CN115332721A - Preparation method of cobalt phosphide-doped honeycomb porous carbon nanofiber modified diaphragm - Google Patents

Preparation method of cobalt phosphide-doped honeycomb porous carbon nanofiber modified diaphragm Download PDF

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CN115332721A
CN115332721A CN202210807395.0A CN202210807395A CN115332721A CN 115332721 A CN115332721 A CN 115332721A CN 202210807395 A CN202210807395 A CN 202210807395A CN 115332721 A CN115332721 A CN 115332721A
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porous carbon
cobalt
honeycomb porous
carbon nanofiber
nanofiber
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邓南平
王浩
康卫民
王晓晓
李亚男
高红静
张禄岗
刘亚荣
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • 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 relates to a preparation method of a cobalt phosphide-doped honeycomb porous carbon nanofiber modified diaphragm, belonging to the technical field of lithium-sulfur battery diaphragm modified materials. The preparation method comprises the following steps: 1) Uniformly mixing polyvinylpyrrolidone (PVP), distilled water, cobalt acetate tetrahydrate and PTFE emulsion with the mass fraction of 60wt% according to a certain proportion to prepare a spinning solution. And then, preparing the spinning solution into a precursor nanofiber membrane by electrostatic solution blowing. Then carrying out pre-oxidation treatment on the precursor fiber film by a temperature programming method to obtain a pre-oxidized precursor nanofiber film; 2) And carbonizing the pre-oxidized precursor nanofiber membrane in a certain atmosphere through a temperature rise program to obtain the cobalt-doped honeycomb porous carbon nanofiber. 3) And then, phosphorizing the cobalt-doped honeycomb porous carbon nanofiber and sodium hypophosphite monohydrate together in a certain atmosphere by a temperature rise program to obtain the cobalt phosphide-doped honeycomb porous carbon nanofiber. 4) Preparing a modified diaphragm: and (3) adding a proper amount of PVDF, carboxymethyl cellulose and the like serving as binders and a proper amount of N-methyl pyrrolidone serving as solvents into the cobalt phosphide-doped honeycomb porous carbon nanofiber prepared in the step (3), and coating the obtained coating on a commercial diaphragm for modification. The method can ensure high conductivity and short transport paths of electrons and ions, and effectively improve the adsorption and catalysis performance of the lithium-sulfur battery diaphragm modified material on polysulfide.

Description

Preparation method of cobalt phosphide-doped honeycomb porous carbon nanofiber modified diaphragm
Technical Field
The invention relates to a preparation method of a cobalt phosphide-doped honeycomb porous carbon nanofiber modified diaphragm, belonging to the technical field of lithium-sulfur battery diaphragm modified materials.
Background
Innovations in energy production and utilization technologies are essential to ensure safety and sustainability for the future. The battery is the key point of research as a necessity in daily life. Researchers have begun to research rechargeable secondary batteries because of the disadvantages of primary batteries, their non-rechargeable nature, their small range of use, and their high environmental impact. The lithium-sulfur battery has higher theoretical capacity (1675 mAh g) -1 ) And energy density (2600 Wh kg) -1 ) Has been the hot spot of research by researchers, and is considered to be one of the most promising next-generation electrochemical energy storage systems.
Currently, lithium sulfur batteries mainly face the problems of large volume expansion (about 80%) of sulfur positive electrode, shuttling effect of polysulfide and irregular growth of lithium dendrite, which seriously hampers the commercialization process. Based on the reaction mechanism of the lithium-sulfur battery, researchers mainly improve the stability and safety of the battery in the modes of electrode modification, diaphragm modification, electrolyte, insertion of an interlayer and the like. The most important thing is to find a high-performance modifier, improve the adsorption capacity to sulfide and accelerate the catalytic conversion kinetics of polysulfide. In the cobalt phosphide-doped carbon particle hybrid composite honeycomb porous carbon nanofiber, the cobalt phosphide has high adsorption and catalysis performance and can adsorb and catalyze the conversion of polysulfide. The porous carbon material has excellent conductivity and can accelerate the transmission of electrons and ions; the huge specific surface area can increase the contact area of cobalt phosphide and polysulfide, and the effect on the cobalt phosphide and the polysulfide can be better realized. The utilization rate of the active material is increased, and the performance of the lithium-sulfur battery is improved.
