CN112723334B - Method for preparing nitrogen-doped carbon material by using fluorine-containing polymer - Google Patents

Method for preparing nitrogen-doped carbon material by using fluorine-containing polymer Download PDF

Info

Publication number
CN112723334B
CN112723334B CN201911029332.1A CN201911029332A CN112723334B CN 112723334 B CN112723334 B CN 112723334B CN 201911029332 A CN201911029332 A CN 201911029332A CN 112723334 B CN112723334 B CN 112723334B
Authority
CN
China
Prior art keywords
nitrogen
doped carbon
carbon material
fluorine
ammonia gas
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
CN201911029332.1A
Other languages
Chinese (zh)
Other versions
CN112723334A (en
Inventor
黄富强
董武杰
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.)
Shanghai Institute of Ceramics of CAS
Original Assignee
Shanghai Institute of Ceramics of CAS
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 Shanghai Institute of Ceramics of CAS filed Critical Shanghai Institute of Ceramics of CAS
Priority to CN201911029332.1A priority Critical patent/CN112723334B/en
Publication of CN112723334A publication Critical patent/CN112723334A/en
Application granted granted Critical
Publication of CN112723334B publication Critical patent/CN112723334B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • B01J35/33—
    • B01J35/617—
    • B01J35/618—
    • B01J35/64—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention relates to a method for preparing a nitrogen-doped carbon material by utilizing fluorine-containing macromolecules, which comprises the steps of placing a precursor material of the fluorine-containing macromolecules in an ammonia atmosphere, and calcining at 360-1200 ℃ to obtain the nitrogen-doped carbon material; the fluorine-containing high polymer precursor material is a polymer with relative molecular mass of 1000-1000 ten thousand and partial hydrogen substituted by fluorine. The nitrogen-doped carbon material can be obtained at a lower temperature, and due to the isoelectronic exchange of fluorine and nitrogen species, the doping of nitrogen elements can be greatly promoted, so that the nitrogen content in the nitrogen-doped carbon material obtained by the method can reach more than 10%, and the controllable doping of the nitrogen content and the type on the conductive carbon felt can be realized by regulating and controlling the reaction temperature.

