CN117509636A - Preparation method of benzoxazine resin-based carbon nano microsphere with high specific surface area, product and application thereof - Google Patents

Preparation method of benzoxazine resin-based carbon nano microsphere with high specific surface area, product and application thereof Download PDF

Info

Publication number
CN117509636A
CN117509636A CN202311498618.0A CN202311498618A CN117509636A CN 117509636 A CN117509636 A CN 117509636A CN 202311498618 A CN202311498618 A CN 202311498618A CN 117509636 A CN117509636 A CN 117509636A
Authority
CN
China
Prior art keywords
carbon nano
surface area
specific surface
microsphere
benzoxazine
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.)
Pending
Application number
CN202311498618.0A
Other languages
Chinese (zh)
Inventor
刘水国
张侃
魏彬彬
张琪
宋涛
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.)
Changzhou Hongju Electronic Technology Co ltd
Original Assignee
Changzhou Hongju Electronic Technology Co ltd
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 Changzhou Hongju Electronic Technology Co ltd filed Critical Changzhou Hongju Electronic Technology Co ltd
Priority to CN202311498618.0A priority Critical patent/CN117509636A/en
Publication of CN117509636A publication Critical patent/CN117509636A/en
Pending legal-status Critical Current

Links

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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • 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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • 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
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/42—Powders or particles, e.g. composition thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a preparation method and a product of benzoxazine resin-based carbon nano-microspheres with high specific surface area and application thereof. The carbon nano microsphere has the following characteristics: (1) The carbon nano microsphere prepared from the precursor has extremely high yield based on the high carbon residue rate of the benzoxazine resin; (2) The precursor contains C, N, O element, so that the prepared carbon nano microsphere contains a small amount of N, O doping; the specific surface area of the prepared carbon nano microsphere is extremely high; (4) The preparation process of the material is simple, and the obtained material has wide application in the energy storage fields of super capacitors, alkali metal batteries and the like.

