CN111554940B - Application of bifunctional oxygen catalyst in preparation of zinc-air battery - Google Patents

Application of bifunctional oxygen catalyst in preparation of zinc-air battery Download PDF

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CN111554940B
CN111554940B CN202010216565.9A CN202010216565A CN111554940B CN 111554940 B CN111554940 B CN 111554940B CN 202010216565 A CN202010216565 A CN 202010216565A CN 111554940 B CN111554940 B CN 111554940B
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catalyst
zinc
air battery
performance
transition metal
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CN111554940A (en
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廖开明
卢千
史仲达
杨广明
周嵬
邵宗平
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Nanjing Tech University
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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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/33—
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to application of a bifunctional catalyst in preparation of a zinc-air battery. By coating the surface of the sulfide with the multi-stage porous nitrogen-doped carbon material, the catalyst with a three-dimensional structure can be obtained, and the three-dimensional sea urchin-shaped structure is favorable for transmission of oxygen species and electrons, so that the oxygen catalytic performance can be effectively improved. The catalyst has simple synthesis process, low cost of used raw materials and performance close to that of the current commercialized Pt/C and IrO 2 A catalyst. The catalyst is used for the anode oxygen catalyst of the zinc-air battery, shows higher power density and energy density, keeps stable performance for a long time, and has obviously better performance than commercial Pt/C and IrO when being used as the cathode catalyst of the zinc-air battery 2 Mixing the catalyst. Meanwhile, the zinc oxide/carbon composite material is used as a positive electrode catalyst of a flexible solid zinc-air battery and also shows excellent performance.

Description

Application of bifunctional oxygen catalyst in preparation of zinc-air battery
Technical Field
The invention relates to application of a bifunctional catalyst in preparation of a zinc-air battery, belonging to the field of electrochemical energy conversion and storage.
Background
In the world today, energy problems are a key issue for the development of human society. With the transition use of fossil energy, environmental and pollution problems such as global warming, greenhouse effect, air pollution, etc. become increasingly severe. The oil used by the fuel oil automobile is non-renewable energy, and the operation process of the oil automobile can discharge pollution gas, while for the pure electric automobile, the oil automobile uses a renewable power supply, and has no pollution emission and high conversion efficiency of electric energy. The development of electric vehicles is a promising approach.
For the development of pure electric vehicles, the main limitation is the safety and endurance of the power battery. Currently, the energy density of the commonly used lithium ion battery is relatively low, and the safety of the lithium ion battery faces a huge challenge due to the use of an organic electrolyte. The specific capacity of the zinc-air battery as an electrochemical system directly using oxygen in air mainly depends on the capacity of negative electrode zinc, and the theoretical capacity density is as high as 1086 Wh kg -1 Is 5 times of the current lithium ion battery.
At present, the research bottleneck of the zinc-air battery is mainly the cathode high-performance oxygen catalyst. The oxygen catalysts commonly used at present are noble metals of platinum/carbon and iridium oxide, but the high price and poor stability thereof greatly limit the practical application. A series of non-noble metal catalysts have been reported to be applied to zinc air recently, but most of the catalysts involve the use of expensive graphene/graphene oxide or complicated preparation procedures, resulting in higher actual preparation cost,
disclosure of Invention
The invention aims to design a high-efficiency non-noble metal bifunctional oxygen catalyst with a simple preparation process, which is applied to a zinc-air battery, so that the cost of the catalyst is greatly reduced, and the commercial application process of the zinc-air battery is accelerated.
In a first aspect of the present invention, there is provided:
a bifunctional oxygen catalyst, the catalyst takes transition metal sulfide as an inner core, and coats heteroatom-doped carbon on the outer part.
In one embodiment, the transition metal is a group VIII transition metal; more preferably, cobalt, nickel or iron.
In one embodiment, the transition metal sulfide is cobalt sulfide, nickel sulfide or iron sulfide.
In one embodiment, the heteroatom is nitrogen.
In one embodiment, the heteroatom-doped carbon has a multi-level structure.