Description

Method for preparing nitrogen-doped carbon material by using fluorine-containing polymer
Technical Field
The invention relates to a method for preparing a nitrogen-doped carbon material by using fluorine-containing polymers, in particular to a carbon material which has high nitrogen doping amount and rich pore structure and is obtained by using a new mechanism that fluorine is removed to promote nitrogen doping when the fluorine-containing polymers are carbonized and decomposed at high temperature in an ammonia atmosphere and forming a porous structure, belonging to the field of material preparation.
Background
The nitrogen-doped carbon material and the composite material thereof have wide application, are concerned about functional materials, and are hot research materials in academia and industry. But at present, the research still has a plurality of bottlenecks to break through: for example, the type of nitrogen in nitrogen-doped carbon materials has a great influence on the functionalization thereof but how to control the synthesis is still a problem; as the existing method is limited by precursor materials or preparation methods, most nitrogen-doped carbon materials can be prepared in a small amount in a laboratory, and industrial large-scale macro preparation cannot be realized; how to realize the nitrogen-doped carbon material with high specific surface area and ordered pore structure still has great difficulty; it remains difficult to achieve uniform loading of metallic carbon/nitrogen/fluorine/oxide on nitrogen-doped carbon when preparing composite materials.
Direct pyrolysis of nitrogen-rich precursors is a simple and common method for preparing nitrogen-doped carbon materials, and can achieve relatively uniform nitrogen doping. Generally, the method can realize graphitization of the carbon material at higher temperature (> 900 ℃) so as to realize high conductivity of the material, but the nitrogen content of the general nitrogen-doped carbon material obtained by the method is difficult to exceed 7% and is difficult to control to obtain the required nitrogen doping type because the nitrogen-doped carbon material easily loses nitrogen therein at the temperature higher than 750 ℃.
Disclosure of Invention
In view of the above problems, the present invention provides a carbon material doped with high nitrogen content (nitrogen-doped carbon material), a conductive carbon felt supported by the nitrogen-doped carbon material, and a preparation method and applications thereof.
In a first aspect, the invention provides a method for preparing a nitrogen-doped carbon material by using a fluorine-containing polymer, wherein a fluorine-containing polymer precursor material is placed in an ammonia atmosphere and calcined at the temperature of 360-1200 ℃ to obtain the nitrogen-doped carbon material; the fluorine-containing high polymer precursor material is a polymer with relative molecular mass of 1000-1000 ten thousand and partial hydrogen substituted by fluorine.
In the invention, a fluorine-containing polymer material is used for preparing the nitrogen-doped carbon material for the first time, specifically, a fluorine-containing polymer precursor material (a polymer with partial hydrogen substituted by fluorine) (the molecular weight is 1000-1000 ten thousand) is used for high-temperature carbonization (360-1200 ℃) in a tubular furnace filled with ammonia gas (1mL/min-10000mL/min), so that the nitrogen-doped carbon material with a porous structure can be obtained. The nitrogen-doped carbon material can be obtained at a lower temperature, and the nitrogen content in the nitrogen-doped carbon material obtained by the method can reach more than 10% because the doping of nitrogen elements can be greatly promoted by the isoelectronic exchange of fluorine and nitrogen species, and the controllable doping of the nitrogen content and the type can be realized by regulating and controlling the reaction temperature.
Preferably, before calcining, a template agent is also added, and the template agent is selected from at least one of mesoporous silica, molecular sieve and magnesium oxide; the mass ratio of the template agent to the fluorine-containing polymer precursor material is (0.1-5): 1; and after calcination, the templating agent is removed with an etchant. Preferably, the nitrogen-doped carbon material with the ordered pore structure can be obtained by mixing the fluorine-containing polymer material with some templates (such as mesoporous silica, molecular sieve, magnesium oxide and the like) in advance, then nitriding at a high temperature in an ammonia atmosphere at a certain temperature, and removing the templates from the obtained product by acid washing.
Preferably, the fluorine-containing polymer precursor material is at least one selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyvinyl fluoride (PVF), Polyperfluoroalkoxy (PFA) resin, Polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and ethylene-tetrafluoroethylene (ETFE) copolymer, and is preferably polyvinylidene fluoride PVDF.
Preferably, the ammonia gas atmosphere is ammonia gas or mixed gas containing ammonia gas;
when an open container is selected for calcination, the gas flow of the ammonia gas atmosphere is 1-10000 mL/min, preferably 300 mL/min;
when the calcining is carried out in a closed container during selection, the pressure of the ammonia atmosphere is 0.1-100 MPa.
Preferably, the calcination temperature is 700 ℃.
Preferably, the heating rate of the calcination is 0.1-100 ℃/min, preferably 20 ℃/min.
Preferably, the calcination time is 1 minute to 10 hours, preferably 4 hours.
In a second aspect, the present invention provides a method of making a nitrogen doped carbon material supported conductive carbon felt comprising:
(1) mixing a fluorine-containing high-molecular precursor material and a solvent to obtain a mixed solution, wherein the fluorine-containing high-molecular precursor material is a polymer of which partial hydrogen is replaced by fluorine and the relative molecular mass is 1000-1000 ten thousand;
(2) and soaking the conductive carbon felt in the obtained mixed solution for 0.1-24 hours, drying, then placing in an ammonia atmosphere, and calcining at 360-1200 ℃ to obtain the conductive carbon felt loaded with the nitrogen-doped carbon material.
In the invention, a fluorine-containing polymer material is used for preparing the conductive carbon felt of the nitrogen-doped carbon material for the first time, and specifically, a fluorine-containing polymer precursor material (a polymer with part of hydrogen substituted by fluorine) (with the molecular weight of 1000-1000 ten thousand) is used for high-temperature carbonization (360-1200 ℃) in a tubular furnace filled with ammonia gas (1-10000 mL/min), so that the nitrogen-doped carbon material with a porous structure can be obtained. The nitrogen-doped carbon material can be obtained at a lower temperature, and the nitrogen content in the nitrogen-doped carbon material obtained by the method can reach more than 10% because the nitrogen element doping can be greatly promoted by the isoelectronic exchange of fluorine and nitrogen species, and the controllable doping of the nitrogen content and the type on the conductive carbon felt can be realized by regulating and controlling the reaction temperature.
Preferably, the solvent is at least one selected from the group consisting of N-methylpyrrolidone, chloroform, water and ethanol; the concentration of the mixed solution is 5-100 mg/mL.
Preferably, a template agent is further added into the mixed solution, wherein the template agent is selected from at least one of mesoporous silica, molecular sieve and magnesium oxide; the mass ratio of the template agent to the fluorine-containing polymer precursor material is (0.1-5): 1; and after calcination, the templating agent is removed with an etchant. Preferably, the nitrogen-doped carbon material with ordered pore structure can be obtained by mixing the fluorine-containing polymer material with some templates (such as mesoporous silica, molecular sieve, magnesium oxide and the like) in advance, then nitriding at high temperature in an ammonia atmosphere at one point, and removing the templates from the obtained product by an etching method such as acid washing and the like.
Preferably, the fluorine-containing polymer precursor material is at least one selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyvinyl fluoride (PVF), Polyperfluoroalkoxy (PFA) resin, Polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and ethylene-tetrafluoroethylene (ETFE) copolymer, and is preferably polyvinylidene fluoride PVDF.
Preferably, the ammonia gas atmosphere is ammonia gas or mixed gas containing ammonia gas; when an open container is selected for calcination, the gas flow of the ammonia gas atmosphere is 1-10000 mL/min, preferably 300 mL/min; and when the material is selected, the pressure of the ammonia atmosphere is 0.1-100 MPa when the closed container is used for calcining. Taking polyvinylidene fluoride (PVDF) as an example, the material is carbonized at high temperature (360-1200 ℃) in a tubular furnace filled with ammonia gas (1-10000 mL/min), and the nitrogen-doped carbon material with a porous structure can be obtained.
Preferably, the calcination temperature is 700 ℃.
Preferably, the heating rate of the calcination is 0.1-100 ℃/min, preferably 20 ℃/min.
Preferably, the calcination time is 1 minute to 10 hours, preferably 4 hours.
In a third aspect, the present invention provides a nitrogen-doped carbon material prepared by the method for preparing a nitrogen-doped carbon material by using a fluorine-containing polymer, wherein the atomic doping amount of nitrogen in the nitrogen-doped carbon material is 1% to 15%; the conductivity of the nitrogen-doped carbon material is 1-100 mS/cm.
In a fourth aspect, the present invention provides a nitrogen doped carbon material loaded conductive carbon felt prepared according to the above method, comprising: the conductive carbon felt comprises a conductive carbon felt and a nitrogen-doped carbon material loaded on the conductive carbon felt, wherein the loading amount of the nitrogen-doped carbon material is 1-70 wt%; the atomic doping amount of nitrogen element in the nitrogen-doped carbon material is 1-15 at%.
In a fifth aspect, the invention provides an application of the nitrogen-doped carbon material in the preparation of super capacitors, lithium ion batteries, catalytic materials, drying materials and metal air batteries.
In a sixth aspect, the invention provides an application of the conductive carbon felt loaded with the nitrogen-doped carbon material in preparation of supercapacitors, lithium ion batteries, catalytic materials, drying materials and metal air batteries.
Compared with the prior art, the invention has the following beneficial effects:
as fluorine is removed to promote nitrogen doping when the fluorine-containing high polymer material is carbonized and decomposed (pyrolyzed), the carbon material with high nitrogen doping amount and rich pore structure is finally obtained;
