CN114068956A - Multifunctional flexible electrode and preparation method thereof - Google Patents
Multifunctional flexible electrode and preparation method thereof Download PDFInfo
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- CN114068956A CN114068956A CN202111307656.4A CN202111307656A CN114068956A CN 114068956 A CN114068956 A CN 114068956A CN 202111307656 A CN202111307656 A CN 202111307656A CN 114068956 A CN114068956 A CN 114068956A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000009987 spinning Methods 0.000 claims description 20
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 239000002048 multi walled nanotube Substances 0.000 claims description 10
- 238000010000 carbonizing Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical group OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 7
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000000467 phytic acid Substances 0.000 claims description 7
- 229940068041 phytic acid Drugs 0.000 claims description 7
- 235000002949 phytic acid Nutrition 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 238000006479 redox reaction Methods 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 4
- 239000002904 solvent Substances 0.000 claims 2
- 229940011182 cobalt acetate Drugs 0.000 claims 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004917 carbon fiber Substances 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 239000011701 zinc Substances 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000010041 electrostatic spinning Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 239000003570 air Substances 0.000 description 50
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000630 rising effect Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 5
- JFRHWQBNJASIQN-UHFFFAOYSA-N CO.CC1=C(N=CN1)C Chemical compound CO.CC1=C(N=CN1)C JFRHWQBNJASIQN-UHFFFAOYSA-N 0.000 description 4
- NVLDSCWHEUSPCV-UHFFFAOYSA-N [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O NVLDSCWHEUSPCV-UHFFFAOYSA-N 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OQGOJRRWCVOAOK-UHFFFAOYSA-N 4,5-dimethyl-1H-imidazole ethanol Chemical compound C(C)O.CC1=C(N=CN1)C OQGOJRRWCVOAOK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000000875 high-speed ball milling Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PYXZMXHEFIQJJU-UHFFFAOYSA-L C(C)(=O)[O-].[Co+2].C(C)O.C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Co+2].C(C)O.C(C)(=O)[O-] PYXZMXHEFIQJJU-UHFFFAOYSA-L 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- LXWRTCKMRTXLRZ-UHFFFAOYSA-L dichlorocobalt;ethanol Chemical compound CCO.Cl[Co]Cl LXWRTCKMRTXLRZ-UHFFFAOYSA-L 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
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- -1 hydroxide ions Chemical class 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- 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
-
- 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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of flexible electrodes, and particularly relates to a multifunctional flexible electrode and a preparation method thereof. The invention prepares the multifunctional flexible electrode which has no adhesive, no extra current collector and self-carried catalyst by adding a conductive reinforcing agent, a ligand required by a growing metal organic framework, a heterogeneous doping source such as phosphorus, sulfur and the like into a polymer precursor such as polyacrylonitrile and the like of electrostatic spinning and carrying out in-situ conversion. The invention has the advantages of low raw material cost, wide source, simple synthesis process, no pollution and environmental protection. The prepared multifunctional flexible porous active carbon fiber shows good mechanical property and self-supporting stability when being used as a zinc air electrode material, and shows high-efficiency catalytic activity when being used as a catalyst. Meanwhile, the zinc-air battery prepared by the flexible electrode and the flexible zinc-air battery show good electrical cycle performance.
Description
Technical Field
The invention relates to the field of flexible electrodes, in particular to a multifunctional flexible electrode and a preparation method thereof.