In a second aspect of the present invention, there is provided:
the preparation method of the bifunctional oxygen catalyst comprises the following steps:
mixing transition metal hydrated nitrate and thiourea, grinding the mixture to form a viscous solution, adding melamine, grinding the mixture to be uniform, calcining the mixture in a tube furnace filled with inert gas, and washing a calcined product by hydrochloric acid to obtain the catalyst.
In one embodiment, the transition metal hydrous nitrate is cobalt nitrate hexahydrate, nickel nitrate hexahydrate, or iron nitrate nonahydrate.
In one embodiment, the mass ratio of the transition metal hydrated nitrate to the thiourea is 1.
In one embodiment, the mass ratio of melamine to transition metal hydrated nitrate/thiourea mixture is 1.
In one embodiment, the inert gas is nitrogen.
In one embodiment, the tube furnace has a temperature rise rate of 5 ℃/min, a maximum temperature of 700 to 900 ℃, and a calcination time of 3 hours.
In one embodiment, 1 mole/liter hydrochloric acid is used.
In a third aspect of the present invention, there is provided:
the application of the bifunctional oxygen catalyst in a zinc-air battery.
In one embodiment, the zinc-air battery refers to a liquid zinc-air battery and a solid zinc-air battery.
In one embodiment, the dual function oxygen catalyst is used to enhance oxygen reduction and oxygen evolution performance.
In one embodiment, the dual function oxygen catalyst is used to increase the power density of a zinc air cell.
In one embodiment, the bifunctional oxygen catalyst is used to improve the discharge stability of a zinc-air battery.
In one embodiment, the bifunctional oxygen catalyst is used to improve the cycling stability performance of a zinc-air cell.
In a fourth aspect of the present invention, there is provided:
a zinc-air battery contains the bifunctional oxygen catalyst as a positive electrode material.
Advantageous effects
The catalyst prepared by the invention has simple preparation process and low cost of raw materials, and the performance of the catalyst can be comparable to that of commercial platinum-carbon and iridium oxide noble metal catalysts.
The preparation method comprises the steps of obtaining an oxygen catalyst with double active sites by adopting the decomposition temperatures of two different materials in a one-pot high-temperature process, compounding a transition metal sulfide with heteroatom-doped carbon, and comparing the power density, the discharge energy density and the cycle performance of the bifunctional catalyst and a platinum carbon/iridium oxide mixture in the application of a zinc-air battery.
In addition, the nitrogen-doped carbon-coated cobalt sulfide catalyst provided by the invention has better performance when applied to a flexible all-solid-state zinc-air battery. The invention relates to a bifunctional oxygen catalyst which has the advantages of excellent performance, very simple preparation method and lower cost, is suitable for large-scale preparation and is beneficial to commercialization.
Drawings
Fig. 1 is a result of characterization of a nitrogen-doped carbon-coated cobalt sulfide catalyst, in which (a) a region scanning electron micrograph, (b) a region transmission electron micrograph, (c) a region X-ray powder diffraction pattern, and (d) a region raman spectrum.
Fig. 2 is a nitrogen sorption and desorption curve of the nitrogen-doped carbon-coated cobalt sulfide catalyst.
Figure 3 is a graph of oxygen reduction performance of nitrogen doped carbon coated cobalt sulfide catalyst and platinum carbon catalyst in 0.1 mol/l potassium hydroxide solution.
Fig. 4 is a graph of oxygen evolution performance of nitrogen doped carbon coated cobalt sulfide catalysts and iridium oxide catalysts in 0.1 mol/l potassium hydroxide solution.
Fig. 5 is a graph of voltage-current density and power-current density for a zinc air cell assembled with a nitrogen doped carbon coated cobalt sulfide catalyst and a platinum carbon catalyst.
Fig. 6 is a graph of energy density for a zinc air cell assembled with a nitrogen doped carbon coated cobalt sulfide catalyst and a platinum carbon catalyst tested at a current density of 10 milliamps per square centimeter.
