CN113851663B - Magnesium air battery catalyst, magnesium air battery air cathode and preparation method thereof, magnesium air battery and electric equipment - Google Patents
Magnesium air battery catalyst, magnesium air battery air cathode and preparation method thereof, magnesium air battery and electric equipment Download PDFInfo
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 88
- 239000011777 magnesium Substances 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229960002635 potassium citrate Drugs 0.000 claims abstract description 14
- 239000001508 potassium citrate Substances 0.000 claims abstract description 14
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims abstract description 14
- 235000011082 potassium citrates Nutrition 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 9
- LGRDAQPMSDIUQJ-UHFFFAOYSA-N tripotassium;cobalt(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LGRDAQPMSDIUQJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- UCFIGPFUCRUDII-UHFFFAOYSA-N [Co](C#N)C#N.[K] Chemical compound [Co](C#N)C#N.[K] UCFIGPFUCRUDII-UHFFFAOYSA-N 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 25
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application provides a magnesium air battery catalyst, a magnesium air battery air cathode, a preparation method of the magnesium air battery air cathode, a magnesium air battery and electric equipment. The preparation method of the magnesium air battery catalyst comprises the following steps: mixing raw materials including copper nitrate, potassium citrate and cobalt potassium cyanide, reacting to obtain a precursor, and performing heat treatment to obtain CuO@Co 3 O 4 And (3) nanoparticles. The magnesium air battery catalyst is prepared by the preparation method. The magnesium air battery air cathode includes a magnesium air battery catalyst. The preparation method of the air cathode of the magnesium air battery comprises the following steps: mixing the raw materials to obtain slurry; and coating the slurry on the pole piece, and drying to obtain the air cathode of the magnesium air battery. A magnesium air battery comprising a magnesium air battery air cathode. The electric equipment comprises a magnesium air battery. The magnesium air battery catalyst provided by the application has excellent oxygen reduction performance and high catalytic efficiency.
Description
Technical Field
The application relates to the field of materials, in particular to a magnesium air battery catalyst, a magnesium air battery air cathode, a preparation method of the magnesium air battery air cathode, a magnesium air battery and electric equipment.
Background
The metal-air battery has the characteristics of high energy density, small volume, long discharge life, simple structure and the like, and is an ideal electrochemical energy storage and conversion device. Among them, the magnesium air battery is a typical metal air battery, and has the advantages of high energy density, high theoretical voltage, large theoretical specific capacity, low cost, light weight, environmental friendliness, abundant reserves and the like. In addition, abundant raw materials, low cost, high safety and environmental protection are also inherent advantages of the magnesium air battery, and the magnesium air battery has great application potential.
The magnesium air battery consists of an air cathode, electrolyte and a magnesium anode, has simple structure and is beneficial to realizing industrial application. In theory, the magnesium air battery is a very ideal power source, but the limiting factors of slow reaction kinetics progress, higher overpotential, low coulombic efficiency caused by self-corrosion of the anode and the like still exist. The oxygen reduction potential is generally low, the reduction reaction is carried out in multiple steps, which can lead to slow cathode oxygen reduction reaction (Oxygen Reduction Reaction, ORR) in the magnesium air battery, cause the problems of higher overpotential, low coulombic efficiency and the like, restrict the performance of the whole battery, and become an important influencing factor for the development and the realization of commercial production of high energy density. The performance of the cathode oxygen reduction catalyst affects the performance of the whole air battery system to a great extent, including energy efficiency, cycle life, cost and the like, and directly determines the energy conversion efficiency of the air battery. Therefore, the search for high performance, efficient, durable, low cost, stable ORR catalysts is critical to the development of metal-air batteries. However, most of the ORR catalysts with better performance are noble metal catalysts such as Pt, and the like, so that the materials have small reserves and high cost, and are difficult to meet the requirements of mass industrial production and industrial application thereof. Therefore, the ORR catalyst with low price, abundant resources and high efficiency is developed to replace noble metal catalysts such as Pt and the like, and has important significance for the research and development and application of the magnesium air battery.