Description

Preparation method of benzoxazine resin-based carbon nano microsphere with high specific surface area, product and application thereof
Technical Field
The invention belongs to the field of carbon nano materials, and particularly relates to a preparation method and a product of benzoxazine resin-based carbon nano microsphere with high specific surface area and application thereof.
Background
The carbon nano microsphere is one branch of a carbon nano material, has various excellent properties such as low density, large specific surface area, good stability, excellent electric conduction and heat conduction properties, good biocompatibility and the like, and is used in catalyst carriers, adsorption materials, wastewater treatment and CO 2 The method is widely applied to the fields of capturing and ion battery cathode materials, super capacitor electrode materials, hydrogen storage materials, drug delivery carriers and the like.
At present, the synthesis method of the carbon nano-microsphere mainly comprises a chemical vapor deposition method, a liquid phase method and a template method. Chemical vapor deposition is a process technique that utilizes reactive species in a gaseous state to chemically react such that a solid product is deposited on the surface of a heated solid substrate and ultimately produces a solid material, which is relatively simple to produce, but typically requires the use of a metal oxide as a catalyst and may be accompanied by the formation of a large amount of byproducts. The liquid phase method mainly uses water or an organic solvent as a medium, and changes reactants under certain temperature and pressure conditions in a closed container (such as a high-pressure reaction kettle) to form the nano microsphere, however, the liquid phase method has high cost and long reaction time, and is not suitable for industrial popularization and application. The template method can limit the nano particles in the matrix structure of the template, so that the stability of the nano particles is improved and the growth direction of the nano particles is controlled, however, a corrosive acid or alkali is usually required to be used for removing the sacrificial inorganic template in the synthesis process, if the sacrificial template is not used, the carbonized product needs to be activated at high temperature to obtain the porous carbon material, and the yield is extremely low; and a large amount of acid is needed for neutralization and washing during post-treatment due to the addition of a large amount of strong alkali, so that the preparation process is relatively complex.
The benzoxazine resin has a plurality of advantages as a novel thermosetting resin material, such as good molecular design, processability, almost zero volume shrinkage in the curing process, high carbon residue, low water absorption, low dielectric property, excellent tolerance and the like. However, the current preparation method of benzoxazine resin is complicated and has low yield. Patent CN 102225996A discloses a preparation method of benzoxazine resin nano polymer spheres and carbon spheres, but the reaction process is complicated, and the obtained carbon nano microspheres have no characteristic of high specific surface area.
Therefore, there is a need in the art for a method for preparing carbon nano-microspheres with simple and efficient preparation process, high yield and high specific surface area.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of the benzoxazine resin-based carbon nano-microsphere with high specific surface area.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing benzoxazine resin-based carbon nano-microspheres with high specific surface area comprises the following steps,
dissolving benzoxazine monomer and surfactant in solvent to obtain dissolved product;
drying the dissolved product at 80-100 ℃ for 12-20 hours to prepare a mixture;
adding an activating agent into the mixture, grinding and uniformly mixing to obtain a precursor;
carbonizing the obtained precursor to obtain the benzoxazine resin-based carbon nano-microsphere with high specific surface area;
wherein, the benzoxazine monomer has the structure:
as a preferred embodiment of the preparation process according to the invention, there is provided: the surfactant is one or more of pluronic F127, pluronic F68, pluronic P105, pluronic P85 and pluronic P123.
As a preferred embodiment of the preparation process according to the invention, there is provided: the solvent is one or more of ethanol, ethyl acetate and N, N-dimethylformamide.
As a preferred embodiment of the preparation process according to the invention, there is provided: the benzoxazine monomer and the surfactant are dissolved in a solvent, wherein the dissolution temperature is 50-80 ℃.
As a preferred embodiment of the preparation process according to the invention, there is provided: the activating agent is one or more of potassium hydroxide, ammonium persulfate and potassium ferrate.
As a preferred embodiment of the preparation process according to the invention, there is provided: the mass ratio of the benzoxazine monomer to the surfactant is 0.1-1: 0.1 to 1, wherein the ratio of the benzoxazine monomer to the solvent is 0.1 to 1g: 20-50 mL.
As a preferred embodiment of the preparation process according to the invention, there is provided: the mass ratio of the activator to the benzoxazine monomer is 0.2-0.4:1.
As a preferred embodiment of the preparation process according to the invention, there is provided: the precursor carbonization treatment comprises the following treatment processes,
and (3) placing the precursor into a tube furnace, and heating to 500-1000 ℃ for carbonization for 1-2 h under the purging of argon.
It is still another object of the present invention to overcome the disadvantages of the prior art and to provide a benzoxazine resin-based carbon nano-microsphere with a high specific surface area, wherein the diameter of the carbon nano-microsphere is 200-600 nm, and the specific surface area is 1000-2000m 2 /g。
The invention further aims to overcome the defects in the prior art and provide application of the benzoxazine resin-based carbon nano-microsphere with high specific surface area as an electrode material of a super capacitor or an alkali metal battery.
The invention has the beneficial effects that:
(1) The invention overcomes the defects of complex preparation method and low yield of polymer as precursor of the traditional nano microsphere, creatively selects benzoxazine resin as precursor of the carbon nano microsphere for the first time, and obtains the benzoxazine resin-based carbon nano microsphere material with high specific surface area by high-temperature carbonization of the prepared benzoxazine precursor.