the used precursors are rich in types: the key point of the method lies in the novel isoelectron exchange mechanism of fluorine and nitrogen species, so that only the high polymer material containing fluorine and the composite material thereof can be used as precursor materials, even some waste fluoroplastic products, the cost is low, large-scale preparation can be realized, environmental protection and waste utilization are realized, the reaction condition is mild, and the porous carbon material (the specific surface area can reach 1000 m) with high nitrogen doping amount (more than 10 percent) can be obtained under the condition of lower temperature (less than 500℃) 2 More than g), energy conservation and environmental protection, and is suitable for industrial mass production, and nitrogen-doped carbon materials with different nitrogen contents can be obtained by controlling the reaction temperature and time, or nitrogen-doped carbon materials containing ordered pore structures can be obtained by adding some templates;
based on a new mechanism that fluorine elements are removed to promote nitrogen element doping when fluorine-containing macromolecules are carbonized and decomposed at high temperature in an ammonia gas atmosphere, and a porous structure is formed, the carbon material with high nitrogen doping amount and rich pore structures is obtained, and the problem of large-scale low-cost production of high-performance nitrogen-doped porous carbon materials for super capacitors, lithium ion batteries and electrocatalytic oxygen reduction can be solved.
Drawings
Fig. 1 shows a transmission electron micrograph of a nitrogen-doped carbon material having a disordered porous structure prepared according to a template-free method of the present invention, from which it can be seen that the nitrogen-doped carbon material obtained in the preparation is amorphous carbon having a porous structure;
FIG. 2 shows a transmission electron micrograph of an ordered mesoporous structure prepared according to the mesoporous silica template method of the present invention, from which it can be seen that the nitrogen-doped carbon material obtained in the preparation is amorphous carbon and has an ordered porous structure;
FIG. 3 shows a TEM image of a hollow-pore structure prepared by the magnesium oxide template method according to the present invention, from which it can be seen that the prepared N-doped carbon material is amorphous carbon and has a hollow-pore structure;
FIG. 4 shows a powder X-ray diffraction pattern of a nitrogen-doped carbon material having an ordered mesoporous structure and a disordered porous structure prepared according to the method of the present invention, from which it can be seen that the product has no significant diffraction peaks within the tested range, indicating that the material is amorphous carbon;
FIG. 5 shows the small-angle powder X-ray diffraction spectra of the nitrogen-doped carbon material with ordered mesoporous structure and the template mesoporous silica SBA-15 prepared by the method of the present invention, wherein the spectra show that the two materials have obvious small-angle diffraction peaks, which indicate the ordered mesoporous structure;
FIG. 6 shows a small-angle powder X-ray diffraction pattern of a nitrogen-doped carbon material with a disordered porous structure prepared according to the method of the present invention, from which it can be seen that the sample has no significant diffraction peaks within the range tested, indicating that the material does not have a periodic ordered structure;
FIG. 7 shows the nitrogen adsorption-desorption isotherm of the porous nitrogen-doped carbon material prepared according to the method of the present invention, from which it can be seen that the material has mesoporous and microporous structures with a specific surface area of 960m 2 g -1 ；
Fig. 8 shows a raman spectrum of a nitrogen-doped carbon material prepared according to the method of the present invention, from which it can be seen that the material contains a large amount of sp2 carbon and a defect structure;
fig. 9 shows a photoelectron spectrum (XPS) of N1s of a nitrogen-doped carbon material prepared according to the method of the present invention, from which it can be seen that the material contains a large amount of nitrogen content of 10.8 wt%, the types of nitrogen being pyrrole type nitrogen and pyridine type nitrogen;
FIG. 10 shows cyclic voltammograms of nitrogen-doped carbon material prepared according to the method of the present invention as a supercapacitor electrode material, and testing shows that the material has typical electrochemical behavior of a supercapacitor and exhibits a pseudocapacitive redox peak;
FIG. 11 shows constant current charge and discharge curves for nitrogen-doped carbon materials prepared according to the method of the present invention as supercapacitor electrode materials, calculations showing that the materials have a value of up to 500F g -1 The mass to capacity ratio of (d);
FIG. 12 shows a graph of cycling performance as a lithium ion battery negative electrode material of nitrogen-doped carbon material prepared according to the method of the present invention, calculated to show that the material has up to 800mAh g -1 The specific capacity of the mass;
figure 13 shows a photograph of a nitrogen doped carbon material loaded large area conductive carbon felt prepared according to the method of the present invention, indicating that the material has the prospect of macro preparation and application;
fig. 14 shows a linear scan curve as an electrocatalytic oxygen reduction (ORR) reaction catalyst for nitrogen-doped carbon materials prepared according to the method of the present invention, which can be found to have similar catalytic performance by comparison with a commercial platinum carbon (20%) catalyst;
FIG. 15 shows the constant current charging and discharging curves of the black amorphous porous nitrogen-doped carbon material prepared in comparative example 1, from which it is calculated that the material has only 120F g -1 The mass to capacity ratio of (d);
fig. 16 shows cyclic voltammograms of the black amorphous porous nitrogen-doped carbon material prepared in comparative example 1, from which it can be seen that there is a typical electrochemical behavior of a supercapacitor, and a redox peak of pseudo-capacitive type occurs.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, a fluorine-containing polymer precursor material (a polymer in which part of hydrogen is replaced by fluorine, and the molecular weight can be 1000 to 1000 ten thousand) is carbonized by removing hydrogen and fluorine in the form of hydrogen fluoride at high temperature (not less than 360 ℃) under oxygen-free conditions. The inventor firstly carries out pyrolysis treatment (or called calcination, high-temperature carbonization and the like) in an ammonia atmosphere, and as hydrogen fluoride and ammonia are isoelectric substances, the removal of fluorine promotes the combination of nitrogen and carbon at the removal site of fluorine, thereby promoting the doping of nitrogen elements into a carbon material formed after the removal of fluorine, and the process is called isoelectric exchange of fluorine and nitrogen species, so that the nitrogen-doped carbon material with a porous structure is obtained. The process can be carried out at a lower temperature (more than or equal to 360 ℃), so that the nitrogen-doped carbon material can be obtained at the lower temperature, and due to the fact that the doping of nitrogen elements can be greatly promoted through the isoelectric exchange of fluorine nitrogen species, the nitrogen content in the nitrogen-doped carbon material obtained through the method can reach more than 10%, and the nitrogen types can be pyrrole type nitrogen and pyridine type nitrogen.
In an alternative embodiment, the fluorine-containing polymer precursor material is at least one selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyvinyl fluoride (PVF), Polyperfluoroalkoxy (PFA) resin, Polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene copolymer (ECTFE), Ethylene Tetrafluoroethylene (ETFE) copolymer, preferably polyvinylidene fluoride PVDF. It should be noted that the fluoropolymer material used in the present invention may be commercial powder directly purchased, or various discarded pipes, films, members and the like made of fluoropolymer to realize the waste utilization of fluoropolymer, and the morphology is preferably powder.
In alternative embodiments, the fluoropolymer precursor material and the templating agent (e.g., mesoporous silica, molecular sieves, magnesia, clay, kaolin, etc.) may be mixed prior to calcination to achieve an adjustment in the pore size and porosity of the carbon material. After calcination, the template agent is removed by acid washing, and the nitrogen-doped carbon material with an ordered pore structure can be obtained. Further preferably, the fluorine-containing polymer precursor material and the template agent may be directly mixed. Alternatively, the fluorine-containing polymer precursor material is mixed with a solvent (for example, at least one of N-methylpyrrolidone, chloroform, water, and ethanol), and then a templating agent is added to obtain a mixed slurry. And then centrifuging and drying to obtain a uniform mixture of the fluorine-containing polymer precursor material and the template agent.
In an alternative embodiment, the pyrolysis treatment may be performed at a temperature ranging from 360 to 1200 ℃. The heating rate of the pyrolysis treatment can be 0.1-100 ℃/min. The holding time for the pyrolysis treatment is 1 minute to 10 hours. Further preferred reaction conditions are: the reaction temperature is 700 ℃, the heating rate is 20 ℃/min, and the temperature is kept for 4 hours.
In an alternative embodiment, the ammonia gas atmosphere can be achieved by continuously introducing ammonia gas or other mixed gas containing ammonia gas into an ammonia gas flow tube furnace (open container), and the gas flow rate ranges from 1mL/min to 10000mL/min, preferably 300 mL/min. Or introducing ammonia gas or other mixed gas containing ammonia gas into a closed container filled with the precursor material, wherein the pressure is 0.1-100 MPa, and preferably 0.2 MPa.
In an embodiment of the present invention, the nitrogen doping amount of the nitrogen element in the nitrogen-doped carbon material prepared by the above method is 1% to 15%. The conductivity of the nitrogen-doped carbon material is 1-100 mS/cm. Moreover, the obtained nitrogen-doped carbon material has the pore sizes of micropores and mesopores, and the nitrogen-doped carbon material directly prepared from the fluorine-containing high polymer material has a disordered porous structure. And the nitrogen-doped carbon material obtained by mixing the fluorine-containing high polymer material with some templates (such as mesoporous silica, molecular sieve and magnesium oxide) and then placing the mixture in an ammonia atmosphere for high-temperature calcination, and removing the templates from the product by etching has a highly ordered micropore or mesoporous structure. The method is simple and effective, has excellent performance, does not need a complicated post-treatment process, and the obtained product can be widely applied to the new energy fields of supercapacitors, lithium ion batteries, electrocatalytic oxygen reduction and the like.
