CN111900423A - Flexible air electrode, flexible metal-air battery and wearable electronic equipment - Google Patents

Flexible air electrode, flexible metal-air battery and wearable electronic equipment Download PDF

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CN111900423A
CN111900423A CN202010606553.7A CN202010606553A CN111900423A CN 111900423 A CN111900423 A CN 111900423A CN 202010606553 A CN202010606553 A CN 202010606553A CN 111900423 A CN111900423 A CN 111900423A
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air electrode
carbon
flexible
flexible air
carbon nanotube
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黄建林
刘亭
牟机熔
陈珩
张文嘉
李梅
徐玉婷
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South China University of Technology SCUT
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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
    • H01M4/96—Carbon-based 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
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8615—Bifunctional electrodes for rechargeable cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/30—Fuel cells in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a flexible air electrode, a flexible metal-air battery and wearable electronic equipment. The flexible air electrode comprises a carbon nano tube macroscopic film and doped carbon nano tubes growing on the carbon nano tube macroscopic film; the carbon nanotube macroscopic film is formed by winding and stacking carbon nanotubes; the doped carbon nanotube is doped with metal simple substance particles and nitrogen elements. The flexible air electrode has the advantages of high flexibility, high conductivity, light weight, high mechanical property, multiple stacked holes and the like, has good catalytic property, is not damaged after being bent for multiple times at 180 degrees, has stable electrochemical property and large operation space, and can improve the electrochemical property and energy density of the flexible metal-air battery.

Description

Flexible air electrode, flexible metal-air battery and wearable electronic equipment
Technical Field
The invention relates to a flexible air electrode, a flexible metal-air battery and wearable electronic equipment, and belongs to the technical field of electrochemical energy storage devices.
Background
Wearable electronic devices are portable electronic devices that can be worn directly on the body or integrated into a user's clothing or accessories, and have achieved unprecedented growth in recent years. However, the electrochemical energy storage device meeting the miniaturization and flexibility requirements of the wearable electronic device at present generally has the problem of low energy density, so that the endurance time of the wearable electronic device is short, and the use experience of people is seriously influenced. The metal-air battery system has the characteristics of high energy density, high safety, low cost, environmental friendliness and the like, and is considered to be one of key options for developing next-generation electrochemical energy storage devices, and the rechargeable zinc-air battery is the most likely metal-air battery system to realize commercialization at present. Therefore, the development of the flexible rechargeable zinc-air battery is an effective way to solve the endurance problem of the wearable electronic equipment.
The main technical problem of the rechargeable zinc-air battery lies in the development of a bifunctional non-noble metal catalyst with high catalytic activity and high stability, while the flexible rechargeable zinc-air battery has the technical problems, and the problem of how to prepare the bifunctional catalyst with high catalytic activity into an air electrode with high flexibility and high stability needs to be solved. At present, the conductive carbon cloth is the only flexible air electrode substrate material which can be practically applied in a large scale, but the conductive carbon cloth has the problems of complex preparation process, high cost, large thickness, insufficient mechanical property and the like. The thickness (0.2-1.0 mm) of the conductive carbon cloth is large, and under the condition of limited catalyst loading capacity, the energy density of the rechargeable zinc-air battery is low. The conductive carbon cloth has poor bending performance and low strength, and the service life of the conductive carbon cloth in a flexible operation state is influenced. Therefore, the conductive carbon cloth has a plurality of problems in the practical application process, and further development and application of the conductive carbon cloth are limited.
The preparation method of the flexible air electrode mainly comprises a dropping coating method, a coating method, an in-situ growth method and the like. The coating method requires the use of a high molecular binder, which not only reduces the conductivity of the electrode and the energy density of the battery, but also causes a large amount of active sites to be masked. The in-situ growth method can effectively expose a large number of active sites, is the current mainstream method, but when the catalyst grows on the conductive carbon cloth in situ, the load capacity of the catalyst is often lower than the mass of the conductive carbon cloth, which is not beneficial to improving the energy density of the battery, and moreover, the combination of the catalyst and the conductive carbon cloth is often not firm enough, and the catalyst is easy to fall off in the oxygen precipitation reaction process, so that the battery fails.
