CN116895770A - Nickel-nickel oxide heterostructure catalyst, electrode, preparation method and application thereof - Google Patents
Nickel-nickel oxide heterostructure catalyst, electrode, preparation method and application thereof Download PDFInfo
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- CN116895770A CN116895770A CN202310701240.3A CN202310701240A CN116895770A CN 116895770 A CN116895770 A CN 116895770A CN 202310701240 A CN202310701240 A CN 202310701240A CN 116895770 A CN116895770 A CN 116895770A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- WZOZCAZYAWIWQO-UHFFFAOYSA-N [Ni].[Ni]=O Chemical compound [Ni].[Ni]=O WZOZCAZYAWIWQO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 42
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 30
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002791 soaking Methods 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 229910002804 graphite Inorganic materials 0.000 claims description 34
- 239000010439 graphite Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000011258 core-shell material Substances 0.000 claims description 14
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical group [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 claims description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- UFNRFBFHJJPDNF-UHFFFAOYSA-N [Zn].[Ce] Chemical compound [Zn].[Ce] UFNRFBFHJJPDNF-UHFFFAOYSA-N 0.000 claims description 3
- CZLMUMZXIXSCFI-UHFFFAOYSA-N [Zn].[I] Chemical compound [Zn].[I] CZLMUMZXIXSCFI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 50
- 239000003792 electrolyte Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000006479 redox reaction Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Hybrid Cells (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts and batteries, and discloses a nickel-nickel oxide heterostructure catalyst, an electrode, a preparation method and application thereof. The catalyst contains 70-90 wt% nickel and 10-30 wt% nickel oxide, based on the total weight of the nickel-nickel oxide heterostructure catalyst. The invention also provides a method for preparing the catalyst electrode, which comprises the following steps: (1) Soaking a current collector material in a precursor solution containing nickel salt and a ligand, and drying to obtain a treated current collector material; (2) Heat treating the treated current collector material in an inert atmosphere to obtain a heat treated current collector material; (3) And roasting the heat-treated current collector material in an air atmosphere to obtain the electrode. The nickel-nickel oxide heterostructure catalyst and the electrode are applied to a flow battery to improve voltage efficiency, energy efficiency and cycling stability of the flow battery.
Description
Technical Field
The invention relates to the field of catalysts and batteries, in particular to a nickel-nickel oxide heterostructure catalyst, an electrode, a preparation method and application thereof.
Background
In recent centuries, a great deal of non-renewable fossil energy is consumed with the development of industrial technology, and environmental problems caused by this are also becoming more and more of a great deal of attention and importance in the world. In order to reduce the specific gravity of fossil energy, at present, renewable energy technologies represented by wind energy, solar energy, hydraulic energy and the like are also in a high-speed development stage. Although renewable energy sources are inexhaustible, in practical use, the renewable energy sources have the characteristics of obvious geographical dispersibility, discontinuous production, randomness, volatility, uncontrollability and the like, and the unstable electric energy cannot be directly used in a grid connection mode, and the grid connection is usually carried out after peak clipping and valley filling are carried out by an energy storage power station so as to reduce the impact on a power grid. Currently, energy storage power stations are generally classified into three categories, namely mechanical energy storage, electromagnetic energy storage and electrochemical energy storage, wherein electrochemical energy storage is various in form, flexible in application and has received a great deal of attention. Common electrochemical energy storage comprises a lead-acid battery, a lithium ion battery, a flow battery and the like, wherein the flow battery has the advantages of long cycle life, deep charge and discharge, higher safety coefficient and the like, so that the flow battery is better commercially applied in the field of energy storage power stations.
However, when the flow battery is applied under the working condition of high current density, voltage efficiency and energy efficiency are lower due to severe polarization in the electrochemical reaction process. Here, we propose a catalyst with nickel/nickel oxide heterostructure, and apply it in flow battery, can show improvement voltage efficiency and energy efficiency, lay a better development foundation for practicality and scale of flow battery.
Disclosure of Invention
The invention aims to solve the problems of low voltage efficiency, low energy efficiency and low cycling stability caused by serious polarization of a flow battery under a high current density working condition in the prior art, and provides a nickel-nickel oxide heterostructure catalyst, an electrode, a preparation method and application thereof.
In order to achieve the above object, the present invention provides in a first aspect a nickel-nickel oxide heterostructure catalyst comprising 70-90 wt% nickel and 10-30 wt% nickel oxide, based on the total weight of the nickel/nickel oxide heterostructure catalyst.
In a second aspect, the invention provides an electrode, wherein the electrode comprises the nickel-nickel oxide heterostructure catalyst.
