CN109830694B - Catalyst with double-coating structure and preparation method and application thereof - Google Patents
Catalyst with double-coating structure and preparation method and application thereof Download PDFInfo
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Abstract
The embodiment of the invention relates to a catalyst with a double-coating structure, a preparation method and application thereof, wherein the specific surface area of the catalyst is 320-490m2The composition comprises the following components in parts by weight: 60-80 parts of spinel, 5-20 parts of manganese oxide and 10-30 parts of carbon-containing material. According to the invention, the spinel catalyst is coated with the manganese oxide on the surface, so that the catalytic activity of the spinel catalyst is increased, and the spinel catalyst is coated with the carbon-containing material in a bulk phase, so that the conductivity is increased, and an excellent synergistic catalytic effect is achieved.
Description
Technical Field
The invention relates to the technical field of metal-air batteries, in particular to a catalyst with a double-coating structure and a preparation method and application thereof.
Background
With the shortage of fossil fuel and the serious air pollution, people are looking for sustainable energy. The fuel cell has the advantages of high energy conversion rate, no pollution and the like, and has become a research hotspot in the direction of new energy. Fuel cells include proton exchange membrane fuel cells, solid oxide fuel cells, metal air fuel cells, and the like.
The metal-air battery takes advantage of the fuel cell, and takes oxygen in the air as a cathode and metal (magnesium, aluminum, zinc, and the like) as an anode, so that the oxygen in the air can continuously reach an electrochemical reaction interface through a gas diffusion electrode to react with the metal (magnesium, aluminum, zinc, and the like) to release electric energy. The metal-air battery has the outstanding advantages of large specific energy, the theoretical specific energy of the magnesium-air battery is 6800Wh/kg, the theoretical specific energy of the aluminum-air battery is 8100Wh/kg, and the theoretical specific energy of the magnesium-air battery is 1350Wh/kg in alkaline electrolyte solution. However, currently, the actual specific energy of the metal-air battery only reaches 600--1And even so, the actual specific energy is 12 times that of the lead-acid battery, 9 times that of the nickel-hydrogen battery and 3 times that of the lithium battery (the energy density of the lead-acid battery is generally only 40Wh/kg, and the energy density of the lithium battery is only 100 and 200 Wh/kg). In metal air cells, the catalyst determines not only the performance of the cell, but also the cost of the cell. At present, noble metal catalysts, such as silver, platinum, iridium and the like, have unfilled d electron orbits and strong surface adsorption, can ensure higher output current under very high electrode potential, have the best catalytic performance, but are expensive, have low reserves in the earth crust and prevent large-scale industrial production. Therefore, in the research of the metal air battery, the search for cheap and efficient catalysts is of great significance.
The spinel oxide is a catalyst with wide application, improves the oxygen reduction catalytic performance of the metal-air battery to a certain extent, but the spinel oxide has low electron transfer rate and needs to be improved in specific surface area, so that the oxygen reduction reaction activity is not good enough, and the application of the spinel oxide in the metal-air battery is limited. CN201510765984.7 discloses a nickel manganate/carbon nano composite catalyst and a preparation method and application thereof, wherein the bifunctional catalyst comprises a nano tube and nickel manganate spinel, and is prepared by dissolving a manganese dioxide precursor, nickel acetate and the nano tube in ammonia water, performing ultrasonic dispersion, performing hydrolysis reaction, cooling, cleaning, drying and calcining. The discharge power density of the catalyst is 170mW/cm2Are still not as expensivePerformance of heavy metal catalysts.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a catalyst with a double-coating structure, which has high-efficiency and stable ORR catalytic activity and low production cost, is applied to a metal-air battery, prolongs the service life of the battery, reduces the cost of the battery, and improves the performance of the battery.
The invention aims to provide a preparation method of a catalyst with a double-coating structure, which is simple to operate and is suitable for industrial large-scale production.
The invention is realized by the following technical scheme:
a catalyst with a double-coating structure, the specific surface area of which is 320-490m2The composition comprises the following components in parts by weight: 60-80 parts of spinel, 5-20 parts of manganese oxide and 10-30 parts of carbon-containing material.
Further preferably, the catalyst has a double-coating structure, and the specific surface area of the catalyst is 380-450m2The composition comprises the following components in parts by weight: 65-75 parts of spinel, 10-15 parts of manganese oxide and 15-25 parts of carbon-containing material.
The catalyst with the double-coating structure is prepared by coating a manganese oxide on the surface of a spinel and coating a carbon-containing material in a re-phase manner.
The spinel is spinel AB2O4, wherein A is one of Mg, Fe, Co, Ni, Cu and Zn, and B is one of Al, Cr, Mn, Fe, Co and Ni. Preferably, A is Ni and B is Co. Wherein the molar ratio of A to B is 1: 2.
preferably, the spinel of the invention is nickel cobaltate spinel, wherein the molar ratio of cobalt to nickel elements is 2: 1.
the catalyst with the double-coating structure is characterized in that manganese oxide is coated outside spinel for improving the oxygen reduction catalytic performance. The manganese oxide comprises one or more of manganese dioxide, manganous oxide and manganous manganic oxide, preferably manganese dioxide, and can increase the catalytic activity of the spinel catalyst. However, the conductivity of the manganese oxide is relatively low, so that the electrode is slow in the positive and negative directions, the actual discharge rate of the common manganese oxide material is low, and the conductivity of the catalyst is influenced.
