CN115064713A - Spinel-loaded negative electrode material and preparation method and application thereof - Google Patents
Spinel-loaded negative electrode material and preparation method and application thereof Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 70
- 239000011029 spinel Substances 0.000 title claims abstract description 70
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 66
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 239000010406 cathode material Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000002070 nanowire Substances 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 239000004202 carbamide Substances 0.000 claims description 22
- 239000004744 fabric Substances 0.000 claims description 20
- 229910003266 NiCo Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 239000011268 mixed slurry Substances 0.000 claims description 6
- 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 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical group [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000007772 electrode material Substances 0.000 abstract description 10
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000010287 polarization Effects 0.000 abstract description 5
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 perovskite Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/10—Fuel cells in stationary systems, e.g. emergency power source in plant
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a spinel-loaded negative electrode material and a preparation method and application thereof, belonging to the technical field of all-vanadium redox flow battery negative electrode materials. The invention aims to provide a spinel-loaded negative electrode material with high electrocatalytic activity. The cathode material takes a carbon material as a matrix, and a spinel material is loaded on the surface of the cathode material, wherein the spinel material is in a nanowire structure and contains Ni, Co and O elements. The electrode material prepared by the invention has higher electrocatalytic activity, can reduce electrochemical polarization in the flow battery, and improves the working efficiency of the batteryMaking current density; meanwhile, the service life of the battery under high current density is prolonged; can greatly improve V 2+ /V 3+ The electrocatalytic activity and reversibility of the oxidation-reduction reaction reduce the charge transfer resistance and improve the cycle performance and energy efficiency of the flow battery. The electrode material is simple in preparation method, cheap and easily available in materials, free of expensive noble metals and high in commercial popularization and application value.
Description
Technical Field
The invention relates to a spinel-loaded negative electrode material and a preparation method and application thereof, belonging to the technical field of all-vanadium redox flow battery negative electrode materials.
Background
Nowadays, fossil energy such as coal, oil and natural gas is still used as a main body of energy structures all over the world, but because of the non-renewable property of the energy and the serious environmental problem caused by the large amount of use, the dependence on the energy is gradually reduced in all countries of the world, and new clean energy is vigorously developed to replace the traditional non-renewable energy. However, clean energy sources such as solar energy, wind energy and tidal energy have uneven and unstable geographical distribution, and if the clean energy sources are directly connected to a power grid, impact is caused on the power grid, and the normal operation of the power grid is influenced. Therefore, the development and utilization of new clean energy needs to be equipped with a large energy storage system, so as to realize the storage and the use on demand of the electric energy converted from the renewable energy.
At present, a large-scale energy storage system mainly comprises a lithium battery, a lead-acid battery and an all-vanadium redox flow battery. Among them, lead-acid batteries are easily causing serious environmental pollution problems and are being gradually eliminated; the lithium battery has the advantages of small volume, high energy density and the like, and is widely used in the field of energy storage, however, the lithium battery is restricted to be widely used in a large-scale energy storage system due to high cost and poor safety; the all-vanadium redox flow battery has the advantages of large capacity, high safety, long service life, flexible structure and the like, and is one of the preferred systems of a large-scale energy storage system.
The conversion between the electric energy and the chemical energy in the all-vanadium redox flow battery is mainly realized through the oxidation-reduction reaction of vanadium species in electrolyte, and the electrode reaction equation is as follows:
and (3) positive electrode:
E o ＝1.0V vs.SHE
negative electrode:
E o ＝-0.26V vs.SHE
and (3) total reaction:
E o ＝1.26V vs.SHE
the electrode material is used as a core component of the all-vanadium redox flow battery, and the quality of the electrode material directly determines the service life and efficiency of the all-vanadium redox flow battery. The traditional electrode material for the flow battery has poor activity, high resistance and the like, and the development of the flow battery technology is limited by the factors. The carbon felt and the carbon cloth are used as porous materials with high conductivity, so that considerable reaction sites can be provided for active substances, and electrochemical polarization is reduced. However, the research focus is generally on how to improve the activity of the carbon felt and the carbon cloth, and therefore, researchers can generally introduce nano materials with special physicochemical properties, such as graphene, perovskite, spinel, and the like, as electrode materials into the all-vanadium flow battery to further improve the battery performance.
