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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- nitrogenous
- carbon materials
- amino
- sulphur
- aldehyde
- 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
Links
Classifications
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C01P2006/12—Surface area
-
- 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
- C01P2006/16—Pore diameter
-
- 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
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The 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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510918904.7A CN106882783B (en) | 2015-12-10 | 2015-12-10 | A kind of method of the nitrogenous sulphur multi-stage porous charcoal of Solid phase synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510918904.7A CN106882783B (en) | 2015-12-10 | 2015-12-10 | A kind of method of the nitrogenous sulphur multi-stage porous charcoal of Solid phase synthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106882783A CN106882783A (en) | 2017-06-23 |
| CN106882783B true CN106882783B (en) | 2018-10-30 |
Family
ID=59173242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510918904.7A Active CN106882783B (en) | 2015-12-10 | 2015-12-10 | A kind of method of the nitrogenous sulphur multi-stage porous charcoal of Solid phase synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106882783B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2023015561A1 (en) * | 2021-08-13 | 2023-02-16 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| 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 |
| CN114715881B (en) * | 2022-04-01 | 2023-09-08 | 浙江工业大学 | Waste plastic derived nano porous carbon material and preparation method and application thereof |
| CN114843114B (en) * | 2022-06-30 | 2022-10-25 | 深圳市今朝时代股份有限公司 | Nitrogen-doping-based electrode material and application thereof to supercapacitor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585527A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | In a kind of being rich in, the charcoal preparation methods of macropore |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2643840A4 (en) * | 2010-11-26 | 2014-05-28 | Basf Se | Process for manufacturing nitrogen-containing porous carbonaceous material |
-
2015
- 2015-12-10 CN CN201510918904.7A patent/CN106882783B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585527A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | In a kind of being rich in, the charcoal preparation methods of macropore |
Non-Patent Citations (2)
| Title |
|---|
| Controllable synthesis and capacitive performance of nitrogen-doped porous carbon from carboxymethyl chitosan by template carbonization method;Ying Jiang et al.;《J Solid State Electrochem》;20150627;第19卷;3087-3096 * |
| 富氮多级孔炭材料的制备及其吸附分离CO2的性能;金振宇 等;《物理化学学报(Wuli Huaxue Xuebao)》;20150618;第31卷(第8期);1602-1608 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106882783A (en) | 2017-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106882783B (en) | A kind of method of the nitrogenous sulphur multi-stage porous charcoal of Solid phase synthesis | |
| CN106601490B (en) | A kind of preparation method of biomass-based nitrogenous porous carbon and porous carbon and application thereof | |
| Cui et al. | Three-dimensionally ordered macro-microporous metal organic frameworks with strong sulfur immobilization and catalyzation for high-performance lithium-sulfur batteries | |
| Hu et al. | Multi-heteroatom self-doped porous carbon derived from swim bladders for large capacitance supercapacitors | |
| CN106654215B (en) | Biological micromolecule and graphene composite material functional membrane and preparation method thereof | |
| CN106744803B (en) | A kind of method preparing porous carbon and porous carbon | |
| Zhang et al. | A novel 2D porous print fabric-like α-Fe2O3 sheet with high performance as the anode material for lithium-ion battery | |
| Wang et al. | From zeolite-type metal organic framework to porous nano-sheet carbon: High activity positive electrode material for bromine-based flow batteries | |
| CN108529619A (en) | A kind of nitrogen sulphur codope porous carbon materials and its preparation method and application | |
| CN105938900A (en) | Research of surface-modified nitrogen-doped porous carbon-sulfur composite material in positive electrode of lithium-sulfur battery | |
| CN106564874B (en) | A kind of lignin-base two dimension carbon nanomaterial and its preparation method and application | |
| CN108649198A (en) | A kind of synthetic method of the nitrogen of cobalt insertion, the carbon nanomaterial of sulphur codope | |
| Gao et al. | Rapid Production of Metal–Organic Frameworks Based Separators in Industrial‐Level Efficiency | |
| CN107055531A (en) | A kind of preparation method of biomass-based nitrogen-doped porous carbon material | |
| CN110117009B (en) | Preparation method of iron-nitrogen co-doped magnetic porous graphitized nano carbon aerogel | |
| CN109399603B (en) | Method for preparing nitrogen-doped porous carbon for supercapacitor by using metal organic framework compound | |
| CN106410116A (en) | Graded porous composite lithium-sulfur battery cathode and preparation method thereof | |
| CN105776170B (en) | A kind of preparation method of the nitrogenous multistage pore canal Carbon Materials of block | |
| CN108404868A (en) | NH is adulterated based on alkali metal cation2- MIL-125 (Ti) materials and preparation method | |
| CN110342489A (en) | A kind of preparation method of the porous carbon-based energy storage material of nonmetal doping | |
| CN108002361A (en) | A kind of preparation method of high sulfur content nitrogen sulphur codope pitch base carbon material | |
| CN106986324A (en) | It is a kind of for hollow porous carbon ball electrode material of ultracapacitor and preparation method thereof | |
| CN106252660A (en) | A kind of preparation method of the nitrogen-doped carbon aeroge being applied to lithium ion battery | |
| CN105375015A (en) | Preparation method of carbon-coated mesoporous lithium titanium phosphate | |
| CN110283288A (en) | A kind of mass producible Heteroatom doping has cavity structure polymer nano-microspheres and preparation method 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 |