(2) The deep crosslinking of the benzoxazine group of the carbon nano-microsphere prepared by the invention has the yield of the carbonized nano-microsphere of more than 50 percent, the diameter of the carbon nano-microsphere of 200-600 nm and the specific surface area of 1000-2000m 2 /g。
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a nuclear magnetic resonance spectrum of a benzoxazine resin obtained in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of the benzoxazine resin obtained in example 1 of the present invention;
FIG. 3 is an SEM image of benzoxazine resin-based carbon nano-spheres obtained in example 1 of the present invention;
fig. 4 is a nitrogen elution isothermal curve of the benzoxazine resin-based carbon nano-microspheres obtained in example 1 of the present invention;
FIG. 5 is a Raman image of a benzoxazine resin-based carbon nano-microsphere obtained in example 1 of the present invention;
fig. 6 is an XRD image of the benzoxazine resin-based carbon nano-microsphere obtained in example 1 of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Pluronic F127 in the present invention was purchased from Sigma-Aldrich.
The method for calculating the yield of the carbon nano microsphere comprises the following steps:
yield (%) = microsphere mass (g)/benzoxazine monomer mass (g) ×100%
The diameter of the carbon nano microsphere is measured by a scanning tunnel microscope; the specific surface area of the carbon nanomicrospheres was measured by a full-automatic specific surface area and porosity analyzer.
Example 1
(1) 1g of benzoxazine monomer (PH-ddm) and 1g of pluronic F127 were poured into a beaker. The PH-ddm structural formula and the specific synthesis method are as follows:
the synthesis method comprises the following steps: 0.01mol of 4,4' -diaminodiphenylmethane, 0.02mol of phenol and 0.04mol of paraformaldehyde are weighed and dissolved in 50ml of toluene, and after reflux reaction for 6 hours at 120 ℃, benzoxazine monomers are obtained through recrystallization.
(2) 50ml of ethyl acetate was added to the beaker, and the sample was completely dissolved in the solvent in ethyl acetate using magnetic stirring at 60 ℃;
placing the beaker and the product in a blast oven, and standing at 80 ℃ for 12 hours until all solvents are completely evaporated;
the mixture was taken out, 0.2g of potassium hydroxide was added, and the mixture was ground and mixed uniformly by means of a mortar to obtain a precursor.
(3) And (3) placing the prepared benzoxazine precursor into a tubular furnace, and heating to 600 ℃ under the purging of argon for carbonization for 1h to obtain the carbon nano-microsphere.
(4) The yield of the obtained carbon nano microsphere is 56%, the diameter is about 400nm, and the specific surface area is 1264.8124m 2 /g。
FIG. 1 is a nuclear magnetic hydrogen spectrum of a benzoxazine resin; from FIG. 1, it can be seen that the characteristic peaks for the two methylene groups on the oxazine are at 4.6 and 5.4ppm, respectively.
FIG. 2 is a nuclear magnetic resonance spectrum of a benzoxazine resin; from FIG. 2, it can be seen that the characteristic peaks for the two methylene groups on the oxazine are at 45 and 80ppm, respectively.
Fig. 3 is an SEM image of the benzoxazine resin-based carbon nano-microsphere, and it can be seen from fig. 3 that the diameter of the benzoxazine resin-based carbon nano-microsphere is about 400nm.
FIG. 4 is a nitrogen elution isothermal curve of the benzoxazine resin-based carbon nano-microspheres obtained in example 1; from the nitrogen-eluting isothermal curve of FIG. 4, a specific surface area of 1264.8124m was obtained 2 /g。
FIG. 5 Raman image of benzoxazine resin based carbon nano-microspheres obtained in example 1; from FIG. 5, it is possible toSee that the carbon nano microsphere is 1350cm -1 D band appearing at 1580cm -1 G bands appear at the location.
Figure 6 XRD image of benzoxazine resin-based carbon nano-microspheres obtained in example 1. The (002) and (100) planes appearing at 23 ° and 43 ° can be seen from fig. 6.
Comparative example 1
Comparative example 1 differs from example 1 in that: the procedure of example 1 was repeated except that the activator was not added.
The yield of the obtained carbon nano microsphere is 55.4%, the diameter is about 400nm, and the specific surface area is 69.2456m 2 /g。
Comparative example 2
Comparative example 2 is different from example 1 in that: only 0.1g of potassium hydroxide was added, and the other contents were the same as in example 1.
The yield of the obtained carbon nano microsphere is 55.1 percent, the diameter is about 400nm, and the specific surface area is 410.1263m 2 /g。
Comparative example 3
Comparative example 3 is different from example 1 in that: 0.3g of potassium hydroxide was added thereto, and the other contents were the same as in example 1.
The yield of the obtained carbon nano microsphere is 55.6%, the diameter is about 400nm, and the specific surface area is 1252.6538m 2 /g。
Comparative example 4
Comparative example 4 differs from example 1 in that: 0.3g F127 was added, and the other contents were the same as in example 1.
The obtained carbon material was in the form of a block, and a microspherical carbon material could not be obtained.
Comparative example 5
Comparative example 5 is different from example 1 in that: 2gF127 was added, and the other contents were the same as in example 1.
The obtained carbon material was 3D foam-like, and no microspherical carbon material could be obtained.
The invention discloses a preparation method and a product of benzoxazine resin-based carbon nano-microspheres with high specific surface area and application thereof. The carbon nano microsphere has the following characteristics: (1) The carbon nano microsphere prepared from the precursor has extremely high yield based on the high carbon residue rate of the benzoxazine resin; (2) The precursor contains C, N, O element, so that the prepared carbon nano microsphere contains a small amount of N, O doping; the specific surface area of the prepared carbon nano microsphere is extremely high; (4) The preparation process of the material is simple, and the obtained material has wide application in the energy storage fields of super capacitors, alkali metal batteries and the like.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, and it should be covered in the scope of the present invention.