Background
The basic structure of the zinc-air battery consists of a zinc electrode, an alkaline electrolyte and a porous air electrode containing an active material. During the discharge, the zinc oxidizes, releasing electrons that reach the air electrode through an external circuit. Meanwhile, atmospheric oxygen molecules diffuse into the air electrode, and are reduced by a strong redox reaction (ORR), forming hydroxide ions at the three-phase boundary of oxygen (gas), electrolyte (liquid), active material (solid). Compared with closed systems such as lithium batteries, zinc-air batteries have a unique semi-open system, utilize oxygen in ambient air to minimize the mass and volume required for air electrodes, and improve energy density, which has caused widespread concern in recent years. Theoretical energy density of zinc-air battery (1218 W.h.kg)-1) Is about 3 times of the lithium ion battery, but the manufacturing cost is lower. Therefore, zinc air batteries are considered to be a promising alternative to lithium ion batteries in future energy applications. Further, the high market demand for consumer electronics, particularly portable and wearable devices, has also driven the development of zinc air batteries towards flexibility and miniaturization, so that flexibility of each component of the battery is the basis for achieving this goal, and the air electrode, as a key site for the chemical reaction of the battery, is more important for its self-supporting flexible design.
The air electrode of a zinc-air cell serves several functions including oxygen diffusion, ion transport, electron transfer, electrocatalytic activity, and accommodates the formation of precipitates. Therefore, the rechargeable zinc-air battery also needs high specific surface area to support and anchor the oxygen electrocatalyst in the catalytically active layer, and appropriate pore channels for effective mass transfer and oxygen diffusion. At present, carbon materials are indispensable components of electrochemical energy storage devices (such as lithium batteries, lithium-sulfur batteries and metal-air batteries), and particularly carbon fiber materials (carbon cloth, carbon paper and the like) become support materials with the most extensive applications due to high specific surface area, rich porous structures, excellent conductivity, good stability and corrosion resistance.
For zinc-air cells, the catalyst is a critical component of the air electrode,it determines the structure, performance and cost of zinc-air cells, and therefore the primary task of the air electrode is an efficient, robust, inexpensive catalyst. At present, the noble metal platinum and the metal oxide IrO2And RuO2Are widely used as reference catalysts for strong redox reactions and oxygen evolution reactions, respectively.
At present, the mainstream flexible electrode substrate is mainly carbon cloth or other metal meshes, and the catalyst and the adhesive are mixed and loaded on the conductive base material, so that the self-supporting structure of the air electrode can be realized to a certain extent to meet the requirements of the flexible zinc-air battery.
For practical metal-air cells, it is traditionally necessary to add a number of auxiliary and inactive additives, including polymer binders and catalyst supports. These additives not only add weight to the final electrode, but also impair the performance of the electrochemical cell due to the increased interfacial resistance and reduced accessible active sites caused by the insulating polymeric binder. During the reaction, decomposition of the additive also causes some of the catalyst to be detached from the electrode surface, and therefore, it is very desirable to minimize the use of an auxiliary additive in the air electrode.
For zinc-air battery, though Pt and IrO2、RuO2Has good activity, but the scarcity, the high price and the insufficient stability of the noble metal catalyst seriously restrict the wide application of the noble metal catalyst in zinc-air batteries. Furthermore, a single noble metal catalyst cannot simultaneously serve as a bifunctional electrocatalyst for both the strong redox reaction and the oxygen evolution reaction. Therefore, the development of an inexpensive, durable, and highly active bifunctional oxygen catalyst is critical to its practical application in zinc-air batteries.
Disclosure of Invention
The invention aims to solve the technical problems and provides a multifunctional flexible electrode and a preparation method thereof.
The preparation method of the multifunctional flexible electrode comprises the following specific steps:
(1) adding polyacrylonitrile, a multi-walled carbon nanotube and dimethylimidazole into an organic solvent, and performing ball milling to obtain a spinning precursor solution;
(2) spinning the spinning precursor solution to obtain a fiber layer, adding the fiber layer into a cobalt salt solution, and reacting to obtain a solution A;
(3) adding a dimethyl imidazole solution into the solution A, and reacting to obtain a fiber sheet; and carbonizing the fiber sheet to obtain the multifunctional flexible electrode.
Preferably, in the step (1), the mass ratio of the multi-walled carbon nanotube, the dimethyl imidazole, the organic solvent, the cobalt salt and the polyacrylonitrile is 1-50: 1-33: 500-2000: 3-14: 100.
preferably, the organic solvent is one of N, N-dimethylacetamide, dimethyl sulfoxide or ethylene carbonate.
