CN111847445B - Conductive aza-mesoporous carbon material and preparation method thereof - Google Patents

Conductive aza-mesoporous carbon material and preparation method thereof Download PDF

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CN111847445B
CN111847445B CN202010641916.0A CN202010641916A CN111847445B CN 111847445 B CN111847445 B CN 111847445B CN 202010641916 A CN202010641916 A CN 202010641916A CN 111847445 B CN111847445 B CN 111847445B
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mesoporous carbon
carbon material
conductive
nitrogen
resin
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CN111847445A (en
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段晓雨
李璐
邢译
李建生
王雪
杜伟业
李忠元
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Tianjin Vocational Institute
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    • 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
    • C01B32/348—Metallic compounds
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    • 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
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention relates to a conductive nitrogen hybridized mesoporous carbon material prepared from waste p-hydroxy phenyl hydantoinThe phenolic aldehyde resin prepared by the reaction of the liquid and formaldehyde is used as a carbon source and a nitrogen source, the conductive oxide is used as a catalytic activator and a doping agent, the conductive oxide is doped into the phenolic urea resin, and the conductive nitrogen hybrid mesoporous carbon material is formed by catalytic carbonization and activation at 350-600 ℃, and has the square resistance of 50-100 omega/\\ 9633, the specific capacity of 300-700F/g and the specific surface area of 1000-1500m 2 The pore diameter is 4-20nm, the mesoporous rate is 70-80%, the mass content of C is 60-80%, the mass content of N is 5-10%, and the mass content of Sn is 5-15%; the conductive oxide catalyst activator and the dopant are nano SnO 2‑x F x Wherein x =0.02-0.2. The conductive nitrogen-hybridized mesoporous carbon material can meet the application requirements of electrodes of super capacitors and lithium ion batteries.

