CN114597423A - Air battery, composite air electrode and preparation method - Google Patents

Air battery, composite air electrode and preparation method Download PDF

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Publication number
CN114597423A
CN114597423A CN202111312490.5A CN202111312490A CN114597423A CN 114597423 A CN114597423 A CN 114597423A CN 202111312490 A CN202111312490 A CN 202111312490A CN 114597423 A CN114597423 A CN 114597423A
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metal oxide
air electrode
composite air
pore
precursor
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苗翠
李士忠
马泽
马中华
李跃华
贾婷婷
闵庆久
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Beijing Machinery Equipment Research Institute
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Beijing Machinery Equipment Research Institute
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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
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses an air battery, a composite air electrode and a preparation method thereof, wherein the composite air electrode comprises 30-80% of polyacrylonitrile, 10-30% of pore-forming agent and 10-40% of metal oxide/metal oxide precursor according to weight percentage. The composite air electrode of the hierarchical porous carbon nanofiber/metal oxide catalyst is prepared by various components according to a specific ratio, and the porous carbon fiber structure can provide sufficient pore channels for the discharge product of the air battery to deposit, so that the discharge termination caused by the pore channel blockage of the air electrode is avoided. In addition, the self-supporting film of the porous electrode structure is beneficial to oxygen diffusion and electrolyte contact, and the cycling stability of the battery can be improved.

Description

Air battery, composite air electrode and preparation method
Technical Field
The invention relates to the technical field of air batteries, in particular to an air battery, a composite air electrode and a preparation method.
Background
In modern society, the demand for breakthrough in battery technology is increasing. The search for higher energy density positive electrode materials has been one direction of lithium battery development. Especially, the development demand of electric vehicles promotes people to further strengthen the development of ultrahigh energy density energy storage devices. The charging mileage of a traditional lithium battery electric vehicle is difficult to exceed 200km once, and the lithium air battery electric vehicle is expected to improve the charging mileage to more than 550 km. The ultrahigh theoretical specific energy of the lithium-air battery exceeding 1000Wh/kg is close to gasoline, and is three times of the specific energy of the current battery. However, the development of the lithium air battery also faces many challenges, for example, the lithium air battery works in the environment, and the common organic electrolyte is easy to volatilize, which results in the reduction of the discharge capacity, and also shortens the service life of the battery, and brings certain potential safety hazard to the battery. The discharge products of the lithium air battery can block air channels, resulting in the termination of discharge, which is also the biggest disadvantage of such an open system of the lithium air battery. In addition, if the lithium ion secondary battery works in the air, the organic electrolyte easily absorbs moisture in the air, so that the lithium sheet of the negative electrode is corroded, and the lithium sheet and carbon dioxide in the air generate lithium carbonate, and the lithium carbonate has no electrochemical reversibility, so that the cycle performance of the battery is reduced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a stable structure of a lithium battery cathode, a preparation method of the lithium battery cathode and a lithium battery, wherein the stable structure of the lithium battery cathode, the lithium battery cathode and the preparation method of the lithium battery cathode are used for improving the conductivity of a silicon/tin-based cathode material and solving the problems of structural pulverization, poor conductivity and the like caused by volume expansion in the circulation process.
In order to achieve the above object, a first aspect of the present invention provides a composite air electrode, which comprises 30% to 80% of polyacrylonitrile, 10% to 30% of pore-forming agent and 10% to 40% of metal oxide, by weight.
Further, the metal oxide includes MnOx、Fe2O3、NiO、Co3O4、NiCo2O4And LaxSr1-xMnO3At least one of (1).
The second aspect of the invention provides a composite air electrode, which comprises 30-80 wt% of polyacrylonitrile, 10-30 wt% of pore-forming agent and 10-40 wt% of metal oxide precursor.
Further, the pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
Further, the metal oxide precursor includes Mn (NO)3)2、Fe(C5H7O2)3、Ni(NO3)2、 Co(NO3)2、La(NO3)3、Sr(NO3)2And Cr (NO)3)3At least one of (1).