The third aspect of the present invention provides a method for producing an electrode, wherein the method comprises:
(1) Soaking a current collector material in a precursor solution containing nickel salt and a ligand, and drying to obtain a treated current collector material;
(2) Heat treating the treated current collector material in an inert atmosphere to obtain a heat treated current collector material;
(3) And roasting the heat-treated current collector material in an air atmosphere to obtain the electrode.
In a fourth aspect, the invention provides an electrode obtained by the method of preparation.
In a fifth aspect the invention provides the use of the nickel-nickel oxide heterostructure catalyst and the electrode in a flow battery.
Preferably, the nickel-nickel oxide heterostructure catalyst is used in a positive electrode material of a flow battery, and the electrode is used as the positive electrode material of the flow battery.
Through the technical scheme, firstly, a precursor solution containing nickel salt and ligand is used for soaking a current collector material, and the current collector material is dried to obtain the current collector material with nickel complex uniformly attached; secondly, thermally treating the current collector material uniformly attached with the nickel-containing complex in an inert atmosphere to reduce nickel in the complex into elemental nickel in situ, wherein other organic matter elements in the complex are removed by pyrolysis; and finally, roasting the heat-treated current collector material at a certain temperature and in a certain time range in an air atmosphere, oxidizing part of elemental nickel attached to the current collector into nickel oxide to obtain a nickel-nickel oxide nano spherical heterostructure catalyst which grows on the surface of the current collector in situ and has a core-shell structure, and applying the current collector loaded with the catalyst as an electrode in a flow battery.
Compared with the prior art, the invention has the following advantages:
(1) The electrode loaded with the nickel-nickel oxide heterostructure has excellent adsorption capacity on active substances of the flow battery.
(2) The electrode loaded with the nickel-nickel oxide heterostructure has good catalytic effect on redox reactions in the flow battery.
(3) The zinc-bromine flow battery using the nickel-nickel oxide heterostructure catalyst has significantly improved voltage efficiency and energy efficiency at a wider current density.
Drawings
FIG. 1 is a schematic illustration of a nickel-nickel oxide heterostructure catalyst preparation with graphite felt as a current collector;
fig. 2a is an SEM test chart of the supported nickel-nickel oxide heterostructure catalyst electrode prepared in example 1, scale: 30 μm;
fig. 2b is an SEM test chart of the supported nickel-nickel oxide heterostructure catalyst electrode prepared in example 1, scale: 5 μm;
fig. 2c is an SEM test chart of the supported nickel-nickel oxide heterostructure catalyst electrode prepared in example 1, scale: 1 μm;
fig. 2d is an SEM test chart of the supported nickel-nickel oxide heterostructure catalyst electrode prepared in example 1, scale: 500nm;
FIG. 3a is a TEM test chart of the electrode-supported nickel-nickel oxide heterostructure catalyst prepared in example 1;
FIG. 3b is an EDS test chart of elemental oxygen and nickel in the example 1 electrode-supported nickel-nickel oxide heterostructure catalyst;
FIG. 3c is an EDS test chart of oxygen element in the nickel-nickel oxide heterostructure catalyst supported on the electrode prepared in example 1;
FIG. 3d is an EDS test chart of the nickel element in the nickel-nickel oxide heterostructure catalyst supported on the electrode prepared in example 1;
FIG. 4 is an XPS test chart of the electrode-supported nickel-nickel oxide heterostructure catalyst prepared in example 1;
FIG. 5 is a high resolution TEM test chart of the electrode-supported nickel-nickel oxide heterostructure catalyst of example 1;
FIG. 6 is a graph of a zinc bromine flow battery at 80mA/cm using the catalyst 2 Cycle performance at current density;
FIG. 7 is a schematic diagram of a preferred embodiment of the present inventionZinc bromine flow battery without catalyst at 80mA/cm 2 Cycle performance at current density;
fig. 8 is a graph comparing cyclic voltammograms of zinc bromine flow batteries with and without catalyst.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the present invention provides a nickel-nickel oxide heterostructure catalyst, wherein the nickel-nickel oxide heterostructure catalyst contains 70-90 wt% nickel and 10-30 wt% nickel oxide, based on the total weight of the nickel-nickel oxide heterostructure catalyst.
In the invention, the mass percentages of nickel oxide and nickel in the nickel-nickel oxide heterostructure catalyst provided by the invention can be calculated according to an EDS test result, and specifically are as follows: and obtaining the content of nickel element and oxygen element in the catalyst through EDS test, and obtaining the mass percent of nickel oxide in the catalyst through calculation.