Description

Conductive aza-mesoporous carbon material and preparation method thereof
Technical Field
The invention relates to a conductive nitrogen hybridized mesoporous carbon material and a preparation method thereof, in particular to a conductive nitrogen hybridized mesoporous carbon material prepared by using novolac aldehyde resin as a carbon source and conductive oxide as a catalytic activator and a dopant for catalytic carbonization activation, belonging to the field of applied chemistry and new energy materials.
Background
The "black technology" and "black materials" represented by graphene, carbon nanotubes and ordered mesoporous carbon are central roles in the field of nanomaterials. The 'black science and technology' and the 'black material' become dual-purpose new materials for military and civil use due to a series of excellent characteristics, and are of great importance to improving national military strength and competitiveness of industrial products.
The graphene and the carbon nano tube have good conductivity, are particularly suitable for being used as electrode materials of super capacitors and lithium ion batteries, but the high production cost and price limit the application and popularization of the graphene and carbon nano tube.
Nitrogen alloying mesoporous carbon is a black porous substance formed by doping nitrogen atoms in the skeleton of the ordered mesoporous carbon to partially replace carbon atoms, and nitrogen alloying greatly changes the chemical composition of the mesoporous carbon, enhances the strength of the skeleton structure of the mesoporous carbon, changes the pore structure of the mesoporous carbon, changes the surface property of the mesoporous carbon, provides a large number of chemical active sites, enhances the surface hydrophilicity of the mesoporous carbon and increases the adsorption capacity. The nitrogen-hybridized mesoporous carbon material not only has high adsorption capacity, but also has the advantage of higher adsorption and desorption speeds.
The nitrogen-hybridized mesoporous carbon material has the nanometer size effect inferior to that of graphene and carbon nanotube materials, but has the advantages of easy realization of large-scale production and low production cost, is easy to realize commercial popularization and application, and is more and more concerned by professionals in the field of new energy. The basic requirements of electrodes of supercapacitors and lithium ion batteries on carbon materials are: (1) having a high specific surface area to adsorb more electrolyte; (2) has high conductivity to reduce the internal resistance of the electrode material; (3) The cost is low, so that the method is convenient for large-scale commercial popularization and application.
The nitrogen-doped mesoporous carbon material has the advantages of high specific surface area and low cost, has no conductivity, is completely conductive by virtue of adsorbed electrolyte, and can be used as an electrode material of a super capacitor and a lithium ion battery only by being matched with other high-conductivity materials such as conductive graphite, conductive polymers, conductive oxides and the like in practical application.
The high-conductivity material is difficult to uniformly dope into the nitrogen-doped mesoporous carbon material. If a high-conductivity material is doped into the nitrogen-doped mesoporous carbon material to prepare the conductive nitrogen-doped mesoporous carbon material, the competitive advantage of the conductive nitrogen-doped mesoporous carbon material with graphene and carbon nanotubes is greatly improved.
The document reports that metal oxides such as cobalt oxide, nickel oxide, manganese oxide, lead oxide, ruthenium oxide and the like and mesoporous carbon form a composite material to serve as an electrode material of a super capacitor, so that the specific capacitance of the electrode can be improved. Often, a large amount of metal oxide needs to be doped to improve the conductivity of mesoporous carbon, and the problem that a high-conductivity material is uniformly doped into the nitrogen-doped mesoporous carbon material is not solved.
The nitrogen content of the existing nitrogen-hybridized mesoporous carbon material is lower and is generally below 5%. The main reason is that nitrogen hybridized mesoporous carbon is usually formed by activation at a high temperature of 800 ℃, the gasification loss of nitrogen atoms at a high temperature is large, and the effect of the nitrogen hybridized mesoporous carbon material is not fully exerted.
Disclosure of Invention
The invention aims to provide a conductive nitrogen hybridized mesoporous carbon material which can meet the application requirements of super capacitors and lithium ion battery electrodes, particularly uses cheap phenol-formaldehyde urea-formaldehyde resin as a carbon source, uses conductive oxide as a catalyst activator and a dopant, enables the conductive oxide to be doped into the phenol-formaldehyde urea-formaldehyde resin, and forms the conductive nitrogen hybridized mesoporous carbon material through catalytic carbonization and activation at 350-600 ℃, wherein the square resistance of the obtained product is 50-100 omega/9633the specific capacity is 300-700F/g, and the specific surface area is 1000-1500m 2 The pore diameter is 4-20nm, the mesoporous rate is 70-80%, the mass content of C is 60-80%, the mass content of N is 5-10%, and the mass content of Sn is 5-15%; the phenolic urea aldehyde resin is prepared by reacting waste liquid from production of p-hydroxy phenyl hydantoin with formaldehyde, and comprises the following components in percentage by mass: 50-75% of C, 3-5% of H, 10-25% of O and 7-25% of N; the conductive oxide catalyst activator and the dopant are nano SnO 2-x F x Wherein x =0.02-0.2.
The invention also aims to provide a preparation method of the conductive nitrogen-hybridized mesoporous carbon material, which adopts the technical scheme that five parts of the preparation of the phenolic urea formaldehyde resin and the catalytic activator, the catalytic carbonization of the phenolic urea formaldehyde resin, the catalytic activation of the carbide and the formation of the conductive nitrogen-hybridized mesoporous carbon material are included.
The phenolic aldehyde urea resin and the catalyst activator are mixed: snF with mass concentration of 10% is used for the phenolic urea formaldehyde resin crushed to 300 meshes 2 Soaking in water solution for 4-8 hr to make the catalyst activator permeate into pores of the resin and adsorb on the surface of the resin; then drying the mixture at 110-120 ℃ to control the phenolic urea formaldehyde resin and the SnF 2 The feeding mass ratio of (1); the phenolic urea aldehyde resin comprises the following components in percentage by mass: 50% -75% of C, 3% -5% of H, 10% -25% of O and 7% -25% of N.