Fig. 7 is an assembly of nitrogen doped carbon coated cobalt sulfide catalyst to provide long term discharge stability of a zinc air cell at a current density of 10 milliamps per square centimeter.
Fig. 8 shows the charge and discharge performance of a zinc-air battery assembled by a nitrogen-doped carbon-coated cobalt sulfide catalyst and a platinum-carbon/iridium oxide mixed catalyst, tested at a current density of 2 milliamperes per square centimeter.
Fig. 9 shows the charge and discharge performance of the flexible solid zinc-air battery assembled by the nitrogen-doped carbon-coated cobalt sulfide catalyst in different bending states, which is tested at a current density of 1 milliampere/square centimeter.
Detailed Description
The invention relates to a high-efficiency low-cost bifunctional oxygen electrocatalyst prepared by a one-pot method easy for large-scale preparation, and application of the catalyst in a zinc-air battery. The catalyst with a three-dimensional structure can be obtained by coating the surface of the sulfide with a multi-stage porous nitrogen-doped carbon material, and the three-dimensional sea urchin-shaped structure of the catalyst is favorable for the transmission of oxygen species and electrons, so that the oxygen catalytic performance can be effectively improved. The catalyst has simple synthesis process, low cost of used raw materials and performance close to that of the current commercialized Pt/C and IrO 2 A catalyst. The catalyst is used for the anode oxygen catalyst of the zinc-air battery, shows higher power density and energy density, can keep stable performance for a long time in the stability test process, and has obviously better performance than commercial Pt/C and IrO when being used as the cathode catalyst of the zinc-air battery 2 Mixing the catalyst. Meanwhile, the zinc oxide/carbon composite material is used as a positive electrode catalyst of a flexible solid zinc-air battery and also shows excellent performance. The preparation method of the bifunctional oxygen electrocatalyst is simple, is easy for large-scale production, can be widely applied to energy storage and conversion equipment, and has good practical value.
The catalyst mainly adopts an autocatalysis growth method, and cobalt ions can generate complexation with sulfur in thiourea, so that cobalt sulfide can be obtained at high temperature. By adding melamine, cobalt sulfide can be reduced at high temperature to obtain simple substance cobalt, so that the obtained cobalt can be used as a catalyst, carbon and nitrogen compounds obtained by pyrolysis of melamine are used as a solid carbon source, and a nitrogen-doped carbon material grows on the surface of the reduced cobalt on the surface of the cobalt sulfide in an autocatalytic manner. The three-dimensional sea urchin-shaped structure is beneficial to the transmission of oxygen species and electrons, so that the oxygen catalytic performance can be improved.
Example 1 preparation of nitrogen doped carbon coated cobalt sulfide
Weighing 3 g of cobalt nitrate hexahydrate and 3 g of thiourea, adding the mixture into a mortar, grinding for 10-20 min to form a dark solution, adding 7 g of melamine, continuously grinding to obtain uniform powder, placing the powder in an alumina square boat, and introducing nitrogen into the tube furnace at 800 ℃ to calcine for 3 hours. Adding the obtained black powder into 100 ml of 1 mol hydrochloric acid solution, stirring for 1 hour, performing suction filtration to wash the powder, and after the powder is drained, adding deionized water to wash for 3 times. The resulting mixture was placed in a vacuum oven at 60 ℃ for 5 hours. Obtaining the bifunctional catalyst.
EXAMPLE 2 preparation of Nitrogen doped carbon coated cobalt sulfide
Weighing 3 g of cobalt nitrate hexahydrate and 1.5 g of thiourea, adding the mixture into a mortar, grinding for 10-20 min to form a dark solution, adding 4 g of melamine, continuously grinding to obtain uniform powder, placing the powder in an alumina ark, and introducing nitrogen into a tube furnace to calcine for 3 hours at 800 ℃. Adding the obtained black powder into 100 ml of 1 mol hydrochloric acid solution, stirring for 1 hour, performing suction filtration to wash the powder, and after the powder is drained, adding deionized water to wash for 3 times. The obtained mixture was placed in a vacuum oven at 60 ℃ for 5 hours. A bifunctional catalyst is obtained.