Therefore, the development of a flexible air electrode with light weight, high flexibility, high conductivity, high mechanical property and low cost is urgent.
Disclosure of Invention
The invention aims to provide a flexible air electrode, a flexible metal-air battery and a wearable electronic device.
The technical scheme adopted by the invention is as follows:
a flexible air electrode comprises a carbon nanotube macroscopic film and doped carbon nanotubes growing on the carbon nanotube macroscopic film; the carbon nanotube macroscopic film is formed by winding and stacking carbon nanotubes; the doped carbon nanotube is doped with metal simple substance particles and nitrogen elements.
Preferably, the thickness of the carbon nanotube macroscopic film is 1-100 μm.
Preferably, the electrical conductivity of the carbon nanotubes in the carbon nanotube macroscopic film is 100-200S/cm, and the tensile strength is 200-350 MPa.
Preferably, the diameter of the carbon nanotube in the carbon nanotube macroscopic film is 20-40 nm.
Preferably, the diameter of the doped carbon nanotube is 50-500 nm, and the length of the doped carbon nanotube is 1-20 μm.
Preferably, the particle size of the metal simple substance particles is 50-200 nm.
The preparation method of the flexible air electrode comprises the following steps:
1) soaking the carbon nano tube macroscopic film in a metal salt solution to obtain a metal salt/carbon nano tube macroscopic film;
2) and putting the carbon-nitrogen source and the metal salt/carbon nano tube macroscopic membrane into a tubular furnace, filling protective gas, and calcining to obtain the flexible air electrode.
Preferably, the metal salt in step 1) is at least one of ferric nitrate, ferric sulfate, ferric chloride, ferric acetate, cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt acetate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetate.
Preferably, the solvent in the metal salt solution in step 1) is at least one of water, methanol, ethanol, propanol, formic acid and acetic acid.
Preferably, the carbon-nitrogen source in step 2) is at least one of melamine, carbon nitride and urea.
Preferably, the protective gas in step 2) is one of nitrogen and argon.
Preferably, the carbon-nitrogen source and the metal salt/carbon nanotube macro-film in step 2) are sequentially placed in a tube furnace along the airflow direction of the shielding gas.
Preferably, the calcination in step 2) is specifically performed by: heating to 600-1200 ℃ at a heating rate of 1-10 ℃/min, and then preserving heat for 1-20 h.
Preferably, the product is further acid washed, water washed and dried after calcination in step 2).
Preferably, the specific operation of pickling is as follows: adding the product into sulfuric acid with the concentration of 0.5-2 mol/L, heating to 50-100 ℃, and soaking for 10-30 h.
A flexible metal-air battery comprises the flexible air electrode.
A wearable electronic device comprises the flexible metal-air battery.
The invention has the beneficial effects that: the flexible air electrode has the advantages of high flexibility, high conductivity, light weight, high mechanical property, multiple stacked holes and the like, has good catalytic property, is not damaged after being bent for multiple times at 180 degrees, has stable electrochemical property and large operation space, and can improve the electrochemical property and energy density of the flexible metal-air battery.
Specifically, the method comprises the following steps:
1) according to the invention, metal salt is loaded on the surface and in the holes of the carbon nanotube macroscopic film as seed crystal, and then the metal-nitrogen doped carbon nanotube with high catalytic activity is induced to grow in situ on the carbon nanotube macroscopic film by calcination, so that the agglomeration of the catalyst can be avoided, the dead zone of the catalyst activity is reduced, and the catalytic activity of the catalyst is effectively released;
2) the flexible air electrode has excellent flexibility, and can still keep the electrode not to be damaged and stable electrochemical performance even if the flexible air electrode is bent for multiple times at 180 degrees;
3) the preparation method of the flexible air electrode has the characteristics of low cost, simplicity in operation, environmental friendliness and the like, is easy for large-scale batch preparation, and can promote practical large-scale application of flexible metal-air batteries and wearable electronic equipment.