In one embodiment of the invention, the conductive carbon felt is used as a base material, and a nitrogen-doped carbon material is directly grown in situ on the conductive carbon felt by utilizing the high-temperature carbonization process of a fluorine-containing polymer precursor material, so that the conductive carbon felt loaded with the nitrogen-doped carbon material is obtained, and the conductive carbon felt has wide application in super capacitors, lithium ion batteries, catalytic materials, drying materials and metal air batteries. The following is an exemplary description of the method of making the nitrogen doped carbon material supported conductive carbon felt.
And preparing mixed slurry. Mixing the fluorine-containing polymer precursor material with a solvent to obtain a mixed solution. The fluorine-containing polymer precursor material is a polymer in which part of hydrogen with relative molecular mass of 1000-1000 ten thousand is replaced by fluorine. Wherein the solvent is at least one selected from N-methylpyrrolidone, chloroform, water and ethanol. The concentration of the mixed solution can be 5-100 mg/mL. Preferably, a template is also added to the mixed solution. The template agent is at least one selected from mesoporous silica, molecular sieve and magnesium oxide. The mass ratio of the template agent to the fluorine-containing polymer precursor material can be (0.1-5): 1. after calcination, the templating agent is removed using an etchant (acid solution to which the templating agent corresponds).
And soaking the conductive carbon felt in the obtained mixed solution for 0.1-24 hours, drying, and then placing in an ammonia atmosphere for high-temperature carbonization. The high temperature carbonization process is substantially identical to the calcination process of the nitrogen-doped carbon material.
In conclusion, the obtained nitrogen-doped carbon material and the conductive carbon felt loaded by the nitrogen-doped carbon material can be used as materials of a super capacitor, a lithium ion battery, a catalyst and a metal air battery, and can also be used for adsorbing pollutants so as to purify air/water or adsorbing water molecules in air so as to be used as a drying agent.
Sample characterization
And collecting the appearance and the ultrastructure information of the sample by using a transmission electron microscope. And collecting the structural information of the sample by using an X-ray diffractometer. And collecting the sample pore structure information by using a specific surface area tester. And analyzing the chemical composition, element valence state, content and other information of the material with an X-ray photoelectron spectrometer. The conductivity of the material was tested using the four-probe method.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, uniformly paving the sample in a corundum ceramic boat, then placing the corundum ceramic boat in a tubular atmosphere furnace, then connecting two ends of the tubular atmosphere furnace by using special flanges and introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, continuously introducing the ammonia gas at the flow rate in the subsequent calcination process, absorbing tail gas by using sulfuric acid solution to prevent atmospheric pollution, introducing gas at normal temperature for at least 60 minutes, then opening a program for heating, heating to 700 ℃ at the heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing the ammonia gas and introducing argon gas at the flow rate of 300mL/min after the temperature is reduced to room temperature, and stopping after the temperature is reduced to at least 60 minutes, taking out the ceramic corundum filled with the product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein transmission electron microscope pictures and X-ray powder diffraction of the product are shown in figure 1, As shown in FIGS. 4 and 6, the nitrogen content of the product was 10%, and the specific surface area was 960m 2 The capacity of the material is 300F/g when the material is used as a super capacitor material, and the capacity of the material is 520mAh/g when the material is used as a lithium battery negative electrode material -1 。
Example 2
Weighing 0.5g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) powder sample, uniformly paving the sample in a corundum porcelain boat, then placing the corundum porcelain boat in a tubular atmosphere furnace, then connecting two ends of the tubular atmosphere furnace by using a special flange and introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, continuously introducing the ammonia gas at the flow rate in the subsequent calcining process, absorbing tail gas by using sulfuric acid solution to prevent atmospheric pollution, opening a program to heat after introducing the tail gas at normal temperature for at least 60 minutes, heating to 700 ℃ at the heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing the ammonia gas and introducing argon gas at the flow rate of 300mL/min after cooling to room temperature, stopping after continuously introducing the tail gas for at least 60 minutes, taking out the corundum porcelain boat filled with the product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 10%, specific surface area of 1030m 2 The capacity of the material as a super capacitor is 320F/g, and the material is used as a lithium battery negative electrodeThe capacity of the electrode material is 450 mAh/g.
Example 3:
weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, mixing and ball-milling 0.5g of mesoporous silica SBA-15 for 4 hours, uniformly laying the mixed sample powder in a corundum porcelain boat, then placing the corundum porcelain boat in a tubular atmosphere furnace, then connecting two ends of the tubular atmosphere furnace by using a special flange, introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, continuously introducing the ammonia gas at the flow rate in the subsequent calcining process, absorbing tail gas by a sulfuric acid solution to prevent atmospheric pollution, opening a program to heat at normal temperature for at least 60 minutes, heating at the heating rate of 20 ℃/min to 700 ℃, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing the ammonia gas and introducing argon gas at the flow rate of 300mL/min after the temperature is reduced to room temperature, stopping after at least 60 minutes, taking out the corundum porcelain boat filled with the product to obtain the black mesoporous silica SBA-15-ordered mesoporous carbon material composite, the material is put into 50mL hydrofluoric acid with the concentration of 15 percent, stirred for 24 hours and filtered to remove mesoporous silicon dioxide in the material, and the obtained product is amorphous ordered mesoporous nitrogen-doped carbon material powder, the nitrogen content of the product is 11 percent, and the specific surface area of the product is 1530m 2 The capacity of the material serving as the supercapacitor material is 450F/g, and the capacity of the material serving as the lithium battery negative electrode material is 600 mAh/g.
Example 4
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample and 1g of mesoporous silica SBA-15, mixing and ball-milling for 4 hours, uniformly laying the mixed sample powder in a corundum porcelain boat, then placing the corundum porcelain boat in a tubular atmosphere furnace, then connecting two ends of the tubular atmosphere furnace by using special flanges, introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, ammonia gas is continuously introduced at the flow rate in the subsequent calcining process, tail gas is absorbed by sulfuric acid solution to prevent atmospheric pollution, and (3) ventilating at normal temperature for at least 60 minutes, then starting the program to heat, raising the temperature to 700 ℃ at the heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing ammonia gas and argon gas with the flow of 300mL/min after the temperature is reduced to the room temperature, stopping after at least 60 minutes, and taking out the corundum porcelain boat filled with the product to obtain the black mesoporous silica SBA.-15-ordered mesoporous carbon material composite, placing the material into 50mL of hydrofluoric acid with the concentration of 15%, stirring for 24 hours, filtering to remove mesoporous silicon dioxide in the material, wherein the obtained product is amorphous ordered mesoporous nitrogen-doped carbon material powder, the transmission electron microscope picture, X-ray powder diffraction, small-angle X-ray powder diffraction, nitrogen adsorption and desorption isotherm, Raman spectrum, photoelectron spectrum (XPS) of the product, and the electrochemical performance and electrocatalytic oxygen reduction reaction performance of the product as the electrode of a super capacitor and a lithium ion battery are shown in the attached figures 2, 4, 5, 7-12 and 14, the nitrogen content is 11%, and the specific surface area is 1630m 2 The capacity of the material is 500F/g as a super capacitor material, and the capacity of the material is 800mAh/g as a lithium battery negative electrode material.
Example 5
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample and 2g of light magnesium oxide powder, mixing and ball-milling for 4 hours, uniformly laying the mixed sample powder in a corundum porcelain boat, then placing the corundum porcelain boat in a tubular atmosphere furnace, connecting two ends of the tubular atmosphere furnace by using a special flange, introducing ammonia gas with the flow rate of 300mL/min, continuously introducing ammonia gas with the flow rate in the subsequent calcining process, absorbing tail gas by using sulfuric acid solution to prevent atmospheric pollution, introducing the gas at normal temperature for at least 60 minutes, then opening a program to heat, heating to 700 ℃ at the heating rate of 20 ℃/min, then preserving the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing the ammonia gas and introducing argon gas with the flow rate of 300mL/min after the temperature is reduced to room temperature, stopping after at least 60 minutes, taking out the corundum porcelain boat containing the product to obtain a black ordered mesoporous carbon-magnesium oxide compound, the material is put into 50mL of sodium hydroxide with the concentration of 6mol/L, stirred for 24 hours, filtered and washed, then diluted hydrochloric acid with the concentration of 1mol/L is repeatedly washed to remove magnesium oxide, the obtained product is amorphous hollow porous nitrogen-doped carbon material powder, a transmission electron microscope picture of the product is shown in figure 3, the nitrogen content is 7 percent, and the specific surface area is 1010m 2 The capacity of the material as a super capacitor material is 400F/g, and the capacity of the material as a lithium battery negative electrode material is 560 mAh/g.