In some examples of the invention, EDS test results are shown in Table 4, and as can be seen from Table 4, the mass percent of nickel oxide in the prepared nickel-nickel oxide heterostructure catalyst is 20% and the mass percent of nickel is 80%.
According to the present invention, in order to make the electrode carrying the nickel-nickel oxide heterostructure have excellent adsorption capacity for the active material of the flow battery and excellent catalytic effect for the redox reaction in the flow battery, it is preferable that the nickel-nickel oxide heterostructure catalyst has an average particle diameter of 50 to 200nm.
Preferably, the nickel-nickel oxide heterostructure catalyst has a core-shell structure, wherein the core is composed of nickel and the shell is composed of nickel oxide. The above structure of the catalyst can be determined by a combination of SEM, TEM, EDS and XPS tests. From SEM test charts of the supported nickel-nickel oxide heterostructure catalyst electrode shown in fig. 2a to 2d and TEM test charts of the nickel-nickel oxide heterostructure catalyst shown in fig. 3a, it can be seen that the nickel-nickel oxide heterostructure catalyst has a nano-sized spherical structure. As can be seen from the EDS test charts of the catalysts shown in fig. 3b, 3c and 3d, the distribution brightness of nickel element is radially decreased from the center to the edge of the obtained quasi-circular test area, because, on the one hand, for the catalyst having a spherical structure, the thickness of the catalyst is decreased from the center to the edge of the spherical structure in the direction perpendicular to the surface of the catalyst, so that the amount of nickel element measured by EDS is also decreased from the center to the edge of the spherical structure for elemental nickel as a core; on the other hand, the material composition in the region of a certain depth inward from the surface of the catalyst having a spherical structure was nickel oxide, the density of the nickel element measured by EDS in this region was also smaller than that of the nickel element contained in the inner nickel core, and in addition, it was found from the EDS test result that the distribution brightness of the oxygen element exhibited a relatively concentrated at the edge of this type of circular test region, because the thickness of the nickel oxide shell layer in the catalyst having a spherical structure was thickest at the edge in the direction perpendicular to the surface of the catalyst, the EDS test result showed that the content of the oxygen element was the largest at the edge, and the EDS test result in the region inside this edge region showed that the distribution brightness of the oxygen element was relatively dispersed and uniform, which also indicated that the oxygen element was uniformly distributed on the surface of the catalyst having a core-shell structure with nickel as the core and nickel oxide as the shell. It is emphasized that EDS is characterized by a depth in the micrometer scale, whereas the average particle size of the catalyst particles in the present invention is 50-200nm, so that the x-rays can penetrate completely through the catalyst. The test of the catalyst by high resolution TEM, such as that of example 1, is shown in FIG. 5, and the lattice fringes in the test pattern can be foundThe (200) crystal plane and the (111) crystal plane corresponding to NiO indicate that the component of the catalyst surface is nickel oxide. XPS test is performed on the catalyst of the present invention, for example, the test results obtained in example 1 are shown in FIG. 4, and valence analysis is performed on the 2p orbitals of Ni element, wherein Sat. Refers to satellite peaks, and the results show that the catalyst contains Ni 2+ And Ni 0 Corresponding to nickel oxide as a shell layer and elemental nickel as a core, respectively. It should be emphasized that the XPS test depth is 3-10nm, and the particle size of the catalyst in the invention is 50-200nm, which indicates that the inner nickel core cannot be completely penetrated when the XPS test is performed, so that the characteristic peak in the XPS test result is mainly nickel oxide as a shell layer, and the core-shell structure of the catalyst is further verified.
In the present invention, the method of preparing the nickel-nickel oxide heterostructure catalyst may be performed by means of a support, for example, the preparation method provided in the third aspect of the present invention, wherein the catalyst is formed on the surface of the current collector by means of a current collector as a support.
The nickel-nickel oxide heterostructure catalyst provided by the invention has a nano-sized core-shell structure, wherein the composition of the core is nickel, so that the catalyst is ensured to have excellent conductivity; the shell is composed of nickel oxide, which is favorable for adsorption of active substances and catalysis of redox reaction, for example, when the catalyst is applied to a flow battery, as can be seen from fig. 6 and 7, when the electrode carrying the nickel/nickel oxide heterostructure catalyst is applied to the flow battery, the voltage efficiency and the energy efficiency of the flow battery are both remarkably improved under a wider current density.
In the invention, the composition and structure of the nickel-nickel oxide heterostructure catalyst can be determined by characterization means such as XRD, raman, SEM, TEM, EDS and XPS, and the like, and also can be determined by the feeding amount of each material in the preparation process.