Disclosure of Invention
The purpose of the application is to provide a magnesium air battery catalyst, a magnesium air battery air cathode, a preparation method of the magnesium air battery air cathode, a magnesium air battery and electric equipment, so as to solve the problems.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a method for preparing a magnesium air battery catalyst, comprising:
mixing raw materials including copper nitrate, potassium citrate and cobalt potassium cyanide, and reacting to obtain a precursor;
performing heat treatment on the precursor to obtain CuO@Co 3 O 4 And (3) nanoparticles.
Preferably, the mixing comprises:
mixing the aqueous solution of copper nitrate and the aqueous solution of potassium citrate to obtain a mixed solution, and then dropwise adding the aqueous solution of potassium cobalt cyanide into the mixed solution.
Preferably, the reaction is carried out under stirring;
preferably, the stirring time is 10-30min;
preferably, the stirring is followed by aging;
preferably, the aging time is 20-24 hours;
preferably, the aging further comprises: carrying out solid-liquid separation on the reaction system to obtain a solid matter, and drying to obtain Cu 3 [Co(CN) 6 ] 2 ·9H 2 O is the precursor;
preferably, the drying temperature is 60-80 ℃ and the drying time is 20-24 hours;
preferably, the precursor has a cubic overall shape and a size of 1-2 μm.
Preferably, the heat treatment comprises:
calcining the precursor for 1-5h at 300-900 ℃ and cooling to obtain the CuO@Co 3 O 4 A nanoparticle;
preferably, the heating rate of the heat treatment is 1-10 ℃/min;
preferably, the CuO@Co 3 O 4 The size of the nano particles is 100-500nm.
The application also provides a magnesium air battery catalyst, and the magnesium air battery catalyst is prepared by using the preparation method of the magnesium air battery catalyst.
The application also provides an air cathode of the magnesium air battery, which comprises the magnesium air battery catalyst.
The application also provides a preparation method of the air cathode of the magnesium air battery, which comprises the following steps:
mixing raw materials including the magnesium air battery catalyst, a binder, a pore-forming agent, a conductive agent and an organic solvent to obtain slurry;
and coating the slurry on a pole piece, and drying to obtain the air cathode of the magnesium air battery.
Preferably, the conductive agent comprises carbon black;
preferably, the pole piece comprises hydrophobic conductive carbon paper.
The application also provides a magnesium air battery, comprising the air cathode of the magnesium air battery.
The application also provides electric equipment, which comprises the magnesium air battery.
Compared with the prior art, the beneficial effects of this application include:
according to the preparation method of the magnesium air battery catalyst, raw materials comprising copper nitrate, potassium citrate and cobalt potassium cyanide are mixed and reacted to obtain Prussian blue analogues serving as precursors, and the bimetallic oxide nano material CuO@Co is obtained by heat treatment 3 O 4 The morphology of the catalyst is effectively regulated and controlled, and the electrochemical performance of the catalyst is improved;
the preparation method adopts a simple coprecipitation method and heat treatment to obtain CuO@Co 3 O 4 The nano particles do not need complex preparation process, are simple and convenient to operate, and are easier to be applied to actual production; no other organic solvents, strong acid, strong alkali and the like are needed to be added, and compared with the traditional acidic or alkaline environment, the method has the advantages of mild reaction conditions, safety, stability and environmental protection; the sources of raw materials are wide, and the cost is low;
the precursor obtained by the preparation method has uniform shape, and can effectively reduce the grain size and increase the specific surface area through heat treatment; in alkaline electrolyte, cuo@co 3 O 4 The limiting current density of the nanoparticles is higher than the quotientWith Pt catalysts, excellent oxygen reduction performance was exhibited; under neutral environment, cuO@Co 3 O 4 The half-wave potential of the nano particles is shifted by only 20mV after 5000 cycles, and the nano particles have extremely excellent stability.
