CN111403758B - Nitrogen-doped carbon catalyst and preparation method and application thereof - Google Patents

Nitrogen-doped carbon catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN111403758B
CN111403758B CN202010197080.XA CN202010197080A CN111403758B CN 111403758 B CN111403758 B CN 111403758B CN 202010197080 A CN202010197080 A CN 202010197080A CN 111403758 B CN111403758 B CN 111403758B
Authority
CN
China
Prior art keywords
benzoxazine
reaction
tpb
nitrogen
triaryl imidazole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010197080.XA
Other languages
Chinese (zh)
Other versions
CN111403758A (en
Inventor
黎华明
李叙锋
陈红飙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiangtan University
Original Assignee
Xiangtan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiangtan University filed Critical Xiangtan University
Priority to CN202010197080.XA priority Critical patent/CN111403758B/en
Publication of CN111403758A publication Critical patent/CN111403758A/en
Application granted granted Critical
Publication of CN111403758B publication Critical patent/CN111403758B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0677—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Catalysts (AREA)
  • Hybrid Cells (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention discloses a nitrogen-doped carbon catalyst, which is prepared by the following preparation method: firstly, triaryl imidazole benzoxazine monomer (TBZ) is adopted to carry out thermal polymerization reaction to obtain triaryl imidazole benzoxazine-containing polymer (TPB). Then carrying out Friedel-Crafts reaction on the triaryl imidazole benzoxazine-containing polymer (TPB) in the presence of a catalyst and a crosslinking agent to synthesize a triaryl imidazole benzoxazine-containing crosslinked polymer (Cross-linked TPB). And finally, carrying out heat treatment and acid treatment on the triaryl imidazole-containing benzoxazine Cross-linked polymer (Cross-linked TPB) to obtain the nitrogen-doped carbon catalyst (NDC). The nitrogen-doped carbon-based (NDC) catalyst has a higher comparative area and a rich pore structure, and shows excellent oxygen reduction (ORR) catalytic performance in the application of a zinc-air battery.

Description

Nitrogen-doped carbon catalyst and preparation method and application thereof
Technical Field
The invention relates to an electrocatalyst, in particular to a nitrogen-doped carbon catalyst, and a preparation method and application thereof, and belongs to the field of zinc-air battery oxygen reduction catalysts.
Background
Metal-air batteries have attracted a great deal of research attention due to their widespread use in hearing aids, flashlights, clocks and toys and some other portable devices. Currently, cadmium, zinc, lithium, aluminum, magnesium, and the like are mainly used as metal anode materials for metal-air batteries, and among them, zinc, which is abundant, low-cost, and environmentally friendly, is most favored by researchers. The theoretical energy density of the zinc-air battery can reach 1350Wh kg -16 times of that of the lithium-air battery, and has longer quality guarantee period compared with the traditional zinc-air battery. However, the slow oxygen reduction (ORR) kinetics of zinc-air battery cathode materials compared to anodization limits their development. Therefore, the development of a high-efficiency and stable zinc-air battery cathode catalyst is significant for reducing the zinc-air cost and accelerating the commercialization process of the zinc-air battery cathode catalyst.
The nitrogen-doped carbon electrocatalyst has the advantages of high ORR activity, high stability, low price, easy obtaining and the like, and is widely applied to the preparation of air electrodes of zinc-air batteries. The introduction of nitrogen atoms can polarize adjacent carbon atoms, so that charge redistribution is caused, the effect not only promotes the chemical adsorption of oxygen, but also weakens O-O bonds, and improves the ORR activity. Of course, the content and type of doped nitrogen also have a great influence on the ORR activity of the material. Currently, most studies demonstrate that pyridine-N and graphite-N are major components of the center of ORR activity in the molecular structure of nitrogen-doped carbon.
Currently, there are two main routes for preparing nitrogen-doped carbon electrocatalysts: post doping and in-situ doping. Post-doping is to pretreat the carbon-based precursor and then introduce nitrogen atoms by pyrolysis together with the nitrogen-rich precursor, and because of incompatibility of the two precursors, the post-doping method is difficult to realize homogeneous doping of nitrogen atoms. In contrast, in-situ doping is a precursor of directly pyrolyzing nitrogen-rich carbon elements, and since nitrogen atoms in the precursor are connected in a covalent bond form, homogeneous doping of the nitrogen atoms can be realized.
Based on the method, the triarylimidazole benzoxazine crosslinked polymer Cross-linked TPB is used as a precursor, and the nitrogen-doped carbon electrocatalyst is prepared by an in-situ doping method, has a higher comparative area and a rich pore structure, and shows excellent catalytic performance in the application of a zinc-air battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a nitrogen-doped carbon catalyst and a preparation method and application thereof; the nitrogen-doped carbon catalyst is prepared by thermally polymerizing triaryl imidazole-containing benzoxazine monomer (TBZ) to obtain triaryl imidazole-containing benzoxazine polymer (TPB); then synthesizing a triaryl imidazole benzoxazine-containing Cross-linked polymer (Cross-linked TPB) through Friedel-Crafts; and finally, carrying out high-temperature heat treatment and acid treatment under the protection of atmosphere to obtain the nitrogen-doped carbon-based catalyst (NDC). The nitrogen-doped carbon-based (NDC) catalyst has a higher comparative area and a rich pore structure, and shows excellent oxygen reduction (ORR) catalytic performance in the application of a zinc-air battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
according to a first embodiment of the present invention, there is provided a nitrogen doped carbon catalyst having the following general structural formula I:
Figure GDA0002894977790000021
wherein: r1Is CCl3、COOH。R2Is CCl2、CO。
In the present invention, the crosslinking agent CCl proceeds with the Friedel-crafts reaction4formed-CCl2-and-CCl3The TPB is gradually linked, and furthermore, during the post-treatment, part-CCl2-or-CCl3Hydrolyzing to-CO-or-COOH.