The second aspect of the invention provides an electrode, wherein the electrode comprises the nickel-nickel oxide heterostructure catalyst provided by the invention. Further, the electrode may include a current collector and the nickel-nickel oxide heterostructure catalyst provided by the present invention formed in situ on the current collector. The catalyst is contained in an amount of 5 to 9wt% and the current collector is contained in an amount of 91 to 95 wt% based on the total weight of the electrode.
The third aspect of the present invention provides a method for producing an electrode, wherein the method comprises:
(1) Soaking a current collector material in a precursor solution containing nickel salt and benzimidazole, and drying to obtain a treated current collector material;
(2) Heat treating the treated current collector material in an inert atmosphere to obtain a heat treated current collector material;
(3) And roasting the heat-treated current collector material in an air atmosphere to obtain the electrode.
According to the preparation method, nickel salt and benzimidazole react to obtain a metal complex, the current collector material is soaked in the metal complex solution, and after drying, the current collector material with the nickel complex uniformly attached is obtained; carrying out high-temperature heat treatment in an inert atmosphere, and carrying out reduction reaction on the nickel-containing complex on the surface of a carbon or copper material to form elemental nickel nano particles; roasting under the air atmosphere, and oxidizing the surface elemental nickel under the action of oxygen in the air to obtain nickel oxide, wherein the structural composition of the nickel oxide is compact, so that the internal elemental nickel is prevented from being oxidized continuously after the nickel oxide with a certain thickness is generated by the oxidation reaction, and finally the nickel-nickel oxide heterostructure catalyst with a core-shell structure is obtained; when the electrode carrying the nickel-nickel oxide heterostructure catalyst is applied to a flow battery, the voltage efficiency and the energy efficiency are both remarkably improved under a wider current density. In addition, in the invention, the nickel-nickel oxide heterostructure catalyst is grown on the current collector material in situ, and is not easy to fall off from the electrode when the catalyst is applied to a flow battery, so that the cycle stability of the flow battery is improved.
According to the preparation method of the present invention, in order to make the electrode carrying the nickel/nickel oxide heterostructure catalyst have excellent adsorption capacity to the active material of the flow battery and excellent catalytic effect to the redox reaction in the battery, preferably, in the step (1), the concentration of the precursor solution is 0.5-5g/mL based on the nickel salt and the ligand as solutes.
Preferably, in the step (1), the mass percentage of the nickel salt is 20-80% and the mass percentage of the benzimidazole is 20-80% based on the total weight of the solutes in the precursor solution.
Preferably, the nickel salt is selected from one or more of nickel nitrate, nickel sulfate, nickel chloride, nickel acetate.
Preferably, the ligand is selected from one or more of imidazole, benzimidazole, dimethylimidazole, 4-bipyridine.
According to the present invention, in the step (1), the solvent used in the precursor solution is a polar solvent, and preferably, the solvent used is one or more of ethanol, methanol, and water.
In some embodiments of the invention, in step (1), the solvent used in the precursor solution is ethanol.
According to the present invention, in order to make the electrode prepared and carrying the nickel-nickel oxide heterostructure catalyst have a good adsorption capacity, preferably, in the step (1), the current collector material is selected from one or more of porous current collector materials including graphite felt, graphite block, carbon cloth, carbon felt and copper foam.
In some embodiments of the invention, in the step (1), the current collector materials are graphite felts, respectively.
According to the preparation method of the present invention, in order to sufficiently soak the current collector material with the precursor solution, preferably, the soaking in the step (1) is performed for 0.5 to 4 hours at room temperature.
In some embodiments of the invention, in the step (1), the soaking is performed for 2 hours at room temperature.
According to the preparation method of the present invention, preferably, in the step (1), the drying temperature is 40 to 80 ℃.
In some embodiments of the invention, in the step (1), the drying temperature is 60 ℃.
According to the preparation method of the present invention, in order to convert all nickel elements in the complex into elemental nickel and simultaneously prevent side reactions such as carbonization and sintering of the current collector substrate after heat treatment of the treated current collector material (current collector material to which the nickel complex is uniformly attached), preferably, in the step (3), the firing temperature is 600 to 900 ℃ and the firing time is 1 to 5 hours under an inert atmosphere.
In some embodiments of the present invention, in the step (3), the baking temperatures under an inert atmosphere are respectively: the roasting time is 1h, 2h and 5h at 600 ℃,800 ℃ and 900 ℃.
