CN113117709A - High-efficiency zinc-air battery catalyst prepared based on MXene and sodium alginate - Google Patents
High-efficiency zinc-air battery catalyst prepared based on MXene and sodium alginate Download PDFInfo
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- CN113117709A CN113117709A CN202110271690.4A CN202110271690A CN113117709A CN 113117709 A CN113117709 A CN 113117709A CN 202110271690 A CN202110271690 A CN 202110271690A CN 113117709 A CN113117709 A CN 113117709A
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- sodium alginate
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 54
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 54
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 55
- 239000004005 microsphere Substances 0.000 claims abstract description 53
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000011258 core-shell material Substances 0.000 claims abstract description 22
- 238000010000 carbonizing Methods 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 230000001112 coagulating effect Effects 0.000 claims abstract description 3
- 238000007590 electrostatic spraying Methods 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000012621 metal-organic framework Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 15
- 238000004108 freeze drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 3
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 230000005686 electrostatic field Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims 1
- 239000010406 cathode material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 239000010411 electrocatalyst Substances 0.000 abstract 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 238000001039 wet etching Methods 0.000 abstract 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000010041 electrostatic spinning Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- -1 Oxygen forms peroxide Chemical class 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229910019762 Nb4C3 Inorganic materials 0.000 description 1
- 241000199919 Phaeophyceae Species 0.000 description 1
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- H01M4/90—Selection of catalytic material
Abstract
The invention belongs to the field of electrocatalysis energy, and particularly relates to an electrocatalyst for a high-efficiency zinc-air battery prepared on the basis of sodium alginate and MXene. The preparation process of the catalyst comprises the steps of firstly preparing an MXene aqueous solution of a graphite-like material by using a wet etching method, mixing sodium alginate solutions with different concentrations with the MXene solution to form a solution A, using a divalent metal salt solution as a coagulating bath solution B, preparing a core-shell microsphere with a similar cell structure by using an electrostatic spraying technology, using MXene as a core and sodium alginate as a shell layer, growing an MOF material in situ, freezing and drying, and carbonizing the sodium alginate through high-temperature treatment to obtain the sodium alginate-MXene core-shell catalyst. The sodium alginate and MXene-based electrocatalyst prepared by the invention is simple in preparation method, green and environment-friendly, has excellent electrocatalytic performance and long-term circulation stability, is rich in sodium alginate source, and is a zinc-air battery cathode catalyst with great prospect.
Description
Technical Field
The invention belongs to the field of electrocatalysis energy, and particularly relates to a high-efficiency zinc-air battery catalyst prepared based on MXene and sodium alginate.
Background
With the consumption of petrochemical fuels and increasing environmental problems, the development of new green energy storage devices and green energy sources is a major task at present, wherein it is very important to vigorously develop energy storage devices and materials with high power density, and among many energy storage devices, metal-air batteries have been a focus of research with their excellent green environmental performance, wherein Oxygen Reduction Reaction (ORR) is an important Reaction for metal-air batteries and fuel cells to realize energy conversion. Oxygen forms peroxide through a two-electron process or forms water through a four-electron process to complete electron transfer. The oxygen reduction reaction path is complex, the intermediates are generated more, the reaction activation energy is higher, and the intrinsic kinetic rate is slow, so that the oxygen reduction reaction efficiency becomes a key factor for limiting the performances of the two devices. Traditional platinum, platinum alloy and other noble metal catalysts have good oxygen reduction catalytic activity but are high in cost and scarce in storage capacity, and are easy to generate a poisoning phenomenon (such as being influenced by methanol and CO) in a working environment, so that the large-scale application of the traditional platinum, platinum alloy and other noble metal catalysts is limited.
