 ℃/min, heating temperature is 400 ℃, heat preservation time is 6h, and the acrylic copolymer is carbonized to coat the titanium dioxide/graphite felt, so that the modified graphite felt is obtained.
Comparative example 1
The preparation process corresponds to example 1, except that the coating is not carried out with acrylic copolymers.
Comparative example 2
Blank graphite felt.
The graphite felts prepared in examples and comparative examples were respectively assembled with a cell stack and subjected to charge and discharge tests under the same test conditions, and the coulombic efficiency, voltage efficiency, energy efficiency and capacity retention rate for 100 cycles of the battery were recorded, and the test results are shown in table 1:
table 1 charge and discharge test results of graphite felt
From table 1, all of examples 1 to 10 have higher energy and voltage efficiencies, which indicates that the modified graphite felt carbon sphere structure obtained by the invention effectively improves the specific surface area of graphite felt fibers, can provide more oxygen-containing functional groups, and provides enough active sites for oxidation-reduction reaction. Compared with comparative example 1, the embodiment has higher voltage efficiency and more stable capacity retention rate, which shows that carbonization can improve the conductivity, and the carbonized layer obtained after carbonization can play a role in fixing titanium dioxide nano particles to ensure the carbon sphere structure of the modified graphite felt. Examples and comparative examples were conducted at a high operating current density (300 mA/cm 2 ) The lower energy and voltage efficiency are reduced, and the main reason is that the electrochemical activity and reversibility of the graphite felt electrode can not meet the application requirements under the high working current density, and higher activation polarization exists. But the example 1-the example 10 and the comparative example 1 are obviously improved, which shows that the modified graphite felt electrode has small polarization, small load transfer resistance, high electrocatalytic activity and good electrochemical reversibility, thereby greatly improving the voltage efficiency and the energy efficiency of a galvanic pile under high working current density.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the modified graphite felt for high density of the vanadium battery is characterized by at least comprising the following steps:
step S1: mixing 30-60 parts of aqueous solution containing template agent and 40-70 parts of amination reagent, heating, stirring, cooling, centrifuging and cleaning to obtain a first precursor;
step S2: immersing graphite felt in the aqueous solution of the first precursor, and drying to obtain a second precursor;
step S3: sequentially adding 30-50 parts of acrylic acid, 20-40 parts of acrylamide, 5-10 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1-2 parts of a cross-linking agent and 0.2-0.5 part of a chain transfer agent into distilled water, stirring fully, and neutralizing by using alkali liquor to obtain a dispersion liquid;
step S4: immersing the second precursor in the dispersion liquid, adding 0.5-1.5 parts of initiator, cooling and drying to obtain a dispersion liquid coated second precursor;
step S5: carbonizing the dispersion liquid to coat the second precursor, so as to obtain the modified graphite felt;
the template agent is titanium dioxide nano particles;
the conditions of heating, stirring, cooling and centrifuging in the step S1 are as follows: heating at 65-80deg.C, stirring for 6-12 hr, ultrasonic oscillating for 20-40min, and ball milling for 10-12 hr;
the raw materials used in the steps S1 to S5 are calculated according to parts by weight.
2. The method for preparing the modified graphite felt for high density of vanadium redox batteries according to claim 1, wherein the amination reagent is at least one selected from aminopropyl triethoxysilane and polydiallyl dimethylamine hydrochloride.
3. The method for preparing the modified graphite felt for high density of vanadium redox batteries according to claim 1, wherein the cross-linking agent is at least one selected from the group consisting of N, N' -methylenebisacrylamide, epichlorohydrin, divinylbenzene and di-tert-butylperoxyisopropylbenzene.
4. The method for preparing a modified graphite felt for high density of a vanadium battery according to claim 1, wherein the chain transfer agent is at least one selected from dodecyl mercaptan, sodium bisulphite, sodium hypophosphite and trithiocarbonate.
5. The method for preparing the modified graphite felt for high density of the vanadium battery according to claim 1, wherein the initiator is at least one selected from ammonium persulfate, sodium persulfate, potassium persulfate, azobisisobutyronitrile, diisopropyl peroxydicarbonate and dilauroyl peroxide.
6. The method for preparing the modified graphite felt for high density of vanadium battery according to claim 1, wherein in step S4,
the carbonization conditions are as follows:
the temperature rising rate is 3-10 ℃/min;
heating to 300-500 ℃;
the heat preservation time is 4-8h.
7. A modified graphite felt for high density of vanadium battery, characterized in that it is prepared by the preparation method according to any one of claims 1-6.
8. An electrode comprising the modified graphite felt for high density vanadium cell of claim 7.
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| CN110534757A (en) * | 2019-09-11 | 2019-12-03 | 上海交通大学 | High performance carbon electrode and preparation method thereof |
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| CN102887567B (en) * | 2012-10-11 | 2014-01-15 | 南开大学 | Method for modifying graphite felt material applied to electro-Fenton system |
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| CN110534757A (en) * | 2019-09-11 | 2019-12-03 | 上海交通大学 | High performance carbon electrode and preparation method thereof |
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