In order to enhance the conductivity and improve the condition of low conductivity of the manganese oxide, the spinel coated with the manganese oxide is coated with a carbon-containing material in an external phase re-phase mode, so that the utilization rate of the manganese oxide is improved, and the capacitance and the energy density are increased. The carbonaceous material of the present invention includes but is not limited to graphene, carbon nanotubes, graphite, and preferably graphene. Due to the large specific surface area of the graphene, the graphene can cooperate with the catalytic and conductive effects of the spinel coated by the manganese oxide.
The invention also provides a preparation method of the catalyst with the double-coating structure, which comprises the following steps:
(1) preparation of spinel: weighing metal A salt and metal B salt, adding a solvent, stirring, performing ultrasonic dispersion, transferring to a high-pressure reaction kettle, performing hydrothermal reaction, cooling, filtering, drying, and calcining to obtain spinel;
(2) preparation of manganese oxide coated spinel: dispersing spinel, manganese oxide and an inducer in a solvent, stirring, ultrasonically dispersing, drying and calcining to obtain manganese oxide coated spinel;
(3) preparing a spinel catalyst with a carbon-containing material coating structure: dispersing manganese oxide coated spinel and a carbon-containing material in a solvent, adding a surfactant, performing ultrasonic dispersion, rapidly drying under reduced pressure, and calcining to obtain a catalyst with a double-coated structure;
preferably, the preparation method of the catalyst with the double-coating structure comprises the following steps:
(1) preparation of spinel: weighing 45-60 parts of metal A salt and 90-120 parts of metal B salt, adding a solvent, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 2-4h at the temperature of 110-;
(2) preparation of manganese oxide coated spinel: adding an inducer into 60-80 parts of spinel and 5-20 parts of manganese oxide, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, drying in an oven at 80 ℃ for 4-6h, and calcining at 400 ℃ and 600 ℃ to obtain manganese oxide coated spinel;
(3) preparing a spinel catalyst with a carbon-containing material coating structure: 75-90 parts of spinel coated by manganese oxide and 10-30 parts of carbon-containing material are dispersed in a solvent, a surfactant is added, ultrasonic dispersion is carried out for 6-12h, rapid decompression drying is carried out, and vacuum calcination is carried out at 800 ℃ under 500 plus materials to obtain the catalyst with the double-coating structure.
The metal A salt in the step (1) is a sulfate A salt, a chloride A salt, a nitrate A salt and the like, preferably a nitrate A salt; the metal B salt is a sulfate B salt, a chloride B salt, a nitrate B salt and the like, and the nitrate B salt is preferred.
Wherein A is one element of Mg, Fe, Co, Ni, Cu and Zn, and B is one element of Al, Cr, Mn, Fe, Co and Ni. Preferably, A is Ni and B is Co. Wherein the molar ratio of A to B is 1: 2.
the solvent in the step (1) is one of terpineol, ethanol, isopropanol, n-butanol and n-hexanol. The invention selects ethanol as solvent, does not generate waste gas at high temperature in the manufacturing process, and is environment-friendly and harmless to human body.
The manganese oxide in the step (2) comprises one or more of manganese dioxide, manganic oxide and manganic oxide, preferably manganese dioxide.
The inducer in the step (2) is one of polyoxyethylene and polyvinylpyrrolidone; the mass of the spinel-manganese oxide composite material is 1-10% of the total mass of the spinel and the manganese oxide.
The solvent in the step (3) is one of terpineol, ethanol, isopropanol, n-butanol and n-hexanol. The invention selects ethanol as solvent, does not generate waste gas at high temperature in the manufacturing process, and is environment-friendly and harmless to human body.
The carbon-containing material in the step (3) is one or more of graphene, carbon nano tubes and graphite.
The surfactant in the step (3) is one or more of sodium dodecyl benzene sulfonate, sodium dioctyl sulfosuccinate, sulfated castor oil and glyceride, and the mass of the surfactant is 1-10% of the total mass percentage of the manganese oxide coated spinel and the carbon-containing material. The surfactant causes the catalyst to adsorb to the surface of the carbonaceous material by van der waals forces.
The catalyst with the double-coating structure is applied to the catalyst of the cathode of the air battery.
The invention also discloses a preparation method of the cathode plate of the air battery, which comprises the following steps:
(1) preparing a catalytic layer: mixing a catalyst, a conductive agent, a binder and a solvent, performing ultrasonic treatment and stirring to obtain catalyst slurry, drying, and pressing into a film to obtain a catalyst layer; the air battery cathode catalyst, the conductive agent and the binder are in a mass part ratio of (1-2): (1-3): (2-5);
(2) preparing a waterproof breathable layer; mixing a conductive agent, a binder and a solvent, performing ultrasonic treatment and stirring to obtain waterproof and breathable layer slurry, drying, and pressing to form a film to obtain a waterproof and breathable layer; the mass part ratio of the conductive agent to the binder is (1-3): (2-5).