In recent years, biomass-based derived carbon materials have attracted great attention in the field of energy storage due to the advantages of wide raw material sources, renewability and low cost. More importantly, the biomass has a natural hierarchical structure and is diversified in composition, so that an ideal raw material is provided for preparing an electrode material with controllable appearance and excellent performance. So far, a series of porous carbon materials are prepared by taking biomass as a raw material and adopting different methods, which becomes an important field for preparing electrochemical catalytic materials. Sodium alginate (sodium alginate) is a by-product after extraction of iodine and mannitol from kelp or gulfweed of brown algae. The molecule is formed by connecting beta-D-mannuronic acid (beta-D-mannuronic, M) and alpha-L-guluronic acid (alpha-L-guluronic acid, G) according to a (1 → 4) bond, is a natural polysaccharide, and has the stability, solubility, viscosity and safety required by pharmaceutical preparation auxiliary materials. Sodium alginate has been widely used in the food industry and in the medical field.
MXene is a novel two-dimensional material with a graphene-like structure and has a chemical formula of Mn+1Xn TxWherein n is 1, 2, 3, M is an early transition metal element (such as Ti, Sc, Zr, Nb, etc.), X is carbon or/and nitrogen, and T isxIs a surface functional group (e.g., -OH, -O, -F). The MAX phase of MXene precursor is a ternary layered compound, and has the excellent characteristics of ceramic and metal, and the chemical formula is Mn+1AXnWherein M, X, n are the same as above, and A is a group III or IV element. More than 20 MXenes, including Ti, are prepared by etching method3C2Tx，Ti2CTx，Nb4C3TxEtc. of Ti3C2TxThe MXene is the first MXene prepared, and is the most extensively researched two-dimensional material which can be applied to supercapacitors, lithium ion batteries, dye adsorption and biosensors. For example, Chinese invention patent CN 111422873A discloses MXene/sodium alginate derived carbon three-dimensional aerogel and a preparation method and application thereof, wherein MXene and sodium alginate are mixed and then freeze-dried for use in a super capacitor, but the subsequent treatment in the experimental process is troublesome, and acid washing is used, so that the preparation method is not beneficial to mass production. For example, chinese invention patent CN105609790A discloses a method for preparing a nickel-cobalt/carbon nanotube aerogel zinc-air battery catalyst, which mixes sodium alginate, cobalt nitrate hexahydrate, nickel chloride hexahydrate and carbon nanotubes, freezes and dries them to be used as a lithium-air battery catalyst, but the dispersibility of the carbon nanotubes in the gel cannot be solved well, which is not favorable for the uniform distribution of catalytic sites.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides a simple and efficient cathode catalyst for an air battery, and aims to solve the technical problems. The method has the advantages of simple preparation process and high future application prospect by using the sodium alginate with rich sources as the raw material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
(1) preparing a sodium alginate aqueous solution, adding an MXene solution with a certain concentration into the sodium alginate solution, and uniformly stirring by ultrasonic to obtain a uniform mixed solution of the sodium alginate MXene;
(2) placing the obtained mixed solution on an electrostatic spraying device, taking a divalent metal salt solution as a coagulating bath solution, continuously stirring, and forming the sodium alginate MXene core-shell microspheres under the action of an electrostatic field;
(3) adding the formed sodium alginate MXene microsphere solution into a DMSO solution of an organic ligand dimethyl imidazole, stirring, growing an MOF material in situ, separating the microspheres in a centrifuge, washing redundant ions and unreacted substances with water and ethanol, and freeze-drying the sodium alginate MXene-MOF microspheres in a freeze dryer;
(4) and (3) placing the prepared sodium alginate MXene-MOF microspheres in a tubular furnace, and carbonizing at different temperatures in the nitrogen atmosphere to obtain the sodium alginate MXene-MOF bifunctional high-efficiency catalyst.
Specifically, MXene is Ti3C2Tx, the concentration of MXene aqueous solution is 1-10mg/ml, and the concentration of sodium alginate solution is 1% -10% wt. Wherein the mass ratio of the sodium alginate to the MXene is 30:1-4: 1.
Specifically, the Ti3C2The Tx two-dimensional material is a small layer MXene, the thickness is 2-4 nm, and the size of the sheet layer is 2-5 μm.