A third aspect of the present invention provides a method of manufacturing a composite air electrode, comprising:
1) preparing polyacrylonitrile, a pore-forming agent and a metal oxide according to the formula of the composite air electrode in the first aspect; or preparing polyacrylonitrile, pore-forming agent and metal oxide precursor according to the formula of the composite air electrode in the second aspect;
2) adding polyacrylonitrile into dimethylformamide solution with concentration of 5% -15%, and stirring at 60 deg.C until the mixture becomes transparent yellow viscous liquid;
3) adding a pore-forming agent and a metal oxide in sequence and stirring uniformly to obtain a mixed solution; or adding the pore-forming agent and the metal oxide precursor in sequence and stirring uniformly to obtain a mixed solution;
4) spraying the mixed solution by an injector by using an electrostatic spinning process to obtain a precursor of the porous carbon nanofiber/metal oxide catalyst;
5) and carrying out pre-oxidation and carbonization processes on the precursor of the porous carbon nanofiber/metal oxide catalyst to obtain the composite air electrode.
Further, the outflow speed of the spinning solution in the electrostatic spinning process is 0.05-1 mL/h, the distance between an injector and a collecting device is 10-50 cm, the negative electrode voltage is-3 kV, and the positive electrode voltage is 5 kV-30 kV in the spinning process.
Further, the pre-oxidation and carbonization process of the precursor of the porous nano carbon fiber/metal oxide catalyst comprises the following steps:
placing the precursor obtained by the electrostatic spinning process in a muffle furnace, raising the pre-oxidation temperature to 200-400 ℃ at the speed of 1-10 ℃/min, and keeping the temperature for 1-6 h;
and (3) placing the pre-oxidized precursor in a tubular furnace protected by Ar, raising the temperature to 600-1000 ℃ at the speed of 1-10 ℃/min, and keeping the temperature for 1-12h to obtain the composite air electrode.
A fourth aspect of the invention provides a composite air electrode produced by the production method according to the third aspect.
A fifth aspect of the invention provides an air battery comprising the composite air electrode of the fourth aspect.
The composite air electrode of the hierarchical porous carbon nanofiber/metal oxide catalyst is prepared by various components according to a specific ratio, and the porous carbon fiber structure can provide sufficient pore channels for the discharge product of the air battery to deposit, so that the discharge termination caused by the pore channel blockage of the air electrode is avoided. In addition, the self-supporting film of the porous electrode structure is favorable for oxygen diffusion and electrolyte contact, and the cycling stability of the battery can be increased.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
Detailed Description
Example embodiments will now be described more fully. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the examples set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the invention provides a composite air electrode, which comprises 30-80% of polyacrylonitrile, 10-30% of pore-forming agent and 10-40% of metal oxide by weight percentage.
The second aspect of the invention provides a composite air electrode, which comprises 30-80 wt% of polyacrylonitrile, 10-30 wt% of pore-forming agent and 10-40 wt% of metal oxide precursor.
Optionally, the metal oxide comprises MnOx、Fe2O3、NiO、Co3O4、NiCo2O4And LaxSr1-xMnO3At least one of (a).
Optionally, the pore-forming agent includes at least one of polystyrene, polymethyl methacrylate, and polyvinylpyrrolidone.
Optionally, the metal oxide precursor comprises Mn (NO)3)2、Fe(C5H7O2)3、Ni(NO3)2、 Co(NO3)2、La(NO3)3、Sr(NO3)2And Cr (NO)3)3At least one of (1).
A third aspect of the present invention provides a method of manufacturing a composite air electrode, comprising:
1) preparing polyacrylonitrile, pore-forming agent and metal oxide according to the formula of the composite air electrode in the first aspect; or preparing polyacrylonitrile, pore-forming agent and metal oxide precursor according to the formula of the composite air electrode in the second aspect;
2) adding polyacrylonitrile into dimethylformamide solution with concentration of 5% -15%, and stirring at 60 deg.C until the mixture becomes transparent yellow viscous liquid;
3) adding a pore-forming agent and a metal oxide in sequence and stirring uniformly to obtain a mixed solution; or adding the pore-forming agent and the metal oxide precursor in sequence and stirring uniformly to obtain a mixed solution;
4) spraying the mixed solution by an injector by using an electrostatic spinning process to obtain a precursor of the porous carbon nanofiber/metal oxide catalyst;
5) and carrying out pre-oxidation and carbonization processes on the precursor of the porous carbon nanofiber/metal oxide catalyst to obtain the composite air electrode.
Optionally, the outflow speed of the spinning solution in the electrostatic spinning process is 0.05-1 mL/h.