Catalyzing and carbonizing phenolic aldehyde urea resin: will load SnF 2 Placing the phenolic aldehyde resin into biscuit firingPutting the ceramic crucible into a high-temperature furnace, carrying out catalytic carbonization for 2-4h at 350-400 ℃ under the protection of simulated flue gas, wherein SnF is generated in the process 2 Melting and permeating into the resin, oxidizing and decomposing into nanometer SnO with particle size of 5-20nm 2-x F x Wherein x =0.02-0.2; nano SnO 2-x F x5 The catalyst has oxidation and dehydration functions on organic matters, so that the resin raw material is catalyzed and carbonized; the flue gas is CO 2 The volume ratio of the gas to the air is 4.
Catalytic activation of the char: heating the high-temperature furnace to 500-600 ℃, catalytically activating the carbide for 2-4h under the protection of flue gas, and then cooling to room temperature, wherein the nano SnO is in the process 2-x F x Oxidizing and etching the carbide contacted with the oxide to form a large number of micropores, and further etching to form mesopores.
Formation of conductive nitrogen-hybridized mesoporous carbon material: soaking the cooled catalytic activation material in hot water to dissolve soluble ash, filtering and separating precipitate, washing the precipitate with deionized water to pH 7-8, and drying at 110 deg.C to obtain conductive aza-mesoporous carbon material with square resistance of 50-100 Ω/9633of 300-700F/g, specific surface area of 1000-1500m 2 The pore diameter is 4-20nm, the mesoporous rate is 70-80%, the mass content of C is 60-80%, the mass content of N is 5-10%, and the mass content of Sn is 5-15%.
The invention is based on the research of the applicant on the production of the activating agent by the transparent conductive film material and the activated carbon of the solar cell. Fluorine-doped tin oxide SnO 2-x F x Has good conductivity, is often used as a transparent conductive film of a solar cell, is formed by high-temperature reaction of tin salt and fluorine salt, and a small amount of fluorine ions are doped into SnO instead of oxygen 2 In the semiconductor, snO is greatly improved 2 The carrier concentration in the semiconductor material makes it have high conductivity without changing SnO obviously 2 Structure, composition and basic properties of (a).
Fluorine-doped tin oxide SnO 2-x F x The principle of using Co and Ni salt as catalyst activator to prepare nitrogen hybridized mesoporous carbon is similar to that of using Co and Ni salt as catalyst activator in the prior art, and is different from that of using Co and Ni salt as catalyst activatorThe fluorine-doped tin oxide has high conductivity and high specific capacitance, and is used as a catalyst activator of a resin raw material and an effective component of a nitrogen-doped mesoporous carbon product.
The tin fluoride in the invention has the characteristics of good water solubility and lower melting point (215 ℃) and boiling point (850 ℃), is easy to permeate into raw material powder in the form of aqueous solution at room temperature, is easy to permeate into carbide in the form of liquid molten salt and sublimation gas at the carbonization temperature, and is oxidized and decomposed into fluorine-doped tin oxide at the melting point temperature.
The invention has the beneficial effects that:
(1) Conductive oxide SnO 2-x F x The doping improves the conductivity of the mesoporous carbon material by 20-50 times, and the mesoporous carbon material has better conductivity than the existing Co, ni or Fe oxide;
(2) Using SnO 2-x F x As a catalytic activator, the activation temperature of the resin carbide is reduced from 800 ℃ to below 600 ℃, the gasification loss of nitrogen atoms at high temperature is reduced, and the mesoporous carbon material with high nitrogen content can be obtained;
(3) SnO 2-x F x The catalyst activator is simultaneously used as an effective component of the conductive nitrogen hybridized mesoporous carbon material, thereby omitting the recovery process of the catalyst activator and simplifying the preparation process of the conductive nitrogen hybridized mesoporous carbon material.
The phenolic urea formaldehyde resin adopted in the invention is porous phenolic urea formaldehyde resin copolymer or mixture powder obtained by condensing waste liquid of p-hydroxy phenyl hydantoin industrial production and excessive formaldehyde under acidic or alkaline conditions and heating and curing at 150-180 ℃, and has good adsorption capacity on a catalytic activator. In the curing process of the novolac aldehyde resin, active methylol and active hydrogen in polymer molecules are condensed to generate water, and the water molecules are gasified into a large number of micro-bubbles during high-temperature curing, so the cured novolac urea resin is generally porous powder.
The raw materials of tin fluoride, formaldehyde, sodium hydroxide, hydrochloric acid and the like adopted in the invention are chemical reagents. The waste liquid from industrial production of p-hydroxy phenyl hydantoin comes from the company of the North chenchen platform and the related production company of Nemont Uilange fabric.
Detailed Description
Example 1
100g of phenolic urea formaldehyde resin powder which is crushed to 300 meshes is taken, and SnF with the mass concentration of 10 percent is used 2 Soaking in water solution for 4h to allow the catalyst activator to penetrate into pores of the resin and be adsorbed on the surface of the resin; then, it was dried at 110 to 120 ℃ to obtain 108g of a solid powder. Will load SnF 2 The phenolic aldehyde resin is put into a biscuit firing ceramic crucible and placed in a high temperature furnace, and under the protection of simulated flue gas, catalytic carbonization is carried out for 2 hours at 350-400 ℃, so as to obtain 65g of conductive carbide. The high-temperature furnace is heated to 500-600 ℃, the carbide is catalytically activated for 2 hours under the protection of flue gas, and then the furnace is cooled to room temperature.
Soaking the cooled catalytic activation material with 500ml of hot water at 70 ℃ to dissolve soluble ash, filtering and separating precipitates, washing the precipitates with deionized water until the pH value is 7-8, and drying at 110 ℃ to obtain 36g of the conductive aza-mesoporous carbon material with the square resistance of 60 omega/\ 9633the specific capacity of 560F/g and the specific surface area of 1300m 2 The specific surface area of the alloy is 8nm, the average pore diameter is 70%, the mesoporous rate is 60-80%, the mass content of C is 7.2%, and the mass content of Sn is 13%.