Drawings
Fig. 1 is a schematic structural view of a flexible air electrode of embodiment 1.
Fig. 2 is an SEM image of the flexible air electrode of example 1.
Fig. 3 is a linear sweep voltammogram for oxygen reduction and oxygen evolution for the flexible air electrode of example 1.
Fig. 4 shows the results of the cycle stability test of the flexible zinc-air battery assembled by the flexible air electrode of example 1 under different bending conditions.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a flexible air electrode is prepared by the following steps:
1) putting the carbon nano tube macroscopic membrane with the size specification of 4cm multiplied by 4cm into 20mL of 1mmol/L cobalt nitrate ethanol solution, soaking for 30min, taking out and drying to obtain the cobalt nitrate/carbon nano tube macroscopic membrane;
2) putting 5g of melamine and cobalt nitrate/carbon nanotube macroscopic films into a tube furnace, introducing nitrogen, sequentially placing the melamine and cobalt nitrate/carbon nanotube macroscopic films along the airflow direction of the nitrogen, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, naturally cooling to room temperature, putting the obtained product into sulfuric acid with the concentration of 0.5mol/L, heating to 80 ℃, soaking for 24h, washing with water, and drying to obtain the flexible air electrode (the structural schematic diagram is shown in figure 1, and the SEM diagram is shown in figure 2).
Example 2:
a flexible air electrode is prepared by the following steps:
1) putting the carbon nano tube macroscopic membrane with the size specification of 4cm multiplied by 4cm into 20mL ferric nitrate ethanol solution with the concentration of 1mmol/L, soaking for 30min, taking out and drying to obtain the ferric nitrate/carbon nano tube macroscopic membrane;
2) putting 5g of melamine and ferric nitrate/carbon nanotube macroscopic films into a tube furnace, filling nitrogen, sequentially placing the melamine and ferric nitrate/carbon nanotube macroscopic films along the airflow direction of the nitrogen, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, naturally cooling to room temperature, putting the obtained product into sulfuric acid with the concentration of 0.5mol/L, heating to 80 ℃, soaking for 24h, washing with water, and drying to obtain the flexible air electrode.
Example 3:
a flexible air electrode is prepared by the following steps:
1) putting the carbon nano tube macroscopic membrane with the size specification of 4cm multiplied by 4cm into 20mL of nickel nitrate ethanol solution with the concentration of 1mmol/L, soaking for 30min, taking out and drying to obtain the nickel nitrate/carbon nano tube macroscopic membrane;
2) putting 5g of melamine and nickel nitrate/carbon nanotube macroscopic films into a tube furnace, introducing nitrogen, sequentially placing the melamine and nickel nitrate/carbon nanotube macroscopic films along the airflow direction of the nitrogen, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, naturally cooling to room temperature, putting the obtained product into sulfuric acid with the concentration of 0.5mol/L, heating to 80 ℃, soaking for 24h, washing with water, and drying to obtain the flexible air electrode.
Example 4:
a flexible air electrode is prepared by the following steps:
1) putting the carbon nano tube macroscopic membrane with the size specification of 4cm multiplied by 4cm into 20mL of cobalt sulfate aqueous solution with the concentration of 1mmol/L, soaking for 30min, taking out and drying to obtain the cobalt sulfate/carbon nano tube macroscopic membrane;
2) putting 2g of urea and a cobalt sulfate/carbon nano tube macroscopic film into a tube furnace, introducing nitrogen, sequentially placing the urea and the cobalt sulfate/carbon nano tube macroscopic film along the airflow direction of the nitrogen, heating to 700 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h, naturally cooling to room temperature, putting the obtained product into sulfuric acid with the concentration of 0.5mol/L, heating to 80 ℃, soaking for 24h, washing with water, and drying to obtain the flexible air electrode.