Optionally, the pre-oxidation and carbonization process of the precursor of the porous filamentous nanocarbon/metal oxide catalyst includes:
placing the precursor obtained by the electrostatic spinning process in a muffle furnace, raising the pre-oxidation temperature to 200-400 ℃ at the speed of 1-10 ℃/min, and keeping the temperature for 1-6 h;
and (3) placing the pre-oxidized precursor in a tubular furnace protected by Ar, raising the temperature to 600-1000 ℃ at the speed of 1-10 ℃/min, and keeping the temperature for 1-12h to obtain the composite air electrode.
A fourth aspect of the invention provides a composite air electrode produced by the production method according to the third aspect.
A fifth aspect of the invention provides an air battery comprising the composite air electrode of the fourth aspect.
Side reactions are generated in the process of oxygen reduction ORR or oxygen evolution OER of the lithium air battery (such as Li)2CO3Etc.) and discharge products (Li)2O2Or LiO2) Deposit on the surface of the air electrode, block air channels, and cause the discharge to be terminated. The invention utilizes the electrostatic spinning technology to form the hierarchical porous carbon fiber, which can provide sufficient pore channels for the products to deposit.
In addition, the invention utilizes the electrostatic spinning technology to form the self-supporting membrane of the integrated hierarchical porous electrode structure by adjusting the electrospinning parameters, the membrane can be used as an independent air electrode without a binder and a current collector, the oxygen diffusion and the electrolyte contact are facilitated, and the circulation stability of the system can be increased. The self-supporting structure can provide abundant catalytic sites, and the open pore structure facilitates the de-intercalation of reactants and products.
Example 1:
(1) composite air electrode formula
The composite air electrode comprises 30 weight percent of polyacrylonitrile, 30 weight percent of pore-forming agent and 40 weight percent of metal oxide. Wherein the metal oxide comprises MnOx、Fe2O3、NiO、Co3O4、 NiCo2O4And LaxSr1-xMnO3At least one of (1). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
(2) Method for manufacturing composite air electrode
The manufacturing method of the composite air electrode comprises the following steps:
1) 30% of polyacrylonitrile, 30% of pore-forming agent and 40% of metal oxide. Wherein the metal oxide comprises MnOx、Fe2O3、NiO、Co3O4、NiCo2O4And LaxSr1-xMnO3At least one of (1). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
2) Adding polyacrylonitrile into 15% Dimethylformamide (DMF) solution, stirring at 60 deg.C for several hours until the mixture becomes transparent yellow viscous liquid, adding a pore-forming agent, and stirring to dissolve. And finally, adding metal oxide particles, stirring until the metal oxide particles are uniformly dispersed, transferring into an injector, wherein the distance between the injector and a collecting device is 10cm, the negative voltage is-3 kV, the positive voltage is 15kV, the outflow speed of a spinning solution is 0.05mL/h, and the like in the spinning process to prepare the precursor of the porous carbon nanofiber/metal oxide catalyst.
3) And (3) placing the precursor obtained by electrospinning in a muffle furnace, raising the pre-oxidation temperature to 250 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1 h.
4) And putting the pre-oxidized precursor into a tube furnace protected by Ar, raising the temperature to 700 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h. The porous carbon nanofiber/metal oxide catalyst composite air electrode is obtained.
Example 2:
the composite air electrode comprises 80% of polyacrylonitrile, 10% of pore-forming agent and 10% of metal oxide by weight percentage. Wherein the metal oxide comprises MnOx、Fe2O3、NiO、Co3O4、 NiCo2O4And LaxSr1-xMnO3At least one of (1). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
(2) Method for manufacturing composite air electrode
The manufacturing method of the composite air electrode comprises the following steps:
1) 80% of polyacrylonitrile, 10% of pore-forming agent and 10% of metal oxide by weight percentage. Wherein the metal oxide comprises MnOx、Fe2O3、NiO、Co3O4、NiCo2O4And LaxSr1-xMnO3At least one of (1). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
2) Adding polyacrylonitrile into 5% Dimethylformamide (DMF) solution, stirring at 60 deg.C for several hours until the mixture becomes transparent yellow viscous liquid, adding a pore-forming agent, and stirring to dissolve. And finally, adding metal oxide particles, stirring until the metal oxide particles are uniformly dispersed, transferring into an injector, wherein the distance between the injector and a collecting device is 10cm, the negative voltage is-3 kV, the positive voltage is 15kV, the outflow speed of a spinning solution is 0.3mL/h, and the like in the spinning process to prepare the precursor of the porous carbon nanofiber/metal oxide catalyst.