Specifically, the Ti3C2The Tx two-dimensional material was prepared as follows:
adding 1g of lithium fluoride and 20mL of hydrochloric acid with the concentration of 9mol/L into a polytetrafluoroethylene beaker, stirring for 30min, and slowly adding 1g of Ti3AlC2(400 meshes, purity 98%), stirring at 35 deg.C for 24h, repeatedly centrifuging with deionized water at 3500rpm until the pH value of the solution is neutral, collecting the upper dark green liquid to obtain Ti3C2A few-layer dispersion of a Tx two-dimensional material.
Specifically, the divalent metal ion comprises Co2+，Zn2+One or two of the sodium alginate and the metal salt are dissolved in dimethyl sulfoxide solution, wherein the mass ratio of the sodium alginate to the metal salt is 1:5-1: 10.
Specifically, the carbonization temperature is 700-900 ℃, wherein the protective gas is nitrogen, the heating rate is 5-15 ℃/min, and the carbonization time is 1-3 h.
Specifically, the catalyst is applied to a cathode of a zinc-air battery.
The invention has the beneficial effects that:
the catalyst prepared by the method has wide sources, is green and environment-friendly, has high safety and has higher catalytic activity.
Detailed Description
The present invention will now be described in further detail with reference to examples.
Example 1
Ultrasonically dissolving 100mg of sodium alginate in 10ml of deionized water, taking 10ml of MXene aqueous dispersion with the concentration of 5mg/ml, continuing stirring for 1h after ultrasonic dispersion, placing the ultrasonic solution on an electrostatic spinning device, adjusting the voltage to be 15kv and the speed to be 3ml/h, and ultrasonically dissolving 6.25g of cobalt nitrate hexahydrate in 20ml of dimethyl sulfoxide solution to be used as a coagulation bath receiving device of the device. And crosslinking sodium alginate and divalent ions to obtain the micron-sized core-shell microspheres.
Dissolving 3.12g of dimethyl imidazole in 20ml of dimethyl sulfoxide solution by ultrasonic, adding the dissolved dimethyl imidazole solution into the solution of the core-shell microspheres, stirring for 30min under magnetic stirring, growing the MOF material (ZIF-67) in situ, separating the microspheres from the obtained core-shell microsphere solution for growing the MOF material in a centrifuge at the rotating speed of 3500rpm, and washing the microspheres with water and ethanol.
Placing the obtained microspheres in a freeze-drying machine, freeze-drying for 48h, placing the microspheres in a tube furnace, carbonizing at 700 ℃ for 2h in nitrogen atmosphere
Example 2
Ultrasonically dissolving 100mg of sodium alginate in 10ml of deionized water, taking 10ml of MXene aqueous dispersion with the concentration of 5mg/ml, continuing stirring for 1h after ultrasonic dispersion, placing the ultrasonic solution on an electrostatic spinning device, adjusting the voltage to be 15kv and the speed to be 3ml/h, and ultrasonically dissolving 6.25g of cobalt nitrate hexahydrate in 20ml of dimethyl sulfoxide solution to be used as a coagulation bath receiving device of the device. And crosslinking sodium alginate and divalent ions to obtain the micron-sized core-shell microspheres.
Dissolving 3.12g of dimethyl imidazole in 20ml of dimethyl sulfoxide solution by ultrasonic, adding the dissolved dimethyl imidazole solution into the solution of the core-shell microspheres, stirring for 30min under magnetic stirring, growing the MOF material (ZIF-67) in situ, separating the microspheres from the obtained core-shell microsphere solution for growing the MOF material in a centrifuge at the rotating speed of 3500rpm, and washing the microspheres with water and ethanol.
Placing the obtained microspheres in a freeze-drying machine, freeze-drying for 48h, placing the microspheres in a tube furnace, carbonizing at 800 deg.C for 2h in nitrogen atmosphere
Example 3
Ultrasonically dissolving 100mg of sodium alginate in 10ml of deionized water, taking 10ml of MXene aqueous dispersion with the concentration of 5mg/ml, continuing stirring for 1h after ultrasonic dispersion, placing the ultrasonic solution on an electrostatic spinning device, adjusting the voltage to be 15kv and the speed to be 3ml/h, and ultrasonically dissolving 6.25g of cobalt nitrate hexahydrate in 20ml of dimethyl sulfoxide solution to be used as a coagulation bath receiving device of the device. And crosslinking sodium alginate and divalent ions to obtain the micron-sized core-shell microspheres.