According to the preparation method of the present invention, in order to obtain the nickel-nickel oxide heterostructure catalyst of the present invention and to have a nano-sized core-shell structure, preferably, in the step (4), the calcination temperature is 200-400 ℃ and the calcination time is 1-5 hours under an air atmosphere.
In some embodiments of the present invention, in the step (4), the baking temperatures under an air atmosphere are respectively: roasting time is 1h, 2h and 5h at 200 ℃,300 ℃ and 400 ℃.
According to some embodiments of the invention, a schematic diagram of the preparation of the nickel-nickel oxide heterostructure catalyst using a graphite felt as a current collector is shown in fig. 1, and it can be seen from fig. 1 that the current collector graphite felt has a typical three-dimensional porous structure, and the nickel-nickel oxide heterostructure catalyst grows on a single fibrous surface. The porous current collector provides more loading sites for the catalyst, can load a nickel-nickel oxide heterostructure catalyst with more nano size, enhances the catalytic effect of the electrode on redox reaction in the flow battery, and is beneficial to adsorbing active substances of the flow battery by the electrode, improving the catalysis of the catalyst on redox reaction in the battery, thereby being more beneficial to improving the voltage efficiency, energy efficiency and cycle stability of the flow battery.
In a fourth aspect, the invention provides an electrode obtained by the method of preparation.
In a fifth aspect, the invention provides a nickel-nickel oxide heterostructure catalyst and the use of the electrode in a flow battery.
According to the present invention, preferably, the nickel-nickel oxide heterostructure catalyst is used in a positive electrode material of a flow battery, and the electrode is used as a positive electrode of the flow battery.
Preferably, the flow battery is a zinc-bromine flow battery, a zinc-iodine flow battery, a zinc-iron flow battery, a zinc-cerium flow battery, or an all-vanadium flow battery.
Under the condition of room temperature, the electrode is used as the positive electrode of a flow battery, the active area of the electrode is 2 multiplied by 2cm, the consumption of electrolyte is 20mL, the flow rate is 30mL/min, and the negative electrode material is graphite felt; when the current densities were 20mA/cm respectively -2 、80mA/cm -2 、160mA/cm -2 When the flow battery performance test results are shown in tables 1-3. As can be seen from the data in tables 1 to 3, the nickel-nickel oxide heterostructure catalyst of the present invention can significantly improve the voltage efficiency, energy efficiency and cycle stability of the flow battery as compared to comparative example 1.
The following examples are presented to illustrate the technical scheme of the invention, wherein all raw materials used are commercially available and room temperature is 15-35 ℃.
Nickel nitrate, 98% pure, was purchased from Shanghai Ala Ding Shenghua reagent company.
Benzimidazole, 98.5% pure, was purchased from Shanghai Ala Ding Shenghua reagent company.
Graphite felt with thickness of 3mm and density of 0.13-0.16g/cm 3 Carbon content was 99%, purchased from North sea carbon company.
The average particle size of the catalyst was determined by SEM and TEM methods.
The core-shell structure of the catalyst was determined by a combination of XRD, XPS and TEM methods.
In the following examples and comparative examples, the composition of the resulting nickel-nickel oxide heterostructure catalyst was determined by calculation of the charge.
Comparative example 1
(1) The graphite felt is put into absolute ethyl alcohol, ultrasonic is carried out for 30min, and the graphite felt is dried in an oven at 60 ℃ after scraps are removed.
(2) Placing the dried graphite felt into a tube furnace, heating up at a heating rate of 3 ℃/min under inert atmosphere, and preserving heat for 1h at 800 ℃;
(3) And (3) preserving heat for 1 hour at 400 ℃ in an air atmosphere, and naturally cooling to room temperature to obtain the treated graphite felt electrode.
Example 1
(1) Dissolving 0.5g of nickel nitrate and 0.5g of benzimidazole in 50mL of absolute ethyl alcohol, and stirring for 5min to obtain a precursor solution;
(2) Soaking graphite felt in the precursor solution for 2 hours at room temperature, and then drying in an oven at 60 ℃;
(3) Placing the dried graphite felt into a tube furnace, heating up at a heating rate of 3 ℃/min under inert atmosphere, and roasting for 1h at 800 ℃;
(4) Roasting for 1h at 300 ℃ in air atmosphere, naturally cooling to room temperature, and obtaining the electrode of the supported catalyst I. The catalyst I content in the electrode was 9wt%.
The catalyst I contained 80% by weight of nickel and 20% by weight of nickel oxide, based on the total weight of the catalyst I obtained.
