CN106882783B - A kind of method of the nitrogenous sulphur multi-stage porous charcoal of Solid phase synthesis - Google Patents

A kind of method of the nitrogenous sulphur multi-stage porous charcoal of Solid phase synthesis Download PDF

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CN106882783B
CN106882783B CN201510918904.7A CN201510918904A CN106882783B CN 106882783 B CN106882783 B CN 106882783B CN 201510918904 A CN201510918904 A CN 201510918904A CN 106882783 B CN106882783 B CN 106882783B
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nitrogenous
carbon materials
amino
sulphur
aldehyde
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CN106882783A (en
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郭德才
陈剑
陶韬
孙春水
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In Kepaisi Energy Storage Technology Co Ltd
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    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/90—Other morphology not specified above
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/16—Pore diameter
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    • C01—INORGANIC CHEMISTRY
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    • C01P2006/40—Electric properties
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The present invention relates to one kind based on schiff bases chemistry, and the synthetic method of the hetero atoms porous charcoal such as nitrogenous, sulphur is prepared using solid phase method in situ.Using the schiff base reaction between amino-containing fragrant cyclics (melamine, p-aminobenzene sulfonic acid etc.) and aldehydes containing aromatic ring (terephthalaldehyde, m-terephthal aldehyde or 4,4'- diphenyl-dimethanals), nitrogenous, sulphur polymer is generated.By the gas-solid phase reaction between reducing atmospheres and lithia such as hydrocarbon of generation during Polymer-pyrolysis, in-situ preparation carbonate removes template and obtains the honeycomb structures porous carbon material such as nitrogenous, sulphur as the template for preparing Carbon Materials, pickling.The method of the invention preparation method is easy to operate, device simple, reaction in-situ generates template, and then can obtain porous structure Carbon Materials, and the heteroatomic hierarchical porous structure Carbon Materials such as the adjustable nitrogenous, sulphur of morphology controllable, pore passage structure can be prepared by regulating and controlling experiment parameter.

Description

A kind of method of the nitrogenous sulphur multi-stage porous charcoal of Solid phase synthesis
Technical field
Nitrogenous, sulphur multi-stage porous charcoal preparation method that the present invention relates to a kind of Solid phase synthesis, can be closed using this process At cellular nitrogenous, sulphur multi-stage artery structure Carbon Materials, belong to novel Heteroatom doping carbon material preparation and its application of electrode Field.
Background technology
Porous charcoal be within the scope of the space scales such as nano-micrometre, it is more with ultramicron and superficiality solid property Permeability carbonaceous material, the porous carbon material of nanostructure, pore passage structure and surface chemistry can be directed to modulation, make it in adsorption material The fields such as material, catalyst carrier and electrode material show good application prospect.
In electrode material application field, research thinks that foramen magnum-mesoporous-micropore tandem type multi-stage porous block structure Carbon Materials can To effectively improve the ion transportation of electrode, meanwhile, the skeleton structure of Carbon Materials perforation effectively increases the transmission speed of electronics Degree.Therefore, the pattern of Carbon Materials and pore passage structure are regulated and controled, can effectively improve its chemical property.Currently report The preparation method of multilevel hole material is usually long by synthesis cycle；Synthetic method is complicated；Special technological requirement (CO2It is overcritical It is dry etc.)；It needs to consume a large amount of solvents, the limitations such as not environment friendly.People use hard template method, can prepare charcoal with Effective Regulation The pattern and pore structure of material.Although this method can prepare the hierarchical porous structure material with specific structure and pattern, Cumbersome preparation process limits its scale application.Therefore, it is particularly necessary to develop a kind of preparation method being simple and efficient.It utilizes Simple solid phase reaction, by the chemical action between charcoal source and template presoma, one step of reaction in-situ obtains charcoal and template Composite construction can efficiently and rapidly prepare porous carbon material.