3) And (3) placing the precursor obtained by electrospinning in a muffle furnace, raising the pre-oxidation temperature to 300 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h.
4) And putting the pre-oxidized precursor into a tube furnace protected by Ar, raising the temperature to 700 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h. The porous carbon nanofiber/metal oxide catalyst composite air electrode is obtained.
Example 3:
the composite air electrode comprises 60% of polyacrylonitrile, 20% of pore-forming agent and 20% of metal oxide by weight percentage. Wherein the metal oxide comprises MnOx、Fe2O3、NiO、Co3O4、 NiCo2O4And LaxSr1-xMnO3At least one of (1). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
(2) Method for manufacturing composite air electrode
The manufacturing method of the composite air electrode comprises the following steps:
1) 60% of polyacrylonitrile, 20% of pore-forming agent and 20% of metal oxide. Wherein the metal oxide comprises MnOx、Fe2O3、NiO、Co3O4、NiCo2O4And LaxSr1-xMnO3At least one of (1). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
2) Adding polyacrylonitrile into 10% Dimethylformamide (DMF) solution, stirring at 60 deg.C for several hours until the mixture becomes transparent yellow viscous liquid, adding a pore-forming agent, and stirring to dissolve. And finally, adding metal oxide particles, stirring until the metal oxide particles are uniformly dispersed, transferring into an injector, wherein the distance between the injector and a collecting device is 30cm, the negative voltage is-3 kV, the positive voltage is 15kV, the outflow speed of a spinning solution is 0.3mL/h, and the like in the spinning process to prepare the precursor of the porous carbon nanofiber/metal oxide catalyst.
3) And (3) placing the precursor obtained by electrospinning in a muffle furnace, raising the pre-oxidation temperature to 250 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h.
4) And putting the pre-oxidized precursor into a tube furnace protected by Ar, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h. The porous carbon nanofiber/metal oxide catalyst composite air electrode is obtained.
Example 4:
the composite air electrode comprises 60% of polyacrylonitrile, 20% of pore-forming agent and 20% of metal oxide precursor by weight percentage. Wherein the metal oxide precursor comprises Mn (NO)3)2、 Fe(C5H7O2)3、Ni(NO3)2、Co(NO3)2、La(NO3)3、Sr(NO3)2And Cr (NO)3)3At least one of (1). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
(2) Method for manufacturing composite air electrode
The manufacturing method of the composite air electrode comprises the following steps:
1) 65% of polyacrylonitrile, 20% of pore-forming agent and 15% of metal oxide precursor. Wherein the metal oxide precursor comprises Mn (NO)3)2、Fe(C5H7O2)3、Ni(NO3)2、 Co(NO3)2、La(NO3)3、Sr(NO3)2And Cr (NO)3)3At least one of (a). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
2) Adding polyacrylonitrile into 10% Dimethylformamide (DMF) solution, stirring at 60 deg.C for several hours until the mixture becomes transparent yellow viscous liquid, adding a pore-forming agent, and stirring to dissolve. And finally adding metal oxide precursor particles, stirring until the metal oxide precursor particles are uniformly dispersed, transferring into an injector, wherein the distance between the injector and a collecting device is 30cm, the negative voltage is-3 kV, the positive voltage is 15kV, the outflow speed of a spinning solution is 0.3mL/h and the like in the spinning process to prepare the precursor of the porous carbon nanofiber/metal oxide catalyst.
3) And (3) placing the precursor obtained by electrospinning in a muffle furnace, raising the pre-oxidation temperature to 250 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h.
4) And putting the pre-oxidized precursor into a tube furnace protected by Ar, raising the temperature to 800 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h. The porous carbon nanofiber/metal oxide catalyst composite air electrode is obtained.
Example 5:
(1) composite air electrode formula
The composite air electrode comprises 30% of polyacrylonitrile, 30% of pore-forming agent and 40% of metal oxide precursor by weight percentage. Wherein the metal oxide precursor comprises Mn (NO)3)2、Fe(C5H7O2)3、Ni(NO3)2、Co(NO3)2、La(NO3)3、Sr(NO3)2And Cr (NO)3)3At least one of (1). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
(2) Method for manufacturing composite air electrode
The manufacturing method of the composite air electrode comprises the following steps:
1) 30% of polyacrylonitrile, 30% of pore-forming agent and 40% of metal oxide precursor. Wherein the metal oxide precursor comprises Mn (NO)3)2、Fe(C5H7O2)3、Ni(NO3)2、 Co(NO3)2、La(NO3)3、Sr(NO3)2And Cr (NO)3)3At least one of (1). The pore-forming agent comprises polystyrene, polymethyl methacrylate and polyAt least one of vinylpyrrolidone.