Furthermore, the catalyst of the invention is connected with two R on the benzene ring1Or R2Radicals or between two benzene rings by an R2The groups are connected because two sites or one site exists in the number of the Friedel-crafts reaction sites on the benzene ring. When only one point position appears on the benzene ring, the benzene ring is connected with one R1A group or an R2Radical (if is R)2When radical, R2The other end of the group may be attached to another benzene ring). And when two points are present on the benzene ring, the benzene ring may be linked to two groups (which may all be R)1Or all are R2Or simultaneously R1And R2. If is R2When radical, R2The other end of the radical may be linked to another benzene ring)
Further, R2The radicals being grafted on both sides, and R1The grafting of the groups on only one side is due to the crosslinking agent CCl during the course of the Friedel-crafts reaction4Formation of-CCl under the action of catalyst3. Further, -CCl3Can form-CCl under the action of catalyst2-. However, not all-CCl3Can form-CCl under the action of catalyst2-。
Preferably, the catalyst is prepared by the following preparation method: firstly, triaryl imidazole benzoxazine monomer (TBZ) is adopted to carry out thermal polymerization reaction to obtain triaryl imidazole benzoxazine-containing polymer (TPB). Then carrying out Friedel-Crafts reaction on the triaryl imidazole benzoxazine-containing polymer (TPB) in the presence of a catalyst and a crosslinking agent to synthesize a triaryl imidazole benzoxazine-containing crosslinked polymer (Cross-linked TPB). And finally, carrying out heat treatment and acid treatment on the triaryl imidazole-containing benzoxazine Cross-linked polymer (Cross-linked TPB) to obtain the nitrogen-doped carbon catalyst (NDC).
Preferably, the triarylimidazole benzoxazine monomer (TBZ) has the following structure II:
Figure GDA0002894977790000031
preferably, the triarylimidazole-containing benzoxazine polymer (TPB) has the following structure III:
Figure GDA0002894977790000032
preferably, the catalyst is AlCl3Or FeCl3。
Preferably, the cross-linking agent is CCl4Or CHCl3。
Preferably, the acid treatment is performed using hydrochloric acid or sulfuric acid.
According to a second embodiment of the present invention, there is provided a method of preparing the nitrogen-doped carbon catalyst of the first embodiment, the method comprising the steps of:
1) and (3) placing a triaryl imidazole benzoxazine monomer (TBZ) in a reactor for thermal polymerization reaction to obtain a triaryl imidazole benzoxazine-containing polymer (TPB).
2) Carrying out Friedel-Crafts reaction on the triaryl imidazole-containing benzoxazine polymer (TPB) obtained in the step 1) in the presence of a catalyst and a crosslinking agent to synthesize a triaryl imidazole-containing benzoxazine crosslinked polymer (Cross-linked TPB).
3) And (2) carrying out heat treatment and acid treatment on the triaryl imidazole-containing benzoxazine-containing Cross-linked polymer (Cross-linked TPB) obtained in the step 2) to obtain the nitrogen-doped carbon catalyst (NDC).
Preferably, step 1) is specifically: the triaryl imidazole benzoxazine monomer (TBZ) is put into a reactor (such as a muffle furnace), and then the reactor is heated for reaction (the reaction temperature is 150-300 ℃, preferably 180-250 ℃, and the reaction time is 0.5-4h, preferably 1-3 h). After the reaction is finished, washing (preferably washing 1-5 times by using methanol) is carried out to obtain the triaryl imidazole benzoxazine-containing polymer (TPB).
Preferably, step 2) is specifically: putting the triaryl imidazole-containing benzoxazine polymer (TPB) obtained in the step 1), a catalyst and a crosslinking agent into a reactor according to a certain proportion. After the dispersion is fully and uniformly dispersed, the temperature of the reactor is firstly raised to 30-70 ℃ (preferably 35-60 ℃, more preferably 40-50 ℃) for reaction for 1-12h (preferably 2-10h, more preferably 3-8 h). Then carrying out reflux reaction for 5-48h (preferably 8-36h, more preferably 12-24h) at 50-100 ℃ (preferably 60-95 ℃, more preferably 70-90 ℃); after the reaction is completed, the product is washed (e.g., 1 to 8 times, preferably 3 to 5 times, with water and \ or dimethylformamide), dried (preferably in vacuum at a drying temperature of 30 to 70 ℃, preferably 40 to 60 ℃) to obtain a triarylimidazole-containing benzoxazine-containing crosslinked polymer (Cross-linked TPB).
Preferably, step 3) is specifically: putting the triaryl-imidazole-containing benzoxazine-crosslinked polymer (Cross-linked TPB) obtained in the step 2) into a heat treatment device (such as a vacuum tube furnace). Then the heat treatment device is heated to the temperature of 300-1500 ℃ (preferably 500-1200 ℃, more preferably 800-1000 ℃) in the protective gas protective atmosphere (for example, in the protective atmosphere of nitrogen, argon or helium), and the carbon material is obtained after heat treatment for 0.5-8h (preferably 0.8-5h, more preferably 1-3 h). The resulting carbon material is then subjected to acid treatment (e.g., washing with hydrochloric acid or sulfuric acid at a concentration of 0.05 to 2mol/L, preferably at a concentration of 0.1 to 1.5mol/L, more preferably at a concentration of 0.2 to 1.2mol/L, 1 to 5 times, preferably 2 to 3 times). Finally, heat treatment is carried out under the same conditions to obtain the nitrogen-doped carbon catalyst (NDC).