The surface chemical property of Carbon Materials influences the performance in its application of electrode field, and usual people are existed using post processing mode Introducing hetero-atoms functional group in Carbon Materials prepares nitrogenous porous carbon material such as by ammonia high-temperature activation porous carbon material.After The content of reason mode introducing hetero-atoms functional group in charcoal skeleton is relatively low, and functional group is distributed only over the surface of Carbon Materials, point Cloth homogeneity is poor.Due to a large amount of toxic gases used in Carbon Materials processing procedure, making this preparation process non-ambient It is friendly.It, also can be to the original pore passage structure of Carbon Materials by post processing mode while carbon surface introducing hetero-atoms functional group Certain destruction is caused with pattern.This method preparation condition controllability is relatively poor, the table of the hetero atom of introducing in Carbon Materials EDS maps homogeneity is also poor.Therefore there is an urgent need for developing simple synthesis technology, to synthesize the porous carbon material of hetero atom modification For target, simplify preparation method.
It is a kind of triazines nitrogen heterocyclic ring organic compound by the amine of representative of melamine, is used as industrial chemicals, Melmac is prepared, plastics and coatings industry are can be used for.Melmac is because it is with abundant nitrogenous function simultaneously Group can obtain nitrogenous Carbon Materials by carbonizing pyrolysis processing.The preparation of usual this kind of Carbon Materials needs to first pass around complexity Mode obtains melmac, while the pore structure of the Carbon Materials prepared and the controllability of pattern are also poor.Thus how Simple synthesizing mean is enough used, using the amino-containing fragrant cyclics such as melamine, is prepared with containing miscellaneous original The multi-stage artery structure Carbon Materials of sub- functional group's morphology controllable are current problems to be solved.
Invention content
The purpose of the present invention is to provide a kind of solid phase methods to prepare the heteroatomic multi-stage artery structure Carbon Materials such as nitrogenous, sulphur Preparation method.
In order to achieve the above object, the present invention adopts the following technical scheme that：With amino-containing fragrant cyclics and containing virtue Ring aldehyde is raw material, is chemically reacted by schiff bases between amino and aldehyde radical, prepares nitrogenous, sulphur polymer, lithia with polymerize Gas-solid phase reaction between the hydrocarbon generated in object pyrolytic process generates its carbonate, is formed in situ and prepares porous carbon The template of material removes template through high temperature pyrolysis and pickling and nitrogenous, the cellular hierarchical porous structure Carbon Materials of sulphur is made.It is prepared by the technology Carbon Materials have perforation foramen magnum-mesoporous-micropore, contain abundant nitrogenous, Liu Deng functional groups, show modification come to the surface Learn property.
A kind of Solid phase synthesis is nitrogenous, sulphur hierarchical porous structure charcoal preparation method, and steps are as follows for the preparation method：
Using the amino-containing fragrant cyclics of solid and solid aromatic ring aldehyde as raw material, solid phase mixing is carried out.Meanwhile claiming The lithia for measuring certain mass, is added in above-mentioned solid mixture and is ground.Amino and aldehyde radical occur poly- at a certain temperature Reaction is closed, and carries out pyrolysis charring under argon gas atmosphere certain temperature.Using acid solution by the carbonic acid in obtained solid mixture Salt removes, that is, obtains nitrogenous, sulphur hierarchical porous structure Carbon Materials.
In preparation method, the amino-containing fragrant cyclics of the solid are the amines such as p-aminobenzene sulfonic acid or melamine One kind or two kinds of mixtures
In preparation method, the molar ratio of the aromatic ring aldehyde and amino-containing fragrant cyclics is 0.5~5:1, wherein virtue Ring aldehyde is terephthalaldehyde, m-terephthal aldehyde or one kind in 4,4'- diphenyl-dimethanals or two kinds of mixtures.
In preparation method, the molar ratio of the oxide and amino-containing fragrant cyclics is 50~8:1, wherein using Oxide be lithia.