(3) Preparing an air battery cathode piece: and carrying out press-fit treatment on the catalyst layer, the waterproof breathable layer and the current collector to obtain the cathode sheet of the air battery.
The catalyst, the conductive agent, the binder and the solvent in the catalyst layer in the step (1) are in a mass part ratio of (5-10): (5-15): (10-20): (60-80); preferably, the mass part ratio of the catalyst, the conductive agent, the binder and the solvent is (6-8): (8-12): (12-18): (64-76), and preferably, the mass part ratio of the catalyst, the conductive agent, the binder and the solvent is 6.5: 9.8: 12.2: 71.5.
the mass part ratio of the conductive agent, the adhesive and the solvent in the waterproof breathable layer in the step (2) is (5-15): (10-25): (60-80). Preferably, the mass part ratio of the conductive agent to the binder to the solvent is (8-12): (18-24): (64-76); further preferably, the mass part ratio of the conductive agent to the binder to the solvent is 11.8: 18.9: 69.3.
the conductive agent in the steps (1) and (2) is one of carbon black, acetylene black and graphite, preferably carbon black, carbon black particles have a very large specific surface area, and the close packing facilitates the close contact of the particles to form a conductive network in the electrode.
The binder in the steps (1) and (2) is one of polyvinylidene fluoride, polytetrafluoroethylene and ethyl cellulose, preferably polyvinylidene fluoride.
The solvent in the steps (1) and (2) is determined according to the properties of the adhesive, and the solvent is one of terpineol, ethanol, isopropanol, n-butanol and n-hexanol. Ethanol is preferred as a solvent for polyvinylidene fluoride. The invention selects ethanol as solvent, does not generate waste gas at high temperature in the manufacturing process, and is environment-friendly and harmless to human body.
The mass ratio of the catalyst, the conductive agent, the binder and the solvent is screened by a large number of tests. The conductivity of the metal oxide is poor, the conductivity of the catalyst is increased by adding the conductive agent, and because oxygen diffuses from the waterproof breathable layer to a gas-liquid-solid three-phase interface of the contact surface of the catalyst layer and the electrolyte, the oxygen is reduced to obtain electrons, the conductivity is high, and the electrons are quickly transmitted through the current collector. Preferably, the catalyst: the mass part ratio of the conductive agent is (1-2): the initial voltage and half-wave voltage of (1-3) are both good. The dosage of the adhesive is also set according to the dosage and the material of the catalyst and the conductive agent, when the content of the adhesive is excessive, the adhesive obstructs the catalyst and the conductive agent, the contact area is reduced, the material utilization rate is reduced, and the capacity is reduced; when the binder content is too small, the viscosity is insufficient, and the contact between the catalyst and the conductive agent is also not tight, resulting in capacity fading during the cycle. Therefore, the optimal ratio of the catalyst, the conductive agent and the binder is (1-2): (1-3): (2-5). The proportion of the conductive agent and the adhesive of the waterproof breathable layer not only ensures the waterproof performance of the layer, but also enhances the breathability.
The ultrasonic dispersion is carried out for 0.5 to 2 hours, preferably for 1 hour.
The stirring is carried out for 1 to 4 hours, preferably 2 to 3 hours, and includes but is not limited to magnetic stirring and electric stirring.
The drying is carried out for 0.5-2 hours, preferably 1 hour, and the drying includes but is not limited to drying, vacuum drying, airing and the like, preferably drying.
Advantageous effects
1. The spinel oxide is a catalyst with wide application, improves the oxygen reduction catalytic performance of the metal-air battery to a certain extent, but the spinel oxide has low electron transfer rate and needs to be improved in specific surface area, so that the oxygen reduction reaction activity is not good enough, the application of the spinel oxide in the metal-air battery is limited, the spinel catalyst is coated with a manganese oxide catalyst on the surface, the catalytic activity of the spinel catalyst is improved, and a carbon-containing material is coated in a bulk phase, so that the conductivity is improved, and an excellent synergistic catalytic effect is achieved.
2. Compared with spinel catalysts which are not coated with manganese oxide and carbon-containing materials in battery discharge test tests, the catalyst provided by the invention has the advantages that the limiting current density is increased, the initial potential and the half-wave potential are positive, the oxygen reduction performance is improved, and the catalytic activity is improved. See test example one for details.
Description of the drawings:
FIG. 1 is a discharge test chart of example 1 of the present invention;
FIG. 2 is a discharge test chart of example 2 of the present invention;
FIG. 3 is a discharge test chart of example 3 of the present invention;
FIG. 4 is a discharge test chart of example 4 of the present invention;
FIG. 5 is a discharge test chart of example 5 of the present invention;
FIG. 6 is an oxygen reduction polarization curve of example 1 of the present invention and a comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Example 1
(1) Weighing 12g of nickel nitrate and 28g of cobalt nitrate, adding ethanol, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 3h at 180 ℃, cooling, filtering, drying, and calcining at 400 ℃ to obtain nickel cobaltate spinel; dispersing 16g of nickel cobaltite spinel, 5g of manganese dioxide and 1.0g of inducer polyoxyethylene in a solvent, magnetically stirring for 2h, ultrasonically dispersing for 2h, drying in an oven at 80 ℃ for 6h, and calcining at 500 ℃ to obtain manganese dioxide coated nickel cobaltite spinel; 20g of nickel cobaltite spinel coated with manganese dioxide and 4.0g of graphene are dispersed by adding ethanol, 1.0g of sodium dodecyl benzene sulfonate serving as a surfactant is added, ultrasonic dispersion is carried out for 10 hours, and the catalyst is quickly dried under reduced pressure and calcined in vacuum at 700 ℃ to obtain the catalyst with the double-coated structure.