Preferably, the triarylimidazole benzoxazine monomer (TBZ) is synthesized by the following method: firstly, dissolving 4- (4, 5-diphenyl-1H-imidazole-2-yl) -aniline and salicylaldehyde in a solvent (preferably ethanol) to react (preferably refluxing reaction is carried out under nitrogen atmosphere; the reaction temperature is 50-100 ℃, preferably 60-80 ℃, the reaction time is 12-48H, preferably 18-36H), pouring the system into petroleum ether, filtering (suction filtering), and washing to obtain a bright yellow product A. And then dissolving the product A in a solvent (preferably tetrahydrofuran), adding a reducing agent (preferably sodium borohydride as the reducing agent) to react (preferably stirring at room temperature for 5-24h, preferably 8-18h), after the reaction is finished, slowly adding a proper amount of water, continuously stirring for 5-24h (preferably 8-18h), then pouring the system into a large amount of cold water, filtering (suction filtration), and recrystallizing (firstly drying the filtered product at the normal temperature in vacuum and then recrystallizing 1-3 times with dioxane) to obtain a white product B. And finally, dissolving the product B and paraformaldehyde (the paraformaldehyde reacts with the product B to dehydrate and close a ring to form an oxazine ring) in a solvent (preferably dimethylformamide) to react (preferably, carrying out reflux reaction under the nitrogen atmosphere, wherein the reaction temperature is 60-150 ℃, preferably, 80-120 ℃, the reaction time is 18-72 hours, preferably, 24-60 hours), cooling a reaction system to room temperature, then dropping the reaction system into a large amount of cold water, filtering (suction filtration), washing to obtain a crude product, dissolving the crude product by using trichloromethane, washing for 1-5 times by using a 20% NaOH solution, washing by using distilled water to be neutral, and finally spin-drying the trichloromethane to obtain a light yellow triarylimidazole benzoxazine monomer (TBZ). The synthesis process comprises the following steps:
Figure GDA0002894977790000051
preferably, in the step 2), the triaryl imidazole-containing benzoxazine polymer (TPB), the catalyst and the crosslinking agent are added in the following molar ratio: 0.3-1.8:2-12: 200-.
According to a third embodiment of the present invention, there is provided a use of the nitrogen-doped carbon catalyst of the first embodiment or the nitrogen-doped carbon catalyst produced by the method of the second embodiment: the nitrogen-doped carbon catalyst is applied as an oxygen reduction catalyst of a zinc-air battery.
In the invention, triaryl imidazole benzoxazine monomer (TBZ) is adopted for thermal polymerization reaction to obtain triaryl imidazole benzoxazine-containing polymer (TPB). Then carrying out Friedel-Crafts reaction on a triaryl imidazole-containing benzoxazine-containing polymer (TPB) in the presence of a catalyst and a crosslinking agent to synthesize a triaryl imidazole-containing benzoxazine-containing crosslinked polymer (Cross-linked TPB), wherein the triaryl imidazole-containing benzoxazine-containing crosslinked polymer (Cross-linked TPB) is of a crosslinked structure, and a nitrogen-doped carbon (NDC) catalyst obtained after pyrolysis has a porous structure, is large in specific surface area, developed in pores and uniform in active site distribution. Meanwhile, the nitrogen species of the catalyst only consist of pyridine-N and graphite-N. Based on the advantages, the electrocatalyst can provide higher power density and specific capacity when used as a cathode of a zinc-air battery.
In the invention, triaryl imidazole benzoxazine monomer (TBZ) is subjected to thermal polymerization reaction to obtain triaryl imidazole benzoxazine-containing polymer (TPB). The reaction formula is as follows:
Figure GDA0002894977790000061
in the present invention, the pyrolysis of the monomer TBZ results in the cleavage of the C-O bond between N, O to form an O-free bond, followed by the formation of an ortho-substituted H to form a hydroxyl group (the phenolic hydroxyl group on the phenyl ring is stable against oxidation).
In the invention, the introduction of the triaryl imidazole group not only increases the nitrogen content of the polymer, but also increases more reaction sites for subsequent Friedel-Crafts, and improves the crosslinking degree of Cross-linked TPB.
In the invention, the triaryl imidazole benzoxazine-containing polymer (TPB) is subjected to Friedel-Crafts reaction in the presence of a catalyst and a crosslinking agent to synthesize the triaryl imidazole benzoxazine-containing crosslinked polymer (Cross-linked TPB). The reaction formula is as follows:
Figure GDA0002894977790000062
wherein the AlCl3Is a catalyst. The CCl4As the crosslinking agent, CCl is mentioned4Also acting as a solvent in this Friedel-Crafts reaction.
In the invention, the triaryl imidazole-containing benzoxazine Cross-linked polymer (Cross-linked TPB) is subjected to heat treatment, acid treatment and heat treatment again in sequence to obtain the nitrogen-doped carbon catalyst (NDC). The first heat treatment builds the porous carbon material network and exposes metal oxide impurities that are encapsulated within the crosslinked precursor. And then removing the metal oxide in the carbon material after acid washing. The purpose of the second heat treatment is to increase the degree of graphitization of the carbon material and to increase the specific surface area of the carbon material.