The polymerization and charing program polymerize 2 using 90 DEG C~200 DEG C~for 24 hours, 450 DEG C~700 DEG C carbonize 0.5~6h. The pickling removes carbonate process, using the water and ethanol solution (3 of 10% hydrochloric acid:1 volume ratio) 60 DEG C remove carbonate For 24 hours, it washes, 90 DEG C of dryings are for 24 hours.Cellular nitrogenous, sulphur porous charcoal the specific surface area is 500~1200m2g-1。
The excellent place of the present invention is：Using the amino-containing fragrant cyclics of solid and solid aromatic ring aldehyde as raw material, lead to The schiff bases polymerisation between amino and aldehyde radical is crossed, solid phase method prepares polymer, and utilizes metal oxide and polymer heat Gas-solid phase reaction between the hydrocarbon generated in solution preocess, the carbonate of in-situ preparation metal oxide, the carbonate Template can be removed by follow-up pickling, can get nitrogenous, sulphur hierarchical porous structure raw material of wood-charcoal as the template for preparing porous carbon material Material.This method utilizes simple solid phase method, can prepare the hierarchical porous structure Carbon Materials of morphology controllable.By to amino-containing virtue The modulation of cyclics and aldehyde molar ratio and amino-containing fragrant cyclics and metal oxide molar ratio, Effective Regulation institute Obtain the pattern and pore structure of Carbon Materials；Simultaneously as amino-containing virtue cyclics have abundant nitrogen-containing functional group, pass through The schiff bases polymerisation of amino and aldehyde radical can obtain the aromatic ring polymer with abundant nitrogen-containing functional group, and then can prepare The hierarchical porous structure Carbon Materials of abundant nitrogen-containing functional group.The present invention breaks through the thinking that conventional hard template method prepares porous charcoal, side Just, sulphur Carbon Materials pore structural nitrogenous with cellular three-dimensional multistage are quickly obtained.Prepared Carbon Materials as lithium from Sub- cell negative electrode material shows good chemical property because of its good electron conduction and unique appearance structure.? There is 1035mAh g under 100mA g-1 current densities-1Reversible specific capacity, 15 times cycle after still have 976mAh g-1's Stable specific capacity.
Compared with prior art, the beneficial effects of the invention are as follows：
1. breaking through the complicated synthetic method that traditional hard template method prepares Carbon Materials, simple and efficient one step of solid phase reaction is used Prepare nitrogenous, sulphur porous carbon material.This method is based on the Schiff alkalization between amino-containing fragrant cyclics and aromatic ring aldehydes It learns, and carries out gas-solid phase reaction with metal oxide using the hydrocarbon produced during Polymer-pyrolysis and be formed in situ Carbonate as synthesis Carbon Materials template, conveniently and efficiently prepare nitrogenous, the cellular hierarchical porous structure Carbon Materials of sulphur.It is this Cellular hierarchical porous structure Carbon Materials have quick ion transportation in application of electrode field, due to its have it is coherent The cellular skeleton structure of 5nm or so, further increases its electronic conductivity.
2. the amino-containing fragrant cyclics of regulation and control and aldehydes and amino-containing fragrant cyclics and metal oxide Molar ratio, the pattern and pore structure of Effective Regulation Carbon Materials are made it have big due to its unique cellular skeleton structure Hole-is mesoporous-the series multistage Pore Characteristics of micropore.Since polymeric precursor used contains the functions such as abundant nitrogenous or sulfur-bearing Group, thus the cellular hierarchical porous structure Carbon Materials prepared, have and enrich nitrogenous, Liu Deng functional groups, Effective Regulation Carbon Materials Surface chemical property.
3. being as lithium ion battery negative material with the hierarchical porous structure charcoal that synthesizes of the present invention, reversible specific capacity is for the first time 1035mAh g-1, in 100mAg-1Specific capacity reaches 798mAh g after lower 35 cycles of current density-1More than, there is good follow Ring stability and good application prospect.
Description of the drawings
Fig. 1 is cellular nitrogenous, sulphur multi-stage porous charcoal the scanning electron microscope (SEM) photograph prepared by the present invention；
Fig. 2 is cellular nitrogenous, sulphur multi-stage porous charcoal the N2 adsorption curve graph prepared by the present invention；
Fig. 3 is cellular nitrogenous, sulphur multi-stage porous charcoal the negative electrode of lithium ion battery cyclical stability figure prepared by the present invention.