Claims (4)

1. A preparation method of a conductive nitrogen-hybridized mesoporous carbon material is characterized in that the adopted technical scheme comprises five parts of blending of phenol-formaldehyde resin and a catalytic activator, catalytic carbonization of the phenol-formaldehyde resin, catalytic activation of a carbide and formation of the conductive nitrogen-hybridized mesoporous carbon material; the phenolic urea formaldehyde resin and the catalyst activator are prepared by crushing the phenolic urea formaldehyde resin to 300 meshes and using SnF with the mass concentration of 10 percent 2 Soaking in water solution for 4-8 hr to make the catalyst activator penetrate into pores of the resin and adsorb on the surface of the resin; then drying the mixture at 110-120 ℃ to control the phenolic urea formaldehyde resin and the SnF 2 The feeding mass ratio of (1) is 0.05-0.1; the phenolic urea aldehyde resin comprises the following components in percentage by mass: 50-75% of C, 3-5% of H, 10-25% of O and 7-25% of N;
the catalytic carbonization of the phenolic aldehyde urea-formaldehyde resin is to load SnF 2 Of phenol formaldehydePutting urea aldehyde resin into a biscuit firing ceramic crucible, putting the biscuit firing ceramic crucible into a high temperature furnace, carrying out catalytic carbonization for 2-4h at 350-400 ℃ under the protection of simulated flue gas, and SnF in the process 2 Melting and permeating into the resin, oxidizing and decomposing into nanometer SnO with particle size of 5-20nm 2-x F x Wherein x =0.02-0.2; the flue gas is CO 2 The volume ratio of the gas to the air is 4.
2. The method for preparing the conductive nitrogen-hybridized mesoporous carbon material as claimed in claim 1, wherein the catalytic activation of the carbide: heating the high-temperature furnace to 500-600 ℃, catalytically activating the carbide for 2-4h under the protection of flue gas, and then cooling to room temperature, wherein the nano SnO is 2-x F x Oxidizing and etching the carbide contacted with the oxide to form a large number of micropores, and further etching to form mesopores.
3. The method of preparing conductive nitrogen-hybridized mesoporous carbon material as claimed in claim 2, wherein the conductive nitrogen-hybridized mesoporous carbon material is formed by immersing the cooled catalytic activation material in hot water to dissolve soluble ash, filtering and separating the precipitate, washing the precipitate with deionized water to pH 7-8, and then drying at 110 ℃; the square resistance of the obtained conductive nitrogen-hybridized mesoporous carbon material is 50-100 omega/\ 9633, the specific capacity is 300-700F/g, and the specific surface area is 1000-1500m 2 The pore diameter is 4-20nm, the mesoporous rate is 70-80%, the mass content of C is 60-80%, the mass content of N is 5-10%, and the mass content of Sn is 5-15%.
4. The conductive aza-mesoporous carbon material obtained by the preparation method of any one of claims 1 to 3, wherein the square resistance of the obtained product is 50-100 Ω/\9633, the specific capacity is 300-700F/g, and the specific surface area is 1000-1500m 2 The pore diameter is 4-20nm, the mesoporous rate is 70-80%, the mass content of C is 60-80%, the mass content of N is 5-10%, and the mass content of Sn is 5-15%.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108950740A (en) * 2018-06-26 2018-12-07 合肥萃励新材料科技有限公司 A kind of synthetic method of FTO load carbon fiber
CN110064366A (en) * 2019-04-27 2019-07-30 天津市职业大学 A kind of phenols waste residue is magnetic active carbon and its preparation and the application of raw material

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WO2012018890A2 (en) * 2010-08-06 2012-02-09 Arizona Board Of Regents For And On Behalf Of Arizona State University Fabricating porous materials using intrepenetrating inorganic-organic composite gels

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108950740A (en) * 2018-06-26 2018-12-07 合肥萃励新材料科技有限公司 A kind of synthetic method of FTO load carbon fiber
CN110064366A (en) * 2019-04-27 2019-07-30 天津市职业大学 A kind of phenols waste residue is magnetic active carbon and its preparation and the application of raw material

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