CN113725447A - Magnesium-air battery with graphene oxide coated copper mesh current collector - Google Patents

Magnesium-air battery with graphene oxide coated copper mesh current collector Download PDF

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CN113725447A
CN113725447A CN202111026057.5A CN202111026057A CN113725447A CN 113725447 A CN113725447 A CN 113725447A CN 202111026057 A CN202111026057 A CN 202111026057A CN 113725447 A CN113725447 A CN 113725447A
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graphene oxide
copper mesh
current collector
coated copper
oxide coated
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张以河
王珂
张硕
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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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
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • 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
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • 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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0206—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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0213—Gas-impermeable carbon-containing materials
    • 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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204—Non-porous and characterised by the material
    • H01M8/0223—Composites
    • H01M8/0228—Composites in the form of layered or coated products
    • 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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Abstract

The invention relates to the technical field of air batteries, in particular to a magnesium-air battery with a graphene oxide coated copper mesh current collector. The invention provides a preparation method of a graphene oxide coated copper mesh current collector, which comprises the following steps: and (3) placing the copper mesh in the graphene oxide dispersion liquid for dipping to obtain the graphene oxide coated copper mesh current collector. The preparation method of the graphene oxide coated copper mesh current collector is environment-friendly and pollution-free; and the prepared graphene oxide coated copper mesh current collector is applied to an air cathode, so that the working voltage of the magnesium-air battery can be improved, and the service life of the air cathode is prolonged.

Description

Magnesium-air battery with graphene oxide coated copper mesh current collector
Technical Field
The invention relates to the technical field of air batteries, in particular to a magnesium-air battery with a graphene oxide coated copper mesh current collector.
Background
Environmental pollution has become a concern for all people, and new clean energy has become a trend of energy development. The magnesium-air battery has the advantages of abundant raw material sources, safety, environmental protection, high energy density, strong environmental adaptability and the like, and has a good development prospect.
The air cathode material of a magnesium-air battery is an important factor in the operating voltage and service life of the battery, in which the metal current collector, which is an important constituent of the cathode, is electrochemically corroded in a neutral electrolyte solution, resulting in degradation of the battery performance with the lapse of operating time. The current state of the art often increases the electrochemical stability of current collectors by making coatings on the surface of the metal current collector, and most current collector corrosion protection work is designed around lithium ion batteries, while less work is done for magnesium-air batteries. For example, in chinese patent publication No. CN104465126A, the conductive anticorrosive coating is coated on the surface of the metal current collector, and multiple layers of coatings are required, so that the thickness controllability is low and the process is complex; the chinese patent publication No. CN108172838A discloses that a high-reduction-degree graphene coated copper foil current collector material is prepared on the surface of a copper foil by using graphene oxide and hydrazine hydrate as raw materials and by a high-temperature reduction method in a hydrogen and argon atmosphere, so that the cycle life and safety of a lithium ion battery are improved. However, the method ignores the phenomenon that the creep deformation of the copper foil at high temperature leads to the reduction of mechanical properties, and the used hydrazine hydrate raw material has toxicity; in chinese patent publication No. CN109565053A, graphene oxide is used to disperse a fluid medium, a colloid is deposited on the surface of a metal foil, the fluid medium is removed, and then the colloid is subjected to heat treatment to prepare a graphene oxide coated current collector material. The method forms a film on the surface of the foil-shaped metal through a fluid medium under the action of stress, and shows good conductivity, scratch resistance and tensile strength. The graphene oxide coating layer constructed by the method has obvious directionality and is suitable for a metal foil current collector, but a more targeted corrosion-resistant modification strategy needs to be developed for a reticular metal current collector with a more complex surface shape.
Disclosure of Invention
The invention aims to provide a graphene oxide coated copper mesh current collector, a preparation method and application thereof, an air cathode, a preparation method and application thereof. The preparation method of the graphene oxide coated copper mesh current collector is environment-friendly and pollution-free; and the prepared graphene oxide coated copper mesh current collector is applied to the air cathode, so that the working voltage of the magnesium-air battery can be improved, the corrosion resistance is improved, and the service life of the air cathode is further prolonged.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a graphene oxide coated copper mesh current collector, which comprises the following steps:
and (3) placing the copper mesh in the graphene oxide dispersion liquid for dipping to obtain the graphene oxide coated copper mesh current collector.