2) Adding polyacrylonitrile into a Dimethylformamide (DMF) solution with the concentration of 15%, stirring for several hours at the temperature of 60 ℃ until the mixture becomes transparent yellow viscous liquid, adding a pore-forming agent, and continuously stirring until the mixture is dissolved. And finally adding metal oxide precursor particles, stirring until the metal oxide precursor particles are uniformly dispersed, transferring the mixture into an injector, wherein the distance between the injector and a collecting device is 10cm, the negative voltage is-3 kV, the positive voltage is 15kV, the outflow speed of a spinning solution is 0.05mL/h, and the like in the spinning process to prepare the precursor of the porous carbon nanofiber/metal oxide catalyst.
3) And (3) placing the precursor obtained by electrospinning in a muffle furnace, raising the pre-oxidation temperature to 250 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1 h.
4) And putting the pre-oxidized precursor into a tube furnace protected by Ar, raising the temperature to 700 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h. The porous carbon nanofiber/metal oxide catalyst composite air electrode is obtained.
Example 6:
the composite air electrode comprises 80% of polyacrylonitrile, 10% of pore-forming agent and 10% of metal oxide precursor by weight percentage. Wherein the metal oxide precursor comprises Mn (NO)3)2、 Fe(C5H7O2)3、Ni(NO3)2、Co(NO3)2、La(NO3)3、Sr(NO3)2And Cr (NO)3)3At least one of (1). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
(2) Method for manufacturing composite air electrode
The manufacturing method of the composite air electrode comprises the following steps:
1) 80% of polyacrylonitrile, 10% of pore-forming agent and 10% of metal oxide precursor. Wherein the metal oxide comprises Mn (NO)3)2、Fe(C5H7O2)3、Ni(NO3)2、Co(NO3)2、La(NO3)3、Sr(NO3)2And Cr (NO)3)3At least one of (1). The pore-forming agent comprises at least one of polystyrene, polymethyl methacrylate and polyvinylpyrrolidone.
2) Adding polyacrylonitrile into 5% Dimethylformamide (DMF) solution, stirring at 60 deg.C for several hours until the mixture becomes transparent yellow viscous liquid, adding a pore-forming agent, and stirring to dissolve. And finally adding metal oxide precursor particles, stirring until the metal oxide precursor particles are uniformly dispersed, transferring into an injector, wherein the distance between the injector and a collecting device is 10cm, the negative voltage is-3 kV, the positive voltage is 15kV, the outflow speed of a spinning solution is 0.3mL/h and the like in the spinning process to prepare the precursor of the porous carbon nanofiber/metal oxide catalyst.
3) And (3) placing the precursor obtained by electrospinning in a muffle furnace, raising the pre-oxidation temperature to 300 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h.
4) And putting the pre-oxidized precursor into a tube furnace protected by Ar, raising the temperature to 700 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 h. The porous carbon nanofiber/metal oxide catalyst composite air electrode is obtained.
The composite air electrode of the hierarchical porous carbon nanofiber/metal oxide catalyst is prepared from various components according to a specific proportion, and the porous carbon fiber structure can provide sufficient pore channels for the discharge product of the air battery to deposit, so that the discharge termination caused by the blockage of the pore channels of the air electrode is avoided. In addition, the self-supporting film of the porous electrode structure is beneficial to oxygen diffusion and electrolyte contact, and the cycling stability of the battery can be improved.
In addition, the invention utilizes the electrostatic spinning technology to form the self-supporting membrane of the integrated hierarchical porous electrode structure by adjusting the electrospinning parameters, the membrane can be used as an independent air electrode without a binder and a current collector, the oxygen diffusion and the electrolyte contact are facilitated, and the circulation stability of the system can be increased. The self-supporting structure can provide abundant catalytic sites, and the open pore structure facilitates the de-intercalation of reactants and products.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to the precise arrangements shown and described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.

Claims (10)

1. The composite air electrode is characterized by comprising 30-80 wt% of polyacrylonitrile, 10-30 wt% of pore-forming agent and 10-40 wt% of metal oxide.