Dissolving 3.12g of dimethyl imidazole in 20ml of dimethyl sulfoxide solution by ultrasonic, adding the dissolved dimethyl imidazole solution into the solution of the core-shell microspheres, stirring for 30min under magnetic stirring, growing the MOF material (ZIF-67) in situ, separating the microspheres from the obtained core-shell microsphere solution for growing the MOF material in a centrifuge at the rotating speed of 3500rpm, and washing the microspheres with water and ethanol.
Placing the obtained microspheres in a freeze-drying machine, freeze-drying for 48h, placing the microspheres in a tube furnace, carbonizing at 900 ℃ for 2h in nitrogen atmosphere
Example 4
Ultrasonically dissolving 100mg of sodium alginate in 10ml of deionized water, taking 10ml of MXene aqueous dispersion with the concentration of 6mg/ml, continuing stirring for 1h after ultrasonic dispersion, placing the ultrasonic solution on an electrostatic spinning device, adjusting the voltage to be 15kv and the speed to be 3ml/h, and ultrasonically dissolving 6.25g of cobalt nitrate hexahydrate in 20ml of dimethyl sulfoxide solution to be used as a coagulation bath receiving device of the device. And crosslinking sodium alginate and divalent ions to obtain the micron-sized core-shell microspheres.
Dissolving 3.12g of dimethyl imidazole in 20ml of dimethyl sulfoxide solution by ultrasonic, adding the dissolved dimethyl imidazole solution into the solution of the core-shell microspheres, stirring for 30min under magnetic stirring, growing the MOF material (ZIF-67) in situ, separating the microspheres from the obtained core-shell microsphere solution for growing the MOF material in a centrifuge at the rotating speed of 3500rpm, and washing the microspheres with water and ethanol.
Placing the obtained microspheres in a freeze-drying machine, freeze-drying for 48h, placing the microspheres in a tube furnace, carbonizing at 700 ℃ for 2h in nitrogen atmosphere
Example 5
Ultrasonically dissolving 100mg of sodium alginate in 10ml of deionized water, taking 10ml of MXene aqueous dispersion with the concentration of 6mg/ml, continuing stirring for 1h after ultrasonic dispersion, placing the ultrasonic solution on an electrostatic spinning device, adjusting the voltage to be 15kv and the speed to be 3ml/h, and ultrasonically dissolving 3.1g of cobalt nitrate hexahydrate and 3.2g of zinc nitrate hexahydrate in 20ml of dimethyl sulfoxide solution to serve as a coagulation bath receiving device of the device. And crosslinking sodium alginate and divalent ions to obtain the micron-sized core-shell microspheres.
Dissolving 3.12g of dimethyl imidazole in 20ml of dimethyl sulfoxide solution by ultrasonic, adding the dissolved dimethyl imidazole solution into the solution of the core-shell microspheres, stirring for 30min under magnetic stirring, growing the MOF material (ZIF-8) in situ, separating the microspheres from the obtained core-shell microsphere solution for growing the MOF material in a centrifuge at the rotating speed of 3500rpm, and washing the microspheres with water and ethanol.
Placing the obtained microspheres in a freeze-drying machine, freeze-drying for 48h, placing the microspheres in a tube furnace, carbonizing at 700 ℃ for 2h in nitrogen atmosphere
Example 6
Ultrasonically dissolving 100mg of sodium alginate in 10ml of deionized water, taking 10ml of MXene aqueous dispersion with the concentration of 6mg/ml, continuing stirring for 1h after ultrasonic dispersion, placing the ultrasonic solution on an electrostatic spinning device, adjusting the voltage to be 15kv and the speed to be 3ml/h, and ultrasonically dissolving 3.1g of cobalt nitrate hexahydrate and 3.2g of zinc nitrate hexahydrate in 20ml of dimethyl sulfoxide solution to serve as a coagulation bath receiving device of the device. And crosslinking sodium alginate and divalent ions to obtain the micron-sized core-shell microspheres.