The magnesium air battery catalyst provided by the application has good catalytic performance, excellent oxygen reduction performance and excellent stability.
The air cathode of the magnesium air battery and the magnesium air battery provided by the application are high in energy conversion efficiency, long in cycle life and low in cost.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a graph of CuO@Co prepared in example 1 3 O 4 XRD pattern of nanoparticles;
FIG. 2 is a graph of CuO@Co prepared in example 1 3 O 4 SEM image of nanoparticles;
FIG. 3 is a graph of CuO@Co prepared in example 2 3 O 4 XRD pattern of nanoparticles;
FIG. 4 is a graph of CuO@Co prepared in example 2 3 O 4 SEM image of nanoparticles;
FIG. 5 is a graph of CuO@Co prepared in example 3 3 O 4 XRD pattern of nanoparticles;
FIG. 6 is a graph of CuO@Co prepared in example 3 3 O 4 SEM image of nanoparticles;
FIG. 7 is an XRD pattern of a Prussian blue analog precursor prepared in example 4;
fig. 8 is an SEM image of the precursor of the prussian blue analog prepared in example 4;
FIG. 9 is a graph of CuO@Co prepared in example 2 3 O 4 An open circuit voltage plot of the nanoparticle assembled air cell;
FIG. 10 is an open circuit voltage plot of an air cell assembled from the precursor catalyst prepared in example 4;
FIG. 11 is a graph of CuO@Co prepared in example 2 3 O 4 An air battery operating voltage diagram of nanoparticle assembly;
fig. 12 is a graph of the operating voltage of an air cell assembled from the precursor catalyst prepared in example 4.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
A method for preparing a magnesium air battery catalyst, comprising:
mixing raw materials including copper nitrate, potassium citrate and cobalt potassium cyanide, and reacting to obtain a precursor;
performing heat treatment on the precursor to obtain CuO@Co 3 O 4 And (3) nanoparticles.
The CuO@Co 3 O 4 The nano particles are the magnesium air battery catalyst.
In an alternative embodiment, the mixing includes:
mixing the aqueous solution of copper nitrate and the aqueous solution of potassium citrate to obtain a mixed solution, and then dropwise adding the aqueous solution of potassium cobalt cyanide into the mixed solution.
In an alternative embodiment, the reaction is carried out under agitation;
in an alternative embodiment, the stirring time is 10-30 minutes;
alternatively, the stirring time may be 10min, 20min, 30min, or any value between 10-30 min.
In an alternative embodiment, the agitating further comprises aging;
in an alternative embodiment, the aging time is from 20 to 24 hours;
alternatively, the aging time may be any value between 20h, 21h, 22h, 23h, 24h, or 20-24 h.
In an alternative embodiment, the aging further comprises: carrying out solid-liquid separation on the reaction system to obtain a solid matter, and drying to obtain Cu 3 [Co(CN) 6 ] 2 ·9H 2 O is the precursor;
in an alternative embodiment, the drying is at a temperature of 60-80 ℃ for a period of 20-24 hours;
in an alternative embodiment, the precursor has a cubic overall shape and a size of 1-2 μm.
Alternatively, the drying temperature may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or any value between 60 and 80 ℃ and the time may be 20 hours, 21 hours, 22 hours, 23 hours, 24 hours or any value between 20 and 24 hours.
In an alternative embodiment, the heat treatment comprises:
calcining the precursor for 1-5h at 300-900 ℃ and cooling to obtain the CuO@Co 3 O 4 A nanoparticle;
in an alternative embodiment, the heat treatment has a heating rate of 1-10deg.C/min;
in an alternative embodiment, the CuO@Co 3 O 4 The size of the nano particles is 100-500nm.
Alternatively, the calcination temperature may be 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, or any value between 300 and 900 ℃, and the time may be 1h, 2h, 3h, 4h, 5h, or any value between 1 and 5 h; the heating rate of the heat treatment can be any value between 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min or 1-10 ℃/min; the CuO@Co 3 O 4 The size of the nano particles is 100nm, 200nm, 300nm, 400nm,500nm or any value between 100 and 500nm.
