CN111653794A - Carbon-based oxygen reduction catalyst utilizing waste battery negative electrode graphite and preparation method thereof - Google Patents

Carbon-based oxygen reduction catalyst utilizing waste battery negative electrode graphite and preparation method thereof Download PDF

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CN111653794A
CN111653794A CN202010376900.1A CN202010376900A CN111653794A CN 111653794 A CN111653794 A CN 111653794A CN 202010376900 A CN202010376900 A CN 202010376900A CN 111653794 A CN111653794 A CN 111653794A
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graphite
carbon
oxygen reduction
reduction catalyst
based oxygen
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CN111653794B (en
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邹柯
阮丁山
李长东
王苑
王凤梅
吴�琳
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

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Abstract

The invention discloses a preparation method of a carbon-based oxygen reduction catalyst by using waste battery cathode graphite, which comprises the following steps: (1) recovering graphite slag from waste batteries, adding the graphite slag, transition metal salt and a nitrogen source into an acid solution, and stirring in an ice bath for reaction to obtain a complex solution; (2) heating the complex solution in a water bath, and drying to obtain a catalyst precursor; (3) and carrying out heat treatment on the catalyst precursor in an inert gas atmosphere to obtain the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite. The method adopts graphite slag generated in the recovery process of the waste lithium ion battery as a raw material, reduces the cost for preparing the catalyst, recycles resources, reduces environmental pollution, and has social benefit and economic benefit.

Description

Carbon-based oxygen reduction catalyst utilizing waste battery negative electrode graphite and preparation method thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a carbon-based oxygen reduction catalyst utilizing waste battery negative electrode graphite and a preparation method thereof.
Background
In recent years, with the vigorous national push on new energy automobiles and energy storage markets, power lithium ion batteries are rapidly developed. Meanwhile, the number of waste lithium ion batteries generated each year is rapidly increased, and the pollution problem and the resource recycling problem of the waste lithium ion batteries become problems to be solved urgently. The waste lithium ion batteries contain a plurality of heavy metal elements, organic electrolyte and graphite, and if the waste lithium ion batteries are randomly discarded, the environment is greatly harmed, and the resources are greatly wasted, so that the recycling of the waste lithium ion batteries is not only beneficial to the environmental protection, but also more beneficial to the recycling of the resources, and has great practical significance.
At present, the recovery of waste lithium ion batteries is mainly focused on the recovery of anode materials, but the structure of a graphite cathode is hardly changed in the charging and discharging processes of the batteries, so that the recovery significance is great. The proton exchange membrane fuel cell technology has the advantages of low emission, high conversion efficiency, high energy density and the like, and is an ideal power cell. Platinum-based catalysts are the best performing catalysts in fuel cell oxygen reduction reactions, but platinum is expensive and scarce in storage, and therefore low platinum or non-platinum catalysts need to be developed. The non-noble metal-doped carbon-based catalyst has good catalytic activity and low preparation cost, and is one of the current research hotspots.
Although the existing non-noble metal-doped carbon-based catalyst is also prepared by adopting a carbothermic reduction method and an impregnation method, the prepared active ingredients are Co and Mo, the cost is high, and the preparation method is complex.
Therefore, it is needed to provide a carbon-based oxygen reduction catalyst using graphite as a negative electrode of a waste battery, which has a simple preparation method, low cost and good economic benefits.
Disclosure of Invention
The invention aims to provide a carbon-based oxygen reduction catalyst utilizing waste battery negative electrode graphite and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a carbon-based oxygen reduction catalyst by using waste battery cathode graphite comprises the following steps:
(1) recovering graphite slag from waste batteries, adding the graphite slag, transition metal salt and a nitrogen source into an acid solution, and stirring in an ice bath for reaction to obtain a complex solution;
(2) heating the complex solution in a water bath, and drying to obtain a catalyst precursor;
(3) and carrying out heat treatment on the catalyst precursor in an inert gas atmosphere to obtain the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite.
Preferably, the graphite slag recovery process in the step (1) is as follows: and drying, crushing and sieving graphite slag left after the metal is recovered from the waste lithium ion battery to obtain the graphite slag.