Example 5:
a flexible air electrode is prepared by the following steps:
1) putting the carbon nano tube macroscopic membrane with the size specification of 4cm multiplied by 4cm into 20mL of 1mmol/L ferric sulfate aqueous solution, soaking for 30min, taking out and drying to obtain the ferric sulfate/carbon nano tube macroscopic membrane;
2) putting 2g of urea and ferric sulfate/carbon nano tube macroscopic membrane into a tube furnace, filling nitrogen, sequentially placing the urea and the ferric sulfate/carbon nano tube macroscopic membrane along the airflow direction of the nitrogen, heating to 700 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h, naturally cooling to room temperature, putting the obtained product into sulfuric acid with the concentration of 0.5mol/L, heating to 80 ℃, soaking for 24h, washing with water, and drying to obtain the flexible air electrode.
Example 6:
a flexible air electrode is prepared by the following steps:
1) putting the carbon nano tube macroscopic membrane with the size specification of 4cm multiplied by 4cm into 20mL of nickel sulfate aqueous solution with the concentration of 1mmol/L, soaking for 30min, taking out and drying to obtain the nickel sulfate/carbon nano tube macroscopic membrane;
2) putting 2g of urea and a nickel sulfate/carbon nano tube macroscopic film into a tube furnace, introducing nitrogen, sequentially placing the urea and the nickel sulfate/carbon nano tube macroscopic film along the airflow direction of the nitrogen, heating to 700 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h, naturally cooling to room temperature, putting the obtained product into sulfuric acid with the concentration of 0.5mol/L, heating to 80 ℃, soaking for 24h, washing with water, and drying to obtain the flexible air electrode.
Example 7:
a flexible air electrode is prepared by the following steps:
1) putting the carbon nano tube macroscopic membrane with the size specification of 4cm multiplied by 4cm into 20mL of 1mmol/L cobalt acetate methanol solution, soaking for 30min, taking out and drying to obtain the cobalt acetate/carbon nano tube macroscopic membrane;
2) putting 10g of carbon nitride and cobalt acetate/carbon nanotube macroscopic film into a tube furnace, introducing argon, sequentially placing the carbon nitride and cobalt acetate/carbon nanotube macroscopic film along the airflow direction of the argon, heating to 900 ℃ at the heating rate of 10 ℃/min, preserving heat for 5h, naturally cooling to room temperature, putting the obtained product into sulfuric acid with the concentration of 0.5mol/L, heating to 80 ℃, soaking for 24h, washing with water, and drying to obtain the flexible air electrode.
Example 8:
a flexible air electrode is prepared by the following steps:
1) putting the carbon nano tube macroscopic membrane with the size specification of 4cm multiplied by 4cm into 20mL of ferric acetate methanol solution with the concentration of 1mmol/L, soaking for 30min, taking out and drying to obtain the ferric acetate/carbon nano tube macroscopic membrane;
2) putting 10g of carbon nitride and iron acetate/carbon nanotube macroscopic films into a tube furnace, introducing argon, sequentially placing the carbon nitride and the iron acetate/carbon nanotube macroscopic films along the airflow direction of the argon, heating to 900 ℃ at the heating rate of 10 ℃/min, preserving heat for 5h, naturally cooling to room temperature, putting the obtained product into sulfuric acid with the concentration of 0.5mol/L, heating to 80 ℃, soaking for 24h, washing with water, and drying to obtain the flexible air electrode.
Example 9:
a flexible air electrode is prepared by the following steps:
1) putting the carbon nano tube macroscopic membrane with the size specification of 4cm multiplied by 4cm into 20mL of nickel acetate methanol solution with the concentration of 1mmol/L, soaking for 30min, taking out and drying to obtain the nickel acetate/carbon nano tube macroscopic membrane;
2) putting 10g of carbon nitride and nickel acetate/carbon nanotube macroscopic films into a tube furnace, introducing argon, sequentially placing the carbon nitride and the nickel acetate/carbon nanotube macroscopic films along the airflow direction of the argon, heating to 900 ℃ at the heating rate of 10 ℃/min, preserving heat for 5h, naturally cooling to room temperature, putting the obtained product into sulfuric acid with the concentration of 0.5mol/L, heating to 80 ℃, soaking for 24h, washing with water, and drying to obtain the flexible air electrode.