Generally, the electrolyte used for the zinc-air cell test is 6M KOH, and the air electrode is composed of a catalytic layer, a hydrophobic layer, and a gas collecting layer. Mixing the catalyst (NDC-900) prepared by the invention with a certain amount of 5% Nafion solution, adding ethanol for ultrasonic dispersion (for example, ultrasonic dispersion for 0.5-3h), then uniformly spraying the mixture on hydrophobic carbon paper supported by foamed nickel, and drying to obtain the air electrode, wherein the modification amount of the catalyst (NDC-900) is 0.3-5mg/cm-2(preferably 1-3 mg/cm)-2). And finally, assembling by using a polished zinc plate as an anode and nitrogen-doped carbon (NDC) as a cathode to obtain the zinc-air battery.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention adopts triaryl imidazole benzoxazine monomer (TBZ) to carry out thermal polymerization reaction to obtain triaryl imidazole benzoxazine-containing polymer (TPB), and then the triaryl imidazole benzoxazine-containing Cross-linked polymer (Cross-linked TPB) prepared by Friedel-Crafts reaction has a Cross-linked structure, and the nitrogen-doped carbon (NDC) catalyst obtained after pyrolysis has a porous structure, larger specific surface area, more developed pores and uniform distribution of active sites.
2. The nitrogen in the nitrogen-doped carbon (NDC) catalyst prepared by the invention only consists of pyridine-N and graphite-N, so that the electrocatalyst can provide higher power density and specific capacity when used as a zinc-air battery cathode.
Drawings
FIG. 1 is a synthetic scheme of a Cross-linked TPB polymer prepared in example 1 of the present invention.
FIG. 2 is a TEM image of the nitrogen-doped carbon catalyst (NDC-900) prepared in example 1 of the present invention.
FIG. 3 is a graph showing nitrogen adsorption and desorption of a nitrogen-doped carbon catalyst (NDC-900) prepared in example 1 of the present invention.
FIG. 4 is a graph showing the pore size distribution of the nitrogen-doped carbon catalyst (NDC-900) prepared in example 1 of the present invention.
FIG. 5 is a photograph of an assembled zinc-air battery using NDC-900 prepared in example 1 of the present invention.
Fig. 6 is an open circuit voltage test of a zinc-air cell assembled using NDC-900 prepared in example 1 of the present invention.
FIG. 7 is a discharge polarization curve and power density curve for a zinc-air cell assembled using NDC-900 prepared in example 1 of the present invention.
FIG. 8 is a graph showing the specific capacity measurements of zinc-air cells assembled using NDC-900 prepared in example 1 of the present invention at different current densities.
FIG. 9 is a graph showing the rate capability of a zinc-air battery assembled by NDC-900 prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
A nitrogen-doped carbon catalyst, which is prepared by the following preparation method: firstly, triaryl imidazole benzoxazine monomer (TBZ) is adopted to carry out thermal polymerization reaction to obtain triaryl imidazole benzoxazine-containing polymer (TPB). Then carrying out Friedel-Crafts reaction on the triaryl imidazole benzoxazine-containing polymer (TPB) in the presence of a catalyst and a crosslinking agent to synthesize a triaryl imidazole benzoxazine-containing crosslinked polymer (Cross-linked TPB). And finally, carrying out heat treatment and acid treatment on the triaryl imidazole-containing benzoxazine Cross-linked polymer (Cross-linked TPB) to obtain the nitrogen-doped carbon catalyst (NDC).
Preferably, theThe catalyst is AlCl3Or FeCl3。
Preferably, the cross-linking agent is CCl4Or CHCl3。
Preferably, the heat treatment is to perform heat treatment on the triaryl imidazole-containing benzoxazine-containing Cross-linked polymer (Cross-linked TPB) in an atmosphere with protective gas protection.
Preferably, the acid treatment is performed using hydrochloric acid or sulfuric acid.
A method for preparing a nitrogen-doped carbon catalyst, comprising the steps of:
1) and (3) placing a triaryl imidazole benzoxazine monomer (TBZ) in a reactor for thermal polymerization reaction to obtain a triaryl imidazole benzoxazine-containing polymer (TPB).
2) Carrying out Friedel-Crafts reaction on the triaryl imidazole-containing benzoxazine polymer (TPB) obtained in the step 1) in the presence of a catalyst and a crosslinking agent to synthesize a triaryl imidazole-containing benzoxazine crosslinked polymer (Cross-linked TPB).
3) And (2) carrying out heat treatment and acid treatment on the triaryl imidazole-containing benzoxazine-containing Cross-linked polymer (Cross-linked TPB) obtained in the step 2) to obtain the nitrogen-doped carbon catalyst (NDC).
Preferably, step 1) is specifically: putting a triarylimidazole benzoxazine monomer (TBZ) into a reactor (such as a muffle furnace), and then heating the reactor to perform reaction (the reaction temperature is 150-300 ℃, preferably 180-250 ℃, and the reaction time is 0.5-4h, preferably 1-3 h); after the reaction is finished, washing (preferably washing 1-5 times by using methanol) is carried out to obtain the triaryl imidazole benzoxazine-containing polymer (TPB).
Preferably, step 2) is specifically: putting the triaryl imidazole-containing benzoxazine polymer (TPB) obtained in the step 1), a catalyst and a crosslinking agent into a reactor according to a certain proportion. After the dispersion is fully and uniformly dispersed, the temperature of the reactor is firstly raised to 30-70 ℃ (preferably 35-60 ℃, more preferably 40-50 ℃) for reaction for 1-12h (preferably 2-10h, more preferably 3-8 h). Then carrying out reflux reaction for 5-48h (preferably 8-36h, more preferably 12-24h) at 50-100 ℃ (preferably 60-95 ℃, more preferably 70-90 ℃); after the reaction is completed, the product is washed (e.g., 1 to 8 times, preferably 3 to 5 times, with water and \ or dimethylformamide), dried (preferably in vacuum at a drying temperature of 30 to 70 ℃, preferably 40 to 60 ℃) to obtain a triarylimidazole-containing benzoxazine-containing crosslinked polymer (Cross-linked TPB).