The application also provides a magnesium air battery catalyst, and the magnesium air battery catalyst is prepared by using the preparation method of the magnesium air battery catalyst.
The application also provides an air cathode of the magnesium air battery, which comprises the magnesium air battery catalyst.
The application also provides a preparation method of the air cathode of the magnesium air battery, which comprises the following steps:
mixing raw materials including the magnesium air battery catalyst, a binder, a pore-forming agent, a conductive agent and an organic solvent to obtain slurry;
and coating the slurry on a pole piece, and drying to obtain the air cathode of the magnesium air battery.
In an alternative embodiment, the conductive agent comprises carbon black;
in an alternative embodiment, the pole piece comprises hydrophobic conductive carbon paper.
The application also provides a magnesium air battery, comprising the air cathode of the magnesium air battery.
The application also provides electric equipment, which comprises the magnesium air battery.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Magnesium air battery catalyst (CuO@Co) 3 O 4 Nanoparticle), the synthesis step is divided into two parts of (A) precursor preparation and (B) precursor sintering.
(A) Preparing a precursor:
firstly, preparing a copper nitrate uniform solution with the concentration of 0.03mol/L for later use.
And secondly, weighing 9.0mmol of potassium citrate, adding the potassium citrate into 200mL of the copper nitrate solution prepared in the first step, and magnetically stirring the solution at normal temperature for 30 minutes to form a uniform mixed solution a.
Thirdly, 200mL of a 0.02mol/L homogeneous solution of potassium cobalt cyanide was prepared as solution b.
Fourthly, slowly dripping the solution b into the mixed solution a, magnetically stirring for 30 minutes to obtain a reaction solution, and aging the reaction solution at room temperature for 24 hours to obtain a precipitate.
Fifthly, centrifugally washing the precipitate obtained in the fourth step for multiple times, and drying at 80 ℃ for 24 hours to obtain the Cu-based ceramic material with the appearance of a cube, the size of about 1 mu m and the chemical formula of Cu 3 [Co(CN) 6 ] 2 ·9H 2 Prussian blue analog precursors of O.
(B) Heat treatment of the precursor:
calcining the precursor obtained in the above steps for 2 hours under the condition of heating to 400 ℃ at the heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain CuO@Co with the size of about 200nm 3 O 4 And (3) nanoparticles.
FIG. 1 is a graph of CuO@Co prepared in example 1 3 O 4 XRD pattern of nanoparticles; FIG. 2 is a graph of CuO@Co prepared in example 1 3 O 4 SEM image of nanoparticles.
The CuO@Co obtained was used as a catalyst 3 O 4 The nano particles are used as cathode catalysts of the magnesium air battery to perform ORR electrochemical performance test, and the assembled magnesium air battery is subjected to discharge performance test, so that good ORR performance, stability, battery discharge voltage platform and energy density are obtained.
Example 2
CuO@Co 3 O 4 The synthesis step of the nanoparticle is divided into two parts of (A) precursor preparation and (B) precursor sintering.
(A) Preparing a precursor:
firstly, preparing a copper nitrate uniform solution with the concentration of 0.03mol/L for later use.
And secondly, weighing 9.0mmol of potassium citrate, adding the potassium citrate into 200mL of the copper nitrate solution prepared in the first step, and magnetically stirring the solution at normal temperature for 30 minutes to form a uniform mixed solution a.
Thirdly, 200mL of a 0.02mol/L homogeneous solution of potassium cobalt cyanide was prepared as solution b.
Fourthly, slowly dripping the solution b into the mixed solution a, magnetically stirring for 30 minutes to obtain a reaction solution, and aging the reaction solution at room temperature for 24 hours to obtain a precipitate.