Preferably, the concentration of the graphene oxide dispersion liquid is 0.1-5 mg/mL;
the volume ratio of the mass of the copper mesh to the graphene oxide dispersion liquid is 5 g: (10-120) mL.
Preferably, before the impregnation, the method further comprises pickling the copper mesh;
the acid adopted by the acid washing comprises hydrochloric acid, sulfuric acid or acetic acid.
The invention also provides a graphene oxide coated copper mesh current collector prepared by the preparation method in the technical scheme, which comprises a copper mesh and graphene oxide coated on the surface of the copper mesh.
Preferably, the mass ratio (100-1000) of the copper mesh to the graphene oxide is 1.
The invention also provides application of the graphene oxide coated copper mesh current collector in the technical scheme in preparation of an air cathode.
The invention also provides an air cathode, which comprises a waterproof breathable layer, a graphene oxide coated copper mesh current collector and a catalyst layer which are sequentially stacked;
the graphene oxide coated copper mesh current collector is the graphene oxide coated copper mesh current collector in the technical scheme.
The invention also provides a preparation method of the air cathode in the technical scheme, which comprises the following steps:
and sequentially stacking the waterproof breathable layer, the graphene oxide-coated copper mesh current collector and the catalyst layer, and then carrying out hot pressing to obtain the air cathode.
Preferably, the hot pressing pressure is 1-20 MPa, the temperature is 80-220 ℃, and the time is 1-30 min.
The invention also provides the application of the air cathode prepared by the technical scheme or the air cathode prepared by the preparation method in the technical scheme in the preparation of a magnesium-air battery.
The invention provides a preparation method of a graphene oxide coated copper mesh current collector, which comprises the following steps: and (3) placing the copper mesh in the graphene oxide dispersion liquid for dipping to obtain the graphene oxide coated copper mesh current collector. In the process of forming the protective layer on the surface of the copper mesh by using the graphene oxide, the thickness of the graphene oxide layer is controllable, the graphene oxide layer is suitable for large-scale production, does not need a binder, is more environment-friendly, and is beneficial to transfer of reaction charges, so that the impedance of the corrosion-resistant coating layer is reduced; the graphene oxide coated copper mesh current collector prepared by the preparation method not only ensures the mechanical strength and the conductivity of the current collector, but also improves the corrosion resistance of the current collector; the graphene oxide-coated copper mesh current collector prepared by the preparation method is applied to an air cathode, so that the initial output voltage of the magnesium-air battery is improved, the problem of output voltage reduction of the magnesium-air battery in long-term operation is solved, and the service life of the air cathode is prolonged. The preparation method is green and environment-friendly, and the product is free from pollution; the method is simple and convenient, has strong operability and is beneficial to mass production.
Drawings
FIG. 1 is an SEM image of the copper mesh after acid washing described in example 1;
fig. 2 is an SEM image of the graphene oxide coated copper current collector described in example 1;
FIG. 3 is an SEM image of a copper mesh in the magnesium-air battery of comparative example 1 after constant current charging and discharging for 100 h;
fig. 4 is an SEM image of the copper mesh current collector after graphene oxide in the graphene oxide coated copper current collector in the magnesium-air battery is removed after constant current charging and discharging for 100 hours in the magnesium-air battery in example 1;
fig. 5 is a linear scan plot of the copper mesh after pickling and the graphene oxide coated copper current collector described in example 1 in a 3.5 wt% sodium chloride electrolyte;
fig. 6 is a Tafel plot of the copper mesh after pickling and the graphene oxide coated copper current collector described in example 1 in a 3.5 wt% sodium chloride electrolyte;
fig. 7 is a graph showing the operating voltage of the magnesium-air battery obtained in example 1 and comparative example 1 over time for different discharge cycles.
Detailed Description
The invention provides a preparation method of a graphene oxide coated copper mesh current collector, which comprises the following steps:
and (3) placing the copper mesh in the graphene oxide dispersion liquid for dipping to obtain the graphene oxide coated copper mesh current collector.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
In the invention, the concentration of the graphene oxide dispersion liquid is preferably 0.1-5 mg/mL, more preferably 0.5-2 mg/mL, and most preferably 1.0-1.5 mg/mL. In the present invention, the solvent in the graphene oxide dispersion liquid is preferably water and/or alcohol; when the solvent is water and alcohol, the proportion of the water and the alcohol is not limited in any way, and the water and the alcohol can be mixed according to any proportion. In the present invention, the graphene oxide dispersion is preferably prepared by a process including: under the ultrasonic condition, mixing graphene oxide with a solvent to obtain the graphene oxide dispersion liquid; the process of the ultrasound is not limited in any way, and can be performed by a process known to those skilled in the art.