Comparative example 1:
a flexible air electrode is prepared by the following steps:
placing 5g of melamine and a carbon nano tube macroscopic film with the size specification of 4cm multiplied by 4cm into a tube furnace, introducing argon gas, sequentially placing the melamine and the carbon nano tube macroscopic film along the airflow direction of the argon gas, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 2h, naturally cooling to room temperature, placing the obtained product into sulfuric acid with the concentration of 0.5mol/L, heating to 80 ℃, soaking for 24h, washing with water, and drying to obtain the flexible air electrode.
Comparative example 2:
a flexible air electrode is prepared by the following steps:
1) dispersing 5mg of platinum carbon (Pt/C) in 1mL of isopropanol solution (the volume ratio of isopropanol to water is 7:3, and 30 mu L of naphthol solution with the mass fraction of 5%) and carrying out ultrasonic treatment for 5 hours to obtain catalyst ink;
2) and dripping 10 mu L of catalyst ink on a carbon nanotube macroscopic film with the diameter of 5mm, and naturally drying to obtain the flexible air electrode.
Comparative example 3:
a flexible air electrode is prepared by the following steps:
1) 5mg of ruthenium dioxide (RuO) was taken2) Dispersing the powder in 1mL of isopropanol solution (the volume ratio of isopropanol to water is 7:3, and the naphthol solution with the mass fraction of 5 percent is 30 mu L) and carrying out ultrasonic treatment for 5 hours to obtain catalyst ink;
2) and dripping 10 mu L of catalyst ink on a carbon nanotube macroscopic film with the diameter of 5mm, and naturally drying to obtain the flexible air electrode.
Note: the carbon nanotube macroscopic films of examples 1 to 9 and comparative examples 1 to 3 had a thickness of 20 μm, wherein the carbon nanotubes had a diameter of 20 to 40nm, an electrical conductivity of 150S/cm and a tensile strength of 270MPa, and the methods for producing the carbon nanotube macroscopic films were referred to CN 102070134A, CN 103922299A and CN 107265439A.
And (3) performance testing:
1) SEM images of the flexible air electrode of example 1 are shown in fig. 2(a is a top view, b and c are cross-sectional views).
As can be seen from fig. 2: the doped carbon nanotube with the end part coated with the metal simple substance nano particle grows along two surfaces of the carbon nanotube macroscopic film; the carbon nanotube macroscopic film substrate reduces the aggregation of the doped carbon nanotubes in the growth process, and realizes the uniform growth of the doped carbon nanotubes; the diameter of the doped carbon nanotube is 100-150 nm, the length is 1-5 μm, and the diameter of the metal nanoparticle is 80-120 nm.
2) The flexible air electrodes of example 1 and comparative examples 1-3 were cut into electrode sheets (Co/N @ CNTs @ CNMF-800, N @ CNMF-800, Pt/C @ CNMF and RuO in this order) with a diameter of 5mm2@ CNMF), 10. mu.L of naphthol solution was dropped and stuck on a glassy carbon electrode having a diameter of 5mm, and at a rotation speed of 1600 rpm, the linear sweep voltammogram of oxygen reduction was measured using a potassium hydroxide solution having a concentration of 0.1mol/L as an electrolyte, and the linear sweep voltammogram of oxygen evolution was measured using a potassium hydroxide solution having a concentration of 1mol/L as an electrolyte, and the measurement results are shown in FIG. 3.
As can be seen from fig. 3: the oxygen reduction half-slope potential of the flexible air electrode of example 1 was up to 0.86V (relative to the reversible hydrogen electrode), which was higher than the platinum-carbon electrode (0.82V); at a current density of 10mA/cm2The oxygen evolution overpotential of the flexible air electrode of example 1 was 310mV, which is higher than the overpotential of the ruthenium dioxide electrode (350 mV).