Example 6
2g of a polyvinylidene fluoride (PVDF) powder sample was weighed and dissolved in 100mL of N-methylpyrrolidone (NMP) to prepare a solutionPreparing a PVDF/NMP solution with the concentration of 20mg m/L, putting 2g of light magnesium oxide powder into the solution, mixing and stirring for 6 hours, carrying out solid-liquid separation by high-speed centrifugation after 6 hours of ultrasound, removing supernatant to obtain a PVDF-magnesium oxide mixture, drying the mixture for 12 hours at 100 ℃, grinding the mixture into powder, uniformly laying the mixed sample powder in a corundum porcelain boat, then placing the corundum porcelain boat in a tubular atmosphere furnace, connecting two ends of the tubular atmosphere furnace by using a special flange, introducing ammonia gas with the flow rate of 300mL/min, continuously introducing ammonia gas with the flow rate in the subsequent calcination process, absorbing tail gas by using a sulfuric acid solution to prevent atmospheric pollution, opening a program to heat after ventilating for at least 60 minutes at normal temperature, heating to 700 ℃ at the heating rate of 20 ℃/min, keeping the temperature for 4 hours, stopping heating, and naturally cooling, after the temperature is reduced to room temperature, stopping introducing ammonia gas and argon gas with the flow rate of 300mL/min, continuing for at least 60 minutes, stopping introducing the ammonia gas, taking out the corundum porcelain boat with the product, thus obtaining a black ordered mesoporous carbon-magnesium oxide compound, putting the material into 50mL of 6mol/L sodium hydroxide, stirring for 24 hours, filtering and washing, repeatedly washing with 1mol/L dilute hydrochloric acid to remove magnesium oxide, wherein the obtained product is amorphous hollow multi-amorphous ordered mesoporous nitrogen-doped carbon material powder, the nitrogen content of the product is 7%, and the specific surface area is 1010m 2 The capacity of the material as a super capacitor material is 420F/g, and the capacity of the material as a lithium battery negative electrode material is 610 mAh/g.
Example 7
Weighing 2g of polyvinylidene fluoride (PVDF) powder sample, dissolving the 2g of PVDF powder sample in 100mL of N-methylpyrrolidone (NMP) to prepare 20mg m/L PVDF/NMP solution, putting 2g of mesoporous silica SBA-15 powder into the solution, mixing and stirring for 6 hours, performing solid-liquid separation by adopting high-speed centrifugation after 6 hours of ultrasound, removing supernatant to obtain a PVDF-magnesium oxide mixture, drying the mixture at 100 ℃ for 12 hours, grinding the mixture into powder, uniformly laying the mixed sample powder in a corundum porcelain boat, then placing the corundum porcelain boat in a tubular atmosphere furnace, connecting two ends of the tubular atmosphere furnace by using special flanges, introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, continuously introducing the ammonia gas at the flow rate in the subsequent calcination process, absorbing tail gas by using sulfuric acid solution to prevent atmospheric pollution, and introducing the mixed sample into the tubular atmosphere furnace at normal temperatureOpening a program to heat after the gas is at least 60 minutes, heating to 700 ℃ at a heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing ammonia gas and argon gas with the flow of 300mL/min after the temperature is reduced to room temperature, stopping after the temperature is kept for at least 60 minutes, taking out a corundum porcelain boat with a product, thus obtaining a black mesoporous silica SBA-15-ordered mesoporous carbon material compound, putting the material into 50mL of 15% hydrofluoric acid, stirring for 24 hours, filtering to remove the mesoporous silica, obtaining the product which is amorphous ordered mesoporous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 12%, and the specific surface area is 1010m 2 The capacity of the material serving as the supercapacitor material is 550F/g, and the capacity of the material serving as the lithium battery negative electrode material is 840 mAh/g.
Example 8
Weighing 2g of polyvinylidene fluoride (PVDF) powder sample, dissolving in 100mL of N-methylpyrrolidone (NMP) to prepare 20mg/mL of PVDF/NMP solution, dropping the solution onto a conductive carbon felt (0.2g), controlling the volume of the solution and the size of the conductive carbon felt to be 2cm x 2cm, so that the load of PVDF is 6mg cm -2 Drying the conductive carbon felt at 100 ℃ for 12 hours, taking out, uniformly laying in a corundum porcelain boat, then placing the tube-type atmosphere furnace, connecting two ends of the tube-type atmosphere furnace by using special flanges, introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, ammonia gas is continuously introduced at the flow rate in the subsequent calcining process, tail gas is absorbed by sulfuric acid solution to prevent atmospheric pollution, and (3) ventilating at normal temperature for at least 60 minutes, then starting a program to heat, raising the temperature to 700 ℃ at a heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing ammonia gas and argon gas with the flow of 300mL/min after the temperature is reduced to the room temperature, stopping after at least 60 minutes, and taking out the corundum porcelain boat filled with the product to obtain the amorphous disordered porous nitrogen-doped carbon-loaded conductive carbon felt (wherein the loading capacity of the nitrogen-doped carbon material is 1mg cm). -2 The atomic doping amount of nitrogen element in the nitrogen-doped carbon material is 12 at%), and the capacity of the electrode serving as the super capacitor is 1F/cm 2 。
Example 9
A20 g sample of polyvinylidene fluoride (PVDF) powder was weighed to dissolve in200mL of N-methylpyrrolidone (NMP) is prepared into 100mg/mL of PVDF/NMP solution, 20cm × 20cm of conductive carbon felt (20g) is taken to be soaked in the solution for 12 hours, then the conductive carbon felt is dried at 100 ℃ for 12 hours and then is taken out and uniformly laid in a corundum porcelain boat, then the corundum porcelain boat is placed in a tubular atmosphere furnace, then two ends of the tubular atmosphere furnace are connected by a special flange, ammonia is introduced, the flow rate of the ammonia is 300mL/min, the ammonia is continuously introduced in the subsequent calcination process at the flow rate, tail gas is absorbed by sulfuric acid solution to prevent atmospheric pollution, the procedure is opened for heating after ventilating at normal temperature for at least 60 minutes, the temperature is increased to 700 ℃ at the heating rate of 20 ℃/min, the heating is stopped after the temperature is maintained for 4 hours, the temperature is naturally reduced, the introduction of the ammonia is stopped after the temperature is reduced to the room temperature, and the introduction of the argon at the flow rate of 300mL/min is stopped, stopping after at least 60 minutes, taking out the corundum porcelain boat with the product to obtain the amorphous disordered porous nitrogen-doped carbon-loaded large-area conductive carbon felt, wherein the picture is shown in figure 13, and the capacity of the electrode as a super capacitor is 10F cm -2 . Wherein the loading capacity of the nitrogen-doped carbon material is 20mg cm -2 (30 wt% in terms of mass content), and the content of nitrogen element in the nitrogen-doped carbon material is 11 at%.
Example 10
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, uniformly laying the sample in a corundum porcelain boat, then placing the tube-type atmosphere furnace, connecting two ends of the tube-type atmosphere furnace by using special flanges, introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, ammonia gas is continuously introduced at the flow rate in the subsequent calcining process, tail gas is absorbed by sulfuric acid solution to prevent atmospheric pollution, and (3) ventilating at normal temperature for at least 60 minutes, then starting the program to heat, raising the temperature to 360 ℃ at the temperature rise rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing ammonia gas and argon gas with the flow of 300mL/min after the temperature is reduced to the room temperature, stopping after at least 60 minutes, and taking out the corundum porcelain boat filled with the product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 3% and the specific surface area is 660 m. 2 The capacity of the material is 200F/g as a super capacitor material, and the capacity of the material is 400mAh/g as a lithium battery negative electrode material.
Example 11
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, uniformly laying the sample in a corundum porcelain boat, then placing the tube-type atmosphere furnace, connecting two ends of the tube-type atmosphere furnace by using special flanges, introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, ammonia gas is continuously introduced at the flow rate in the subsequent calcining process, tail gas is absorbed by sulfuric acid solution to prevent atmospheric pollution, and (3) ventilating at normal temperature for at least 60 minutes, then starting the program to heat, raising the temperature to 500 ℃ at the heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing ammonia gas and introducing argon gas with the flow of 300mL/min after the temperature is reduced to the room temperature, stopping after at least 60 minutes, and taking out the corundum porcelain boat filled with the product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 4% and the specific surface area is 870 m. 2 The capacity of the material serving as the supercapacitor material is 240F/g, and the capacity of the material serving as the lithium battery negative electrode material is 460 mAh/g.
Example 12
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, uniformly laying the sample in a corundum porcelain boat, then placing the tube-type atmosphere furnace, connecting two ends of the tube-type atmosphere furnace by using special flanges, introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, ammonia gas is continuously introduced at the flow rate in the subsequent calcining process, tail gas is absorbed by sulfuric acid solution to prevent atmospheric pollution, and (3) ventilating at normal temperature for at least 60 minutes, then starting the program to heat, raising the temperature to 600 ℃ at the heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing ammonia gas and introducing argon gas with the flow of 300mL/min after the temperature is reduced to the room temperature, stopping after at least 60 minutes, and taking out the corundum porcelain boat filled with the product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 5% and the specific surface area is 890 m. 2 The capacity of the material is 260F/g as a super capacitor material, and the capacity of the material is 500mAh/g as a lithium battery negative electrode material.