(2) According to the mass ratio of the catalyst to the conductive agent to the binder to the solvent of 6.5%: 9.8%: 12.2%: 71.5%, respectively weighing 16g of the catalyst, 24g of conductive carbon black, 30g of polyvinylidene fluoride and 176g of ethanol, putting the mixture into a beaker for mixing, performing ultrasonic dispersion for 1h, performing magnetic stirring for 3h to obtain catalyst slurry, then drying the catalyst slurry in an oven for 1h, and pressing the catalyst slurry into a film to obtain the catalyst layer. The mass part ratio of the conductive agent to the binder to the solvent is 11.8%: 18.9%: 69.3%, respectively weighing 30g of conductive carbon black, 48g of polyvinylidene fluoride and 176g of ethanol, putting the conductive carbon black, the polyvinylidene fluoride and the ethanol into a beaker for mixing, ultrasonically dispersing for 1h, magnetically stirring for 2h to obtain waterproof breathable layer slurry, then drying in an oven for 1h, and pressing to form a film to obtain the waterproof breathable layer slurry. And pressing the catalyst layer, the waterproof breathable layer and the current collector into a sheet to obtain the air battery cathode sheet.
(3) The cathode piece and the aluminum anode of the air battery are assembled into a battery in a battery testing device, the electrolyte is 4mol/L potassium hydroxide solution, and a discharge test is carried out, and the result is shown in figure 1. As can be seen from FIG. 1, the power density was 255.5mW/cm at a discharge voltage of about 1.0V2。
Example 2
(1) Weighing 12g of nickel nitrate and 27g of cobalt nitrate, adding ethanol, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 2h at 150 ℃, cooling, filtering, drying, and calcining at 600 ℃ to obtain nickel cobaltate spinel; dispersing 15g of nickel cobaltite spinel, 5g of manganese dioxide and 1.0g of polyvinylpyrrolidone serving as an inducer in a solvent, magnetically stirring for 2 hours, ultrasonically dispersing for 2 hours, drying in an oven at 80 ℃ for 4 hours, and calcining at 500 ℃ to obtain manganese dioxide coated nickel cobaltite spinel; and coating 18g of nickel cobaltate and 4.5g of graphene with manganese dioxide, adding ethanol for dispersion, adding 1.0g of dioctyl sodium sulfosuccinate serving as a surfactant, performing ultrasonic dispersion for 12 hours, quickly drying under reduced pressure, and calcining at 600 ℃ to obtain the catalyst with the double-coating structure.
(2) According to the mass ratio of the catalyst to the conductive agent to the binder to the solvent of 6.5%: 9.8%: 12.2%: 71.5%, respectively weighing 16g of the catalyst, 24g of conductive carbon black, 30g of polyvinylidene fluoride and 176g of ethanol, putting the mixture into a beaker for mixing, performing ultrasonic dispersion for 1h, performing magnetic stirring for 3h to obtain catalyst slurry, then drying the catalyst slurry in an oven for 1h, and pressing the catalyst slurry into a film to obtain the catalyst layer. The mass ratio of the conductive agent to the binder to the solvent is 11.8%: 18.9%: 69.3%, respectively weighing 30g of conductive carbon black, 48g of polyvinylidene fluoride and 176g of ethanol, putting the conductive carbon black, the polyvinylidene fluoride and the ethanol into a beaker for mixing, ultrasonically dispersing for 1h, magnetically stirring for 2h to obtain waterproof breathable layer slurry, then drying in an oven for 1h, and pressing to form a film to obtain the waterproof breathable layer slurry. And pressing the catalyst layer, the waterproof breathable layer and the current collector into a sheet to obtain the air battery cathode sheet.
(3) The cathode piece and the aluminum anode of the air battery are assembled into a battery in a battery testing device, the electrolyte is 4mol/L potassium hydroxide solution, and a discharge test is carried out, and the result is shown in figure 2. As can be seen from FIG. 2, the power density was 293.9mW/cm at a discharge voltage of about 1.0V2。
Example 3
(1) Weighing 13g of nickel nitrate and 26g of cobalt nitrate, adding ethanol, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 1h at 110 ℃, cooling, filtering, drying, and calcining at 400 ℃ to obtain nickel cobaltate spinel; dispersing 25g of nickel cobaltate spinel, 6g of manganese dioxide and 1.0g of inducer polyoxyethylene in a solvent, magnetically stirring for 1h, ultrasonically dispersing for 1h, drying in an oven at 80 ℃ for 5h, and calcining at 500 ℃ to obtain manganese dioxide coated nickel cobaltate spinel; 28g of manganese dioxide coated nickel cobaltate and 5.0g of carbon nano tube are dispersed by adding ethanol, 1.0g of surfactant sulfated castor oil is added, ultrasonic dispersion is carried out for 6 hours, rapid decompression drying is carried out, and calcination is carried out at 800 ℃ to obtain the catalyst with double coating structure.