2. The composite air electrode of claim 1, wherein the metal oxide comprises MnOx、Fe2O3、NiO、Co3O4、NiCo2O4And LaxSr1-xMnO3At least one of (1).
3. The composite air electrode is characterized by comprising 30-80 wt% of polyacrylonitrile, 10-30 wt% of pore-forming agent and 10-40 wt% of metal oxide precursor.
4. The composite air electrode of claim 1 or 3, wherein the pore former comprises at least one of polystyrene, polymethylmethacrylate, and polyvinylpyrrolidone.
5. Composite air as claimed in claim 3An electrode, characterized in that the metal oxide precursor comprises Mn (NO)3)2、Fe(C5H7O2)3、Ni(NO3)2、Co(NO3)2、La(NO3)3、Sr(NO3)2And Cr (NO)3)3At least one of (1).
6. A method of manufacturing a composite air electrode, comprising:
1) preparing polyacrylonitrile, pore formers and metal oxides according to the formulation of the composite air electrode as claimed in any one of claims 1, 2 and 4; or preparing polyacrylonitrile, a pore-forming agent and a metal oxide precursor according to the formula of the composite air electrode as described in any one of claims 3 to 5;
2) adding polyacrylonitrile into dimethylformamide solution with concentration of 5% -15%, and stirring at 60 deg.C until the mixture becomes transparent yellow viscous liquid;
3) adding a pore-forming agent and a metal oxide in sequence and stirring uniformly to obtain a mixed solution; or adding the pore-forming agent and the metal oxide precursor in sequence and stirring uniformly to obtain a mixed solution;
4) spraying the mixed solution by an injector by using an electrostatic spinning process to obtain a precursor of the porous carbon nanofiber/metal oxide catalyst;
5) and carrying out pre-oxidation and carbonization processes on the precursor of the porous carbon nanofiber/metal oxide catalyst to obtain the composite air electrode.
7. The method according to claim 6, wherein the flow rate of the spinning solution in the electrospinning process is 0.05 to 1mL/h, the distance between the injector and the collecting device is 10 to 50cm, the negative electrode voltage during spinning is-3 kV, and the positive electrode voltage during spinning is 5kV to 30 kV.
8. The method of manufacturing according to claim 6, wherein the pre-oxidizing and carbonizing a precursor of the porous filamentous nanocarbon/metal oxide catalyst comprises:
placing the precursor obtained by the electrostatic spinning process in a muffle furnace, raising the pre-oxidation temperature to 200-400 ℃ at the speed of 1-10 ℃/min, and keeping the temperature for 1-6 h;
and (3) placing the pre-oxidized precursor in a tubular furnace protected by Ar, raising the temperature to 600-1000 ℃ at the speed of 1-10 ℃/min, and keeping the temperature for 1-12h to obtain the composite air electrode.
9. A composite air electrode produced by the production method according to any one of claims 6 to 8.
10. An air battery comprising the composite air electrode of claim 9.
CN202111312490.5A 2021-11-08 2021-11-08 Air battery, composite air electrode and preparation method Pending CN114597423A (en)

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CN103219527A (en) * 2013-04-12 2013-07-24 中国科学院长春应用化学研究所 Air electrode for lithium-air battery and preparation method for air electrode
CN103337641A (en) * 2013-03-12 2013-10-02 上海中聚佳华电池科技有限公司 Oxygen electrode composite catalyst used for lithium-air batteries and preparation method of the oxygen electrode composite catalyst
CN104342852A (en) * 2014-10-27 2015-02-11 东华大学 Preparation methods of porous carbon nanofiber felt and porous carbon nanofiber electrode
CN110359098A (en) * 2019-06-19 2019-10-22 五邑大学 A kind of mesoporous carbon fiber electrode material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102637879A (en) * 2012-04-09 2012-08-15 中南大学 Micro-nano-structure anode material for Li-air battery and preparation method of micro-nano-structure anode material
CN103337641A (en) * 2013-03-12 2013-10-02 上海中聚佳华电池科技有限公司 Oxygen electrode composite catalyst used for lithium-air batteries and preparation method of the oxygen electrode composite catalyst
CN103219527A (en) * 2013-04-12 2013-07-24 中国科学院长春应用化学研究所 Air electrode for lithium-air battery and preparation method for air electrode
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