In the present invention, before the impregnation, the present invention further preferably comprises pickling the copper mesh; before the pickling, the invention also preferably comprises cutting; the cutting process is not limited in any way, and the copper mesh with the proper size can be cut according to actual needs by adopting a process well known to those skilled in the art.
In the present invention, the mesh shape of the copper mesh is preferably a diamond shape; the aperture size (rhombus long diagonal line multiplied by short diagonal line) is (0.6-6) × (0.3-3) mm; the diameter of the net wire is preferably 0.3-1 mm2。
In the invention, the acid solution used for acid washing is preferably hydrochloric acid, sulfuric acid or acetic acid; the mass concentration of the hydrochloric acid is preferably 1 mol/L; the mass concentration of the sulfuric acid is preferably 0.5 mol/L; the mass concentration of the acetic acid is preferably 3 mol/L.
The specific process of the acid washing is not limited in any way, and the oxides and hydroxides on the surface of the copper mesh can be completely removed by adopting the process known by the technical personnel in the field.
After the acid washing is finished, the invention also preferably comprises the steps of cleaning and drying which are carried out in sequence; preferably, deionized water and ethanol are sequentially adopted for cleaning; the washing frequency is preferably more than or equal to 3 times; in the invention, the drying temperature is preferably 60-80 ℃, and more preferably 65-75 ℃; the time is preferably 1 to 2 hours, and more preferably 1.4 to 1.6 hours.
In the present invention, the ratio of the mass of the copper mesh to the volume of the graphene oxide dispersion is preferably 5 g: (10-120) mL, more preferably 5 g: (30-100) mL, most preferably 5 g: (50-80) mL.
In the invention, the dipping temperature is preferably 0-50 ℃, and more preferably 10-30 ℃; the time is preferably 1 to 30min, and more preferably 5 to 20 min.
In the present invention, the impregnation process is preferably: after the copper mesh is fixed on the surface of a glassware, adding the graphene oxide dispersion liquid into the glassware for dipping. In the present invention, the graphene oxide dispersion is preferably added in 10 times; the adding mode is preferably dropwise adding; the dropping process is not particularly limited, and may be carried out by a process known to those skilled in the art. Drying is preferably carried out after each addition; the drying temperature is preferably 40-150 ℃, more preferably 50-120 ℃, and most preferably 70-100 ℃; the time is preferably 10 to 60min, more preferably 20 to 50min, and most preferably 30 to 40 min. After the drying is finished, the invention also preferably comprises cooling; the process of temperature reduction is not limited in any way, and can be carried out by adopting a process known by a person skilled in the art. After each impregnation, drying and cooling process, the copper mesh is preferably turned over and fixed again on the bottom surface of the glassware for the next impregnation.
The invention also provides a graphene oxide coated copper mesh current collector prepared by the preparation method in the technical scheme, which comprises a copper mesh and graphene oxide coated on the surface of the copper mesh.
In the invention, the mass ratio of the copper mesh to the graphene oxide is preferably (100-1000): 1, and more preferably (200-600): 1.
The invention also provides application of the graphene oxide coated copper mesh current collector in the technical scheme in preparation of an air cathode.
The invention also provides an air cathode, which comprises a waterproof breathable layer, a graphene oxide coated copper mesh current collector and a catalyst layer which are sequentially stacked;
the graphene oxide coated copper mesh current collector is the graphene oxide coated copper mesh current collector in the technical scheme.
In the present invention, the thickness of the graphene oxide-coated copper mesh current collector is preferably 0.1 to 100 μm, and more preferably 0.5 to 50 μm.
In the invention, the raw materials for preparing the waterproof breathable layer preferably comprise the following components in a mass ratio of 1: (1-5) the activated carbon, the pore-forming agent and the acetylene black of (1-4), and also comprises polytetrafluoroethylene; the amount of the polytetrafluoroethylene used in the present invention is not particularly limited, and may be any amount of a binder known to those skilled in the art; in the invention, the pore-forming agent is preferably ammonium bicarbonate; the thickness of the waterproof breathable layer is preferably 0.05-5 mm, and more preferably 0.1-1 mm.