(2) According to the mass ratio of the catalyst to the conductive agent to the binder to the solvent of 6.5%: 9.8%: 12.2%: 71.5%, respectively weighing 16g of the catalyst, 24g of conductive carbon black, 30g of polyvinylidene fluoride and 176g of ethanol, putting the mixture into a beaker for mixing, performing ultrasonic dispersion for 1h, performing magnetic stirring for 3h to obtain catalyst slurry, then drying the catalyst slurry in an oven for 1h, and pressing the catalyst slurry into a film to obtain the catalyst layer. The mass ratio of the conductive agent to the binder to the solvent is 11.8%: 18.9%: 69.3%, respectively weighing 30g of conductive carbon black, 48g of polyvinylidene fluoride and 176g of ethanol, putting the conductive carbon black, the polyvinylidene fluoride and the ethanol into a beaker for mixing, ultrasonically dispersing for 1h, magnetically stirring for 2h to obtain waterproof breathable layer slurry, then drying in an oven for 1h, and pressing to form a film to obtain the waterproof breathable layer slurry. And pressing the catalyst layer, the waterproof breathable layer and the current collector into a sheet to obtain the air battery cathode sheet.
(3) The cathode sheet and the aluminum anode of the air battery are assembled into a battery in a battery testing device, the electrolyte is 4mol/L potassium hydroxide solution, and a discharge test is carried out, and the result is shown in figure 3. As can be seen from FIG. 3, the power density was 306.6mW/cm at a discharge voltage of about 1.0V2。
Example 4
(1) Weighing 13.5g of nickel nitrate and 25.5g of cobalt nitrate, adding ethanol, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 2h at 160 ℃, cooling, filtering, drying, and calcining at 300 ℃ to obtain nickel cobaltate spinel; dispersing 16.5g of nickel cobaltite spinel, 3.5g of manganese oxide and 1.0g of polyvinylpyrrolidone serving as an inducer in a solvent, magnetically stirring for 2 hours, then ultrasonically dispersing for 2 hours, drying in an oven at 80 ℃ for 6 hours, and calcining at 500 ℃ to obtain manganese sesquioxide coated nickel cobaltite spinel; the method comprises the steps of coating 19g of nickel cobaltate and 5.5g of graphite with manganese sesquioxide, adding ethanol and 1.0g of surfactant glyceride, performing ultrasonic dispersion for 10 hours, performing rapid reduced pressure drying, and calcining at 600 ℃ to obtain the catalyst with the double-coating structure.
(2) According to the mass ratio of 8.6% of the catalyst, the conductive agent, the binder and the solvent: 10.3%: 18%: 63.1%, respectively weighing 16g of the catalyst, 19g of conductive carbon black, 33g of polyvinylidene fluoride and 117g of ethanol, putting the mixture into a beaker for mixing, performing ultrasonic dispersion for 1h, performing magnetic stirring for 3h to obtain catalyst slurry, then drying the catalyst slurry in an oven for 1h, and pressing the catalyst slurry into a film to obtain the catalyst layer. The mass ratio of the conductive agent to the binder to the solvent is 11.8%: 18.9%: 69.3%, respectively weighing 30g of conductive carbon black, 48g of polyvinylidene fluoride and 220ml of ethanol, putting the conductive carbon black, the polyvinylidene fluoride and the ethanol into a beaker for mixing, performing ultrasonic dispersion for 1h, then performing magnetic stirring for 2h to obtain waterproof breathable layer slurry, then drying the waterproof breathable layer slurry in an oven for 1h, and pressing the waterproof breathable layer slurry into a film to obtain the waterproof breathable layer slurry. And pressing the catalyst layer, the waterproof breathable layer and the current collector into a sheet to obtain the air battery cathode sheet.
(3) The air cell cathode piece and the aluminum anode were assembled into a cell in a cell testing apparatus, and a discharge test was performed with an electrolyte of 4mol/L potassium hydroxide solution, and the results are shown in fig. 4. As can be seen from FIG. 4, the power density was 306.1mW/cm at a discharge voltage of about 1.0V2。
Example 5
(1) Weighing 14g of nickel nitrate and 25g of cobalt nitrate, adding ethanol, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 2h at 180 ℃, cooling, filtering, drying, and calcining at 600 ℃ to obtain nickel cobaltate spinel; dispersing 17g of nickel cobaltate spinel, 3g of manganous manganic oxide and 2.0g of inducer polyoxyethylene in a solvent, magnetically stirring for 2 hours, ultrasonically dispersing for 2 hours, drying in an oven at 80 ℃ for 6 hours, and calcining at 500 ℃ to obtain manganous manganic oxide coated nickel cobaltate spinel; and (3) coating manganous-manganic oxide on nickel cobaltate and 6.0 parts of graphene, adding 2.0g of ethanol and surfactant sodium dodecyl benzene sulfonate, performing ultrasonic dispersion for 10 hours, rapidly drying under reduced pressure, and calcining at 500 ℃ to obtain the catalyst with the double-coating structure.