Fifthly, centrifugally washing the precipitate obtained in the fourth step for multiple times, and drying at 80 ℃ for 24 hours to obtain the Cu-based ceramic material with the appearance of a cube, the size of about 1 mu m and the chemical formula of Cu 3 [Co(CN) 6 ] 2 ·9H 2 Prussian blue analog precursors of O.
(B) Heat treatment of the precursor:
calcining the precursor obtained in the above steps for 2 hours under the condition of heating to 600 ℃ at the heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain CuO@Co with the size of about 100nm 3 O 4 And (3) nanoparticles.
FIG. 3 is a graph of CuO@Co prepared in example 2 3 O 4 XRD pattern of nanoparticles; FIG. 4 is a graph of CuO@Co prepared in example 2 3 O 4 SEM image of nanoparticles.
The CuO@Co obtained was used as a catalyst 3 O 4 The nano particles are used as cathode catalysts of the magnesium air battery to perform ORR electrochemical performance test, and the assembled magnesium air battery is subjected to discharge performance test, so that good ORR performance, stability, battery discharge voltage platform and energy density are obtained.
Example 3
CuO@Co 3 O 4 The synthesis step of the nanoparticle is divided into two parts of (A) precursor preparation and (B) precursor sintering.
(A) Preparing a precursor:
firstly, preparing a copper nitrate uniform solution with the concentration of 0.03mol/L for later use.
And secondly, weighing 9.0mmol of potassium citrate, adding the potassium citrate into 200mL of the copper nitrate solution prepared in the first step, and magnetically stirring the solution at normal temperature for 30 minutes to form a uniform mixed solution a.
Thirdly, 200mL of a 0.02mol/L homogeneous solution of potassium cobalt cyanide was prepared as solution b.
Fourthly, slowly dripping the solution b into the mixed solution a, magnetically stirring for 30 minutes to obtain a reaction solution, and aging the reaction solution at room temperature for 24 hours to obtain a precipitate.
Fifthly, centrifugally washing the precipitate obtained in the fourth step for multiple times, and drying at 80 ℃ for 24 hours to obtain the Cu-based ceramic material with the appearance of a cube, the size of about 1 mu m and the chemical formula of Cu 3 [Co(CN) 6 ] 2 ·9H 2 Prussian blue analog precursors of O.
(B) Heat treatment of the precursor:
calcining the precursor obtained in the above steps for 2 hours under the condition of heating to 800 ℃ at the heating rate of 5 ℃/min, and naturally cooling to room temperature to obtain CuO@Co with the size of about 500nm 3 O 4 And (3) nanoparticles.
FIG. 5 is a graph of CuO@Co prepared in example 3 3 O 4 XRD pattern of nanoparticles; FIG. 6 is a graph of CuO@Co prepared in example 3 3 O 4 SEM image of nanoparticles.
The CuO@Co obtained was used as a catalyst 3 O 4 The nano particles are used as cathode catalysts of the magnesium air battery to perform ORR electrochemical performance test, and the assembled magnesium air battery is subjected to discharge performance test, so that good ORR performance, stability, battery discharge voltage platform and energy density are obtained.
Comparative example 1
Unlike example 1, step (B) was not performed.
And (3) performing ORR electrochemical performance test by taking the Prussian blue analog precursor as an oxygen reduction catalyst, and performing discharge performance test by taking the Prussian blue analog precursor as an air battery assembled by a magnesium air battery cathode catalyst.
FIG. 7 is an XRD pattern of a Prussian blue analog precursor prepared in comparative example 1; fig. 8 is an SEM image of the precursor of the prussian blue analog prepared in comparative example 1.
CuO@Co obtained in example 2 3 O 4 The nano particles and the Prussian blue analog precursor obtained in the comparative example 1 are respectively dissolved in an organic solvent together with a binder, a pore-forming agent and carbon black, stirred for 24 hours to form uniform slurry, then coated on hydrophobic conductive carbon paper, dried to be used as an air cathode of a magnesium air battery, 3.5wt% NaCl is used as an electrolyte solution, and a magnesium alloy is used as an anode material to assemble the magnesium air battery.