Claims (10)

1. A preparation method of benzoxazine resin-based carbon nano-microspheres with high specific surface area is characterized by comprising the following steps: comprising the steps of (a) a step of,
dissolving benzoxazine monomer and surfactant in solvent to obtain dissolved product;
drying the dissolved product at 80-100 ℃ for 12-20 hours to prepare a mixture;
adding an activating agent into the mixture, grinding and uniformly mixing to obtain a precursor;
carbonizing the obtained precursor to obtain the benzoxazine resin-based carbon nano-microsphere with high specific surface area;
wherein, the benzoxazine monomer has the structure:
2. the method of manufacturing according to claim 1, wherein: the surfactant is one or more of pluronic F127, pluronic F68, pluronic P105, pluronic P85 and pluronic P123.
3. The preparation method according to claim 1 or 2, characterized in that: the solvent is one or more of ethanol, ethyl acetate and N, N-dimethylformamide.
4. A method of preparation as claimed in claim 3, wherein: the benzoxazine monomer and the surfactant are dissolved in a solvent, wherein the dissolution temperature is 50-80 ℃.
5. The method of manufacturing according to claim 1, wherein: the activating agent is one or more of potassium hydroxide, ammonium persulfate and potassium ferrate.
6. The method of any one of claims 1, 2, 4 or 5, wherein: the mass ratio of the benzoxazine monomer to the surfactant is 0.1-1: 0.1 to 1, wherein the ratio of the benzoxazine monomer to the solvent is 0.1 to 1g: 20-50 mL.
7. The method of manufacturing according to claim 6, wherein: the mass ratio of the activator to the benzoxazine monomer is 0.2-0.4:1.
8. The method of manufacturing according to claim 1, wherein: the precursor carbonization treatment comprises the following treatment processes,
and (3) placing the precursor into a tube furnace, and heating to 500-1000 ℃ for carbonization for 1-2 h under the purging of argon.
9. The benzoxazine resin-based high specific surface area carbon nano-microsphere prepared by the preparation method of any one of claims 1 to 8, which is characterized in that: the diameter of the carbon nano microsphere is 200-600 nm, and the specific surface area is 1000～2000m 2 /g。
10. The use of the benzoxazine resin-based high specific surface area carbon nano-microsphere according to claim 9 as an electrode material of a supercapacitor and/or an alkali metal battery.
CN202311498618.0A 2023-11-13 2023-11-13 Preparation method of benzoxazine resin-based carbon nano microsphere with high specific surface area, product and application thereof Pending CN117509636A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311498618.0A CN117509636A (en) 2023-11-13 2023-11-13 Preparation method of benzoxazine resin-based carbon nano microsphere with high specific surface area, product and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311498618.0A CN117509636A (en) 2023-11-13 2023-11-13 Preparation method of benzoxazine resin-based carbon nano microsphere with high specific surface area, product and application thereof

Publications (1)