In the invention, the preparation raw materials of the catalyst layer preferably comprise the following components in mass ratio of (1-6): 1: (1-4) activated carbon, acetylene black, manganese dioxide and polytetrafluoroethylene; the amount of the polytetrafluoroethylene used in the present invention is not particularly limited, and may be any amount of a binder known to those skilled in the art; the thickness of the catalyst layer is preferably 0.05-5 mm, and more preferably 0.1-1 mm.
The invention also provides a preparation method of the air cathode in the technical scheme, which comprises the following steps:
and sequentially stacking the waterproof breathable layer, the graphene oxide-coated copper mesh current collector and the catalyst layer, and then carrying out hot pressing to obtain the air cathode.
In the invention, the pressure of the hot pressing is preferably 1-20 MPa, more preferably 5-15 MPa, and most preferably 8-12 MPa; the temperature is preferably 80-220 ℃, more preferably 100-200 ℃, and most preferably 130-160 ℃; the time is preferably 1 to 30min, more preferably 5 to 25min, and most preferably 10 to 20 min.
The invention also provides the application of the air cathode prepared by the technical scheme or the air cathode prepared by the preparation method in the technical scheme in the preparation of a magnesium-air battery.
In the present invention, the magnesium-air battery includes an air cathode and a magnesium alloy plate; the air cathode is preferably the air cathode in the technical scheme; the present invention does not have any particular requirement for the kind of the magnesium alloy sheet, and may be a magnesium alloy sheet for a magnesium-air battery, which is well known to those skilled in the art.
The assembling process of the magnesium-air battery is not limited in any way, and the magnesium-air battery can be assembled by adopting a process well known to those skilled in the art.
The graphene oxide-coated copper mesh current collector, the preparation method and the application thereof, the air cathode, the preparation method and the application thereof provided by the invention are described in detail below with reference to the examples, but the invention is not to be construed as limiting the scope of the invention.
Example 1
Mixing 8 × 12cm2The copper net (5g, the net hole shape is diamond, the size of the long diagonal line and the short diagonal line of the diamond is 6 multiplied by 3 mm;the diameter of the net wire is 0.5mm2. ) Washing with 1mol/L diluted hydrochloric acid, washing with deionized water and alcohol sequentially for three times, drying at 60 ℃ for 1h, cooling to room temperature, fixing the washed copper mesh on the bottom surface of a glassware, and dropwise adding 60mL of graphene oxide dispersion liquid with the concentration of 0.1mg/mL to the surface of the copper mesh by 10 times: after each dripping, drying at 80 ℃ for 15min and cooling, turning over the copper mesh, fixing the copper mesh on the bottom surface of a glassware again, and dripping for the next time to obtain a graphene oxide coated current collector (the mass ratio of the graphene oxide to the copper mesh is 1:235, and the thickness of the graphene oxide layer is 12 microns);
stacking a waterproof breathable layer (comprising activated carbon, ammonium bicarbonate and acetylene black in a mass ratio of 1:3:2, and further comprising a proper amount of polytetrafluoroethylene with a thickness of 0.3mm), and a graphene oxide coated current collector and a catalyst layer (comprising activated carbon, acetylene black and manganese dioxide in a mass ratio of 5:1:1, and further comprising a proper amount of polytetrafluoroethylene with a thickness of 0.3mm), and then performing hot pressing treatment at the temperature of 120 ℃, under the pressure of 3MPa for 5min to obtain an air cathode;
assembling the air cathode and the magnesium alloy plate into a magnesium-air battery;
performing SEM test on the copper mesh after acid washing, wherein the test result is shown in figure 1; the graphene oxide coated copper current collector is subjected to SEM test, the test result is shown in figure 2, and comparing the figure 1 with the figure 2 shows that after coating, the surface of a copper mesh is coated by a layer of compact graphene oxide layer with a fold shape, and the graphene oxide layer can effectively prevent copper from contacting with electrolyte.
Comparative example 1
Referring to example 1, the only difference is that the process of impregnation in the graphene oxide dispersion is not included.
Test example
The magnesium-air batteries obtained in example 1 and comparative example 1 were subjected to constant current charge and discharge test, with a distance between the anode and the cathode of 1.2cm and a current density of 1mA/cm2；
In the magnesium-air battery in the comparative example 1, after the constant-current charging and discharging for 100 hours, the copper mesh in the magnesium-air battery is subjected to SEM test, the test result is shown in figure 3, and the comparison between the figure 1 and the figure 3 shows that the surface of the copper current collector is completely corroded after the battery is discharged for a long time;
after the magnesium-air battery in the embodiment 1 is charged and discharged for 100 hours at a constant current, SEM test is performed on the copper mesh current collector after graphene oxide in the graphene oxide coated copper current collector in the magnesium-air battery is removed, and the test result is shown in fig. 4, and it can be seen by comparing fig. 3 with fig. 4 that no obvious corrosion phenomenon is found on the surface of the copper mesh.