Among them, spinel materials have stable chemical properties and tunable electronic structures, and in recent years, have been used for H in photocatalytic water splitting, oxygen reduction and as green energy storage materials 2 And CO 2 The storage and the like of the computer system are all made important progress.
Chinese patent application No. 201810510211.8 discloses a nano nickel cobaltate carbon cloth electrode and a method for preparing the same, wherein a hydrothermal method and an electroplating method are combined to load nickel cobaltate on carbon cloth to obtain the nano nickel cobaltate carbon cloth electrode. The material is in a nanosheet structure, is used in an all-vanadium redox flow battery, and needs to be further improved in electrocatalytic activity.
Disclosure of Invention
In view of the defects, the technical problem solved by the invention is to provide a spinel-loaded negative electrode material with high electrocatalytic activity.
The spinel material loaded cathode material takes a carbon material as a matrix, and the surface of the spinel material is loaded, wherein the spinel material is in a nanowire structure and contains Ni, Co and O elements.
In one embodiment of the invention, the spinel material is NiCo 2 O 4 Or Fe-doped NiCo 2 O 4 。
In some embodiments of the invention, the carbonaceous material is at least one of a carbon felt, a carbon cloth, and a graphite felt.
In one embodiment of the invention, the spinel material is present at a loading of 0.1 to 5 wt%. In a preferred embodiment of the present invention, the spinel material is present at a loading of 0.2 to 3 wt%.
The invention also provides a preparation method of the spinel material-loaded negative electrode material.
The preparation method of the spinel material loaded negative electrode material comprises the following steps:
a. preparing a spinel material: preparation of NiCo by the a1 Process 2 O 4 Or preparing Fe-doped NiCo by adopting a2 step 2 O 4 ；
The step a1 is as follows: mixing a Ni source, a Co source, urea, ammonium fluoride and water, reacting for 10-14 h at 110-130 ℃, cooling, taking a precipitate, washing, drying, heating to 300-400 ℃, calcining for 3-5 h to obtain NiCo 2 O 4 ；
The step a2 is as follows: mixing a Ni source, a Co source, a Fe source, urea, ammonium fluoride and water, reacting for 10-14 h at 110-130 ℃, cooling, taking a precipitate, washing, drying, heating to 300-400 ℃, calcining for 3-5 h to obtain Fe-doped NiCo 2 O 4 ；
b. Mixing a spinel material, a conductive agent, a binder and a solvent to obtain mixed slurry, coating the mixed slurry on a carbon material, and drying to obtain the spinel material-loaded cathode material.
In a specific embodiment of the present invention, the Ni source is nickel acetate, nickel nitrate or nickel chloride, the Co source is cobalt acetate, cobalt nitrate or cobalt chloride, and the Fe source is iron acetate, iron nitrate or iron chloride; preferably, the Ni source is nickel nitrate, the Co source is cobalt nitrate, and the Fe source is ferric nitrate.
In one embodiment of the invention, in the step a1, the molar ratio of the Ni source to the Co source to the urea to the ammonium fluoride is 1: 1.8-2.2: 13-17: 4-6; in the step a2, the molar ratio of the Ni source to the Co source to the Fe source to the urea to the ammonium fluoride is 1: 1.4-1.6: 0.4-0.6: 13-17: 4-6.
In a preferred embodiment of the invention, in the step a1, the molar ratio of the Ni source to the Co source to the urea to the ammonium fluoride is 1:2:15: 5; in the step a2, the molar ratio of the Ni source to the Co source to the Fe source to the urea to the ammonium fluoride is 1:1.5:0.5:15: 5.
In one embodiment of the invention, in the step a1, reaction is carried out for 12h at 120 ℃, and calcination is carried out for 4h at 350 ℃; in the step a2, reaction is carried out for 12h at 120 ℃, and calcination is carried out for 4h at 350 ℃.
In a specific embodiment of the invention, in the step b, the weight ratio of the spinel material, the conductive agent and the binder is 7-9: 0.5-1.5. In a preferred embodiment, in the step b, the weight ratio of the spinel material to the conductive agent to the binder is 8:1: 1.
The invention also provides application of the spinel material-loaded negative electrode material in an all-vanadium flow battery.