Publication Number Publication Date
CN117509636A true CN117509636A (en) 2024-02-06

Family

ID=89747291

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311498618.0A Pending CN117509636A (en) 2023-11-13 2023-11-13 Preparation method of benzoxazine resin-based carbon nano microsphere with high specific surface area, product and application thereof

Country Status (1)

Country Link
CN (1) CN117509636A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080019921A1 (en) * 2006-06-30 2008-01-24 Invitrogen Corporation Uniform fluorescent microsphere with hydrophobic surfaces
CN102225996A (en) * 2011-05-06 2011-10-26 大连理工大学 Preparation method for benzoxazine resin nano-polymer sphere and benzoxazine resin nano-polymer carbon sphere
CN108559042A (en) * 2018-04-18 2018-09-21 成都天羽新材料有限公司 A kind of preparation method of benzoxazine colophony

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080019921A1 (en) * 2006-06-30 2008-01-24 Invitrogen Corporation Uniform fluorescent microsphere with hydrophobic surfaces
CN102225996A (en) * 2011-05-06 2011-10-26 大连理工大学 Preparation method for benzoxazine resin nano-polymer sphere and benzoxazine resin nano-polymer carbon sphere
CN108559042A (en) * 2018-04-18 2018-09-21 成都天羽新材料有限公司 A kind of preparation method of benzoxazine colophony

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LIU WAN ET AL.: "Nitrogen-Enriched Hierarchically Porous Carbons Prepared from Polybenzoxazine for High-Performance Supercapacitors", 《ACS APPLIED MATERIALS & INTERFACES》, vol. 6, 19 August 2014 (2014-08-19), pages 15584 *

Similar Documents

Publication Publication Date Title
JP4410775B2 (en) Mesoporous carbon composite, process for producing the same, supported catalyst containing the same, and fuel cell using the same
CN107265433A (en) Three-dimensional porous nitrating carbon material and its preparation method and application
CN106654278A (en) Novel carbon spheres and preparation method and application thereof
CN108711518B (en) Nitrogen-oxygen co-doped porous carbon nanoribbon as well as preparation method and application thereof
CN111463019B (en) Preparation method of core-shell structure electrode material
CN113178338B (en) Carbazolyl porous carbon/polyaniline composite electrode material and preparation method thereof
CN109524244B (en) Nitrogen-containing two-dimensional conjugated carbon material and preparation method and application thereof
CN111056545A (en) Preparation method of MOFs-derived hollow porous carbon microspheres
CN108640113B (en) Preparation method of nitrogen and oxygen co-doped porous carbon material based on bio-based benzoxazine
CN107963620A (en) A kind of preparation method of high nitrogen doped Carbon Materials
CN110690054B (en) Preparation method of atomic-level dispersed zinc carbon nitrogen material for super capacitor
CN117509636A (en) Preparation method of benzoxazine resin-based carbon nano microsphere with high specific surface area, product and application thereof
CN113060724A (en) Hollow carbon sphere and preparation method and application thereof
CN109110744B (en) Preparation method of hollow tubular polyaniline-based carbon material
CN113355918B (en) Microporous carbon fiber grafted polyaniline/CoNi 2 S 4 Preparation method and application of composite material
CN108455563A (en) A kind of preparation method of Nitrogen-rich porous carbon microballoon
CN110444411B (en) Conductive organic polymer coated phenolic resin matrix porous carbon composite material
CN110117842B (en) Preparation method of hollow silicon carbide ceramic fiber
CN109898179B (en) Preparation method of titanium carbide fiber material
CN115432702B (en) Method for preparing carbon super-structure material based on Lewis acid-base interaction self-assembly
CN113880067B (en) Preparation method of porous carbon super-structure material
CN113914015B (en) Preparation method of porous carbon film based on Schiff base polymer
CN115448310B (en) Nitrogen-containing porous carbon material and preparation method and application thereof
CN111940721B (en) Method for loading nano metal oxide or nano metal material on porous carbon
CN113831532B (en) Nano spherical polypyrrole, preparation method thereof, nitrogen-doped carbon material 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