Dissolving 3.12g of dimethyl imidazole in 20ml of dimethyl sulfoxide solution by ultrasonic, adding the dissolved dimethyl imidazole solution into the solution of the core-shell microspheres, stirring for 30min under magnetic stirring, growing the MOF material (ZIF-8) in situ, separating the microspheres from the obtained core-shell microsphere solution for growing the MOF material in a centrifuge at the rotating speed of 3500rpm, and washing the microspheres with water and ethanol.
Placing the obtained microspheres in a freeze-drying machine, freeze-drying for 48h, placing the microspheres in a tube furnace, carbonizing at 800 deg.C for 2h in nitrogen atmosphere
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (7)
1. The preparation method of the zinc-air battery catalyst with a similar cell structure based on MXene and sodium alginate is characterized in that: the preparation of the catalyst comprises the following steps:
(1) preparing a sodium alginate aqueous solution, adding an MXene solution with a certain concentration into the sodium alginate solution, and uniformly stirring by ultrasonic to obtain a uniform mixed solution of the sodium alginate MXene;
(2) placing the obtained mixed solution on an electrostatic spraying device, taking a divalent metal salt solution as a coagulating bath solution, continuously stirring, and forming the sodium alginate MXene core-shell microspheres under the action of an electrostatic field;
(3) adding the formed sodium alginate MXene microsphere solution into a DMSO solution of an organic ligand dimethyl imidazole, stirring, growing an MOF material in situ, separating the microspheres in a centrifuge, washing redundant ions and unreacted substances with water and ethanol, and freeze-drying the sodium alginate MXene-MOF microspheres in a freeze dryer;
(4) and (3) placing the prepared sodium alginate MXene-MOF microspheres in a tubular furnace, and carbonizing at different temperatures in the nitrogen atmosphere to obtain the sodium alginate MXene-MOF bifunctional high-efficiency catalyst.
2. MXene as claimed in claim 1 being Ti3C2Tx, wherein the concentration of the MXene aqueous solution is 5-10mg/ml, the concentration of the sodium alginate solution is 1% -10% wt, and the mass ratio of the sodium alginate to the MXene is 30:1-4: 1.
3. The divalent metal ion of claim 1 comprising Co2+，Zn2+One or two of the sodium alginate and the metal salt are dissolved in dimethyl sulfoxide solution, wherein the mass ratio of the sodium alginate to the metal salt is 1:5-1: 10.
4. The mass ratio of metal salt to dimethylimidazole according to claim 1 is from 2:1 to 5:1, wherein the stirring time is from 0.5h to 6h, and wherein the MOF material is ZIF-67 or ZIF-8.
5. The carbonization temperature of 700-900 ℃ as claimed in claim 1, wherein the protective gas is nitrogen, the temperature-increasing rate is 5 ℃/min-15 ℃/min, and the carbonization time is 1-3 h.
6. The nucleocapsid structure of claim 1, wherein MXene is used as core, sodium alginate is used as shell, MOF material is uniformly distributed, and the shell obtained after carbonization plays a role in protecting active substances.
7. The catalyst prepared as set forth in claim 1 is mainly applied to a cathode material of a zinc-air battery.
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| CN115117307A (en) * | 2022-08-26 | 2022-09-27 | 昆明理工大学 | Preparation method and application of gel-state sulfur-fixing positive electrode |
| CN115188606A (en) * | 2022-06-14 | 2022-10-14 | 石河子大学 | Flexible self-supporting MXene quantum dot/MXene thin film electrode and preparation method and application thereof |
| CN116454543A (en) * | 2023-06-16 | 2023-07-18 | 深圳海辰储能控制技术有限公司 | Diaphragm, preparation method thereof, energy storage device and electric equipment |
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