3) The flexible air electrode of example 1 was bent at 180 ° for 2000 times, the appearance of the flexible air electrode maintained its original appearance, and further assembled into a flexible zinc-air battery, and the stability of voltage was tested at different bending degrees, and the test results are shown in fig. 4.
As can be seen from fig. 4: the flexible zinc-air battery assembled by the flexible air electrode in the embodiment 1 is bent at 90 degrees and 180 degrees, and the electrochemical performance is not obviously reduced.
Note:
the flexible air electrodes of examples 2 to 9 were all tested according to the above method, and the test results show that the structures and performances of the flexible air electrodes of examples 2 to 9 are close to those of the flexible air electrode of example 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A flexible air electrode characterized by: the composition of the carbon nanotube film comprises a carbon nanotube macroscopic film and doped carbon nanotubes growing on the carbon nanotube macroscopic film; the carbon nanotube macroscopic film is formed by winding and stacking carbon nanotubes; the doped carbon nanotube is doped with metal simple substance particles and nitrogen elements.
2. The flexible air electrode of claim 1, wherein: the diameter of the carbon nano tube in the carbon nano tube macroscopic film is 20-40 nm.
3. The flexible air electrode according to claim 1 or 2, characterized in that: the diameter of the doped carbon nanotube is 50-500 nm, and the length of the doped carbon nanotube is 1-20 μm.
4. The flexible air electrode according to claim 1 or 2, characterized in that: the particle size of the metal simple substance particles is 50-200 nm.
5. A method of manufacturing a flexible air electrode according to any of claims 1 to 4, characterized in that: the method comprises the following steps:
1) soaking the carbon nano tube macroscopic film in a metal salt solution to obtain a metal salt/carbon nano tube macroscopic film;
2) and putting the carbon-nitrogen source and the metal salt/carbon nano tube macroscopic membrane into a tubular furnace, filling protective gas, and calcining to obtain the flexible air electrode.
6. The method of claim 5, wherein: the metal salt in the step 1) is at least one of ferric nitrate, ferric sulfate, ferric chloride, ferric acetate, cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt acetate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetate.
7. The production method according to claim 5 or 6, characterized in that: and 2) the carbon-nitrogen source is at least one of melamine, carbon nitride and urea.
8. The production method according to claim 5 or 6, characterized in that: the calcination in the step 2) is specifically carried out as follows: heating to 600-1200 ℃ at a heating rate of 1-10 ℃/min, and then preserving heat for 1-20 h.
9. A flexible metal-air battery, characterized by: comprising a flexible air electrode according to any one of claims 1 to 4.
10. A wearable electronic device, characterized in that: comprising the flexible metal-air battery of claim 9.
CN202010606553.7A 2020-06-29 2020-06-29 Flexible air electrode, flexible metal-air battery and wearable electronic equipment Pending CN111900423A (en)

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DONGXIAO JI等: "Hierarchical catalytic electrodes of cobalt-embedded carbon nanotube/carbon flakes arrays for flexible solid-state zinc-air batteries", 《CARBON》 *
QIAN LU等: "Direct growth of ordered N-doped carbon nanotube arrays on carbon fiber cloth as a free-standing and binder-free air electrode for flexible quasi‐solid‐state rechargeable Zn-Air batteries", 《CARBON ENERGY》 *
TING LIU等: "Engineering the Surface/Interface of Horizontally Oriented Carbon Nanotube Macrofilm for Foldable Lithium-Ion Battery Withstanding Variable Weather", 《ADVANCED ENERGY MATERIALS》 *
WENHAN NIU等: "Apically Dominant Mechanism for Improving Catalytic Activities of N-Doped Carbon Nanotube Arrays in Rechargeable Zinc-Air Battery", 《ADVANCED ENERGY MATERIALS》 *
ZHENGKUN YANG等: "Trifunctional Self-Supporting Cobalt-Embedded Carbon Nanotube Films for ORR, OER, and HER Triggered by Solid Diffusion from Bulk Metal", 《ADVANCED MATERIALS》 *

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