Example 13
A0.5 g sample of polyvinylidene fluoride (PVDF) powder was weighed, uniformly spread in a corundum porcelain boat, then placed in a tubular atmosphere furnace,then connecting two ends of a tubular atmosphere furnace by using a special flange and introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, continuously introducing the ammonia gas at the flow rate in the subsequent calcining process, absorbing tail gas by using a sulfuric acid solution to prevent air pollution, introducing the tail gas for at least 60 minutes at normal temperature, then opening a program to heat, raising the temperature to 1200 ℃ at the temperature raising rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing the ammonia gas and introducing the argon gas with the flow rate of 300mL/min after the temperature is reduced to the room temperature, stopping after at least 60 minutes, taking out a corundum porcelain boat containing a product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 5%, and the specific surface area is 1220m 2 The capacity of the material serving as the supercapacitor material is 250F/g, and the capacity of the material serving as the lithium battery negative electrode material is 420 mAh/g.
Example 14
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, uniformly laying the sample in a corundum porcelain boat, then placing the tube-type atmosphere furnace in a tube-type atmosphere furnace, connecting two ends of the tube-type atmosphere furnace by using special flanges, introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, ammonia gas is continuously introduced at the flow rate in the subsequent calcining process, tail gas is absorbed by sulfuric acid solution to prevent atmospheric pollution, and (3) ventilating at normal temperature for at least 60 minutes, then starting the program to heat, raising the temperature to 700 ℃ at the heating rate of 20 ℃/min, then keeping the temperature for 2 hours, stopping heating, naturally cooling, stopping introducing ammonia gas and introducing argon gas with the flow of 300mL/min after the temperature is reduced to the room temperature, stopping after at least 60 minutes, and taking out the corundum porcelain boat filled with the product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 6% and the specific surface area is 960 m. 2 The capacity of the material serving as the supercapacitor material is 270F/g, and the capacity of the material serving as the lithium battery negative electrode material is 520 mAh/g.
Example 15
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, uniformly paving the sample in a corundum porcelain boat, then placing the corundum porcelain boat in a tubular atmosphere furnace, connecting two ends of the tubular atmosphere furnace by using special flanges, introducing ammonia gas with the flow of 100mL/min, continuously introducing ammonia gas with the flow in the subsequent calcination process, and leading tail gas to pass through a sulfuric acid solutionAbsorbing to prevent atmospheric pollution, introducing air at normal temperature for at least 60 minutes, starting a program to heat, heating to 700 ℃ at a heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing ammonia gas and argon gas at a flow rate of 300mL/min after the temperature is reduced to the room temperature, stopping after at least 60 minutes, taking out a corundum porcelain boat containing a product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 5%, and the specific surface area of the product is 760m 2 The capacity of the material is 220F/g as a super capacitor material, and the capacity of the material is 480mAh/g as a lithium battery negative electrode material.
Example 16
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, uniformly laying the sample in a corundum porcelain boat, then placing the tube-type atmosphere furnace, connecting two ends of the tube-type atmosphere furnace by using special flanges, introducing ammonia gas, wherein the flow rate of the ammonia gas is 1000mL/min, ammonia gas is continuously introduced at the flow rate in the subsequent calcining process, tail gas is absorbed by sulfuric acid solution to prevent atmospheric pollution, and (3) ventilating at normal temperature for at least 60 minutes, then starting a program to heat, raising the temperature to 700 ℃ at a heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing ammonia gas and argon gas with the flow of 300mL/min after the temperature is reduced to the room temperature, stopping after at least 60 minutes, and taking out the corundum porcelain boat filled with the product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 5% and the specific surface area is 1260 m. 2 The capacity of the material serving as the super capacitor is 320F/g, and the capacity of the material serving as the lithium battery negative electrode is 680 mAh/g.
Example 17
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, uniformly paving the sample in a corundum ceramic boat, then placing the corundum ceramic boat in a tubular atmosphere furnace, then connecting two ends of the tubular atmosphere furnace by using special flanges and introducing ammonia gas, wherein the flow rate of the ammonia gas is 10mL/min, continuously introducing the ammonia gas at the flow rate in the subsequent calcining process, absorbing tail gas by using sulfuric acid solution to prevent atmospheric pollution, introducing gas at normal temperature for at least 60 minutes, then opening a program for heating, heating to 700 ℃ at the heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing the ammonia gas and introducing argon gas at the flow rate of 300mL/min after the temperature is reduced to room temperature, stopping after the temperature is reduced to at least 60 minutes, taking out the porcelain boat filled with the product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 4%, and the specific surface area is 1260m2/g, the capacity of the material as a super capacitor material is 120F/g, and the capacity of the material as a lithium battery negative electrode material is 380 mAh/g.
Example 18
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, then placing the PVDF powder sample in a high-pressure reaction kettle, then connecting two ends of the high-pressure reaction kettle by using a special interface and introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, introducing the ammonia gas at normal temperature for at least 60 minutes to completely remove the air in the high-pressure reaction kettle, absorbing tail gas by using a sulfuric acid solution to prevent atmospheric pollution, then closing an air outlet and continuously introducing the ammonia gas into the high-pressure reaction kettle until the pressure reaches 10MPa, stopping introducing the ammonia gas, opening a program to heat, heating to 700 ℃ at the heating rate of 20 ℃/min, keeping the temperature for 4 hours, stopping heating, naturally cooling, opening the air outlet to slowly discharge gas in the reaction kettle after the temperature is reduced to room temperature, absorbing the tail gas by using the sulfuric acid solution to prevent atmospheric pollution, introducing the argon gas with the flow rate of 300mL/min after the normal pressure is recovered, and stopping after the heating for at least 60 minutes, and opening the high-pressure reaction kettle to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 15%, the specific surface area is 1160m2/g, the capacity of the product as a super capacitor material is 520F/g, and the capacity of the product as a lithium battery negative electrode material is 820 mAh/g.
Example 19
Weighing 0.5g of polyvinylidene fluoride (PVDF) powder sample, uniformly paving the sample in a corundum porcelain boat, then placing the corundum porcelain boat in a tubular atmosphere furnace, then connecting two ends of the tubular atmosphere furnace by using special flanges and introducing a mixed gas of ammonia gas and argon gas, wherein the flow rate of the ammonia gas is 10mL/min, the flow rate of the argon gas is 190mL/min, continuously introducing the mixed gas of the ammonia gas and the argon gas at the flow rate in the subsequent calcining process, absorbing tail gas by a sulfuric acid solution to prevent atmospheric pollution, opening a program for heating after introducing the gas for at least 60 minutes at normal temperature, heating to 700 ℃ at the heating rate of 20 ℃/min, then keeping the temperature for 4 hours, and stopping heatingStopping heating, naturally cooling, stopping introducing the mixed gas of ammonia gas and argon gas after the temperature is reduced to room temperature, introducing the argon gas with the flow rate of 300mL/min, stopping after at least 60 minutes, taking out the corundum porcelain boat with the product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 5%, and the specific surface area is 1160m 2 The capacity of the material serving as the supercapacitor material is 150F/g, and the capacity of the material serving as the lithium battery negative electrode material is 420 mAh/g.
Comparative example 1
Weighing 0.5g of Polytetrafluoroethylene (PTFE) powder sample, uniformly laying the sample in a corundum porcelain boat, then placing the tube-type atmosphere furnace, connecting two ends of the tube-type atmosphere furnace by using special flanges, introducing ammonia gas, wherein the flow rate of the ammonia gas is 300mL/min, ammonia gas is continuously introduced at the flow rate in the subsequent calcining process, tail gas is absorbed by sulfuric acid solution to prevent atmospheric pollution, and (2) ventilating at normal temperature for at least 60 minutes, then starting a program to heat, raising the temperature to 700 ℃ at a heating rate of 20 ℃/min, then keeping the temperature for 4 hours, stopping heating, naturally cooling, stopping introducing ammonia gas and argon gas at a flow rate of 300mL/min after the temperature is reduced to the room temperature, continuing for at least 60 minutes, stopping, and taking out the corundum porcelain boat containing the product to obtain black amorphous porous nitrogen-doped carbon material powder, wherein the nitrogen content of the product is 2% and the specific surface area is 860 m. 2 The capacity of the material serving as the super capacitor is only 120F/g, and the capacity of the material serving as the negative electrode material of the lithium battery is only 230mAhg -1 。
Table 1 shows the performance parameters of the nitrogen-doped carbon materials prepared in examples 1 to 19 of the present invention and comparative example 1:
Figure GDA0003750152450000141
Figure GDA0003750152450000151
Figure GDA0003750152450000161