As can be seen from the SEM topography shown in fig. 2 and the TEM and EDS of fig. 3, the average particle size of the catalyst I was 50-200nm, and as can be seen from fig. 3, 4, and 5, the catalyst I was a nickel-nickel oxide heterostructure catalyst having a core-shell structure. In addition, according to the EDS test results, the content of nickel element and oxygen element in the catalyst I is obtained, the mass percentages of nickel oxide and nickel contained in the catalyst I can be obtained through calculation, and the calculated result is consistent with the result obtained through calculation of the feeding ratio.
TABLE 4 Table 4
| Element(s) | Mass fraction (%) | Strength of |
| O | 4.3 | 5016 |
| Ni | 95.7 | 90932 |
Example 2
(1) Dissolving 0.2g of nickel nitrate and 0.8g of benzimidazole in 100mL of absolute ethyl alcohol, and stirring for 5min to obtain a precursor solution;
(2) Soaking graphite felt in the precursor solution for 2 hours at room temperature, and then drying in an oven at 60 ℃;
(3) Placing the dried graphite felt into a tube furnace, heating at a heating rate of 1 ℃/min under inert atmosphere, and roasting at 600 ℃ for 5 hours;
(4) Roasting for 5 hours at 200 ℃ in air atmosphere, naturally cooling to room temperature, and obtaining the electrode of the supported catalyst II. The catalyst II content in the electrode was 5wt%.
Based on the total weight of the obtained catalyst II, the catalyst II contains 90% of nickel and 10% of nickel oxide.
And (3) carrying out SEM, TEM, XPS and EDS measurement on the obtained catalyst II, wherein the average particle size of the catalyst II is 50-100nm, and the catalyst II is a nickel-nickel oxide heterostructure catalyst with a core-shell structure.
Example 3
(1) Dissolving 0.8g of nickel nitrate and 0.2g of benzimidazole in 50mL of absolute ethyl alcohol, and stirring for 5min to obtain a precursor solution;
(2) Soaking graphite felt in the precursor solution for 2 hours at room temperature, and then drying in an oven at 60 ℃;
(3) Placing the dried graphite felt into a tube furnace, heating up at a heating rate of 10 ℃/min under inert atmosphere, and roasting for 2 hours at 800 ℃;
(4) Roasting for 2 hours at 400 ℃ in an air atmosphere, naturally cooling to room temperature, and obtaining the electrode of the supported catalyst III. The catalyst III content in the electrode was 5% by weight.
The catalyst III contained 75% nickel and 25% nickel oxide, based on the total weight of the resulting catalyst III.
And (3) carrying out SEM, TEM, XPS and EDS measurement on the obtained catalyst III, wherein the average particle size of the catalyst III is 100-200nm, and the catalyst III is a nickel-nickel oxide heterostructure catalyst with a core-shell structure.
Example 4
(1) Dissolving 0.3g of nickel nitrate and 0.3g of benzimidazole in 20mL of absolute ethyl alcohol, and stirring for 5min to obtain a precursor solution;
(2) Soaking graphite felt in the precursor solution for 2 hours at room temperature, and then drying in an oven at 60 ℃;
(3) Placing the dried graphite felt into a tube furnace, heating at a heating rate of 3 ℃/min under inert atmosphere, and roasting at 900 ℃ for 1h;
(4) Roasting for 1h at 400 ℃ in air atmosphere, naturally cooling to room temperature, and obtaining the electrode of the supported catalyst IV. The catalyst IV content in the electrode was 7wt%.
The catalyst IV contained 78% nickel and 22% nickel oxide, based on the total weight of the resulting catalyst IV.
And (3) carrying out SEM, TEM, XPS and EDS measurement on the obtained catalyst IV, wherein the average particle size of the catalyst IV is 150-200nm, and the catalyst IV is a nickel-nickel oxide heterostructure catalyst with a core-shell structure.
Example 5
(1) Dissolving 0.3g of nickel nitrate and 0.3g of benzimidazole in 50mL of absolute ethyl alcohol, and stirring for 5min to obtain a precursor solution;
(2) Soaking graphite felt in the precursor solution for 2 hours at room temperature, and then drying in an oven at 60 ℃;
(3) Placing the dried graphite felt into a tube furnace, heating at a heating rate of 5 ℃/min under inert atmosphere, and roasting at 800 ℃ for 1h;
(4) Roasting for 5 hours at 400 ℃ in an air atmosphere, naturally cooling to room temperature, and obtaining the electrode of the supported catalyst V. The catalyst V content in the electrode was 7% by weight.
The catalyst V contained 70% nickel and 30% nickel oxide based on the total weight of the catalyst V obtained.