The copper mesh after acid washing and the graphene oxide coated copper current collector described in example 1 were subjected to linear scanning in 3.5 wt% sodium chloride electrolyte, the conditions of the linear scanning being: the test area of the current collector immersed in the electrolyte is 1 multiplied by 1cm2The scanning speed is 5mV/s, and the reference electrode is Ag/AgCl; as shown in fig. 5, as can be seen from fig. 5, compared with the copper mesh after pickling, the response current value of the graphene oxide-coated copper mesh current collector does not change significantly with the change of the potential, and the graphene oxide-coated copper mesh current collector shows good corrosion resistance;
carrying out a polarization curve test on the copper mesh subjected to acid washing and the graphene oxide coated copper current collector described in the embodiment 1 in 3.5 wt% of sodium chloride electrolyte, wherein the test conditions are as follows: the test area of the current collector immersed in the electrolyte is 1 multiplied by 1cm2The scanning speed is 5mV/s, and the reference electrode is Ag/AgCl; fig. 6 is a Tafel curve of the copper mesh after the pickling and the graphene oxide-coated copper current collector described in example 1 in 3.5 wt% sodium chloride electrolyte, and as can be seen from fig. 6, the corrosion potential of the copper mesh after the pickling is-0.223V, and the corrosion current is 16.90 mA; the graphene oxide-coated copper current collector described in example 1 has a more positive corrosion potential (corrosion potential is-0.192V) and a lower corrosion current (corrosion current is 3.197mA), and shows better corrosion resistance, and the slow release rate reaches 82.25%.
The magnesium-air batteries obtained in example 1 and comparative example 1 were subjected to constant current charge and discharge test at a current density of 4mA/cm2(ii) a The test result is shown in fig. 7, wherein a is the variation curve of the working voltage of the first discharge period with time; as can be seen from a, the stable operating voltage of the magnesium-air battery described in comparative example 11.26V, while the stable operating voltage of the magnesium-air battery described in example 1 is 1.28V, there is a higher stable operating voltage because graphene oxide has oxygen reduction catalytic ability; b is a change curve of the operating voltage of the second discharge period with time, and it can be known from b that the operating voltage of the magnesium-air battery described in comparative example 1 decreases with time from 1.26V to 1.18V, which is 0.08V; the working voltage of the magnesium-air battery in example 1 is only slightly reduced along with time (from 1.28V to 1.26V, and is reduced by 0.02V), and a more stable working voltage is shown; c is the change curve of the working voltage of the third discharge period along with time, d is the change curve of the working voltage of the fourth discharge period along with time, and as can be seen from c to d, after 100h of constant current discharge, the working voltage of the magnesium-air battery in the comparative example 1 is in the range of 1.15 to 1.1V, and is reduced by 0.16V compared with the initial working voltage. The magnesium-air battery described in example 1 has a higher operating voltage range (1.25-1.20V), which is higher than 0.1V on average, and the voltage drop is significantly reduced to only 0.08V compared with the initial operating voltage.
Therefore, the graphene oxide coated current collector has better corrosion resistance, and can improve the discharge performance (more stable and higher working voltage) of the magnesium-air battery.
Example 2
Mixing 8 × 12cm2The mesh shape is diamond, the size of a long diagonal line and a short diagonal line of the diamond is 6 multiplied by 3mm, and the diameter of the mesh wire is 0.5mm2. ) Washing with 1mol/L diluted hydrochloric acid, washing with deionized water and alcohol sequentially for three times, drying at 60 ℃ for 1h, cooling to room temperature, fixing the washed copper mesh on the bottom surface of a glassware, and dropwise adding 60mL of graphene oxide dispersion liquid with the concentration of 0.2mg/mL to the surface of the copper mesh by 10 times: after each dripping, drying at 80 ℃ for 15min and cooling, turning over the copper mesh, fixing the copper mesh on the bottom surface of a glassware again, and dripping for the next time to obtain a graphene oxide coated current collector (the mass ratio of the graphene oxide to the copper mesh is 1:415, and the thickness of the graphene oxide layer is 18 mu m);
laminating a waterproof breathable layer (comprising activated carbon, ammonium bicarbonate and acetylene black in a mass ratio of 1:3:2, and further comprising a proper amount of polytetrafluoroethylene with a thickness of 0.3mm), a graphene oxide coated current collector and a catalyst layer (comprising activated carbon, acetylene black and manganese dioxide in a mass ratio of 5:1:1, and further comprising a proper amount of polytetrafluoroethylene with a thickness of 0.3mm), and then carrying out hot pressing treatment at the temperature of 150 ℃, under the pressure of 3MPa for 5min to obtain an air cathode;
and assembling the air cathode and the magnesium alloy plate into the magnesium-air battery.