Preferably, in the step (1), a phosphorus source or a sulfur source is further added to the organic solvent, and the mass ratio of the phosphorus source or the sulfur source to the polyacrylonitrile is 0.01-20: 100, respectively; the phosphorus source is phytic acid or phosphoric acid, and the sulfur source is thiourea or sulfur powder.
Preferably, in the step (2), the spinning condition is 18-25kV of voltage and 0.01-0.03mL/min of advancing speed.
Preferably, in the step (2), the reaction time is 0.5 to 1 hour.
Preferably, in the step (3), the mass ratio of the dimethylimidazole to the polyacrylonitrile is 0.1-7: 5.
preferably, in the step (3), the reaction condition is standing for 24-48 h.
Preferably, in the step (3), the carbonization is performed by pre-oxidizing at 280 ℃ and raising the temperature to 260 ℃ at the rate of 1-5 ℃/min for 0.5-4h, raising the temperature to 1000 ℃ at the rate of 1-10 ℃/min under the protection of inert gas, and the carbonization time is 2-7 h.
The invention provides a multifunctional flexible electrode prepared by the preparation method.
Further, the multifunctional flexible electrode can be used as a catalytic material for strong oxidation reduction reaction and oxygen evolution reaction.
Furthermore, the multifunctional flexible electrode can be used as a zinc-air battery and a flexible zinc-air battery air electrode material.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the precursor raw materials in the invention have low price and wide sources.
2. The fiber obtained by electrostatic spinning can be produced and synthesized in a large scale, and the method for growing the MOF on the surface is mild and simple, thereby being convenient for industrial large-scale production.
3. The composite material has the advantages of simple synthesis process, no pollution and environmental protection.
4. The multifunctional flexible porous active carbon fiber material prepared by the invention has good mechanical property and self-supporting stability when being used as a zinc air electrode material, and has high-efficiency catalytic activity when being used as a catalyst.
5. The metal air electrode with the bifunctional catalytic performance is applied to a zinc-air battery and a flexible zinc-air battery and shows good cycle performance.
Drawings
Fig. 1 shows the flexible electrode material after folding, bending and rolling.
FIG. 2 shows example 3 and Pt/C-RuO2The prepared zinc-air battery shows a comparative graph of long cycle performance.
FIG. 3 shows example 3 and Pt/C-RuO2The prepared zinc-air battery optical photo and a stable open-circuit voltage chart.
FIG. 4 shows example 3 and Pt/C-RuO2The discharge performance of the prepared zinc-air battery is shown in a comparative graph.
Fig. 5 is an SEM image of the porous multifunctional flexible electrode prepared in example 1.
Fig. 6 is an SEM image of the porous multifunctional flexible electrode prepared in example 2.
Fig. 7 is an SEM image of the porous multifunctional flexible electrode prepared in example 3.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
1.5g Polyacrylonitrile (PAN), 0.3g multi-walled Carbon Nanotubes (CNT) and 0.2g dimethylimidazole were added to 18g DMF and ball milled at high speed for 4h to obtain a viscous and uniform spinning precursor solution. And spinning the precursor solution at 21kV and a propelling speed of 0.01mL/min to obtain a black fiber layer. Cutting a fiber sheet with a fixed size of 3 x 6cm, putting the fiber sheet into a cobalt nitrate methanol solution with a concentration of 0.01g/mL, standing and growing for 0.5h, and then adding a dimethyl imidazole methanol solution with a concentration of 8mL and 0.1g/mL, and continuing standing and growing for 36 h. After the growth, the cells were washed with methanol repeatedly and dried at room temperature. Putting the whole fiber with the grown MOF on a quartz plate, pre-oxidizing for 4h at the temperature rising speed of 1 ℃/min to 260 ℃ in the air atmosphere, and then carbonizing at the temperature rising speed of 1 ℃/min to 1000 ℃ under the protection of nitrogen or argon for 2 h. Obtaining the Co @ CF-900 self-supporting porous multifunctional flexible electrode.