Specific implementation mode
The following examples can make those skilled in the art that the present invention be more fully understood, but not with any shape The formula limitation present invention.
Embodiment 1
0.6g melamines and 0.7g terephthalaldehydes are taken, mixing is ground in mortar, meanwhile, take 0.6g to aoxidize Lithium, and add it in above-mentioned solid mixture, grind 30min.By this solid mixture under inert atmosphere protection, 3 DEG C min-1150 DEG C, constant temperature 240min are warming up to, then 550 DEG C are warming up to same heating rate, constant temperature 240min.It is dense using quality The water and ethanol solution (3 of the hydrochloric acid of degree 10%:1 volume ratio) 60 DEG C of pickling for 24 hours, then wash 90 DEG C of dryings for 24 hours.
The scanning electron microscope of porous carbon material obtained by this example is as shown in Figure 1.Sample has similar cellular topographical property, The honeycomb structure wall thickness of perforation is 5nm or so, and prepared hierarchical porous structure charcoal has the macropore of 80~200nm.Institute is much Grade is pore structural nitrogenous, sulphur Carbon Materials have 583.6m2g-1Specific surface area, Fig. 2 is its N2 adsorption curve.
Embodiment 2
0.6g melamines and 0.7g m-terephthal aldehydes are taken, mixing is ground in mortar, meanwhile, take 2.1g to aoxidize Lithium, and add it in above-mentioned solid mixture, grind 30min.By this solid mixture under inert atmosphere protection, 3 DEG C min-1100 DEG C, constant temperature 240min are warming up to, then 600 DEG C are warming up to same heating rate, constant temperature 240min.Using 10% The water and ethanol solution (3 of hydrochloric acid:1 volume ratio) 60 DEG C of pickling for 24 hours, then wash 90 DEG C of dryings for 24 hours.
Embodiment 3
The nitrogenous porous charcoal of block prepared by Example 1, the negative material as lithium ion battery.By charcoal, acetylene black and PVDF in mass ratio 8:1:1 grinding, is added suitable N-Methyl pyrrolidone after mixing, the coating preparation pole on aluminium foil Piece.By electrode slice (size 1cm × 1cm, about 25~50 μ m-thicks) lithium piece and diaphragm, be assembled into button cell, and test its Chemical property under the multiplying power current density of 100mA g-1.Fig. 3 is the electrochemical cycle stability linearity curve of material.For the first time may be used Inverse specific capacity is 1035mAh g-1, 35 times cycle after specific capacity reach 798mAh g-1More than, there is good cyclical stability.

Claims (5)

1. a kind of method of the nitrogenous sulphur multi-stage porous charcoal of Solid phase synthesis, it is characterised in that：With amino-containing fragrant cyclics and Aldehyde containing aromatic ring is raw material, is chemically reacted by the schiff bases between amino and aldehyde radical, prepares nitrogenous, sulphur polymer；Polymer heat Gas-solid phase reaction between the hydrocarbon and lithia that are generated in solution preocess generates lithium carbonate, the carbonic acid that reaction in-situ generates Lithium removes template as the template for preparing porous carbon material, through pickling can prepare nitrogenous, sulfur heteroatom cellular multi-stage porous Road structure Carbon Materials；Amino-containing fragrant cyclics used are p-aminobenzene sulfonic acid, one kind of melamine or two kinds of mixing Object；Aldehyde containing aromatic ring used is terephthalaldehyde, one kind of m-terephthal aldehyde or 4,4'- diphenyl-dimethanals or two kinds of mixtures；
Specific steps include：Amino-containing fragrant cyclics, aldehyde containing aromatic ring, lithia solid powder are ground first mixed It closes, is carbonized again through high temperature pyrolysis after low temperature polymerization, remove the carbonate that reaction process generates through acid, nitrogenous, sulfur heteroatom is made Multi-stage artery structure block Carbon Materials；
The molar ratio of aldehyde containing aromatic ring and amino-containing fragrant cyclics is 0.5 ~ 5 in solid mixture:1；Oxygen in mixture The molar ratio for changing lithium and amino-containing fragrant cyclics is 50 ~ 8:1；
Solid mixture carries out low temperature polymerization under gaseous nitrogen or argon, using 2 ~ 5 DEG C of min-1Heating rate by room temperature It is 90 DEG C ~ 200 DEG C to rise to polymerization temperature, and polymerization time is 2 ~ 24 h；It is using 2 ~ 5 DEG C to carbonize pyrolysis procedure min-1Heating rate rise to 450 DEG C ~ 700 DEG C by room temperature or polymerization temperature, constant temperature 0.5 h ~ 6 h.