The common method for preparing the one-dimensional porous carbon nanofiber is to prepare a one-dimensional precursor by an electrostatic solution-blowing method, preoxidize the precursor and calcine the precursor to obtain the porous carbon nanofiber. The porous carbon nanofibers obtained by this method can ensure high conductivity and short transport paths for electrons and ions. However, for the synthesis of cobalt phosphide, the amount of the phosphorus source used is difficult to control, too little phosphorus source causes insufficient cobalt phosphorization, and too much phosphorus source causes other products to be generated. Therefore, how to successfully introduce cobalt phosphide into the one-dimensional porous carbon nano material to obtain the synergistic effect of catalyzing polysulfide conversion, namely, maintaining high conductivity of the material and short transport paths of electrons and ions are the key points for realizing excellent adsorption and catalysis performance of the material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a cobalt phosphide-doped honeycomb porous carbon nanofiber modified diaphragm. The cobalt phosphide-doped carbon nanomaterial is successfully prepared by utilizing the good stability and chemical activity of the pre-oxidized cobalt-doped carbon material precursor. The method can ensure high conductivity and short transport paths of electrons and ions, and effectively improve the adsorption and catalysis performance of the lithium-sulfur battery diaphragm modified material.
In order to realize the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a cobalt phosphide-doped honeycomb porous carbon nanofiber modified diaphragm comprises the following steps:
(1) Preparing a preoxidized precursor nanofiber membrane: uniformly mixing polyvinylpyrrolidone (PVP), water, cobalt acetate tetrahydrate and 60wt% of PTFE emulsion according to a certain proportion to prepare a spinning solution; preparing the prepared spinning solution into a precursor nanofiber membrane through an electrostatic solution-blowing device; and then heating the precursor nanofiber membrane in an air atmosphere by a program to obtain the pre-oxidized precursor nanofiber membrane.
(2) Preparing cobalt-doped honeycomb porous carbon nanofiber: and (2) heating and carbonizing the pre-oxidized precursor nanofiber membrane prepared in the step (1) in a nitrogen atmosphere by a certain program to obtain the cobalt-doped honeycomb porous carbon precursor nanofiber.
(3) Preparing cobalt phosphide-doped honeycomb porous carbon nanofiber: and (3) heating and phosphorizing the cobalt-doped honeycomb porous carbon nanofiber prepared in the step (2) and sodium hypophosphite monohydrate together in a nitrogen atmosphere by a certain procedure to obtain the cobalt phosphide-doped honeycomb porous carbon nanofiber.
(4) Preparing a modified diaphragm: grinding the cobalt phosphide-doped honeycomb porous carbon nanofiber prepared in the step (3), adding a proper amount of binder (mainly one or more of PVDF, carboxymethyl cellulose and other binders), adding a proper amount of N-methyl pyrrolidone as a solvent, and coating the obtained coating on a commercial diaphragm for modification
Due to the adoption of the technical scheme, the lithium-sulfur battery diaphragm modified material has the following characteristics:
1) The three-dimensional interconnected conductive network of the porous carbon nanofiber provides a transport channel for electrons and ions, is beneficial to the rapid transmission of the electrons and the ions, ensures high conductivity, has good conductivity of cobalt phosphide, and cannot inhibit the conductivity of materials.
2) The cobalt phosphide has high adsorption and catalytic capability, and can effectively adsorb and catalyze the conversion of polysulfide.