Example 2
Adding 1.5g of Polyacrylonitrile (PAN), 0.3g of multi-walled Carbon Nanotubes (CNT), 0.1g of Phytic Acid (PA) and 0.2g of dimethyl imidazole into 18g of DMF, and carrying out high-speed ball milling for 3h to obtain a viscous and uniform spinning precursor solution. And spinning the precursor solution at 18kV and a propelling speed of 0.02mL/min to obtain a black fiber layer. Cutting a fiber sheet with a fixed size of 3 x 6cm, putting the fiber sheet into a cobalt nitrate methanol solution with a concentration of 0.01g/mL, standing and growing for 1h, and then adding a dimethyl imidazole methanol solution with a concentration of 2mL and 0.3g/mL, and continuing standing and growing for 24 h. After the growth, the cells were washed with methanol repeatedly and dried at room temperature. Putting the whole fiber with the grown MOF on a quartz plate, pre-oxidizing for 4h at the temperature rising speed of 2 ℃/min to 270 ℃ in the air atmosphere, and then carbonizing at the temperature rising speed of 5 ℃/min to 900 ℃ under the protection of nitrogen or argon for 5 h. To obtain Co2P @ CF-900 self-supporting porous multifunctional flexible electrode.
Example 3
Adding 1.5g of Polyacrylonitrile (PAN), 0.3g of multi-walled Carbon Nanotubes (CNT), 0.2g of Phytic Acid (PA) and 0.2g of dimethyl imidazole into 18g of DMF, and carrying out high-speed ball milling for 2 hours to obtain a viscous and uniform spinning precursor solution. And spinning the precursor solution at 25kV and a propelling speed of 0.03mL/min to obtain a black fiber layer. Cutting a fiber sheet with a fixed size of 3 x 6cm, putting the fiber sheet into a cobalt nitrate methanol solution with a concentration of 0.01g/mL, standing and growing for 1h, and then adding a dimethyl imidazole methanol solution with a concentration of 5mL and 0.2g/mL, and continuing standing and growing for 48 h. After the growth, the cells were washed with methanol repeatedly and dried at room temperature. Putting the whole fiber with the grown MOF on a quartz plate, pre-oxidizing for 4h at the temperature rising speed of 5 ℃/min to 280 ℃ in the air atmosphere, and then carbonizing at the temperature rising speed of 10 ℃/min to 700 ℃ under the protection of nitrogen or argon for 7 h. Obtaining the CoP @ CF-900 self-supporting porous multifunctional flexible electrode.
Example 4
1.5g Polyacrylonitrile (PAN), 0.3g multi-walled Carbon Nanotubes (CNT), 0.1g thiourea and 0.2g dimethylimidazole were added into 18g DMF and ball milled at high speed for 3h to obtain a viscous and uniform spinning precursor solution. And spinning the precursor solution at 18kV and a propelling speed of 0.02mL/min to obtain a black fiber layer. Cutting a fiber sheet with a fixed size of 3 x 6cm, putting the fiber sheet into a cobalt nitrate methanol solution with a concentration of 0.01g/mL, standing and growing for 1h, and then adding 8mL of a dimethyl imidazole methanol solution with a concentration of 0.1g/mL, and continuing standing and growing for 24 h. After the growth, the cells were washed with methanol repeatedly and dried at room temperature. And putting the whole fiber with the grown MOF on a quartz plate, pre-oxidizing for 0.5h at the temperature rising speed of 2 ℃/min to 270 ℃ in the air atmosphere, and then carbonizing at the temperature rising speed of 5 ℃/min to 900 ℃ under the protection of nitrogen or argon for 5 h. Obtaining the CoS @ CF-900 self-supporting porous multifunctional flexible electrode.