And (3) carrying out SEM, TEM, XPS and EDS measurement on the obtained catalyst V, wherein the average particle size of the catalyst V is 150-200nm, and the catalyst V is a nickel-nickel oxide heterostructure catalyst with a core-shell structure.
Test case
Zinc bromine flow battery performance testing was performed using catalyst I obtained in example 1: the positive electrode electrolyte contains 2mol/L zinc bromide, 3mol/L ammonium chloride and 0.8 mol/L1-methyl-1-ethyl pyrrolidine bromide; the negative electrode electrolyte contains 2mol/L zinc bromide and 3mol/L ammonium chloride; the volume of the electrolyte is 20mL, and the flow rate is 30mL/min; the diaphragm isHP200; the negative electrode is graphite felt, the positive electrode is an electrode for supporting the catalyst I and the graphite felt electrode obtained in comparative example 1, and the electrode areas are all 2X 2cm 2 . Testing at 10mAh/cm at room temperature using a New Wipe battery test System 2 At a capacity of 20mA/cm 2 、80mA/cm 2 、160mA/cm 2 Cell performance at current density. The test results are shown in tables 1-3.
Zinc-iodine flow battery performance test was performed using catalyst II obtained in example 2: zinc sulfate with the concentration of 1mol/L is used as both the positive and negative electrolyte; the volume of the electrolyte is 20mL, and the flow rate is 30mL/min; the diaphragm is Nafion212; the negative electrode is a zinc sheet with the thickness of 100 mu m, the positive electrode is an electrode for supporting a catalyst II and a graphite felt electrode obtained in comparative example 1 respectively, and the load is 100mg/cm 2 The area of the electrode is 2X 2cm 2 . Testing at 10mAh/cm at room temperature using a New Wipe battery test System 2 At a capacity of 20mA/cm 2 、80mA/cm 2 、160mA/cm 2 Cell performance at current density. The test results are shown in tables 1-3.
Performance test of zinc cerium flow battery using catalyst III prepared in example 3: the positive electrode electrolyte contains 0.1mol/L cerium sulfate, 3mol/L methanesulfonic acid, 0.1mol/L sulfuric acid and 0.25mol/L sodium sulfate; the negative electrode electrolyte is sodium hydroxide with the concentration of 0.5 mol/L; the volume of the electrolyte is 20mL, and the flow rate is 30mL/min; the diaphragm is Nafion212; the negative electrode is a zinc sheet with the thickness of 100 mu m, the positive electrode is an electrode loaded with a catalyst III and the graphite felt electrode obtained in comparative example 1, and the electrode areas are all 2 multiplied by 2cm 2 . Testing at 10mAh/cm at room temperature using a New Wipe battery test System 2 At a capacity of 20mA/cm 2 、80mA/cm 2 、160mA/cm 2 Cell performance at current density. The test results are shown in tables 1-3.
Zinc-iron flow battery performance test was performed using catalyst IV prepared in example 4: the positive electrode electrolyte contains 0.4mol/L potassium ferrocyanide and 3mol/L sodium hydroxide; the negative electrode electrolyte contains 0.4mol/L zinc oxide and 3mol/L sodium hydroxide; the volume of the electrolyte is 20mL, and the flow rate is 30mL/min; the diaphragm is Nafion212; the negative electrode is graphite felt, the positive electrode is an electrode for supporting a catalyst IV and the graphite felt electrode obtained in comparative example 1 respectively, and the area is 2 multiplied by 2cm 2 . Testing at 10mAh/cm at room temperature using a New Wipe battery test System 2 At a capacity of 20mA/cm 2 、80mA/cm 2 、160mA/cm 2 Cell performance at current density. The test results are shown in tables 1-3.
All vanadium redox flow battery performance test was performed using catalyst V prepared in example 5: the positive electrode electrolyte contains 1.1mol/L vanadium oxide and 3mol/L sulfuric acid; the negative electrode electrolyte contains 1.1mol/L sodium vanadate and 3mol/L sulfuric acid; the volume of the electrolyte is 20mL, and the flow rate is 30mL/min; the diaphragm is Nafion212; the negative electrode is graphite felt, the positive electrode is an electrode for supporting catalyst V and the graphite felt electrode obtained in comparative example 1 respectively, and the area is 2 multiplied by 2cm 2 . Testing at 10mAh/cm at room temperature using a New Wipe battery test System 2 At a capacity of 20mA/cm 2 、80mA/cm 2 、160mA/cm 2 Cell performance at current density. The test results are shown in tables 1-3.