Claims (12)

1. a method for preparing a nitrogen-doped carbon material by utilizing fluorine-containing macromolecules is characterized in that a fluorine-containing macromolecule precursor material is placed in an ammonia atmosphere and calcined at the temperature of 360-1200 ℃ to obtain the nitrogen-doped carbon material; the fluorine-containing polymer precursor material is a polymer with relative molecular mass of 1000-1000 ten thousand and partial hydrogen substituted by fluorine, and is at least one selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyvinyl fluoride (PVF), ethylene-chlorotrifluoroethylene copolymer (ECTFE) and ethylene-tetrafluoroethylene (ETFE) copolymer;
the atomic doping amount of nitrogen element in the nitrogen-doped carbon material is 4-15 at%; the conductivity of the nitrogen-doped carbon material is 1-100 mS/cm.
2. The method of claim 1, wherein a template agent is further added before calcining, wherein the template agent is selected from at least one of mesoporous silica, molecular sieve and magnesium oxide; the mass ratio of the template agent to the fluorine-containing polymer precursor material is (0.1-5): 1; and after calcination, the templating agent is removed with an etchant.
3. A method of making a nitrogen doped carbon material loaded conductive carbon felt, comprising:
(1) mixing a fluorine-containing polymer precursor material and a solvent to obtain a mixed solution, wherein the fluorine-containing polymer precursor material is an organic polymer with relative molecular mass of 1000-1000 ten thousand and partial hydrogen substituted by fluorine, and is at least one selected from polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyvinyl fluoride (PVF), ethylene-chlorotrifluoroethylene copolymer (ECTFE) and ethylene-tetrafluoroethylene (ETFE) copolymer;
(2) soaking a conductive carbon felt in the obtained mixed solution for 0.1-24 hours, drying, then placing in an ammonia atmosphere, and calcining at 360-1200 ℃ to obtain the conductive carbon felt loaded with the nitrogen-doped carbon material;
the nitrogen-doped carbon material loaded conductive carbon felt comprises: the conductive carbon felt comprises a conductive carbon felt and a nitrogen-doped carbon material loaded on the conductive carbon felt, wherein the loading amount of the nitrogen-doped carbon material is 1-70 wt%; the atomic doping amount of nitrogen element in the nitrogen-doped carbon material is 4-15 at%.
4. The method according to claim 3, wherein the solvent is selected from at least one of N-methylpyrrolidone, chloroform, water, and ethanol; the concentration of the mixed solution is 5-100 mg/mL.
5. The method according to claim 3, wherein a template is further added to the mixed solution, wherein the template is at least one selected from the group consisting of mesoporous silica, molecular sieves, and magnesium oxide; the mass ratio of the template agent to the fluorine-containing polymer precursor material is (0.1-5): 1; and after calcination, the template is removed with an etchant.
6. The method according to any one of claims 1 to 5, wherein the ammonia gas atmosphere is ammonia gas, or a mixed gas containing ammonia gas;
when an open container is selected for calcination, the gas flow of the ammonia gas atmosphere is 1-10000 mL/min;
when the calcining is carried out in a closed container during selection, the pressure of the ammonia atmosphere is 0.1-100 MPa.
7. The method of claim 6, wherein the ammonia gas atmosphere has a gas flow rate of 300mL/min when an open vessel is selected for calcination.
8. The method according to any one of claims 1 to 5, wherein the calcination temperature is 700 ℃.
9. The method according to any one of claims 1 to 5, wherein the temperature increase rate of the calcination is 0.1 to 100 ℃/min; the calcination time is 1 minute to 10 hours.
10. The method of claim 9, wherein the calcination is carried out at a ramp rate of 20 ℃/min; the calcination time was 4 hours.
11. Use of a nitrogen-doped carbon material prepared according to the method of claim 1 in the preparation of supercapacitors, lithium ion batteries, catalytic materials, desiccant materials and metal air batteries.
12. Use of the nitrogen-doped carbon material loaded conductive carbon mat made according to the method of claim 3 in the manufacture of supercapacitors, lithium ion batteries, catalytic materials, desiccant materials and metal air batteries.
CN201911029332.1A 2019-10-28 2019-10-28 Method for preparing nitrogen-doped carbon material by using fluorine-containing polymer Active CN112723334B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911029332.1A CN112723334B (en) 2019-10-28 2019-10-28 Method for preparing nitrogen-doped carbon material by using fluorine-containing polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911029332.1A CN112723334B (en) 2019-10-28 2019-10-28 Method for preparing nitrogen-doped carbon material by using fluorine-containing polymer