Example 5
1.5g Polyacrylonitrile (PAN), 0.3g multi-walled Carbon Nanotubes (CNT), 0.2g sulfur powder and 0.2g dimethylimidazole were added to 18g ethylene carbonate and ball milled at high speed for 3h to obtain a viscous and uniform spinning precursor solution. And spinning the precursor solution at 18kV and a propelling speed of 0.02mL/min to obtain a black fiber layer. Cutting a fiber sheet with a fixed size of 3 x 6cm, putting the fiber sheet into a cobalt chloride ethanol solution with a concentration of 0.01g/mL, standing and growing for 1h, and then adding 8mL of a dimethyl imidazole ethanol solution with a concentration of 0.1g/mL, and continuing standing and growing for 24 h. After the growth, the cells were washed with methanol repeatedly and dried at room temperature. And putting the whole fiber with the grown MOF on a quartz plate, pre-oxidizing for 0.5h at the temperature rising speed of 2 ℃/min to 270 ℃ in the air atmosphere, and then carbonizing at the temperature rising speed of 5 ℃/min to 900 ℃ under the protection of nitrogen or argon for 5 h. Obtaining the CoS @ CF-900 self-supporting porous multifunctional flexible electrode.
Example 6
1.5g Polyacrylonitrile (PAN), 0.3g multi-walled Carbon Nanotubes (CNT), 0.2g phosphoric acid and 0.2g dimethyl imidazole were added into 18g dimethyl sulfoxide and ball milled at high speed for 3h to obtain a viscous and uniform spinning precursor solution. And spinning the precursor solution at 18kV and a propelling speed of 0.02mL/min to obtain a black fiber layer. Cutting a fiber sheet with a fixed size of 3 x 6cm, putting the fiber sheet into a cobalt acetate ethanol solution with a concentration of 0.01g/mL, standing and growing for 1h, and then adding 8mL of a dimethyl imidazole ethanol solution with a concentration of 0.1g/mL, and continuing standing and growing for 24 h. After the growth, the cells were washed with methanol repeatedly and dried at room temperature. Putting the whole fiber with the grown MOF on a quartz plate, pre-oxidizing for 2h at the temperature rising speed of 2 ℃/min to 270 ℃ in the air atmosphere, and then carbonizing at the temperature rising speed of 5 ℃/min to 900 ℃ under the protection of nitrogen or argon for 5 h. Obtaining the CoP @ CF-900 self-supporting porous multifunctional flexible electrode.
Referring to fig. 1, it can be seen that the multifunctional flexible porous activated carbon fiber material prepared by the invention shows good mechanical properties and self-supporting stability when being applied as a zinc-air electrode material.
Referring to FIGS. 2,3 and 4, the catalyst showed high catalytic activity at 50mA cm-2The overpotential under the current density is only 330mV, the ORR half-wave potential performance reaches 0.82V, and is close to the noble metal Pt/C, and the metal air electrode with the bifunctional catalytic performance is applied to a zinc-air battery and a flexible zinc-air battery and shows good cycle performance (the open-circuit voltage of the zinc-air battery is 1.4V, and is 10 mA.cm)-2Current densityThe flexible zinc-air battery can be stably charged and discharged for 150h, the open-circuit voltage of the flexible zinc-air battery can be kept at 1.29V and 5 mA-cm under 30 degrees, 90 degrees and 180 degrees of bending-2Cyclic charge and discharge at current density for at least 50 h).
Effect evaluation 2
Referring to FIGS. 5,6 and 7, the presence of ligands is effective to grow MOF in situ on the fiber surface. In the subsequent carbonization process, the heterogeneous doping elements obtained by the precursor decomposition react with the metal in the surface MOF to generate metal compounds. The metal compound catalysts with different contents and types can be obtained by regulating the content of the doping source and the type of the MOF. The catalyst can be anchored on the surface of the conductive carbon fiber by the method, so that the internal resistance between the catalyst and the carbon fiber is effectively reduced, and the charge transfer in the material is accelerated; furthermore, the electrostatic spinning fibers can directly obtain flexible self-supporting three-dimensional carbon fibers after high-temperature carbonization, have high conductivity and porosity, greatly promote the transfer of charges and substances, can be directly used as flexible electrodes, avoid the use of additives such as binders and the like, and ensure the integrity of the electrodes.