TABLE 1
TABLE 2
TABLE 3 Table 3
The battery performance of each test example at different current densities is shown in tables 1-3, and it can be seen that the voltage efficiency, energy efficiency and cycle performance of the flow battery of the example are significantly better than those of comparative example 1. Taking zinc bromine battery as an example, FIGS. 6 and 7 are at 20mA/cm 2 The battery was able to cycle 400 cycles with 86% energy efficiency when the graphite felt loaded with the nickel-nickel oxide heterostructure catalyst prepared in example 1 was used as the positive electrode of the battery, whereas the graphite felt prepared in comparative example 1 was used as the positive electrode of the battery, and the energy efficiency of the battery was only 60% and was able to cycle 40 cycles stably. Fig. 8 is a cyclic voltammetry test result of a zinc bromine flow battery, wherein the oxidation potential of the battery using the catalyst is reduced, the reduction potential is increased, and the potential difference is lower, which shows that the catalyst has a remarkable catalytic effect on the oxidation-reduction reaction.
As can be seen from the above examples and comparative examples, when the preparation method of the present invention is used to apply the nickel-nickel oxide heterostructure catalyst grown on the current collecting material in situ to the flow battery, the voltage efficiency and energy efficiency of the flow battery can be significantly improved under the same test conditions as those of the comparative examples; in addition, unlike the electrode obtained by coating the prepared catalyst on the current collecting material in the prior art, the catalyst is loaded on the current collecting material by using an in-situ growth method, so that the catalyst is not easy to fall off from the electrode, and the cycle stability of the electrode material is obviously improved.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, various simple modifications can be made to the technical solution of the invention, including that each specific technical feature is combined in any suitable way, but these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the protection scope of the invention.
Claims (13)
1. A nickel-nickel oxide heterostructure catalyst, characterized in that the nickel-nickel oxide heterostructure catalyst contains 70-90 wt% nickel and 10-30 wt% nickel oxide, based on the total weight of the nickel-nickel oxide heterostructure catalyst.
2. The nickel-nickel oxide heterostructure catalyst of claim 1, wherein the average particle size of the nickel-nickel oxide heterostructure catalyst is 50-200nm.
3. The nickel-nickel oxide heterostructure catalyst of claim 1 or 2, wherein the nickel-nickel oxide heterostructure catalyst has a core-shell structure in which the composition of the core is nickel and the composition of the shell is nickel oxide.
4. An electrode comprising the nickel-nickel oxide heterostructure catalyst of any one of claims 1-3.
5. A method of preparing an electrode, the method comprising:
(1) Soaking a current collector material in a precursor solution containing nickel salt and a ligand, and drying to obtain a treated current collector material;
(2) Carrying out heat treatment on the treated current collector material in an inert atmosphere to obtain a heat treated current collector material;
(3) And roasting the heat-treated current collector material in an air atmosphere to obtain the electrode.
6. The preparation method according to claim 5, wherein in the step (1), the concentration of the precursor solution is 0.5-5g/mL in terms of nickel salt and ligand as solutes;
preferably, the mass percentage of the nickel salt is 20-80% and the mass percentage of the ligand is 20-80% based on the total weight of solutes in the precursor solution;
preferably, the nickel salt is selected from one or more of nickel nitrate, nickel sulfate, nickel chloride and nickel acetate;
preferably, the ligand is selected from one or more of imidazole, benzimidazole, dimethylimidazole, 4-bipyridine.
7. The method of claim 5 or 6, wherein in step (1), the current collector material is selected from one or more of graphite felt, graphite block, carbon cloth, carbon felt, copper foam.
8. The production method according to any one of claims 5 to 7, wherein in the step (1), the conditions of soaking include: the temperature is room temperature and the time is 0.5-4h;
preferably, the drying temperature is 40-80 ℃.
9. The production method according to any one of claims 5 to 8, wherein in the step (2), the heat treatment process comprises: and heating the treated current collector material at a heating rate of 3-10 ℃/min under an inert atmosphere, and preserving heat for 1-5h at 600-900 ℃.
10. The production process according to any one of claims 5 to 9, wherein in step (3), the firing temperature is 200 to 400 ℃ and the firing time is 1 to 5 hours.
11. An electrode obtained by the production method according to any one of claims 5 to 10.
12. Use of the nickel-nickel oxide heterostructure catalyst of any of claims 1-3, the electrode of any of claims 4 and 11 in a flow battery.
13. The use of claim 12, wherein the flow battery is a zinc-bromine flow battery, a zinc-iodine flow battery, a zinc-iron flow battery, a zinc-cerium flow battery, or an all-vanadium flow battery.
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