(2) According to the mass ratio of 8.6% of the catalyst, the conductive agent, the binder and the solvent: 10.3%: 18%: 63.1%, respectively weighing 16g of the catalyst, 19g of conductive carbon black, 33g of polyvinylidene fluoride and 117g of ethanol, putting the mixture into a beaker for mixing, performing ultrasonic dispersion for 1h, performing magnetic stirring for 3h to obtain catalyst slurry, then drying the catalyst slurry in an oven for 1h, and pressing the catalyst slurry into a film to obtain the catalyst layer. The mass ratio of the conductive agent to the binder to the solvent is 11.8%: 18.9%: 69.3%, respectively weighing 30g of conductive carbon black, 48g of polyvinylidene fluoride and 220ml of ethanol, putting the conductive carbon black, the polyvinylidene fluoride and the ethanol into a beaker for mixing, performing ultrasonic dispersion for 1h, then performing magnetic stirring for 2h to obtain waterproof breathable layer slurry, then drying the waterproof breathable layer slurry in an oven for 1h, and pressing the waterproof breathable layer slurry into a film to obtain the waterproof breathable layer slurry. And pressing the catalyst layer, the waterproof breathable layer and the current collector into a sheet to obtain the air battery cathode sheet.
(3) The air cell cathode sheet and the aluminum anode were assembled into a cell in a cell testing apparatus, and a discharge test was performed using a 4mol/L potassium hydroxide solution as an electrolyte, and the results are shown in FIG. 5. As can be seen from FIG. 5, the power density was 305.4mW/cm at a discharge voltage of about 1.0V2。
Example 6
(1) Weighing 14.5g of nickel nitrate and 24.5g of cobalt nitrate, adding ethanol, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 2h at 180 ℃, cooling, filtering, drying, and calcining at 600 ℃ to obtain nickel cobaltate spinel; dispersing 17.5g of nickel cobaltate spinel, 2.5g of manganese dioxide and 1.0g of inducer polyoxyethylene in a solvent, magnetically stirring for 2h, ultrasonically dispersing for 2h, drying in an oven at 80 ℃ for 6h, and calcining at 500 ℃ to obtain manganese dioxide coated nickel cobaltate spinel; coating manganese dioxide on nickel cobaltate and 6.5 parts of graphene, adding ethanol and 1.0g of surfactant dioctyl sodium sulfosuccinate, performing ultrasonic dispersion for 8 hours, rapidly drying under reduced pressure, and calcining at 600 ℃ to obtain the catalyst with the double-coating structure.
(2) Weighing 5g of the catalyst, 12g of conductive carbon black, 15g of polyvinylidene fluoride and 60g of ethanol, putting the mixture into a beaker for mixing, performing ultrasonic dispersion for 1h, performing magnetic stirring for 3h to obtain catalyst slurry, drying the catalyst slurry in an oven for 1h, and pressing the catalyst slurry into a film to obtain the catalyst layer. Respectively weighing 12g of conductive carbon black, 19g of polyvinylidene fluoride and 70g of ethanol, putting the conductive carbon black, the polyvinylidene fluoride and the ethanol into a beaker for mixing, performing ultrasonic dispersion for 1h, then performing magnetic stirring for 2h to obtain waterproof breathable layer slurry, drying the waterproof breathable layer slurry in an oven for 1h, and pressing the waterproof breathable layer slurry into a film to obtain the waterproof breathable layer slurry. And pressing the catalyst layer, the waterproof breathable layer and the current collector into a sheet to obtain the air battery cathode sheet.
(3) And assembling the cathode plate and the aluminum anode of the air battery into a battery in a battery testing device.
Example 7
(1) Weighing 15g of nickel nitrate and 24g of cobalt nitrate, adding ethanol, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 2h at 110 ℃, cooling, filtering, drying, and calcining at 600 ℃ to obtain nickel cobaltate spinel; dispersing 18g of nickel cobaltite spinel, 2g of manganese oxide and 0.5g of inducer polyvinylpyrrolidone in a solvent, magnetically stirring for 2h, then ultrasonically dispersing for 2h, drying in an oven at 80 ℃ for 6h, and calcining at 500 ℃ to obtain manganese sesquioxide coated nickel cobaltite spinel; and adding 7.0g of ethanol, surfactant sulfated castor oil and 0.5g of glyceride into 7.0g of manganese sesquioxide coated nickel cobaltate, ultrasonically dispersing for 10 hours, rapidly drying under reduced pressure, and calcining at 400 ℃ to obtain the catalyst with the double-coated structure.
(2) Weighing 10g of the catalyst, 12g of conductive carbon black, 20g of polyvinylidene fluoride and 80g of ethanol, putting the mixture into a beaker for mixing, performing ultrasonic dispersion for 1h, performing magnetic stirring for 3h to obtain catalyst slurry, drying the catalyst slurry in an oven for 1h, and pressing the catalyst slurry into a film to obtain the catalyst layer. Respectively weighing 5g of conductive carbon black, 10g of polyvinylidene fluoride and 60g of ethanol, putting the conductive carbon black, the polyvinylidene fluoride and the ethanol into a beaker for mixing, performing ultrasonic dispersion for 1h, then performing magnetic stirring for 2h to obtain waterproof breathable layer slurry, drying the waterproof breathable layer slurry in an oven for 1h, and pressing the waterproof breathable layer slurry into a film to obtain the waterproof breathable layer slurry. And pressing the catalyst layer, the waterproof breathable layer and the current collector into a sheet to obtain the air battery cathode sheet.