The design idea of the patent is novel, the multi-element electrostatic spinning and surface MOF functionalization strategies are combined, the porous characteristic of the MOF is utilized to capture decomposition products of phosphorus and sulfur precursors (such as phytic acid) in the carbonization process, so that catalytic sites are constructed, the catalytic sites are used as flexible air electrodes of zinc-air batteries, and the capacity of the catalytic sites can be 5 mA-cm-2The current density of the transformer is stable for more than 50h, and the stable output voltage is still kept under the bending angle of 0-180 degrees. Overall, more efficient and environment-friendly, and has extremely high application prospect.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The preparation method of the multifunctional flexible electrode is characterized by comprising the following steps:
(1) adding polyacrylonitrile, a multi-walled carbon nanotube and dimethylimidazole into an organic solvent, and performing ball milling to obtain a spinning precursor solution;
(2) spinning the spinning precursor solution to obtain a fiber layer, adding the fiber layer into a cobalt salt solution, and reacting to obtain a solution A;
(3) adding a dimethyl imidazole solution into the solution A to obtain a fiber sheet; and carbonizing the fiber sheet to obtain the multifunctional flexible electrode.
2. The method for preparing a multifunctional flexible electrode according to claim 1, wherein: in the step (1), the mass ratio of the multi-walled carbon nanotube to the dimethylimidazole to the organic solvent to the cobalt salt to the polyacrylonitrile is 1-50: 1-33: 500-2000: 3-14: 100, the organic solvent is one of N, N-dimethylacetamide, dimethyl sulfoxide or ethylene carbonate.
3. The method for preparing a multifunctional flexible electrode according to claim 1, wherein: in the step (1), a phosphorus source or a sulfur source is added into the organic solvent, and the mass ratio of the phosphorus source or the sulfur source to the polyacrylonitrile is 0.01-20: 100, respectively; the phosphorus source is phytic acid or phosphoric acid, and the sulfur source is thiourea or sulfur powder.
4. The method for preparing a multifunctional flexible electrode according to claim 1, wherein: in the step (2), the spinning condition is that the voltage is 18-25kV, and the advancing speed is 0.01-0.03 mL/min.
5. The method for preparing a multifunctional flexible electrode according to claim 1, wherein:
the cobalt salt solution is one of cobalt chloride, cobalt acetate or cobalt nitrate, and the solvent is methanol or ethanol;
the dimethyl imidazole solution solvent is methanol or ethanol.
6. The method for preparing a multifunctional flexible electrode according to claim 1, wherein: in the step (3), the mass ratio of the dimethyl imidazole to the polyacrylonitrile is 0.1-7: 5.
7. the method for preparing a multifunctional flexible electrode according to claim 1, wherein: in the step (3), the reaction condition is standing for 24-48 h.
8. The method for preparing a multifunctional flexible electrode according to claim 1, wherein: in the step (3), the carbonization is performed by pre-oxidizing at a rate of 1-5 ℃/min to 260-280 ℃ for 0.5-4h, heating at a rate of 1-10 ℃/min to 700-1000 ℃ under the protection of inert gas, and the carbonization time is 2-7 h.
9. A multifunctional flexible electrode prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the multifunctional flexible electrode according to claim 9 as catalytic material for strong redox reactions and oxygen evolution reactions.
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| CN110416495A (en) * | 2019-06-26 | 2019-11-05 | 广东工业大学 | A kind of CNF- metallic compound absolute electrode material and its preparation method and application |
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| CN112928287A (en) * | 2021-03-11 | 2021-06-08 | 济南易航新材料科技有限公司 | N, P double-doped carbon fiber loaded CoP composite catalytic material and preparation method and application thereof |
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