Example 3
Mixing 8 × 12cm2The mesh shape is diamond, the size of a long diagonal line and a short diagonal line of the diamond is 6 multiplied by 3mm, and the diameter of the mesh wire is 0.5mm2. ) Washing with 1mol/L diluted hydrochloric acid, washing with deionized water and alcohol sequentially for three times, drying at 60 ℃ for 1h, cooling to room temperature, fixing the washed copper mesh on the bottom surface of a glassware, and dropwise adding 30mL of graphene oxide dispersion liquid with the concentration of 0.3mg/mL to the surface of the copper mesh by 15 times: after drying at 80 ℃ for 15min after each dripping, turning over the copper mesh and fixing the copper mesh on the bottom surface of a glassware again, and dripping for the next time to obtain a graphene oxide coated current collector (the mass ratio of the graphene oxide to the copper mesh is 1:342, and the thickness of the graphene oxide layer is 15 microns);
laminating a waterproof breathable layer (comprising activated carbon, ammonium bicarbonate and acetylene black in a mass ratio of 1:3:2, and further comprising a proper amount of polytetrafluoroethylene with a thickness of 0.3mm), a graphene oxide coated current collector and a catalyst layer (comprising activated carbon, acetylene black and manganese dioxide in a mass ratio of 5:1:1, and further comprising a proper amount of polytetrafluoroethylene with a thickness of 0.3mm), and then carrying out hot pressing treatment at the temperature of 150 ℃, under the pressure of 10MPa for 5min to obtain an air cathode;
and assembling the air cathode and the magnesium alloy plate into the magnesium-air battery.
The samples in the embodiments 2 to 3 are detected according to the method of the test example, and the detection result is similar to that of the embodiment 1, and is not described herein again.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the graphene oxide coated copper mesh current collector is characterized by comprising the following steps:
and (3) placing the copper mesh in the graphene oxide dispersion liquid for dipping to obtain the graphene oxide coated copper mesh current collector.
2. The preparation method according to claim 1, wherein the concentration of the graphene oxide dispersion is 0.1-5 mg/mL;
the volume ratio of the mass of the copper mesh to the graphene oxide dispersion liquid is 5 g: (10-120) mL.
3. The method of claim 1, further comprising pickling the copper mesh prior to said impregnating;
the acid adopted by the acid washing comprises hydrochloric acid, sulfuric acid or acetic acid.
4. The graphene oxide-coated copper mesh current collector prepared by the preparation method of any one of claims 1 to 3, which is characterized by comprising a copper mesh and graphene oxide coated on the surface of the copper mesh.
5. The graphene oxide coated copper mesh current collector of claim 4, wherein the mass ratio of the copper mesh to the graphene oxide is (100-1000): 1.
6. Use of the graphene oxide coated copper mesh current collector of claim 4 or 5 in the preparation of an air cathode.
7. An air cathode comprises a waterproof breathable layer, a graphene oxide coated copper mesh current collector and a catalyst layer which are sequentially stacked;
the graphene oxide coated copper mesh current collector is the graphene oxide coated copper mesh current collector of claim 4 or 5.
8. The method of manufacturing an air cathode according to claim 7, comprising the steps of:
and sequentially stacking the waterproof breathable layer, the graphene oxide-coated copper mesh current collector and the catalyst layer, and then carrying out hot pressing to obtain the air cathode.
9. The method according to claim 8, wherein the hot pressing is performed under a pressure of 1 to 20MPa, at a temperature of 80 to 220 ℃ and for a time of 1 to 30 min.
10. Use of the air cathode according to claim 7 or the air cathode produced by the production method according to claim 8 or 9 for producing a magnesium-air battery.
CN202111026057.5A 2021-09-02 2021-09-02 Magnesium-air battery with graphene oxide coated copper mesh current collector Pending CN113725447A (en)

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