3) The cobalt phosphide-doped honeycomb porous carbon nanofiber shows a large specific surface area due to the one-dimensional structure and the internal penetration porous structure thereof, rich active sites are exposed, the contact area of cobalt phosphide and polysulfide is increased, and the adsorption and catalytic conversion capacity of the cobalt phosphide-doped honeycomb porous carbon nanofiber on polysulfide is improved.
The three characteristics enable the prepared modified diaphragm of the lithium-sulfur battery to have more excellent electrochemical performance and practicability in the lithium-sulfur battery. The invention provides a preparation method of a modified diaphragm for a lithium-sulfur battery. The prepared lithium-sulfur battery assembled with the cobalt phosphide-doped honeycomb porous carbon nanofiber modified diaphragm is good in cycling stability and high in capacity retention rate, and a new idea is provided for research on diaphragm modification of the lithium-sulfur battery.
Drawings
FIG. 1 is a schematic diagram of a preparation process of cobalt phosphide-doped honeycomb porous carbon nanofiber;
fig. 2 (a) is an SEM image of the precursor nanofiber membrane;
fig. 2 (b) is an SEM image of a pre-oxidized precursor nanofiber membrane;
fig. 2 (c) is an SEM image of cobalt-doped honeycomb porous carbon nanofibers;
fig. 2 (d) is an SEM image of cobalt phosphide-doped honeycomb porous carbon nanofibers;
fig. 3 (a) is an XRD image of cobalt-doped honeycomb porous carbon nanofiber;
fig. 3 (b) is an XRD image of cobalt phosphide-doped honeycomb porous carbon nanofiber.
Detailed Description
The invention will be described in further detail below with reference to the accompanying drawings and specific embodiments.
Example 1
(1) Preparing a preoxidized precursor nanofiber membrane: 2g of polyvinylpyrrolidone (PVP), 9g of water and 3g of cobalt acetate tetrahydrate were added to 25g of a 60wt% PTFE emulsion and stirred for 24 hours to obtain a uniformly distributed spinning solution. The spinning solution was then fed to an electrostatic blowing apparatus. Wherein the extrusion speed of the spinning solution is 2mL min -1 The inner diameter of the spinning needle is 2mm, the distance between the spinning needle and the fiber membrane receiving device is 80cm, the spinning voltage is 35kV, and the air pressure of the air outlet is 0.1MPa. Before reaching the collecting plate, the spinning solution jet can be fully stretched under the action of the quick airflow and the electrostatic repulsion force due to the action of the quick airflow and the high-voltage electrostatic field, and finally, a porous carbon nanofiber membrane can be formed on the collecting plate. And collecting the fiber film on the collecting plate to obtain the precursor nanofiber film. The prepared precursor fiber film was raised in an air atmosphere at a temperature rise rate of 2 ℃ per minuteAnd (3) heating to 230 ℃ and preserving the temperature for 2 hours to obtain the preoxidized precursor nanofiber membrane.
(2) Preparing the cobalt-doped honeycomb porous carbon nanofiber: and (2) heating the pre-oxidized precursor nanofiber membrane prepared in the step (1) to 1000 ℃ in a nitrogen atmosphere for carbonization to obtain the cobalt-doped honeycomb porous carbon nanofiber.
(3) Preparing the cobalt phosphide-doped honeycomb porous carbon nanofiber: and (3) heating the cobalt-doped honeycomb porous carbon nanofiber prepared in the step (2) and sodium hypophosphite monohydrate together in a mass ratio of 1: 15 to 450 ℃ in a nitrogen atmosphere for phosphorization to obtain the cobalt phosphide-doped honeycomb porous carbon nanofiber.