Preferably, step 3) is specifically: putting the triaryl-imidazole-containing benzoxazine-crosslinked polymer (Cross-linked TPB) obtained in the step 2) into a heat treatment device (such as a vacuum tube furnace). Then the heat treatment device is heated to the temperature of 300-1500 ℃ (preferably 500-1200 ℃, more preferably 800-1000 ℃) in the protective gas protective atmosphere (for example, in the protective atmosphere of nitrogen, argon or helium), and the carbon material is obtained after heat treatment for 0.5-8h (preferably 0.8-5h, more preferably 1-3 h). The resulting carbon material is then subjected to acid treatment (e.g., washing with hydrochloric acid or sulfuric acid at a concentration of 0.05 to 2mol/L, preferably at a concentration of 0.1 to 1.5mol/L, more preferably at a concentration of 0.2 to 1.2mol/L, 1 to 5 times, preferably 2 to 3 times). Finally, heat treatment is carried out under the same conditions to obtain the nitrogen-doped carbon catalyst (NDC).
Preferably, the triarylimidazole benzoxazine monomer (TBZ) is synthesized by the following method: firstly, dissolving 4- (4, 5-diphenyl-1H-imidazole-2-yl) -aniline and salicylaldehyde in a solvent (preferably ethanol) to react (preferably refluxing reaction is carried out under nitrogen atmosphere; the reaction temperature is 50-100 ℃, preferably 60-80 ℃, the reaction time is 12-48H, preferably 18-36H), pouring the system into petroleum ether, filtering (suction filtering), and washing to obtain a bright yellow product A. And then dissolving the product A in a solvent (preferably tetrahydrofuran), adding a reducing agent (preferably sodium borohydride) to react (preferably stirring at room temperature for 5-24h, preferably 8-18h), after the reaction is finished, slowly adding a proper amount of water, continuously stirring for 5-24h (preferably 8-18h), then pouring the system into a large amount of cold water, filtering (suction filtration), and recrystallizing (firstly drying the filtered product at the normal temperature in vacuum and then recrystallizing 1-3 times with dioxane) to obtain a white product B. And finally, dissolving the product B and paraformaldehyde in a solvent (preferably dimethylformamide) to perform reaction (preferably performing reflux reaction under the nitrogen atmosphere, wherein the reaction temperature is 60-150 ℃, preferably 80-120 ℃, the reaction time is 18-72 hours, preferably 24-60 hours), cooling a reaction system to room temperature, then dropping the reaction system into a large amount of cold water, filtering (suction filtration) to obtain a crude product, dissolving the crude product by using trichloromethane, washing the crude product for 1-5 times by using a 20% NaOH solution, washing the crude product to be neutral by using distilled water, and finally spin-drying the trichloromethane to obtain a light yellow triarylimidazole benzoxazine monomer (TBZ).
Preferably, in the step 2), the triaryl imidazole-containing benzoxazine polymer (TPB), the catalyst and the crosslinking agent are added in the following molar ratio: 0.3-1.8:2-12: 200-.
Example 1
1) Synthesis of triarylimidazole benzoxazine monomer (TBZ):
synthesis of Compound A (2- { [4- (4, 5-diphenyl-1H-imidazol-2-yl) -phenylimino ] -methyl } -phenol): 10g (32mmol) of 4- (4, 5-diphenyl-1H-imidazol-2-yl) -aniline and 5.52g (48mmol) of salicylaldehyde are weighed out and dissolved in 300ml of ethanol, and then heated to 100 ℃ under nitrogen atmosphere for reflux reaction for 24H. After the reaction is finished, pouring the system into 1000ml of petroleum ether, carrying out suction filtration and washing to obtain a bright yellow compound A with the yield of 95%.
Synthesis of Compound B (2- { [4- (4, 5-diphenyl-1H-imidazol-2-yl) -phenylamino ] -methyl } -phenol): a250 ml round bottom flask was charged with 1.67g (43.2mmol) of sodium borohydride, 9g (21.6mmol) of Compound A and 100ml of dry tetrahydrofuran, and the reaction was stirred at room temperature for 12 h. After the reaction is finished, 70ml of water is slowly added, stirring is continued for 12 hours, and then the system is poured into a large amount of cold water and filtered. The obtained product is firstly dried in vacuum at normal temperature, and then recrystallized for 2 times by using dioxane to obtain a white compound B with the yield of 85 percent.
Synthesis of TBZ: a250 ml round bottom flask was charged with 1.32g (42.2mmol) of paraformaldehyde, 8g (19.0mmol) of Compound B and 150ml of dimethylformamide; the reaction was then stirred for 48h with heating to 100 ℃ under nitrogen. After the reaction solution is cooled to room temperature, the reaction solution is dropped into 1000ml of cold water, and the solution is filtered, washed. The crude product was dissolved with chloroform and washed 2 times with 20% NaOH solution, then washed with distilled water to neutral and finally the chloroform was spin dried to give pale yellow TBZ with 73% yield.
2) Preparation of triarylimidazole-containing benzoxazine polymer (TPB):
and (3) putting the triarylimidazole benzoxazine monomer (TBZ) into a muffle furnace, and then heating to 210 ℃ for reaction for 2 h. After the reaction is finished, methanol is adopted to wash for 3 times, and the triaryl imidazole-containing benzoxazine polymer (TPB) is obtained.
3) Preparation of triarylimidazole-containing benzoxazine-containing crosslinked polymer (Cross-linked TPB):
1.80g (4.18mmol) TPB and 3.38g (25.0mmol) anhydrous AlCl were weighed out3Dispersed in 200ml of anhydrous CCl4(2.074mol) in a reactor; firstly, heating a reaction system to 45 ℃ to react for 5 hours; then the reaction system is heated to 80 ℃ and refluxed for 19 hours. After the reaction was completed, it was cooled, filtered, and washed 3 times with DMF and MeOH, and dried in vacuo to obtain triarylimidazole benzoxazine crosslinked polymer (Cross-linked TPB).