The open circuit voltage and the operating voltage of the two air cells were tested, and FIG. 9 is a graph of CuO@Co prepared in example 2 3 O 4 The open-circuit voltage of the air battery assembled by the catalyst is stabilized at about 1.76V after 30min of operation; FIG. 10 is an open circuit voltage of an air cell assembled from the precursor catalyst prepared in comparative example 1, which is only about 1.66V after 30min of operation; FIG. 11 is a graph of CuO@Co prepared in example 2 3 O 4 Catalyst assembled air cell operating voltage at 1.0mA.cm -2 After the stable discharge for 56 hours under the current density of (2), the working voltage of about 1.25V is still maintained; FIG. 12 is an operating voltage of an air cell assembled from the precursor catalyst prepared in comparative example 1, at 1.0mA cm -2 After a stable discharge of 56 hours at a current density of (3) it is only possible to achieve an operating voltage of about 1.19V. As can be seen from the comparison of the discharge performance of the above air battery, cuO@Co prepared in example 2 3 O 4 The catalyst-assembled air cell had more excellent discharge performance than the precursor catalyst-assembled air cell prepared in comparative example 1. This is due to the CuO@Co prepared in example 2 3 O 4 The catalyst has smaller grain size and larger specific surface area, and shows more excellent ORR performance in alkaline and neutral electrolytes. Thus, the CuO@Co prepared in example 2 3 O 4 The air battery assembled by the catalyst has more excellent discharge performance.
The application provides a CuO@Co 3 O 4 Nanoparticle and preparation method thereof, simple process and low cost, and can be used as cathode catalyst of magnesium air battery for catalysisCan be excellent, and can effectively solve the technical problems of low catalytic activity and poor discharge performance of the cathode of the existing magnesium air battery.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (7)
1. A method for preparing a magnesium air battery catalyst, comprising the steps of:
mixing raw materials including copper nitrate, potassium citrate and cobalt potassium cyanide, and reacting to obtain a precursor;
performing heat treatment on the precursor to obtain CuO@Co 3 O 4 A nanoparticle;
the mixing includes:
mixing the aqueous solution of copper nitrate and the aqueous solution of potassium citrate to obtain a mixed solution, and then dropwise adding the aqueous solution of potassium cobalt cyanide into the mixed solution;
the reaction is carried out in a stirring state;
the stirring time is 10-30min;
the stirring is followed by aging;
the aging time is 20-24 hours;
the aging further comprises: carrying out solid-liquid separation on the reaction system to obtain a solid matter, and drying to obtain Cu 3 [Co(CN) 6 ] 2 •9H 2 O is the precursor;
the drying temperature is 60-80 ℃ and the drying time is 20-24 hours;
the whole precursor is cube-shaped and has a size of 1-2 mu m;
the heat treatment includes:
calcining the precursor for 1-5h at 300-900 ℃ and cooling to obtain the CuO@Co 3 O 4 A nanoparticle;
the heating rate of the heat treatment is 1-10 ℃/min;
the CuO@Co 3 O 4 The size of the nano particles is 100-500nm.
2. A magnesium air battery catalyst characterized by being produced by the method for producing a magnesium air battery catalyst according to claim 1.
3. An air cathode for a magnesium air battery comprising the magnesium air battery catalyst of claim 2.
4. A method of making an air cathode for a magnesium air battery according to claim 3, comprising:
mixing raw materials including the magnesium air battery catalyst, a binder, a pore-forming agent, a conductive agent and an organic solvent to obtain slurry;
and coating the slurry on a pole piece, and drying to obtain the air cathode of the magnesium air battery.
5. The method of manufacturing according to claim 4, wherein the conductive agent comprises carbon black;
the pole piece comprises hydrophobic conductive carbon paper.
6. A magnesium air battery comprising the air cathode of the magnesium air battery of claim 3.
7. A powered device comprising the magnesium air battery of claim 6.
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