(4) Preparing a modified diaphragm: grinding the cobalt phosphide-doped honeycomb porous carbon nanofiber prepared in the step (3), adding 0.1g of PVDF as a binder, and adding a proper amount of N-methylpyrrolidone as a solvent. The resulting coating was coated onto a commercial membrane for modification, with a doctor blade thickness of 150 μm and dried in an oven at 50 deg.C
Example 2
(1) Preparing a preoxidized precursor nanofiber membrane: 2g of polyvinylpyrrolidone (PVP), 9g of water and 3g of cobalt acetate tetrahydrate are added to 25g of a 60wt% PTFE emulsion and stirred for 24h to give a uniformly distributed spinning solution. The spinning solution was then fed to an electrostatic blowing apparatus. Wherein the extrusion speed of the spinning solution is 2mL min -1 The inner diameter of the spinning needle is 2mm, the distance between the spinning needle and the fiber membrane receiving device is 80cm, the spinning voltage is 35kV, and the air pressure of the air outlet is 0.1MPa. Before reaching the collecting plate, the spinning solution jet can be fully stretched under the action of the quick airflow and the electrostatic repulsion force due to the action of the quick airflow and the high-voltage electrostatic field, and finally, a porous carbon nanofiber membrane can be formed on the collecting plate. And collecting the fiber film on the collecting plate to obtain the precursor nanofiber film. And heating the prepared precursor fiber film to 230 ℃ at a heating rate of 2 ℃ per minute in an air atmosphere, and keeping the temperature for 2 hours to obtain the pre-oxidized precursor nanofiber film.
(2) Preparing cobalt-doped honeycomb porous carbon nanofiber: and (2) heating the pre-oxidized precursor nanofiber membrane prepared in the step (1) to 1000 ℃ in a nitrogen atmosphere for carbonization to obtain the cobalt-doped honeycomb porous carbon nanofiber.
(3) Preparing the cobalt phosphide-doped honeycomb porous carbon nanofiber: and (3) heating the cobalt-doped honeycomb porous carbon nanofiber prepared in the step (2) and sodium hypophosphite monohydrate together in a mass ratio of 1: 5 to 450 ℃ in a nitrogen atmosphere for phosphorization to obtain the cobalt phosphide-doped honeycomb porous carbon nanofiber.
(4) Preparing a modified diaphragm: grinding the cobalt phosphide-doped honeycomb porous carbon nanofiber prepared in the step (3), adding 0.1g of PVDF as a binder, and adding a proper amount of N-methylpyrrolidone as a solvent. The resulting coating was coated onto a commercial membrane for modification, with a doctor blade thickness of 150 μm and dried in an oven at 50 ℃.
Example 3
(1) Preparing a preoxidized precursor nanofiber membrane: 2g of polyvinylpyrrolidone (PVP), 9g of water and 3g of cobalt acetate tetrahydrate were added to 25g of a 60wt% PTFE emulsion and stirred for 24 hours to obtain a uniformly distributed spinning solution. The spinning solution was then fed to an electrostatic blowing apparatus. Wherein the extrusion speed of the spinning solution is 2mL min -1 The inner diameter of the spinning needle is 2mm, the distance between the spinning needle and the fiber membrane receiving device is 80cm, the spinning voltage is 35kV, and the air pressure of the air outlet is 0.1MPa. Before reaching the collecting plate, the spinning solution jet can be fully stretched under the action of the quick airflow and the electrostatic repulsion force due to the action of the quick airflow and the high-voltage electrostatic field, and finally, a porous carbon nanofiber membrane can be formed on the collecting plate. And collecting the fiber film on the collecting plate to obtain the precursor nanofiber film. And heating the prepared precursor fiber film to 230 ℃ at the heating rate of 2 ℃ per minute in the air atmosphere, and preserving the heat for 2 hours to obtain the pre-oxidized precursor nanofiber film.
(2) Preparing the cobalt-doped honeycomb porous carbon nanofiber: and (2) heating the pre-oxidized precursor nanofiber membrane prepared in the step (1) to 1000 ℃ in a nitrogen atmosphere for carbonization to obtain the cobalt-doped honeycomb porous carbon nanofiber.
(3) Preparing cobalt phosphide-doped honeycomb porous carbon nanofiber: and (3) heating the cobalt-doped honeycomb porous carbon nanofiber prepared in the step (2) and sodium hypophosphite monohydrate together in a mass ratio of 1: 10 to 450 ℃ in a nitrogen atmosphere for phosphorization to obtain the cobalt phosphide-doped honeycomb porous carbon nanofiber.