The spinel material loaded negative electrode material can be used as a negative electrode and used in an all-vanadium redox flow battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the electrode material prepared by the invention is prepared by loading a nano spinel electrocatalyst on the surface of a carbon material and reacting spinel NiCo 2 O 4 The electronic structures of Ni and Co can be adjusted after Fe doping, and the change of the electronic structures enables the material to have higher electrocatalytic activity, can reduce electrochemical polarization in the flow battery, and improve the working current density of the battery; while improving the life of the battery at high current densities.
(2) The electrode material prepared by the invention greatly improves V due to the nano spinel electrocatalyst loaded on the surface of the carbon material 2+ /V 3+ The electrocatalytic activity and reversibility of the oxidation-reduction reaction reduce the charge transfer resistance and improve the cycle performance and energy efficiency of the flow battery.
(3) The electrode material prepared by the invention has simple preparation method, the used material is cheap and easy to obtain, and the electrode material does not contain noble metal with very high price, thereby having commercial popularization and application value.
Drawings
Fig. 1 is an XRD pattern of spinel materials prepared in examples 1 and 2 of the present invention.
Fig. 2 is an SEM image of spinel materials prepared in examples 1 and 2 of the present invention.
Fig. 3 is an SEM image of spinel materials prepared in comparative examples 1 and 2 of the present invention.
Fig. 4 is an XPS chart of materials prepared in examples 1 and 2 of the present invention.
FIG. 5 shows electrodes prepared in examples 1 to 2 of the present invention and comparative examples 1 to 2 at 100mA/cm 2 Charge and discharge curves at current density.
FIG. 6 shows the results of the AC impedance test of the electrodes prepared in examples 1 to 2 of the present invention and comparative examples 1 to 2.
Fig. 7 is a result of energy efficiency test of the electrodes prepared in examples 1 and 2 of the present invention.
Detailed Description
The spinel material loaded cathode material takes a carbon material as a matrix, and the surface of the spinel material is loaded, wherein the spinel material is in a nanowire structure and contains Ni, Co and O elements.
In one embodiment of the invention, the spinel material is NiCo 2 O 4 Or Fe-doped NiCo 2 O 4 。
In some embodiments of the invention, the carbonaceous material is at least one of a carbon felt, a carbon cloth, and a graphite felt.
In one embodiment of the invention, the spinel material is present at a loading of 0.1 to 5 wt%. In a preferred embodiment of the present invention, the spinel material is present at a loading of 0.2 to 3 wt%.
The preparation method of the spinel material loaded negative electrode material comprises the following steps:
a. preparing a spinel material: preparation of NiCo by the a1 Process 2 O 4 Or preparing Fe-doped NiCo by adopting a2 step 2 O 4 ；
The step a1 is as follows: mixing a Ni source, a Co source, urea, ammonium fluoride and water, reacting for 10-14 h at 110-130 ℃, cooling, taking a precipitate, washing, drying, heating to 300-400 ℃, calcining for 3-5 h to obtain NiCo 2 O 4 ；
The step a2 is as follows: mixing a Ni source, a Co source, a Fe source, urea, ammonium fluoride and water, reacting for 10-14 h at 110-130 ℃, cooling, taking a precipitate, washing, drying, heating to 300-400 ℃, calcining for 3-5 h to obtain Fe-doped NiCo 2 O 4 ；
b. Mixing a spinel material, a conductive agent, a binder and a solvent to obtain mixed slurry, coating the mixed slurry on a carbon material, and drying to obtain the spinel material-loaded cathode material.
In a specific embodiment of the present invention, the Ni source is nickel acetate, nickel nitrate or nickel chloride, the Co source is cobalt acetate, cobalt nitrate or cobalt chloride, and the Fe source is iron acetate, iron nitrate or iron chloride; preferably, the Ni source is nickel nitrate, the Co source is cobalt nitrate, and the Fe source is ferric nitrate.
In a specific embodiment of the invention, in the step a1, the molar ratio of the Ni source to the Co source to the urea to the ammonium fluoride is 1: 1.8-2.2: 13-17: 4-6; in the step a2, the molar ratio of the Ni source to the Co source to the Fe source to the urea to the ammonium fluoride is 1: 1.4-1.6: 0.4-0.6: 13-17: 4-6.
In a preferred embodiment of the invention, in the step a1, the molar ratio of the Ni source to the Co source to the urea to the ammonium fluoride is 1:2:15: 5; in the step a2, the molar ratio of the Ni source to the Co source to the Fe source to the urea to the ammonium fluoride is 1:1.5:0.5:15: 5.