4) Preparation of nitrogen-doped carbon catalyst (NDC-900):
weighing 150mg of Cross-linked TPB, putting the Cross-linked TPB into a vacuum tube furnace, heating the vacuum tube furnace to 900 ℃ in a nitrogen atmosphere, and keeping the temperature for 1 h; and taking out the obtained carbon material, washing the carbon material with 0.5M hot HCl and water, finally heating the carbon material to 900 ℃ in a vacuum tube furnace in the nitrogen atmosphere, and preserving the heat for 1h for secondary carbonization to obtain 45mg of nitrogen-doped carbon catalyst (NDC-900) with the carbon forming rate of 30%.
Example 2
1) Synthesis of triarylimidazole benzoxazine monomer (TBZ):
synthesis of Compound A (2- { [4- (4, 5-diphenyl-1H-imidazol-2-yl) -phenylimino ] -methyl } -phenol): 10g (32mmol) of 4- (4, 5-diphenyl-1H-imidazol-2-yl) -aniline and 5.52g (48mmol) of salicylaldehyde are weighed out and dissolved in 300ml of ethanol, and then heated to 100 ℃ under nitrogen atmosphere for reflux reaction for 24H. After the reaction is finished, pouring the system into 1000ml of petroleum ether, carrying out suction filtration and washing to obtain a bright yellow compound A with the yield of 95%.
Synthesis of Compound B (2- { [4- (4, 5-diphenyl-1H-imidazol-2-yl) -phenylamino ] -methyl } -phenol): a250 ml round bottom flask was charged with 1.67g (43.2mmol) of sodium borohydride, 9g (21.6mmol) of Compound A and 100ml of dry tetrahydrofuran, and the reaction was stirred at room temperature for 12 h. After the reaction is finished, 70ml of water is slowly added, stirring is continued for 12 hours, and then the system is poured into a large amount of cold water and filtered. The obtained product is firstly dried in vacuum at normal temperature, and then recrystallized for 2 times by using dioxane to obtain a white compound B with the yield of 85 percent.
Synthesis of TBZ: a250 ml round bottom flask was charged with 1.32g (42.2mmol) of paraformaldehyde, 8g (19.0mmol) of Compound B and 150ml of dimethylformamide; the reaction was then stirred for 48h with heating to 100 ℃ under nitrogen. After the reaction solution is cooled to room temperature, the reaction solution is dropped into 1000ml of cold water, and the solution is filtered, washed. The crude product was dissolved with chloroform and washed 2 times with 20% NaOH solution, then washed with distilled water to neutral and finally the chloroform was spin dried to give pale yellow TBZ with 73% yield.
2) Preparation of triarylimidazole-containing benzoxazine polymer (TPB):
and (3) putting the triarylimidazole benzoxazine monomer (TBZ) into a muffle furnace, and then heating to 210 ℃ for reaction for 2 h. After the reaction is finished, methanol is adopted to wash for 3 times, and the triaryl imidazole-containing benzoxazine polymer (TPB) is obtained.
3) Preparation of triarylimidazole-containing benzoxazine-containing crosslinked polymer (Cross-linked TPB):
2.0g (4.64mmol) TPB and 3.38g (25.0mmol) anhydrous AlCl were weighed out3Dispersed in anhydrous CCl filled with 180ml4(1.867mol) in a reactor; firstly, heating a reaction system to 50 ℃ to react for 5 hours; then the reaction system is heated to 80 ℃ and refluxed for reaction for 15 hours. After the reaction was completed, it was cooled, filtered, and washed 3 times with DMF and MeOH, and dried in vacuo to obtain triarylimidazole benzoxazine crosslinked polymer (Cross-linked TPB).
4) Preparation of nitrogen-doped carbon catalyst (NDC-1000):
weighing 150mg of Cross-linked TPB, putting the Cross-linked TPB into a vacuum tube furnace, heating the vacuum tube furnace to 1000 ℃ in a nitrogen atmosphere, and preserving heat for 1.5 hours; taking out the obtained carbon material, washing with 0.8M hot HCl and water, heating to 1000 ℃ in a vacuum tube furnace in nitrogen atmosphere, keeping the temperature for 1.5h, and performing secondary carbonization to obtain 54mg of nitrogen-doped carbon catalyst (NDC-1000) with the carbon forming rate of 36%.

Claims (15)

1. A nitrogen-doped carbon catalyst, characterized by: the nitrogen-doped carbon catalyst is prepared by the following preparation method: firstly, a triaryl imidazole benzoxazine monomer (TBZ) with a structural general formula II is adopted for carrying out thermal polymerization reaction to obtain a triaryl imidazole benzoxazine-containing polymer (TPB) with a structural general formula III; then carrying out Friedel-Crafts reaction on the triaryl imidazole-containing benzoxazine polymer (TPB) with the general structural formula III in the presence of a catalyst and a crosslinking agent to synthesize triaryl imidazole-containing benzoxazine crosslinked polymer (Cross-linked TPB) with the general structural formula I; finally, carrying out heat treatment and acid treatment on the triaryl imidazole-containing benzoxazine Cross-linked polymer (Cross-linked TPB) with the structural general formula I to obtain a nitrogen-doped carbon catalyst (NDC);
Figure FDA0002960667680000011
wherein: r1Is CCl3Or COOH; r2Is CCl2Or CO;
Figure FDA0002960667680000012
2. the nitrogen-doped carbon catalyst of claim 1, wherein: the catalyst is AlCl3Or FeCl3(ii) a And/or
The cross-linking agent is CCl4Or CHCl3(ii) a And/or
The acid treatment is hydrochloric acid or sulfuric acid.