(3) And assembling the cathode plate and the aluminum anode of the air battery into a battery in a battery testing device.
Example 8
(1) Weighing 10g of nickel sulfate and 20g of cobalt sulfate, adding ethanol, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 2h at 180 ℃, cooling, filtering, drying, and calcining at 600 ℃ to obtain nickel cobaltate spinel; dispersing 16g of nickel cobaltite spinel, 4g of manganese dioxide and 1.0g of polyvinylpyrrolidone serving as an inducer in a solvent, magnetically stirring for 2 hours, ultrasonically dispersing for 2 hours, drying in an oven at 80 ℃ for 6 hours, and calcining at 500 ℃ to obtain manganese dioxide coated nickel cobaltite spinel; and coating manganese dioxide on nickel cobaltate and 5g of graphene, adding ethanol and 1.0g of surfactant sodium dodecyl benzene sulfonate, performing ultrasonic dispersion for 10 hours, quickly drying under reduced pressure, and calcining at 500 ℃ to obtain the catalyst with the double-coating structure.
(2) Weighing 8g of the catalyst, 15g of conductive carbon black, 25g of polyvinylidene fluoride and 80g of ethanol, putting the mixture into a beaker for mixing, performing ultrasonic dispersion for 1h, performing magnetic stirring for 3h to obtain catalyst slurry, drying the catalyst slurry in an oven for 1h, and pressing the catalyst slurry into a film to obtain the catalyst layer. Respectively weighing 8g of conductive carbon black, 18g of polyvinylidene fluoride and 64g of ethanol, putting the conductive carbon black, the polyvinylidene fluoride and the ethanol into a beaker for mixing, performing ultrasonic dispersion for 1h, then performing magnetic stirring for 2h to obtain waterproof breathable layer slurry, drying the waterproof breathable layer slurry in an oven for 1h, and pressing the waterproof breathable layer slurry into a film to obtain the waterproof breathable layer slurry. And pressing the catalyst layer, the waterproof breathable layer and the current collector into a sheet to obtain the air battery cathode sheet.
(3) And assembling the cathode plate and the aluminum anode of the air battery into a battery in a battery testing device.
Example 9
(1) Weighing 8g of nickel chloride and 16g of cobalt chloride, adding ethanol, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 2h at 180 ℃, cooling, filtering, drying, and calcining at 600 ℃ to obtain nickel cobaltate spinel; dispersing 12g of nickel cobaltite spinel, 3g of manganese dioxide and 1.0g of polyvinylpyrrolidone serving as an inducer in a solvent, magnetically stirring for 2 hours, ultrasonically dispersing for 2 hours, drying in an oven at 80 ℃ for 6 hours, and calcining at 500 ℃ to obtain manganese dioxide coated nickel cobaltite spinel; and coating manganese dioxide on nickel cobaltate and 4g of graphene, adding ethanol and 1.0g of surfactant sulfated castor oil, performing ultrasonic dispersion for 10 hours, quickly drying under reduced pressure, and calcining at 600 ℃ to obtain the catalyst with the double-coating structure.
(2) Weighing 10g of the catalyst, 12g of conductive carbon black, 18g of polyvinylidene fluoride and 80g of ethanol, putting the mixture into a beaker for mixing, performing ultrasonic dispersion for 1h, performing magnetic stirring for 3h to obtain catalyst slurry, drying the catalyst slurry in an oven for 1h, and pressing the catalyst slurry into a film to obtain the catalyst layer. Respectively weighing 12g of conductive carbon black, 24g of polyvinylidene fluoride and 76g of ethanol, putting the conductive carbon black, the polyvinylidene fluoride and the ethanol into a beaker for mixing, ultrasonically dispersing for 1h, magnetically stirring for 2h to obtain waterproof breathable layer slurry, drying the waterproof breathable layer slurry in an oven for 1h, and pressing the waterproof breathable layer slurry into a film to obtain the waterproof breathable layer slurry. And pressing the catalyst layer, the waterproof breathable layer and the current collector into a sheet to obtain the air battery cathode sheet.
(3) And assembling the cathode plate and the aluminum anode of the air battery into a battery in a battery testing device.