(4) Preparing a modified diaphragm: grinding the cobalt phosphide-doped honeycomb porous carbon nanofiber prepared in the step (3), adding 0.1g of PVDF as a binder, and adding a proper amount of N-methylpyrrolidone as a solvent. The resulting coating was coated onto a commercial membrane for modification, with a doctor blade thickness of 150 μm, and dried in an oven at 50 ℃.
Example 4
(1) Preparing a preoxidized precursor nanofiber membrane: 2g of polyvinylpyrrolidone (PVP), 9g of water and 3g of cobalt acetate tetrahydrate are added to 25g of a 60wt% PTFE emulsion and stirred for 24h to give a uniformly distributed spinning solution. The spinning solution was then fed to an electrostatic blowing apparatus. Wherein the extrusion speed of the spinning solution is 2mL min -1 The inner diameter of the spinning needle is 2mm, the distance between the spinning needle and the fiber membrane receiving device is 80cm, the spinning voltage is 35kV, and the air pressure of the air outlet is 0.1MPa. Before reaching the collecting plate, the spinning solution jet can be fully stretched under the action of the quick airflow and the electrostatic repulsion force due to the action of the quick airflow and the high-voltage electrostatic field, and finally, a porous carbon nanofiber membrane can be formed on the collecting plate. And collecting the fiber film on the collecting plate to obtain the precursor nanofiber film. And heating the prepared precursor fiber film to 230 ℃ at a heating rate of 2 ℃ per minute in an air atmosphere, and keeping the temperature for 2 hours to obtain the pre-oxidized precursor nanofiber film.
(2) Preparing the cobalt-doped honeycomb porous carbon nanofiber: and (2) heating the pre-oxidized precursor nanofiber membrane prepared in the step (1) to 1000 ℃ in a nitrogen atmosphere for carbonization to obtain the cobalt-doped honeycomb porous carbon nanofiber.
(3) Preparing the cobalt phosphide-doped honeycomb porous carbon nanofiber: and (3) heating the cobalt-doped honeycomb porous carbon nanofiber prepared in the step (2) and sodium hypophosphite monohydrate together in a mass ratio of 1: 20 to 450 ℃ in a nitrogen atmosphere for phosphorization to obtain the cobalt phosphide-doped honeycomb porous carbon nanofiber.
(4) Preparing a modified diaphragm: grinding the cobalt phosphide-doped honeycomb porous carbon nanofiber prepared in the step (3), adding 0.1g of PVDF as a binder, and adding a proper amount of N-methylpyrrolidone as a solvent. The resulting coating was coated onto a commercial membrane for modification, with a doctor blade thickness of 150 μm and dried in an oven at 50 ℃.
And (3) performance testing:
the lithium-sulfur battery diaphragm modified material disclosed by the application is characterized in that a hybrid carbon nanomaterial taking porous carbon nanofibers as a framework and attached with cobalt phosphide is successfully prepared by utilizing the good stability and chemical activity of a pre-oxidized carbon material precursor. The method can ensure high conductivity and short transport paths of electrons and ions, and effectively improve the adsorption and catalytic performance of the modified material of the lithium-sulfur battery diaphragm on polysulfide. The lithium-sulfur battery prepared by the cobalt phosphide-doped carbon nanomaterial has excellent electrochemical performance.
Fig. 1 is a schematic diagram of a preparation process of cobalt phosphide-doped honeycomb porous carbon nanofiber. The cobalt phosphide-doped honeycomb porous carbon nanofiber is prepared by an electrostatic solution blowing technology, a pre-oxidation process, a carbonization process and a phosphating process. After pre-oxidation, the carbon material precursor has good stability and chemical activity, and can maintain basic morphology in the carbonization process. Compared with the common direct solvent loading of the carbon material, the method has the advantages that corresponding salt is directly added into the solution, and then spinning is carried out, so that the carbon material can better load the high-activity material. In addition, corresponding salt is added into the spinning solution, so that the processes of spinning, pre-oxidation, carbonization and phosphorization are realized, the increase of the process of carbonization after carbon material loading is effectively reduced, and the method has obvious commercial value.