3. A method of preparing the nitrogen-doped carbon catalyst of claim 1 or 2, wherein: the method comprises the following steps:
1) putting a triaryl imidazole benzoxazine monomer (TBZ) with a structural general formula II into a reactor for thermal polymerization reaction to obtain a triaryl imidazole benzoxazine-containing polymer (TPB) with a structural general formula III;
2) carrying out Friedel-Crafts reaction on the triaryl imidazole benzoxazine-containing polymer (TPB) with the general structural formula III obtained in the step 1) in the presence of a catalyst and a crosslinking agent to synthesize a triaryl imidazole benzoxazine-containing crosslinked polymer (Cross-linked TPB) with the general structural formula I;
3) and (2) carrying out heat treatment and acid treatment on the triaryl imidazole-containing benzoxazine Cross-linked polymer (Cross-linked TPB) with the structural general formula I obtained in the step 2) to obtain the nitrogen-doped carbon catalyst (NDC).
4. The method of claim 3, wherein: the step 1) is specifically as follows: putting a triarylimidazole benzoxazine monomer (TBZ) with a structural general formula II into a reactor, and then heating the reactor for reaction at the temperature of 150 ℃ and 300 ℃ for 0.5-4 h; after the reaction is finished, washing is carried out to obtain the triaryl imidazole-containing benzoxazine polymer (TPB) with the structural general formula III.
5. The method of claim 4, wherein: in the step 1), the reactor is a muffle furnace; the reaction temperature of the reaction is 180-250 ℃; the reaction time is 1-3 h; the washing is carried out for 1 to 5 times by adopting methanol.
6. The method of claim 3, wherein: the step 2) is specifically as follows: putting the triaryl imidazole-containing benzoxazine polymer (TPB) with the general structural formula III obtained in the step 1), a catalyst and a cross-linking agent into a reactor in proportion; after the mixture is fully and uniformly dispersed, the temperature of the reactor is firstly raised to 30-70 ℃ for reaction for 1-12 h; then carrying out reflux reaction for 5-48h at 50-100 ℃; and after the reaction is finished, washing the product, and drying to obtain the triaryl imidazole benzoxazine-containing crosslinked polymer (Cross-linked TPB) with the structural general formula I.
7. The method of claim 6, wherein: in the step 2), the reaction is as follows: firstly, heating the reactor to 35-60 ℃ to react for 2-10 h; then carrying out reflux reaction at 60-95 ℃ for 8-36 h; washing with water and/or dimethylformamide for 1-8 times; the drying is vacuum drying, and the drying temperature is 30-70 ℃.
8. The method of claim 6, wherein: in the step 2), the reaction is as follows: firstly, heating a reactor to 40-50 ℃ and reacting for 3-8 h; then carrying out reflux reaction at 70-90 ℃ for 12-24 h; washing for 3-5 times by using water and/or dimethylformamide; the drying temperature is 40-60 ℃.
9. The method of claim 3, wherein: the step 3) is specifically as follows: putting the triaryl imidazole-containing benzoxazine Cross-linked polymer (Cross-linked TPB) with the structural general formula I obtained in the step 2) into a heat treatment device; then heating the heat treatment device to 300-1500 ℃ under the protective atmosphere of protective gas, and carrying out heat treatment for 0.5-8h to obtain a carbon material; then, treating the obtained carbon material with acid; finally, heat treatment is carried out under the same conditions to obtain the nitrogen-doped carbon catalyst (NDC).
10. The method of claim 9, wherein: the heat processor is a vacuum tube furnace; the protective gas is nitrogen, argon or helium atmosphere; the heat treatment comprises the following steps: heating the heat treatment device to 500-1200 ℃, and carrying out heat treatment for 0.8-5 h; the acid treatment is performed for 1 to 5 times by adopting hydrochloric acid or sulfuric acid, and the concentration of the hydrochloric acid or the sulfuric acid is 0.05 to 2 mol/L.
11. The method of claim 10, wherein: in step 3), the heat treatment is as follows: heating the heat treatment device to 800-1000 ℃ for heat treatment for 1-3 h; the acid treatment is carried out for 2-3 times by adopting hydrochloric acid or sulfuric acid, and the concentration of the hydrochloric acid or the sulfuric acid is 0.1-1.5 mol/L.
12. The method according to any one of claims 3-11, wherein: the triaryl imidazole benzoxazine monomer (TBZ) with the general structural formula II is prepared by the following method: dissolving 4- (4, 5-diphenyl-1H-imidazole-2-yl) -aniline and salicylaldehyde in a solvent to perform reflux reaction under the atmosphere of nitrogen; the reaction temperature is 50-100 ℃, the reaction time is 12-48h, and a product A is obtained by filtering and washing; then dissolving the product A in a solvent, adding sodium borohydride, stirring and reacting for 5-24h at room temperature, filtering, and recrystallizing to obtain a product B; finally, dissolving the product B and paraformaldehyde in a solvent to perform reflux reaction in a nitrogen atmosphere; the reaction temperature is 60-150 ℃, the reaction time is 18-72h, and a triarylimidazole benzoxazine monomer (TBZ) with a structural general formula III is obtained by filtering and washing; and/or
In the step 2), the triaryl imidazole benzoxazine-containing polymer (TPB) with the general structural formula II, the catalyst and the crosslinking agent are added in a molar ratio of 0.3-1.8:2-12: 200-800.