Test example 1
In the metal-air battery, manganese oxide surface coating is not performed on the spinel catalyst, a carbonaceous material bulk phase coating is performed, only nickel cobaltate spinel is used as the catalyst (comparative example 1), only nickel cobaltate spinel is subjected to manganese oxide surface coating as the catalyst (comparative example 2), the oxygen reduction polarization curves of example 1 and comparative examples 1 and 2 are tested by using a rotating disk, and the results are shown in fig. 6 and table 1,
TABLE 1 oxygen reduction reaction of catalyst
And (4) conclusion: compared with the catalysts of comparative examples 1 and 2, the catalyst of example 1 has the advantages that the limiting current density is increased, the initial potential and the half-wave potential are both positive, the oxygen reduction performance is improved, and the catalytic activity is improved.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (12)
1. A preparation method of a catalyst with a double-coating structure comprises the following steps:
(1) preparation of spinel: weighing 45-60 parts of metal A salt and 90-120 parts of metal B salt, adding a solvent, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, transferring to a high-pressure reaction kettle, reacting for 2-4h at the temperature of 110-; the metal A salt is sulfuric acid A, chloride A or nitric acid A; the metal B salt is sulfuric acid B, chlorination B or nitric acid B; wherein A is one element of Mg, Fe, Co, Ni, Cu and Zn, and B is one element of Al, Cr, Mn, Fe, Co and Ni;
(2) preparation of manganese oxide coated spinel: adding an inducer into 65-75 parts of spinel and 10-15 parts of manganese oxide, magnetically stirring for 1-2h, ultrasonically dispersing for 1-2h, drying in an oven at 80 ℃ for 4-6h, and calcining at 400 ℃ and 600 ℃ to obtain manganese oxide coated spinel; the manganese oxide is one of manganese dioxide, manganic oxide and manganic manganous oxide;
(3) preparing a spinel catalyst with a carbon-containing material coating structure: dispersing 75-90 parts of spinel coated by manganese oxide and 15-25 parts of carbon-containing material in a solvent, adding a surfactant, ultrasonically dispersing for 6-12h, quickly drying under reduced pressure, and vacuum calcining at 800 ℃ to obtain a catalyst with a double-coated structure; the carbon-containing material is graphene;
the solvent in the steps (1) and (3) is one of terpineol, ethanol, isopropanol, n-butanol and n-hexanol;
the inducer in the step (2) is one of polyoxyethylene or polyvinylpyrrolidone, and the mass of the inducer is 1-10% of the total mass of spinel and manganese oxide;
the surfactant in the step (3) is one or more of sodium dodecyl benzene sulfonate, sodium dioctyl sulfosuccinate, sulfated castor oil and glyceride, and the mass of the surfactant is 1-10% of the total mass of the manganese oxide coated spinel and the carbon-containing material.
2. The method for preparing a catalyst having a double coating structure according to claim 1, wherein: in the step (2), the manganese oxide is manganese dioxide.
3. The method for preparing a catalyst having a double coating structure according to claim 1, wherein: the metal A salt is nitric acid A; the metal B salt is nitric acid B.
4. The method for preparing a catalyst having a double coating structure according to claim 1, wherein: in the step (1), A is Co, and B is Ni.
5. The method for preparing a catalyst having a double coating structure according to claim 1, wherein: the spinel is nickel cobaltate spinel.
6. A preparation method of an air battery cathode plate comprises the following steps:
(1) preparing a catalytic layer: mixing the catalyst with the double-coating structure, a conductive agent, a binder and a solvent, performing ultrasonic treatment and stirring to obtain catalyst slurry, drying, and pressing into a film to obtain a catalyst layer; the catalyst, the conductive agent and the binder with the double-coating structure are in a mass part ratio of (1-2): (1-3): (2-5);
(2) preparing a waterproof breathable layer; mixing a conductive agent, a binder and a solvent, performing ultrasonic treatment and stirring to obtain waterproof and breathable layer slurry, drying, and pressing to form a film to obtain a waterproof and breathable layer; the mass part ratio of the conductive agent to the binder is (1-3): (2-5);
(3) preparing an air battery cathode piece: carrying out pressing treatment on the catalyst layer, the waterproof breathable layer and the current collector to obtain an air battery cathode sheet;
the preparation method of the catalyst with the double-coated structure is as described in any one of claims 1 to 5.
7. The method for preparing the cathode sheet of the air battery according to claim 6, wherein the catalyst, the conductive agent, the binder and the solvent in the double-coating structure in the catalyst layer in the step (1) are in a mass ratio of (5-10): (5-15): (10-20): (60-80).
8. The preparation method of the air battery cathode plate according to claim 7, wherein the catalyst, the conductive agent, the binder and the solvent in the double-coating structure in the catalyst layer in the step (1) are in a mass ratio of (6-8): (8-12): (12-18): (64-76).
9. The method for preparing the cathode sheet of the air battery according to claim 8, wherein the catalyst, the conductive agent, the binder and the solvent of the double-coating structure in the catalyst layer in the step (1) are mixed in a mass ratio of 6.5: 9.8: 12.2: 71.5.
10. the method for preparing the cathode sheet of the air battery according to claim 6, wherein the mass part ratio of the conductive agent, the adhesive and the solvent in the waterproof and breathable layer in the step (2) is (5-15): (10-25): (60-80).
11. The method for preparing an air battery cathode sheet according to claim 10, wherein the waterproof and breathable layer in the step (2) comprises the following components in parts by mass (8-12): (18-24): (64-76).
12. The method for preparing an air battery cathode sheet according to claim 11, wherein the mass part ratio of the conductive agent, the binder and the solvent in the waterproof and breathable layer in the step (2) is 11.8: 18.9: 69.3.
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