EXAMPLE 3 preparation of Nitrogen doped carbon coated cobalt sulfide
Weighing 3 g of cobalt nitrate hexahydrate and 3 g of thiourea, adding the mixture into a mortar, grinding for 10-20 min to form a dark solution, adding 7 g of melamine, continuously grinding to obtain uniform powder, placing the powder in an alumina square boat, and introducing nitrogen into the tube furnace at 900 ℃ to calcine for 3 hours. Adding the obtained black powder into 100 ml of 1 mol hydrochloric acid solution, stirring for 1 hour, performing suction filtration to wash the powder, and after the powder is drained, adding deionized water to wash for 3 times. The obtained mixture was placed in a vacuum oven at 60 ℃ for 5 hours. Obtaining the bifunctional catalyst.
Characterization of materials
The morphology of the nitrogen-doped carbon-coated cobalt sulfide catalyst can be obtained through an S-4800 scanning electron microscope image and an S-TWIN projection electron microscope test. The specific surface area was measured by a BEL desorption apparatus. Discharge and cycling performance was measured by the novice test instrument. The power density was measured by Solartron instrument. The characterization results were as follows:
1. scanning electron micrographs of nitrogen-doped carbon-coated cobalt sulfide
The area (a) in fig. 1 is a scanning electron microscope image of the nitrogen-doped carbon-coated cobalt sulfide catalyst, and it can be seen that the surface of the prepared catalyst is coated with porous carbon and carbon nanotubes, and the transmission electron microscope image in the area (b) in fig. 1 can see that certain carbon nanotubes grow on the outer surface of the catalyst, and the catalyst presents a sea urchin-like three-dimensional structure. X-ray diffraction showed that the catalyst was predominantly octacobalt nonasulfide phase structure and that some amount of cobalt was present, primarily for catalytic growth of nitrogen-doped carbon. Raman spectroscopy indicates that for nitrogen-doped carbon-coated cobalt sulfide, it is mainly a co-existing structure of cobalt sulfide and carbon material.
2. Nitrogen adsorption and desorption curve of nitrogen-doped carbon-coated cobalt sulfide
Fig. 2 is a nitrogen adsorption and desorption curve of the nitrogen-doped carbon-coated cobalt sulfide catalyst, and it can be seen that the catalyst mainly consists of mesopores and macropores, and the specific surface area reaches 95 square meters per gram.
3. Oxygen reduction and oxygen evolution Performance test
FIG. 3 is a test of oxygen reduction performance of nitrogen doped carbon coated cobalt sulfide, nitrogen doped carbon and platinum carbon catalysts in 0.1 mol/l KOH solution, showing that the prepared bifunctional catalyst has oxygen reduction performance close to that of noble metal platinum carbon catalyst and superior to that of pure cobalt sulfide and nitrogen doped carbon. Figure 4 is a test of oxygen evolution performance of nitrogen doped carbon coated cobalt sulfide, nitrogen doped carbon and iridium oxide catalysts in 0.1 mol/l potassium hydroxide solution, and it can be seen that the oxygen evolution performance of the bifunctional catalyst is superior to commercial iridium oxide and to pure cobalt sulfide and nitrogen doped carbon, primarily because the transition metal sulfide is coated with nitrogen doped carbon, which can act as an electron conducting network.
4. Research on air discharge performance of liquid zinc
Discharge performance is an important criterion for zinc-air cell performance. Fig. 5 is a voltage-current density and power-current density curve of a zinc-air battery assembled by the bifunctional catalyst and the platinum-carbon catalyst, and it is obvious that the maximum power density of the prepared bifunctional catalyst can reach 103 milliwatts per square centimeter and is higher than 87 milliwatts per square centimeter of the platinum-carbon catalyst. Fig. 6 is a graph of energy density of zinc-air cells assembled with nitrogen-doped carbon-coated cobalt sulfide and platinum-carbon catalyst tested at a current density of 10 milliamps/cm, the nitrogen-doped carbon-coated cobalt sulfide showing a higher discharge potential than the platinum-carbon catalyst, and the maximum discharge energy density of the nitrogen-doped carbon-coated cobalt sulfide being as high as 924 Wh/kg, significantly higher than 860 Wh/kg of platinum-carbon.
Further evaluating the discharge stability of the nitrogen-doped carbon-coated cobalt sulfide catalyst, fig. 7 shows that the zinc-air battery assembled by the nitrogen-doped carbon-coated cobalt sulfide has long-time discharge temperature performance at a current density of 10 milliampere/square centimeter, and the nitrogen-doped carbon-coated cobalt sulfide catalyst still maintains good discharge performance after the zinc sheet is replaced five times and the test lasts for 185 hours, so that the catalyst has good stability.
5. Study on air circulation performance of liquid zinc
Fig. 8 shows the charge and discharge performance of a zinc-air battery assembled by nitrogen-doped carbon-coated cobalt sulfide and platinum carbon/iridium oxide mixed catalyst, tested at a current density of 2 milliamperes per square centimeter. It can be seen that the nitrogen-doped carbon-coated cobalt sulfide catalyst can still keep stable after being charged and discharged for 200 hours circularly, and the charging and discharging polarization is smaller. And after 50 hours of charge and discharge, the platinum carbon/iridium oxide mixed catalyst is deactivated, so that the performance is rapidly reduced. The excellent cycling stability of the nitrogen-doped carbon-coated cobalt sulfide catalyst is demonstrated.
6. Research on flexible solid zinc-air battery
The PVA alkaline gel which is most commonly used at present is used as an electrolyte, the nitrogen-doped carbon-coated cobalt sulfide catalyst is sprayed on the surface of carbon cloth to be used as a positive electrode, zinc foil is used as a negative electrode, and the solid zinc-air battery is assembled. Fig. 9 shows the charge and discharge performance of the flexible solid zinc-air battery assembled by the nitrogen-doped carbon-coated cobalt sulfide catalyst in different bending states tested at a current density of 1 milliampere/square centimeter, and the folding angle is changed without circulating 5 cycles, so that the performance is not greatly attenuated at different folding angles, and the charge and discharge polarization is small, which indicates that the flexible solid zinc-air battery has a practical potential application value.
Through the experiments, the prepared nitrogen-doped carbon-coated cobalt sulfide catalyst has excellent catalytic performance which is close to that of a commercial noble metal catalyst, and the zinc air performance is superior to that of the commercial noble metal catalyst. The application of the zinc-air battery can greatly reduce the overall cost of the zinc-air battery.

Claims (2)

1. The application of the bifunctional oxygen catalyst in preparing a zinc-air battery is characterized in that the bifunctional oxygen catalyst takes transition metal sulfide as an inner core and is coated with a carbon material at the outer part, wherein the transition metal sulfide is cobalt sulfide, and the carbon material is composed of a multi-stage porous nitrogen-doped carbon material; the preparation method of the bifunctional oxygen catalyst comprises the following steps:
the method comprises the following steps: mixing transition metal hydrated nitrate and thiourea, grinding the mixture to form a viscous solution, adding melamine, grinding the mixture to be uniform, calcining the mixture in a tube furnace filled with inert gas, and washing a calcined product with hydrochloric acid to obtain the catalyst;
the transition metal hydrated nitrate is cobalt nitrate hexahydrate, nickel nitrate hexahydrate or ferric nitrate nonahydrate;
the mass ratio of the transition metal hydrated nitrate to the thiourea is 1;
the mass ratio of the melamine to the transition metal hydrated nitrate/thiourea mixture is 1;
the temperature rising speed of the tubular furnace is 5 ℃/min, the highest temperature is 700-900 ℃, and the calcining time is 3h;
the hydrochloric acid is 1 mol/l hydrochloric acid.
2. The use according to claim 1, wherein the zinc-air battery is a liquid zinc-air battery or a solid zinc-air battery.
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