More preferably, the screen mesh used for the screening is 100-400 mesh.
Preferably, the transition metal salt in step (1) is at least one of ferric chloride, ferric nitrate, ferric sulfate, ferric acetate, cobalt nitrate, cobalt chloride or cobalt acetate.
Preferably, the nitrogen source in step (1) is at least one of melamine, polyaniline, aniline or ammonium persulfate.
Preferably, the mass ratio of the graphite slag, the transition metal salt and the nitrogen source in the step (1) is (2-4): (1-3): (3-7).
Preferably, the acid solution in the step (1) is one of sulfuric acid, hydrochloric acid or nitric acid, and the concentration of the acid solution is 0.5-3 mol/L.
Preferably, the ice bath temperature in the step (1) is-10 ℃, the stirring speed is 200-600 r/min, and the stirring time is 4-24 h.
Preferably, the temperature of the water bath in the step (2) is 60-120 ℃, and the time is 2-4 h.
Preferably, the drying temperature in the step (2) is 60-120 ℃, and the drying is vacuum drying.
Preferably, the inert gas in the step (3) is N2Or Ar.
Preferably, the heat treatment temperature in the step (3) is 600-1100 ℃, the heating rate is 3-8 ℃/min, and the heat preservation time is 1-5 h.
The invention also provides a carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite, and the catalyst is prepared by the method.
Preferably, the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite comprises graphite with pores and loose structure, transition metal embedded in the graphite and a nitrogen source coated on the surface of the graphite; the transition metal is at least one of Fe, Co, Mn or Ni; wherein the surface area of the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite is 517.13-700m2·g-1The particle size is 4-22 μm.
The invention also provides a fuel cell, which comprises the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite.
Advantageous effects
(1) The method adopts graphite slag generated in the recovery process of the waste lithium ion battery as a raw material, reduces the cost for preparing the catalyst, recycles resources, reduces environmental pollution, and has social benefit and economic benefit.
(2) The invention has simple process flow, simple and convenient operation, low requirement on equipment and high product value, and can be widely used for preparing fuel cells.
(3) The carbon-based oxygen reduction catalyst prepared by using the waste battery cathode graphite has very high catalytic activity. The invention creatively adopts the waste graphite cathode as the raw material, and the waste graphite contains a small amount of battery plastics, diaphragms, organic impurities and metal impurities; in the process of preparing the carbon-based oxygen reduction catalyst by using the waste battery cathode graphite, plastic, diaphragm and organic impurities are removed, and the residual metal impurities are transition metals with catalytic activity, such as Fe, Co, Mn, Ni and the like, and have promotion effect on the catalytic performance of the catalyst; the initial potential of the carbon-based oxygen reduction catalyst prepared by using the waste battery cathode graphite is 0.83-0.95V (vs. RHE), the half-wave potential is 0.66-0.83V (vs. RHE), and the limiting current density can reach 4.04-6.48mA/cm2And the catalytic performance of the catalyst is equivalent to that of a Pt/C catalyst.
Drawings
FIG. 1 is an SEM image of a graphite carbon-based oxygen reduction catalyst prepared by using a negative electrode of a waste battery in example 1 of the present invention;
FIG. 2 is a polarization curve of the graphite carbon-based oxygen reduction catalyst prepared by the method of example 1 in a 0.1M KOH solution of saturated oxygen at different rotation speeds;
FIG. 3 is a cyclic voltammogram of a graphite carbon-based oxygen reduction catalyst using a negative electrode of a waste battery prepared in example 2 of the present invention in a 0.1M KOH solution of saturated nitrogen and saturated oxygen;
fig. 4 is an oxygen reduction polarization curve of the carbon-based oxygen reduction catalyst using graphite of the negative electrode of the waste battery and the commercialized Pt/C catalyst in a 0.1M KOH solution of saturated oxygen prepared in example 2 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
The preparation method of the carbon-based oxygen reduction catalyst using the waste battery cathode graphite comprises the following specific steps:
(1) drying and crushing graphite slag left after metal recovery of the waste lithium ion battery, and sieving the graphite slag through a 300-mesh sieve to separate diaphragm fragments in the graphite slag;
(2) 4g of sieved graphite slag and 3g of Fe2(SO4)36g of melamine is added into 100mL of 2mol/L HCl solution, and the mixture is stirred for 18 hours at the stirring speed of 300 r/min in an ice bath at the temperature of 5 ℃ to react to form a complex solution;
(3) heating the complex solution in a water bath at 90 ℃, evaporating the water in the solution to dryness, and drying the residual substance under the vacuum condition at 90 ℃ to obtain a catalyst precursor;
(4) adding a catalyst precursor to N2Heating and raising the temperature in an air atmosphere at the heating rate of 5 ℃/min, and carrying out heat treatment at 850 ℃ for 3h to obtain the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite.
Example 2
The preparation method of the carbon-based oxygen reduction catalyst using the waste battery cathode graphite in the embodiment comprises the following steps:
(1) drying and crushing graphite slag left after metal recovery of the waste lithium ion battery, and sieving the graphite slag with a 400-mesh sieve to obtain graphite slag for separating diaphragm fragments;
(2) 4g of sieved graphite slag and 5g of FeCl3·6H2O, 4mL of aniline and 10g of ammonium persulfate were added to 80mL of 1.5mol/L H2SO4In the solution, stirring for 12 hours at the stirring speed of 400 r/min in an ice bath at the temperature of-5 ℃ to react and form a complex solution;
(3) heating the complex solution in a water bath at 90 ℃, evaporating the water in the solution to dryness, and drying the residual substance under the vacuum condition at 90 ℃ to obtain a catalyst precursor;
(4) before the catalystIs in N2Heating and raising the temperature in an air atmosphere at the heating rate of 5 ℃/min, and carrying out heat treatment at 800 ℃ for 4h to obtain the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite.
Example 3
The preparation method of the carbon-based oxygen reduction catalyst using the waste battery cathode graphite in the embodiment comprises the following steps:
(1) drying and crushing graphite slag left after metal recovery of the waste lithium ion battery, and sieving the graphite slag through a 200-mesh sieve to obtain graphite slag for separating diaphragm fragments;
(2) 5g of sieved graphite slag and 6g of CoSO4·7H2O, 2g of melamine, 2mL of aniline and 5g of ammonium persulfate are added into 120mL of 3mol/L HCl solution, and the mixture is stirred for 8 hours in an ice bath at the temperature of 0 ℃ and the stirring speed is 350 revolutions per minute, so that the mixture is fully reacted to form complex solution;
(3) heating the fully reacted complex solution in a water bath at 85 ℃, evaporating the water in the solution to dryness, and drying the residual substance under the vacuum condition at 85 ℃ to obtain a catalyst precursor;
(4) and heating the catalyst precursor in an Ar atmosphere at the heating rate of 3 ℃/min, and carrying out heat treatment at 1000 ℃ for 2h to obtain the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite.
Example 4
The preparation method of the carbon-based oxygen reduction catalyst using the waste battery cathode graphite in the embodiment comprises the following steps:
(1) drying and crushing graphite slag left after metal recovery of the waste lithium ion battery, and sieving the graphite slag through a 100-mesh sieve to separate diaphragm fragments in the graphite slag;
(2) sieving 8g of graphite slag and 2g of Fe (NO)3)3·9H2O、4g Co(NO3)2·6H2O and 6g of melamine to 150mL of 1mol/LH2SO4Stirring the solution in an ice bath at the temperature of 5 ℃ for 12 hours at the stirring speed of 450 rpm to react to form a complex solution;
(3) heating the complex solution in a water bath at 75 ℃, evaporating water in the solution to dryness, and drying the residual substance under the vacuum condition at 75 ℃ to obtain a catalyst precursor;
(4) adding a catalyst precursor to N2Heating and raising the temperature in an air atmosphere at the heating rate of 5 ℃/min, and carrying out heat treatment at 800 ℃ for 4h to obtain the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite.
Example 5
The preparation method of the carbon-based oxygen reduction catalyst using the waste battery cathode graphite in the embodiment comprises the following steps:
(1) drying and crushing graphite slag left after metal recovery of the waste lithium ion battery, and sieving the graphite slag through a 100-mesh sieve to separate diaphragm fragments in the graphite slag;
(2) 4g of sieved graphite slag and 4g of FeCl3·6H2O、3g CoCl2Adding 2g of melamine, 3mL of aniline and 6g of ammonium persulfate into 150mL of 1.5mol/L HCl solution, stirring for 8 hours at the stirring speed of 350 revolutions/min in an ice bath at the temperature of-5 ℃, and reacting to form a complex solution;
(3) heating the complex solution in a water bath at 85 ℃, evaporating water in the solution to dryness, and drying the residual substance under the vacuum condition at 85 ℃ to obtain a catalyst precursor;
(4) and heating the catalyst precursor in an Ar atmosphere at the heating rate of 3 ℃/min, and carrying out heat treatment at 1000 ℃ for 2h to obtain the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite.
Example 6
The preparation method of the carbon-based oxygen reduction catalyst using the waste battery cathode graphite in the embodiment comprises the following steps:
(1) drying and crushing graphite slag left after metal recovery of the waste lithium ion battery, and sieving the graphite slag through a 100-mesh sieve to separate diaphragm fragments in the graphite slag;
(2) 5g of sieved graphite slag and 4g of Fe2(SO4)3、3g Co(NO3)2·6H2O, 4mL of aniline and 8g of ammonium persulfate were added to 130mL of 1.8M H2SO4In the solution, stirring for 24 hours at a stirring speed of 380 r/min in an ice bath at the temperature of-5 ℃ to react to form a complex solution;
(3) heating the complex solution in a water bath at 95 ℃, evaporating water in the solution to dryness, and drying the residual substance under the vacuum condition at 95 ℃ to obtain a catalyst precursor;
(4) adding a catalyst precursor to N2Heating and raising the temperature in an air atmosphere at the heating rate of 4 ℃/min, and carrying out heat treatment at 950 ℃ for 3h to obtain the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite.
Comparative example 1
The performance of the commercial Pt/C catalyst was tested in the same manner as in example 1.
And (3) performance testing:
the carbon-based oxygen reduction catalyst prepared in examples 1 to 6 and using the graphite of the negative electrode of the waste battery was subjected to performance testing as follows:
(1) adding 6mg of catalyst into 1m of ethanol and 5% of Nafion solution by mass, wherein the volume ratio of the ethanol to the Nafion is 9:1, ultrasonically dispersing for 2 hours, taking 20uL of the catalyst solution on a disk electrode of a rotating disk with the diameter of 5mm by using a liquid transfer gun, and naturally airing in the air.
(2) Electrochemical tests were performed on a P3000A-DX electrochemical workstation using the above electrode as the working electrode, a platinum wire as the counter electrode, and an Ag/AgCl electrode as the reference electrode.
(3) The catalyst was tested in a 0.1M KOH solution at a sweep rate of 5mVs-1 for cyclic voltammograms under saturated oxygen and polarization curves at different rotational speeds.
Fig. 1 is an SEM image of the carbon-based oxygen reduction catalyst using the negative electrode graphite of the waste battery prepared in example 1 of the present invention, and fig. 2 is a polarization curve of the carbon-based oxygen reduction catalyst using the negative electrode graphite of the waste battery prepared in example 1 at different rotation speeds in a 0.1m koh solution of saturated oxygen. Fig. 3 is a cyclic voltammetry curve of the carbon-based oxygen reduction catalyst using the waste battery negative electrode graphite in a 0.1M KOH solution of saturated nitrogen and saturated oxygen in example 2, and fig. 4 is an oxygen reduction polarization curve of the carbon-based oxygen reduction catalyst using the waste battery negative electrode graphite and a commercial Pt/C catalyst in a 0.1M KOH solution of saturated oxygen in example 2. As can be seen from FIG. 1, the prepared catalyst has a loose structure, the surface of the catalyst is uniformly wrapped by polyaniline, and the catalyst has certain pores. According to the polarization curves of the catalyst in different rotating speeds in the figure 2, the catalyst is calculated by a Koutech-Levich equation to react by a four-electron transfer mechanism. From fig. 3, it can be seen that the prepared catalyst has no obvious oxygen reduction peak in the saturated nitrogen atmosphere and has an obvious oxygen reduction peak in the saturated oxygen atmosphere, which indicates that the prepared carbon-based oxygen reduction catalyst using the waste battery negative electrode graphite has good catalytic performance. As can be seen from the comparison of the oxygen reduction polarization curves of the carbon-based catalyst prepared in fig. 4 and the commercial Pt/C catalyst, the limiting current density of the carbon-based oxygen reduction catalyst prepared in example 2 using the negative electrode graphite of the waste battery is equivalent to that of the commercial Pt/C catalyst, and the initial potential and the half-wave potential are slightly superior to those of the commercial Pt/C catalyst.
While the present invention has been described in detail with reference to specific embodiments and examples thereof, the description of the embodiments is merely illustrative of the principles and implementations of the present invention, including the best mode, and is provided to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. A preparation method of a carbon-based oxygen reduction catalyst by using waste battery cathode graphite is characterized by comprising the following steps:
(1) recovering graphite slag from waste batteries, adding the graphite slag, transition metal salt and a nitrogen source into an acid solution, and stirring in an ice bath for reaction to obtain a complex solution;
(2) heating the complex solution in a water bath, and drying to obtain a catalyst precursor;
(3) and carrying out heat treatment on the catalyst precursor in an inert gas atmosphere to obtain the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite.
2. The method according to claim 1, wherein the transition metal salt in the step (1) is at least one of ferric chloride, ferric nitrate, ferric sulfate, ferric acetate, cobalt nitrate, cobalt chloride or cobalt acetate.
3. The preparation method according to claim 1, wherein the nitrogen source in step (1) is at least one of melamine, polyaniline, aniline, or ammonium persulfate.
4. The method according to claim 1, wherein the acid solution in step (1) is one of sulfuric acid, hydrochloric acid or nitric acid, and the concentration of the acid solution is 0.5 to 3 mol/L.
5. The method of claim 1, wherein the temperature of the ice bath in step (1) is-10 ℃ to 10 ℃; the stirring speed is 200-600 r/min, and the stirring time is 4-24 h.
6. The preparation method of claim 1, wherein the temperature of the water bath heating in the step (2) is 60-120 ℃ and the time is 2-24 h.
7. The method according to claim 1, wherein the inert gas in the step (3) is N2Or Ar; the temperature of the heat treatment in the step (3) is 600-110 DEG CThe temperature rise rate is 3-8 ℃/min at 0 ℃, and the heat preservation time is 1-5 h.
8. A carbon-based oxygen reduction catalyst using waste battery negative electrode graphite, which is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The carbon-based oxygen reduction catalyst using the waste battery negative electrode graphite as claimed in claim 8, wherein the carbon-based oxygen reduction catalyst using the waste battery negative electrode graphite comprises graphite with pores and a loose structure, transition metal embedded in the graphite and a nitrogen source coated on the surface of the graphite; the transition metal is at least one of Fe, Co, Mn or Ni; wherein the surface area of the carbon-based oxygen reduction catalyst utilizing the waste battery cathode graphite is 517.13-700m2·g-1The particle size is 4-22 μm.
10. A fuel cell comprising the carbon-based oxygen reduction catalyst using graphite of negative electrode of spent battery according to any one of claims 8 to 9.
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CN112652779A (en) * 2020-12-11 2021-04-13 广东邦普循环科技有限公司 High-activity oxygen reduction catalyst and preparation method and application thereof
WO2022121494A1 (en) * 2020-12-11 2022-06-16 广东邦普循环科技有限公司 High-activity oxygen reduction catalyst, preparation method therefor, and application thereof
CN115425318A (en) * 2022-08-29 2022-12-02 哈尔滨工业大学 Method for preparing efficient electrolytic water electrode based on waste ternary lithium ion battery electrode mixed powder

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