Publications (2)

Publication Number Publication Date
CN112723334A CN112723334A (en) 2021-04-30
CN112723334B true CN112723334B (en) 2022-09-09

Family

ID=75589374

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911029332.1A Active CN112723334B (en) 2019-10-28 2019-10-28 Method for preparing nitrogen-doped carbon material by using fluorine-containing polymer

Country Status (1)

Country Link
CN (1) CN112723334B (en)

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101306807B (en) * 2008-04-30 2011-08-03 中国科学院上海硅酸盐研究所 Method for preparing nitrogen-doped porous carbon material
CN102239112A (en) * 2008-06-18 2011-11-09 阿肯色大学理事会 Microwave-assisted synthesis of carbon and carbon-metal composites from lignin, tannin and asphalt derivatives and applications of same
CN103183345A (en) * 2011-12-28 2013-07-03 大连理工大学 Method for preparation of nitrogen doped activated carbon from chlorine-containing organic polymer waste
KR101340009B1 (en) * 2013-03-06 2013-12-11 한국과학기술원 Method for the synthesis of carbon materials using carbon dioxide
CN103213968B (en) * 2013-04-22 2015-01-14 北京化工大学 Heteroatom doped carbon material, and preparation method and application thereof
WO2015165762A1 (en) * 2014-04-30 2015-11-05 Basf Se Process for producing a monolithic body of a porous carbon material, monolithic bodies of special porous carbon materials and their use
CN104192824B (en) * 2014-08-12 2017-01-11 南京航空航天大学 Preparation method of nitrogen-doped ordered mesoporous carbon material
CN105645408B (en) * 2016-03-09 2017-10-13 湘潭大学 A kind of utilization jujube core prepares the technique of nitrogen-doped porous carbon material and the preparation method of electrode of super capacitor
CN105932234A (en) * 2016-05-05 2016-09-07 华东师范大学 Doped porous carbon spheres used for negative electrode material of sodium ion battery and preparation method for doped porous carbon spheres
CN106698410B (en) * 2016-12-05 2019-11-26 四川大学 The preparation method of nitrogen atom doping carbon nanomaterial
CN106629652B (en) * 2016-12-29 2018-07-27 华南农业大学 The biomass-based Carbon Materials of high-specific surface area and its exempt from process for preparing activated and application
CN107163071A (en) * 2017-05-22 2017-09-15 上海大学 Boron N doping guan class compounds and preparation method thereof
CN107739074B (en) * 2017-09-08 2021-07-09 南开大学 Preparation method of nitrogen-doped graphene composite cathode with high catalytic activity and technology for degrading organic pollutants
CN108878900B (en) * 2018-06-20 2021-06-11 湖南国昶能源科技有限公司 Preparation method of nitrogen-doped graphene modified carbon felt
CN109824029B (en) * 2019-03-28 2022-05-27 桂林电子科技大学 Nitrogen-doped porous carbon material based on polyvinylidene chloride and preparation method and application thereof
CN110002424A (en) * 2019-04-17 2019-07-12 安徽大学 Nitrogen and oxygen codope porous carbon materials, preparation method and applications
CN110078047A (en) * 2019-05-20 2019-08-02 中国科学院上海硅酸盐研究所 A kind of nitrogen-doped porous carbon material and preparation method thereof and the application in supercapacitor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Facile synthesis of nitrogen and fluorine co-doped carbon materials as efficient electrocatalysts for oxygen reduction reactions in air-cathode microbial fuel cells;Kai Meng et al;《Journal of Materials Chemistry A》;20150205(第13期);说明书第6874页左栏第3段和右栏第4段 *

Also Published As

Publication number Publication date
CN112723334A (en) 2021-04-30

Similar Documents

Publication Publication Date Title
Hamouda et al. Synthesis of porous carbon material based on biomass derived from hibiscus sabdariffa fruits as active electrodes for high-performance symmetric supercapacitors
CN110642238B (en) Graphene-like nitrogen-doped porous carbon material and preparation method and application thereof
JP2012508155A (en) Very porous activated carbon with controlled oxygen content
CN111320172B (en) Directional synthesis method and application of biomass activated carbon-based electrode material containing micropore-mesoporous pore canal
CN110937601A (en) Walnut shell based activated carbon, preparation method and application thereof
CN113943488B (en) Composite material based on polytetrafluoroethylene-coated MOFs material and preparation method thereof
CN112933955B (en) Preparation method and application of carbon nanofiber material capable of realizing high sulfur capacity
CN109437165B (en) Fluorine and nitrogen co-doped three-dimensional graphene material and one-step carbonization preparation method thereof
CN113871598B (en) MOF composite material and preparation method and application thereof
CN107651687A (en) A kind of preparation method and applications of the Carbon Materials rich in pyridine nitrogen
CN112723334B (en) Method for preparing nitrogen-doped carbon material by using fluorine-containing polymer
CN109205622B (en) Preparation method of biomass tar derived porous carbon material
CN111377446A (en) Preparation method of nitrogen and boron double-doped humic acid based porous carbon material with high thermal stability
CN111389448A (en) Graded porous g-C for photocatalytic degradation3N4Preparation method of @ wood composite material
CN114300274B (en) Boron-sulfur co-doped porous carbon material and preparation method and application thereof
CN113716546B (en) Graphene/mesoporous carbon/ZIF-derived carbon composite three-dimensional graded porous carbon material, and preparation method and application thereof
CN110330015B (en) Polymer-based carbon material and method for regulating and controlling microporous structure thereof
JP2003183014A (en) Porous carbon material, its producing method and electric double layer capacitor
CN114314556A (en) Resin-based carbon negative electrode material, preparation method and application thereof, and battery containing resin-based carbon negative electrode material
CN111627727A (en) Preparation method of biomass carbon material based on moso bamboo shoot shells and application of biomass carbon material in diaphragm-free supercapacitor
CN111252866A (en) CDI electrode active material and preparation and application thereof
CN116443877B (en) Coal-based three-dimensional porous carbon and preparation method and application thereof
CN115206693B (en) Biomass high-doping high-defect carbon material and preparation method and application thereof
CN114956035B (en) Ultra-microporous carbon material, sulfur positive electrode material and application research of ultra-microporous carbon material and sulfur positive electrode material in lithium sulfur battery
CN114724862A (en) Flexible self-supporting multifunctional interface AC @ PVDF electrode material and preparation method and application thereof

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