In one embodiment of the invention, in the step a1, reaction is carried out for 12h at 120 ℃, and calcination is carried out for 4h at 350 ℃; in the step a2, reaction is carried out for 12h at 120 ℃, and calcination is carried out for 4h at 350 ℃.
In a specific embodiment of the invention, in the step b, the weight ratio of the spinel material, the conductive agent and the binder is 7-9: 0.5-1.5. In a preferred embodiment, in the step b, the weight ratio of the spinel material to the conductive agent to the binder is 8:1: 1.
The spinel material loaded negative electrode material can be used as a negative electrode and used in an all-vanadium redox flow battery.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
1.45g of Ni (NO) was taken 3 ) 2 ·6H 2 O and 2.91g Co (NO) 3 ) 2 ·6H 2 O was dissolved in 60ml of deionized water, and 0.8g of urea and 0.15g of ammonium fluoride were added to the solution to prepare a solution. The solution was stirred on a magnetic stirrer for 0.5 hours to form a homogeneous and transparent solution. The clear solution was then transferred to a teflon lined autoclave and reacted at 120 ℃ for 12 hours. The resulting precipitate was cooled to room temperature, centrifuged three times with ethanol and deionized water, and dried at 70 ℃ overnight. And then putting the dried material into a tubular furnace to anneal for 4h at 350 ℃ in an air atmosphere, wherein the heating rate is 5 ℃/min. And mixing the annealed material, a conductive agent and a binder according to a mass ratio of 8:1:1, adding N-methyl pyrrolidone, continuously stirring to form slurry, and drying the carbon cloth uniformly coated with the slurry in a drying box at 70 ℃ for 6 hours to obtain the cathode material for the all-vanadium redox flow battery. The loading of the sample was about 2.5 wt% by weighing the mass of the carbon cloth before and after coating.
Example 2
1.45g of Ni (NO) was taken 3 ) 2 ·6H 2 O，2.18g Co(NO 3 ) 2 ·6H 2 O and 1.01g Fe (NO) 3 ) 3 ·9H 2 O dissolved in 60mlIn the ionized water, 0.8g of urea and 0.15g of ammonium fluoride were added to the solution to prepare a solution. The solution was stirred on a magnetic stirrer for 0.5 hours to form a homogeneous and transparent solution. The clear solution was then transferred to a teflon lined autoclave and reacted at 120 ℃ for 12 hours. The resulting precipitate was cooled to room temperature, centrifuged three times with ethanol and deionized water, and dried at 70 ℃ overnight. And then putting the dried material into a tubular furnace to anneal for 4h at 350 ℃ in an air atmosphere, wherein the heating rate is 5 ℃/min. And mixing the annealed material, a conductive agent and a binder according to a mass ratio of 8:1:1, adding N-methyl pyrrolidone, continuously stirring to form slurry, and drying the carbon cloth uniformly coated with the slurry in a drying box at 70 ℃ for 6 hours to obtain the cathode material for the all-vanadium redox flow battery. The loading of the sample was about 2.5 wt% by weighing the mass of the carbon cloth before and after coating.
Comparative example 1
Directly depositing nickel cobaltate nanosheets on carbon cloth by a hydrothermal method, wherein the specific method comprises the following steps:
1.45g of Ni (NO) was taken 3 ) 2 ·6H 2 O and 2.91g Co (NO) 3 ) 2 ·6H 2 O was dissolved in 60ml of deionized water, and 0.8g of urea and 0.15g of ammonium fluoride were added to the solution to prepare a solution. The solution was stirred on a magnetic stirrer for 0.5 hours to form a homogeneous and transparent solution. The clear solution was then transferred to a teflon-lined autoclave, into which a clean carbon cloth was placed, and then reacted at 120 ℃ for 12 hours. After cooling to room temperature, the carbon cloth was taken out, washed several times with ethanol and deionized water alternately, and dried at 70 ℃ overnight. And then putting the dried material into a tubular furnace to anneal for 4h at 350 ℃ in an air atmosphere, wherein the heating rate is 5 ℃/min. The annealed material can be directly used in the all-vanadium redox flow battery. The loading of the sample was approximately 2.5 wt% by weighing the mass of the carbon cloth before and after deposition.
Comparative example 2
Directly depositing iron-doped nickel cobaltate nanosheets on carbon cloth by adopting a hydrothermal method, wherein the specific method comprises the following steps:
1.45g of Ni (NO) was taken 3 ) 2 ·6H 2 O，2.18g Co(NO 3 ) 2 ·6H 2 O and 1.01g Fe (NO) 3 ) 3 ·9H 2 O was dissolved in 60ml of deionized water, and 0.8g of urea and 0.15g of ammonium fluoride were added to the solution to prepare a solution. The solution was stirred on a magnetic stirrer for 0.5 hours to form a homogeneous and transparent solution. The clear solution was then transferred to a teflon-lined autoclave, into which a clean carbon cloth was placed, and then reacted at 120 ℃ for 12 hours. After cooling to room temperature, the carbon cloth was taken out, washed several times with ethanol and deionized water alternately, and dried at 70 ℃ overnight. And then putting the dried material into a tubular furnace to anneal for 4h at 350 ℃ in an air atmosphere, wherein the heating rate is 5 ℃/min. The annealed material can be directly used in the all-vanadium redox flow battery. The loading of the sample was about 2.5 wt% by weighing the mass of the carbon cloth before and after coating.
Fig. 1 is an XRD pattern of spinel materials prepared in examples 1 and 2. Fig. 2 is an SEM image of the spinel materials prepared in examples 1 and 2, and fig. 3 is an SEM image of the spinel materials prepared in comparative examples 1 and 2. As can be seen from fig. 2 and 3, the nanowire structure prepared in the embodiment of the present invention, while the nanosheet structure prepared in comparative examples 1 and 2. Fig. 4 is an XPS plot of spinel materials prepared in examples 1 and 2. Wherein NiCoO is the spinel material prepared in example 1, and NiCoFeO is the spinel material prepared in example 2.
The anode materials prepared in examples 1 and 2 and comparative examples 1 and 2 were measured at 100mA/cm 2 The charge-discharge performance at current density is shown in fig. 5. The NiCoO is the negative electrode material of the embodiment 1, the NiCoFeO is the negative electrode material of the embodiment 2, the NiCoO @ CC is the negative electrode material of the comparative example 1, and the NiCoFeO @ CC is the negative electrode material of the comparative example 2. It can be seen from the figure that at the same current density, the NiCoFeO battery possesses a lower charging plateau, a higher discharging plateau and a smaller overpotential. The NiCoFeO cell thus has minimal electrochemical polarization. NiCoO cell at 100mA/cm 2 The discharge capacity was 2012.9mA · h at the current density of (1); while NiCoO @ CC cell was at 100mA/cm 2 The discharge capacity is only 1396.4 mA.h under the current density, which shows that compared with the nano-sheet, the nano-wire structure active site is moreAbundant, is beneficial to the reaction and improves the electrocatalytic activity. And for NiCoFeO cell, at 100mA/cm 2 The discharge capacity reaches 2989.4 mA.h under the current density of (1), NiCoFeO @ CC battery is at 100mA/cm 2 The discharge capacity reaches 2242.3 mA.h, and the increase of the discharge capacity also indicates that the NiCoFeO cell obviously reduces the electrochemical polarization process in the cell during the reaction process.
And testing the charge transfer impedance and the ion diffusion resistance of the vanadium ions on the surface of the electrode by adopting alternating current impedance. The electrode used was the negative electrode material prepared in examples 1 and 2 and comparative examples 1 and 2. The NiCoO is the negative electrode material of the embodiment 1, the NiCoFeO is the negative electrode material of the embodiment 2, the NiCoO @ CC is the negative electrode material of the comparative example 1, and the NiCoFeO @ CC is the negative electrode material of the comparative example 2. The voltage amplitude and the frequency range of the impedance test are respectively 0.5mV and 0.01-100 kHz. The magnitude of the charge transfer resistance (Rct) during the redox process was measured by electrochemical impedance spectroscopy, and the results are shown in fig. 6. As shown in fig. 6, a semicircle in the high frequency region is associated with Rct, and the smaller the diameter of the semicircle, the smaller the charge transfer resistance. The diagonal line of the low frequency region belongs to the ion diffusion resistance of the electrolyte. The NiCoFeO battery has the smallest semicircular diameter in a high-frequency region, which shows that the Rct of the electrode is smaller and is obviously lower than that of the NiCoO battery, and shows that the charge transfer speed between the NiCoFeO electrode and the electrolyte is accelerated and the electrocatalytic performance is improved.
The change in energy efficiency of the electrodes of examples 1-2 over 200 charge/discharge cycles was measured, and the results are shown in FIG. 6. For fig. 6a and 6b, it can be seen that the NiCoFeO cell has a higher discharge capacity than the NiCoO cell. And during 200 cycles, the NiCoFeO cell had less capacity reduction and was more stable than the NiCoO cell, indicating that the NiCoFeO cell was chemically more stable. For fig. 6c and 6d, it can be seen that the energy efficiency of NiCoFeO cell is maintained around 86.7%, while the energy efficiency of NiCoO cell can reach around 94.3%, which also demonstrates better catalytic effect of NiCoFeO.
Claims (10)
1. The spinel material loaded negative electrode material is characterized in that: the material takes a carbon material as a matrix, and a spinel material is loaded on the surface of the matrix, wherein the spinel material is in a nanowire structure and contains Ni, Co and O elements.
2. The spinel material-supporting anode material of claim 1, wherein: the spinel material is NiCo 2 O 4 Or Fe-doped NiCo 2 O 4 。
3. The spinel material-supporting anode material of claim 1, wherein: the carbon material is at least one of carbon felt, carbon cloth and graphite felt.
4. The spinel material-supporting anode material of claim 1, wherein: the load capacity of the spinel material is 0.1-5 wt%; preferably, the loading amount of the spinel material is 0.2-3 wt%.
5. The method for preparing the spinel material-supported anode material of any one of claims 1 to 4, comprising the steps of:
a. preparing a spinel material: preparation of NiCo by the a1 Process 2 O 4 Or preparing Fe-doped NiCo by adopting a2 step 2 O 4 ；
The step a1 is as follows: mixing a Ni source, a Co source, urea, ammonium fluoride and water, reacting for 10-14 h at 110-130 ℃, cooling, taking a precipitate, washing, drying, heating to 300-400 ℃, calcining for 3-5 h to obtain NiCo 2 O 4 ；
The step a2 is as follows: mixing a Ni source, a Co source, a Fe source, urea, ammonium fluoride and water, reacting for 10-14 h at 110-130 ℃, cooling, taking a precipitate, washing, drying, heating to 300-400 ℃, calcining for 3-5 h to obtain Fe-doped NiCo 2 O 4 ；
b. Mixing a spinel material, a conductive agent, a binder and a solvent to obtain mixed slurry, coating the mixed slurry on a carbon material, and drying to obtain the spinel material-loaded cathode material.
6. The method for preparing a spinel material-supporting anode material according to claim 5, wherein: the Ni source is nickel acetate, nickel nitrate or nickel chloride, the Co source is cobalt acetate, cobalt nitrate or cobalt chloride, and the Fe source is ferric acetate, ferric nitrate or ferric chloride; preferably, the Ni source is nickel nitrate, the Co source is cobalt nitrate, and the Fe source is ferric nitrate.
7. The method for preparing a spinel material-supporting anode material according to claim 5, wherein: in the step a1, the molar ratio of the Ni source to the Co source to the urea to the ammonium fluoride is 1: 1.8-2.2: 13-17: 4-6; in the step a2, the molar ratio of the Ni source to the Co source to the Fe source to the urea to the ammonium fluoride is 1: 1.4-1.6: 0.4-0.6: 13-17: 4-6; preferably, in the step a1, the molar ratio of the Ni source to the Co source to the urea to the ammonium fluoride is 1:2:15: 5; in the step a2, the molar ratio of the Ni source to the Co source to the Fe source to the urea to the ammonium fluoride is 1:1.5:0.5:15: 5.
8. The method for preparing a spinel material-supporting anode material according to claim 5, wherein: in the step a1, reacting at 120 ℃ for 12h, and calcining at 350 ℃ for 4 h; in the step a2, reaction is carried out for 12h at 120 ℃, and calcination is carried out for 4h at 350 ℃.
9. The method for preparing a spinel material-supporting anode material according to claim 5, wherein: in the step b, the weight ratio of the spinel material to the conductive agent to the binder is 7-9: 0.5-1.5; the weight ratio of the spinel material to the conductive agent to the binder is preferably 8:1: 1.
10. The application of the spinel material loaded negative electrode material in the vanadium redox flow battery according to any one of claims 1 to 4.
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