2. according to the method described in claim 1, it is characterized in that：Using mortar by amino-containing fragrant cyclics, containing virtue Ring aldehyde, lithia solid powder are ground 0.5 ~ 1 h of mixing.
3. according to the method described in claim 1, it is characterized in that：Remove the acid that uses of carbonate template that generates for hydrochloric acid or One or two or more kinds in salpeter solution, the solvent that solution uses in water and ethyl alcohol one kind or two kinds, sour quality is dense Degree is 10% ~ 30%, and it is 3 ~ 6 to prepare the volume ratio of water and ethyl alcohol in the water and alcohol solvent of acid solution:1.
4. according to the method described in claim 1, it is characterized in that：The multi-stage porous refers to the concatenated hole of foramen magnum-mesoporous-micropore Road structure, wherein macropore refer to the duct more than 50 nm, and mesoporous refers to the duct of 2 ~ 50 nm, and micropore refers to being less than 2 nm Duct；Prepared Carbon Materials have the macropore of 80 ~ 200 nm, and it is 1.5 ~ 2.5 cm that macropore hole, which holds,3·g-1, have 20 ~ 50 nm's is mesoporous, 0.2 ~ 0.6 cm of mesoporous Kong Rongwei3·g-1, the micropore with 0.4-0.8 nm integrated distributions, micropore hole It is 0.2 ~ 0.5 cm to hold3·g-1。
5. method according to claim 1 or 2, it is characterised in that：Gained is nitrogenous, sulphur modification hierarchical porous structure Carbon Materials It is used to prepare lithium ion battery electrode material.
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CN108689408B (en) * 2018-08-02 2022-03-22 南昌大学 Method for preparing high-nitrogen porous carbon polymer precursor by solvent-free method
CN110212205A (en) * 2019-05-16 2019-09-06 中国科学院上海硅酸盐研究所 A kind of method that ball-milling method combination pyrolysis prepares elctro-catalyst
CN111009652A (en) * 2019-12-25 2020-04-14 河北工业大学 Sulfur/melamine-based porous framework composite material and preparation method and application thereof
CN111333836A (en) * 2020-03-12 2020-06-26 江苏科技大学 Porous covalent organic polymer based on melamine, preparation method and application thereof
CN111627725A (en) * 2020-06-09 2020-09-04 刘庆信 N, S co-doped porous carbon electrode material with adjustable pore space and preparation method thereof
CN112480345B (en) * 2020-10-20 2021-09-24 厦门大学 Metal salt @ ammonia aldehyde polymer nanosphere, preparation method and application
CN113248672A (en) * 2021-06-25 2021-08-13 安徽大学 Schiff base polymer electrode material with increased capacity in circulation process and preparation method thereof
JP2024528269A (en) * 2021-08-13 2024-07-26 寧徳新能源科技有限公司 Electrochemical and Electronic Devices
CN113735191A (en) * 2021-08-24 2021-12-03 南通金通储能动力新材料有限公司 Porous structure ternary precursor and preparation method thereof
CN114031737A (en) * 2021-12-14 2022-02-11 四川金象赛瑞化工股份有限公司 Large-size melamine-based covalent organic framework material, and preparation method and application thereof
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