Fig. 2 (a), (b), (c) and (d) are SEM image surface morphologies of the precursor nanofiber membrane, the cobalt-doped honeycomb porous carbon nanofiber and the cobalt phosphide-doped honeycomb porous carbon nanofiber, respectively. It can be seen that the surface of the precursor nanofiber film had many particles; after pre-oxidation is finished, the PTFE nano particles are more prominent due to the reduction of polyvinylpyrrolidone; after carbonization, the PTFE particles are pyrolyzed to form internal through holes, and protruding cobalt particles are attached to the honeycomb porous carbon nanofibers; after phosphorization, cobalt phosphide is uniformly attached to the honeycomb porous carbon nanofibers.
Fig. 3 (a) and (b) are XRD images of the cobalt-doped honeycomb porous carbon nanofiber and the cobalt phosphide-doped honeycomb porous carbon nanofiber, respectively. As can be seen, after carbonization, cobalt acetate is decomposed into a cobalt simple substance which is attached to the surface of the porous carbon; after phosphating, cobalt phosphide is generated.
Example 1 is the best example of the present application, and examples 2-4 also show the same performance characteristics through the above performance tests. Therefore, in conclusion, the cobalt phosphide-doped honeycomb porous carbon nanofiber disclosed by the application fully combines the large specific surface area of the porous carbon fiber, the good conductivity and the excellent adsorption and catalysis performance of cobalt phosphide, can ensure that the adsorption and catalysis performance of the lithium-sulfur battery diaphragm modified material can be effectively improved by high conductivity and short transport paths of electrons and ions, and has a wide application prospect in lithium-sulfur battery cells.

Claims (2)

1. A preparation method of a cobalt phosphide-doped honeycomb porous carbon nanofiber modified diaphragm is characterized by comprising the following steps:
(1) Preparing the cobalt phosphide-doped honeycomb porous carbon nanofiber: uniformly mixing polyvinylpyrrolidone (PVP), distilled water, cobalt acetate tetrahydrate and PTFE emulsion with the mass fraction of 60wt% according to a certain proportion to prepare a spinning solution. And then, preparing the spinning solution into a precursor nanofiber membrane by electrostatic solution blowing. Then carrying out pre-oxidation treatment on the precursor fiber film by a temperature programming method to obtain a pre-oxidized precursor nanofiber film; and carbonizing the pre-oxidized precursor nanofiber membrane in a certain atmosphere by a temperature rise program to obtain the cobalt-doped honeycomb porous carbon nanofiber. And then, phosphorizing the cobalt-doped honeycomb porous carbon nanofiber and sodium hypophosphite monohydrate together in a certain atmosphere by a temperature rise program to obtain the cobalt phosphide-doped honeycomb porous carbon nanofiber.
(2) Preparing a modified diaphragm: grinding the cobalt phosphide-doped honeycomb porous carbon nanofiber prepared in the step (1), adding a proper amount of PVDF, carboxymethyl cellulose and the like serving as binders and a proper amount of N-methyl pyrrolidone serving as a solvent, and coating the obtained coating on a commercial diaphragm for modification.
2. The preparation of the CoP doped honeycomb porous carbon nanofiber according to claim 1, wherein: the mass ratio of the cobalt-doped honeycomb porous carbon precursor nanofiber to the sodium hypophosphite monohydrate in the phosphating process is 1: 5 to 1: 20.
CN202210807395.0A 2022-07-11 2022-07-11 Preparation method of cobalt phosphide-doped honeycomb porous carbon nanofiber modified diaphragm Pending CN115332721A (en)

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