13. The method according to any one of claims 3-11, wherein: the triaryl imidazole benzoxazine monomer (TBZ) with the general structural formula II is prepared by the following method: dissolving 4- (4, 5-diphenyl-1H-imidazole-2-yl) -aniline and salicylaldehyde in ethanol, and performing reflux reaction under the nitrogen atmosphere; the reaction temperature is 60-80 ℃, the reaction time is 18-36h, and a product A is obtained by filtering and washing; then dissolving the product A in tetrahydrofuran, adding sodium borohydride, stirring and reacting at room temperature for 8-18h, filtering, and recrystallizing to obtain a product B; finally, dissolving the product B and paraformaldehyde in dimethylformamide to carry out reflux reaction in a nitrogen atmosphere; the reaction temperature is 80-120 ℃, the reaction time is 24-60h, and a triarylimidazole benzoxazine monomer (TBZ) with a structural general formula III is obtained by filtering and washing; and/or
In the step 2), the triaryl imidazole benzoxazine-containing polymer (TPB) with the general structural formula II, the catalyst and the crosslinking agent are added in a molar ratio of 0.5-1.5:3-10: 300-700.
14. The method according to any one of claims 3-11, wherein: in the step 2), the triaryl imidazole benzoxazine-containing polymer (TPB) with the general structural formula II, the catalyst and the crosslinking agent are added in a molar ratio of 0.8-1.2:4-8: 400-600.
15. Use of a nitrogen doped carbon catalyst according to any one of claims 1-2 or a nitrogen doped carbon catalyst prepared by a method according to any one of claims 3-14, wherein: the nitrogen-doped carbon catalyst is applied as an oxygen reduction catalyst of a zinc-air battery.
CN202010197080.XA 2020-03-19 2020-03-19 Nitrogen-doped carbon catalyst and preparation method and application thereof Active CN111403758B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010197080.XA CN111403758B (en) 2020-03-19 2020-03-19 Nitrogen-doped carbon catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010197080.XA CN111403758B (en) 2020-03-19 2020-03-19 Nitrogen-doped carbon catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111403758A CN111403758A (en) 2020-07-10
CN111403758B true CN111403758B (en) 2021-04-30

Family

ID=71413463

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010197080.XA Active CN111403758B (en) 2020-03-19 2020-03-19 Nitrogen-doped carbon catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111403758B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114773598A (en) * 2022-05-30 2022-07-22 南通斐腾新材料科技有限公司 Ionic type hypercrosslinked porous polymer and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104998673B (en) * 2015-06-18 2018-01-19 湘潭大学 Nitrogen, sulphur codope carbon carry base metal type oxygen reduction catalyst and preparation method
CN107335458B (en) * 2017-07-06 2019-10-01 华东师范大学 A kind of preparation method of nitrogen-doped carbon or iron nitrogen-phosphor codoping carbon electrocatalysis material
CN108640113B (en) * 2018-05-24 2020-04-21 中国科学院宁波材料技术与工程研究所 Preparation method of nitrogen and oxygen co-doped porous carbon material based on bio-based benzoxazine
CN109193011B (en) * 2018-08-20 2021-09-21 深圳大学 Polymer for manufacturing proton exchange membrane, preparation method and application

Also Published As

Publication number Publication date
CN111403758A (en) 2020-07-10

Similar Documents

Publication Publication Date Title
CN111313040B (en) Fe-N-C catalyst and preparation and application thereof
CN102447115B (en) Magnesium air battery cathode
CN113659158B (en) Carbon-based Fe/S/N co-doped oxygen reduction catalyst and preparation method and application thereof
CN112877714B (en) Double-defect ultrathin metal organic framework nanosheet catalyst and preparation method and application thereof
CN111203264B (en) Iron-nickel-nitrogen co-doped carbon catalyst and preparation method and application thereof
CN115092906A (en) Biomass-based hard carbon negative electrode material of sodium ion battery and preparation method
CN108461752B (en) Triphenylamine polymer with side chain having conjugated carbonyl compound, preparation and application thereof
CN111193038A (en) Nickel cobalt iron hydroxide coated nickel cobaltate flexible electrode material and preparation and application thereof
CN111403758B (en) Nitrogen-doped carbon catalyst and preparation method and application thereof
CN115043970A (en) Cross-linked porous polymer lithium-sulfur battery positive electrode carrier material containing maleimide structure, preparation method and application thereof
CN109360744B (en) MOFs-based composite supercapacitor electrode and preparation and application thereof
CN112687958A (en) Long-endurance button lithium battery and manufacturing method thereof
CN108962622B (en) A kind of preparation method of Carbon anode electrode plate
CN114361485B (en) Double-phenanthroline imidazole based multielement co-doped carbon zinc air battery catalyst and preparation method and application thereof
CN114957578B (en) Covalent organic framework material based on thienyl and oxazinyl, and preparation method and application thereof
CN114604905B (en) Preparation method of ternary battery anode material combining plasmas with sulfate
CN110387036A (en) A kind of random polyarylether electrode active material and preparation method thereof containing purpurine side chain
CN111584851B (en) Positive electrode composite material and preparation method thereof
CN111211327B (en) Compound for lithium ion battery anode material and preparation method and application thereof
CN116799219B (en) Tin-based oxide nanocrystalline modified hard carbon, sodium ion battery and vehicle
CN116598436B (en) Preparation method and application of positive electrode material
CN116496495B (en) Crown ether group covalent organic polymer and light-assisted lithium battery cell device thereof
CN113299935B (en) Preparation method of cathode cobalt-based catalyst of rechargeable zinc-air battery
CN115057862B (en) Pyrazine-quinoxaline organic electrode material and application thereof in lithium ion battery
CN112993203B (en) Preparation method of novel lithium-sulfur battery positive electrode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant