CN111682224B - Monoatomic cobalt-loaded nitrogen-doped graphite-like carbon cathode catalyst for metal-air battery - Google Patents

Monoatomic cobalt-loaded nitrogen-doped graphite-like carbon cathode catalyst for metal-air battery Download PDF

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CN111682224B
CN111682224B CN202010564117.8A CN202010564117A CN111682224B CN 111682224 B CN111682224 B CN 111682224B CN 202010564117 A CN202010564117 A CN 202010564117A CN 111682224 B CN111682224 B CN 111682224B
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catalyst
zinc
cobalt
solution
cathode catalyst
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CN111682224A (en
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班锦锦
胡俊华
刘新红
曹国钦
张志刚
王瑞智
肖建军
李荣荣
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Zhengzhou University
Zhengzhou Foguang Power Generation Equipment 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
    • H01M4/90—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
    • 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
    • H01M4/88—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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a monatomic cobalt-loaded nitrogen-doped graphitic carbon cathode catalyst for a rechargeable zinc-air battery, which is prepared by carbonizing dicyandiamide and a bimetallic Zn-Co-ZIF precursor material at the temperature of 800-. Under the condition of dicyandiamide existing, the button-shaped Zn-Co-ZIF precursor is gradually decomposed to form the monatomic cobalt-loaded graphite-like carbon material. The catalyst material has excellent ORR/OER dual-functional catalytic activity in 0.1M KOH solution, and can be used as a cathode catalyst to be applied to a chargeable and dischargeable zinc-air battery. Under the voltage of 0.5V, the current density of the catalyst material can reach 290 mA cm‑2Higher than commercial Pt/C + RuO2248 mA cm of catalyst‑2。

Description

Monoatomic cobalt-loaded nitrogen-doped graphite-like carbon cathode catalyst for metal-air battery
Technical Field
The invention belongs to the technical field of battery materials, and particularly discloses a monatomic cobalt-loaded nitrogen-doped graphite carbon cathode catalyst, a preparation method and application thereof in the field of batteries, and the catalyst is mainly used for rechargeable zinc-air batteries.
Background
Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) are the basic redox reaction steps that make up rechargeable Zinc Air Batteries (ZABs). In order to improve the overall performance of the zinc-air battery and expand the actual application range of the zinc-air battery, the exploration of the bifunctional catalyst becomes a research hotspot of researchers. Compared with expensive noble metal catalyst (Pt/C, RuO)2) Hetero atom of transition metalSub-doped carbon is one of the most effective electrocatalytic alternatives due to its unique electronic and structural properties. In order to improve the catalytic performance of the catalyst material, the single-atom catalysts (SACs) loaded on the carbon substrate provide a new selectivity for the catalytic process, improve the utilization rate of atoms and increase the catalytic activity.
In order to improve the selectivity of the catalyst material and overcome the limitations of activity and stability, advanced carbon materials with an ordered graphitized structure, including Carbon Nanotubes (CNTs), carbon nanoparticles, onion-like carbon, graphene, etc., have been widely studied as carriers of electrocatalytic materials, mainly because of their unique surface structure, high electrical conductivity, corrosion resistance and large specific surface area, which can expose more catalytic active centers. According to the specific composition characteristics and porosity of the metal organic framework Material (MOF), a proper precursor is selected and the accurate pyrolysis condition is controlled, so that the MOF can be converted into a required single-atom loaded porous carbon material, and the porous carbon material can be applied to a bifunctional catalyst to create more conditions for the application of a zinc-air battery.
Disclosure of Invention
In view of the above, the present invention aims to provide a nitrogen-doped graphitic carbon cathode catalyst supported on monoatomic cobalt for a rechargeable zinc-air battery and a preparation method thereof, wherein the catalyst material has excellent ORR and OER dual-functional catalytic performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a monatomic cobalt-loaded nitrogen-doped graphite-like carbon cathode catalyst for a rechargeable zinc-air battery comprises the following steps:
a) mixing dicyandiamide and a precursor material Zn-Co-ZIF, and uniformly grinding;
b) heating the mixture obtained in the step a) to 800-900 ℃ and preserving the heat for 1.5-2 h to obtain the catalyst.
Specifically, in the step a), the mass ratio of Zn-Co-ZIF serving as a precursor material to dicyandiamide is 1: 9-10.
Preferably, the precursor material Zn-Co-ZIF is prepared by a room-temperature solution method, the selected metal salts are cobalt nitrate hexahydrate and zinc nitrate hexahydrate, the ligand is benzimidazole, and the reaction solvent is methanol; the preparation method specifically comprises the following steps:
1) dissolving cobalt nitrate hexahydrate and zinc nitrate hexahydrate in methanol to obtain a solution A for later use; the molar ratio of the cobalt nitrate hexahydrate to the zinc nitrate hexahydrate is 1: 1-1.5;
2) dissolving benzimidazole in methanol to obtain a solution B;
3) and mixing and stirring the solution A and the solution B for reaction for 2-3 hours, standing for 24-26 hours, and then washing and drying to obtain the catalyst.
In the process of preparing the precursor material Zn-Co-ZIF, the addition amount of the benzimidazole is 4-5 times of the sum of the molar weight of the cobalt nitrate hexahydrate and the molar weight of the zinc nitrate hexahydrate.
More preferably, in step c), the temperature is raised to 800 ℃ at a temperature rise rate of 5 ℃/min and kept for 2 h.
The invention provides a monatomic cobalt-loaded nitrogen-doped graphite carbon cathode catalyst for a rechargeable zinc-air battery, which is prepared by the preparation method and is a catalyst material loaded by metal cobalt monatomic; has excellent oxygen reduction (ORR) and Oxygen Evolution (OER) dual-functional catalytic activity. The bifunctional catalyst is synthesized based on a Zn-Co-ZIF precursor at high temperature. The graphite-like carbon substrate in the invention is composed of a graphene-like carbon layer and bamboo-like carbon nanotubes.
The application of the monatomic cobalt-loaded nitrogen-doped graphite carbon cathode catalyst as an ORR or OER electrocatalytic working electrode has the following test requirements: the glassy carbon electrode loaded with the catalyst is a working electrode, the silver/silver chloride electrode is a counter electrode, the platinum wire is an auxiliary electrode, and the test solution is 0.1M KOH.
The application of the monatomic cobalt-loaded nitrogen-doped graphite-like carbon cathode catalyst as a cathode catalyst of a zinc-air battery is characterized in that the test method comprises the following steps: polishing zinc plate as anode, carbon paper with catalyst attached to air electrode as cathode, and electrolyte of 6M KOH + 0.2M Zn (OAc)2The mixed solution of (1).
In the invention, the Zn-Co-ZIF precursor material is in a button shape, the shape of the prepared catalyst material is converted into a composite material of a low-dimensional graphite-like laminated structure and a bamboo-like carbon nanotube structure, and the metal cobalt is loaded on a carbon substrate in a single atom form. The catalyst material provided by the invention is prepared by one-step carbonization of a Zn-Co-ZIF precursor in the presence of dicyandiamide; the oxygen reduction and oxygen precipitation catalytic performances of the catalyst in 0.1M KOH are tested, and the application of the catalyst in a zinc-air battery is further researched, and the result shows that the catalyst can effectively improve the power density of the zinc-air battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a Zn-Co-ZIF precursor-based cobalt monoatomic load nitrogen-doped graphite carbon bifunctional catalyst and application thereof in a zinc-air battery. The bifunctional catalyst material is prepared by one-step carbonization of a precursor material Zn-Co-ZIF in the presence of dicyandiamide, and does not contain any other additives and a subsequent acid washing process. The graphite-like carbon substrate consists of a graphene-like carbon layer and bamboo-like carbon nanotubes, in the high-temperature pyrolysis process, the existence of dicyandiamide promotes a Zn-Co-ZIF precursor material to be converted into a graphite-like carbon structure from a blocky structure, cobalt and zinc ions in the precursor are reduced into metal simple substances, zinc volatilizes at 800 ℃, and cobalt is loaded on the carbon substrate in a single-atom form. The bifunctional catalyst material provided by the invention shows good activity in a zinc-air battery, and keeps excellent cycle stability.
Drawings
FIG. 1 SEM image of precursor material Zn-Co-ZIF;
FIG. 2 TEM image of the catalyst obtained in example 1;
FIG. 3 is a HAADF-STEM image of the wall of the carbon nanotube in FIG. 2;
FIG. 4 is a linear voltammogram of the oxygen reduction performance of the catalyst prepared in example 1;
FIG. 5 comparison graph of cycle performance of the catalyst prepared in example 1 and commercial Pt/C;
FIG. 6 is a linear voltammogram of the oxygen evolution performance of the catalyst prepared in example 1;
FIG. 7 example 1 catalyst prepared and commercial Pt/C + IrO2The charge-discharge curve and the power density of (d);
FIG. 8 is a TEM image of a catalyst obtained by comparative example 1;
FIG. 9 TEM image of the catalyst prepared in comparative example 2.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the following examples, the precursor material Zn-Co-ZIF used was obtained by reacting a metal salt with benzimidazole in a molar ratio of 1:5 in a methanol solution, wherein the metal salt was cobalt nitrate hexahydrate and zinc nitrate hexahydrate, the molar ratio was 1: 1; the preparation method comprises the following specific steps:
1) weighing 0.1455g of cobalt nitrate hexahydrate and 0.1487g of zinc nitrate hexahydrate, placing the weighed materials in a 50mL beaker, adding 20mL of anhydrous methanol for ultrasonic dissolution to obtain a solution A, and placing the solution A on a magnetic stirrer for stirring for later use;
2) weighing 0.5907g of benzimidazole, placing the benzimidazole in a 50mL beaker, adding 20mL of anhydrous methanol, and performing ultrasonic dissolution to obtain a solution B;
3) slowly dropping the clear solution B into the solution A, stirring and reacting for 2 hours at room temperature, and standing for 24 hours; finally, centrifugally washing the mixture for 3 times by using absolute ethyl alcohol, and carrying out vacuum drying at the temperature of 60 ℃ to obtain a purple pink precursor material;
the SEM image of the prepared precursor material Zn-Co-ZIF is shown in figure 1, and the precursor material has a stable 3D structure, a button-shaped appearance, a smooth surface and no other impurities. The material is uniform in size, about 2.5-3 mu m in diameter and about 600nm thick.
Example 1
A preparation method of a monatomic cobalt-loaded nitrogen-doped graphite-like carbon cathode catalyst for a rechargeable zinc-air battery comprises the following steps:
a) weighing 0.2 g of precursor material Zn-Co-ZIF and 2 g of dicyandiamide, and putting into a mortar for mixing and grinding for 15 min; standby;
b) placing the mixture obtained in the step a) into a tube furnace, heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and keeping the temperature at 800 ℃ for 2 h. And cooling to room temperature, and taking out to be tested.
The prepared single-atom cobalt-loaded nitrogen-doped graphite-like carbon cathode catalyst for the rechargeable zinc-air battery keeps the basic morphology of a precursor material, and mainly comprises a graphene-like carbon layer and bamboo-like carbon nanotubes. As shown in FIG. 2, the diameter of the carbon nanotube is about 30nm, and the length of each segment of bamboo joint is about 25 nm. The HAADF-STEM image of the carbon nanotubes shown in FIG. 3 shows that the Co atoms (shown as white circles) are uniformly distributed on the carbon bamboo joints.
And (3) testing the catalytic performance:
the oxygen reduction and oxygen evolution performance tests were conducted using a three-electrode system, the working electrode was a glassy carbon electrode supporting the catalyst prepared in example 1, the counter electrode was a silver/silver chloride electrode, and the auxiliary electrode was a platinum wire. The test solution was a 0.1M potassium hydroxide solution. The mixed slurry is composed of 5mg of catalyst material, 490 μ L of deionized water, 490 μ L of ethanol, and 20 μ L of Nafion. According to the invention, 5 muL of mixed slurry is dripped on a glassy carbon electrode and dried for standby. Stability testing of catalytic performance was compared to commercial Pt/C.
And (3) testing the zinc-air battery:
the zinc-air test apparatus uses a polished zinc plate as an anode and carbon paper with catalyst (2 mg of catalyst is loaded at 1 x 1cm by a conventional method in the art)2Carbon paper) attached to the air electrode as cathode, and the electrolyte is 6M KOH + 0.2M Zn (OAc)2The mixed solution of (1). Mixing commercial Pt/C and RuO in a mass ratio of 1:12The mixtures of (a) were used as control samples and tested under the same conditions.
The catalyst provided by the invention has good oxygen reduction and oxygen precipitation catalytic performances, and FIG. 4 shows that the oxygen reduction linear voltammetry LSV scanning result tested at different rotating speeds increases the ultimate current density obtained by the test along with the increase of the rotating speed, mainly because the migration rate of oxygen at high rotating speed is increased. The initial potential is 0.99V, the half-wave potential is 0.89V, and the limiting current density is 6.00 mA/cm at 1600 rotation speeds2. It can be calculated from this that the material follows four in the oxygen reduction processAnd (4) an electron transfer process.
FIG. 5 shows a graph of the cycle performance of the catalyst of example 1 versus commercial Pt/C. As shown in fig. 5, the catalyst retention of the present invention was 86.2% over 2000 hours of cycling, while the standard control commercial Pt/C retained 57.9%, indicating that the catalyst material of the present invention had excellent cycling stability during oxygen reduction catalysis. FIG. 6 is a LSV curve of linear voltammetry scan of the catalyst material of the invention with oxygen evolution at 1600 rpm, with an initial potential of 1.5V and 10 mA/cm2The potential at current density was 1.76. The results prove that the catalyst material has good oxygen reduction and oxygen precipitation dual-function catalytic activity.
The catalyst material can be used as a cathode catalyst to be applied to a chargeable and dischargeable zinc-air battery. FIG. 7 shows the catalyst material of the present invention and commercial Pt/C + RuO2The charge and discharge curves and the power density comparison graph. As can be seen from fig. 7: under the voltage of 0.5, the current density of the catalyst material can reach 290 mA/cm2Higher than commercial Pt/C + RuO2Current density of the catalyst 248 mA/cm2. The ultimate power density of the catalyst material of the invention is about 150 mW/cm2121 mW/cm higher than that of commercial catalyst2。
Comparative example 1
A preparation method of the catalyst specifically comprises the following steps:
a) weighing 0.2 g of precursor material Zn-Co-ZIF and 3 g of dicyandiamide, and putting into a mortar for mixing and grinding for 15 min; standby;
b) placing the mixture obtained in the step a) into a tube furnace, heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and keeping the temperature at 800 ℃ for 2 h. And cooling to room temperature, and taking out to be tested.
Comparative example 1 Zn-Co-ZIF and dicyandiamide were used as reactants, and the mass ratio of addition was changed to 1: 15, under the same carbonization conditions as in example 1. Comparative example 1 increased the amount of dicyandiamide in the mixture compared to example 1. FIG. 8 shows a TEM image of the catalyst prepared in comparative example 1. As shown in fig. 8, the catalyst of comparative example 1 consists essentially of a layered material, and no significant amount of carbon nanotubes is present relative to example 1, indicating that the dicyandiamide content plays a critical role in catalytically producing carbon nanotube material.
Comparative example 2
A preparation method of the catalyst specifically comprises the following steps:
a) weighing 0.2 g of precursor material Co-ZIF and 2 g of dicyandiamide, and putting into a mortar for mixing and grinding for 15 min; standby; the precursor material Co-ZIF is obtained by reacting metal salt cobalt nitrate hexahydrate and benzimidazole in a methanol solution according to the molar ratio of 1:5, and the specific preparation process refers to Zn-Co-ZIF, except that zinc nitrate hexahydrate is not added;
b) placing the mixture obtained in the step a) into a tube furnace, heating the mixture from room temperature to 800 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and keeping the temperature at 800 ℃ for 2 h. And cooling to room temperature, and taking out to be tested.
Comparative example 2 Co-ZIF is used as a reaction precursor material, zinc in the precursor is removed, and the mass addition ratio of Co-ZIF to dicyandiamide is 1:5, under the same carbonization conditions as in example 1. Compared with the embodiment 1, the comparative example 2 changes the type of the precursor from Zn-Co-ZIF to Co-ZIF. The Co-ZIF precursor is formed by coordination of metal Co and benzimidazole and does not contain metal zinc. FIG. 9 shows a TEM image of the catalyst prepared in comparative example 2. As shown in fig. 9, comparative example 2 was made of irregular carbon nanotubes and a few layered materials, with some Co particles present. The comparison reveals that the presence of a single atom is related to the choice of precursor. The material formed by the participation of Co-ZIF has Co particles, and shows that the existence of Zn in the precursor is the key for forming the monatomic supported catalyst.

Claims (5)

1. A preparation method of a monatomic cobalt-loaded nitrogen-doped graphite-like carbon cathode catalyst for a rechargeable zinc-air battery is characterized by comprising the following steps:
a) mixing dicyandiamide and a precursor material Zn-Co-ZIF, and uniformly grinding;
b) heating the mixture obtained in the step a) to 800-900 ℃ and preserving the heat for 1.5-2 h to obtain the catalyst;
the precursor material Zn-Co-ZIF is prepared by the following steps:
1) dissolving cobalt nitrate hexahydrate and zinc nitrate hexahydrate in methanol to obtain a solution A for later use; the molar ratio of the cobalt nitrate hexahydrate to the zinc nitrate hexahydrate is 1: 1-1.5;
2) dissolving benzimidazole in methanol to obtain a solution B;
3) mixing and stirring the solution A and the solution B for reaction for 2-3 hours, standing for 24-26 hours, and then washing and drying to obtain the catalyst;
in the step a), the mass ratio of Zn-Co-ZIF and dicyandiamide added in the precursor material is 1: 9-10;
the addition amount of benzimidazole is 4-5 times of the sum of the molar weight of cobalt nitrate hexahydrate and zinc nitrate hexahydrate.
2. The method for preparing the monatomic cobalt-supported nitrogen-doped graphitic carbon-based cathode catalyst for a rechargeable zinc-air battery according to claim 1, wherein the temperature increase rate in the step b) is 5 ℃/min.
3. The monoatomic cobalt-supported nitrogen-doped graphitic carbon cathode catalyst for a rechargeable zinc-air battery, which is prepared by the preparation method of any one of claims 1 to 2.
4. The application of the monatomic cobalt-loaded nitrogen-doped graphitic carbon cathode catalyst as a bifunctional catalytic material for oxygen reduction reaction and oxygen evolution reaction according to claim 3, wherein the test requirements are as follows: the glassy carbon electrode loading the catalyst is a working electrode, the silver/silver chloride electrode is a counter electrode, the platinum wire is an auxiliary electrode, and the test solution is 0.1M KOH.
5. The application of the monatomic cobalt-loaded nitrogen-doped graphitic carbon cathode catalyst as defined in claim 3 as a cathode catalyst for a zinc-air cell, wherein the test method comprises: using polished zinc plate as anode, carbon paper with catalyst attached to air electrode as cathode, and electrolyte solution of 6M KOH and 0.2M Zn (OAc)2In the mixing ofAnd (3) solution.
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CN114308094B (en) * 2020-10-10 2023-09-29 中国石油大学(北京) Cobalt monoatomic/nitrogen doped mesoporous carbon fiber material, and preparation method and application thereof
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Patentee after: Zhengzhou University

Patentee after: Zhengzhou Foguang power generation equipment Co., Ltd

Address before: 450001 No. 100 science Avenue, hi tech Zone, Henan, Zhengzhou

Patentee before: Zhengzhou University

Patentee before: Zhengzhou Foguang power generation equipment Co., Ltd