CN107963620A - A kind of preparation method of high nitrogen doped Carbon Materials - Google Patents
A kind of preparation method of high nitrogen doped Carbon Materials Download PDFInfo
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- CN107963620A CN107963620A CN201711183772.3A CN201711183772A CN107963620A CN 107963620 A CN107963620 A CN 107963620A CN 201711183772 A CN201711183772 A CN 201711183772A CN 107963620 A CN107963620 A CN 107963620A
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- carbon materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- 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
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 a kind of preparation method of high nitrogen doped Carbon Materials, which solves the technical problems higher than low, cost of material N/C made from existing method, it includes the following steps：Hexa and metal salt are weighed, is then dissolved in solvent, is reacted at room temperature, unreacting material is washed away after filtering and with solvent, then drying obtains hexa polymerization of olefin using catalyst polymer precursor；Gained coordination polymer precursor is taken, is progressively heated in an inert atmosphere, high nitrogen doped Carbon Materials are obtained after pickling or not pickling.The present invention can be used for the preparation field of high nitrogen doped Carbon Materials.
Description
Technical field
The present invention relates to Material Field, relates in particular to a kind of preparation method of high nitrogen doped Carbon Materials.
Background technology
Carbon Materials are since it is with specific surface area is big, excellent electric conductivity, physicochemical properties are stable and cheap and easy to get etc.
Advantage, makes it be with a wide range of applications in fields such as energy storage, absorption, sensing, catalysis.In addition, by mixing Carbon Materials
Miscellaneous modification, can adjust its electronic structure and surface characteristic, can greatly improve the performance of its each side, further expand
Its application range.
N doping has been obtained for widely studying as a kind of highly effective modified method.By drawing in charcoal skeleton
Enter electron rich N atoms, thus it is possible to vary the band structure of material, makes the valence band of material reduce, and increases the electricity on material fermi level
Sub- density；In addition, N atoms can bring sp due to its extra lone pair electrons2Hydridization charcoal skeleton delocalization pi system negative electrical charge, from
And strengthen electron transport property and chemical reactivity.N doping Carbon Materials electro-catalysis, ultracapacitor, ion battery, with
And CO2Good performance has been presented in terms of absorption.And from the point of view of the document reported at present, N doping is horizontal in Carbon Materials
It is higher, tend to show better performance [L.Zhao, L.Z.Fan, M.Q.Zhou, H.Guan, S.Y.Qiao,
M.Antonietti,M.M.Titirici,Adv.Mater.,2010,22,5202-5206].Therefore, high nitrogen doped Carbon Materials
Preparation have become one it is particularly significant the problem of.
At present, the preparation of N doping Carbon Materials mainly has following two methods：1) by being directly pyrolyzed rich nitrogen precursor, i.e.,
Situ Nitrogen Doping；2) by the method for post processing introduce nitrogen-containing functional group on Carbon Materials.In general, the side of post processing
Method can only introduce nitrogen-containing functional group and nitrogen content in charcoal material surface and be generally below 10at%, and body before the rich nitrogen being directly pyrolyzed
Body is believed to obtain higher N doping level.At present, common nitrogenous precursor is concentrated mainly on polyaniline, poly- pyrrole
Cough up and some high molecular polymers such as polyacrylonitrile.But these polymer often have than relatively low N/C ratios, and by
In limited dissolubility so that the building-up process of polymer is also more complicated.
Coordination polymer, is also metal-organic framework materials (MOFs), is to pass through coordination by metal center and organic ligand
Act on the porous material formed.Recent years, coordination polymer are used as template or precursor to prepare the porous charcoal of N doping
Material.At present, the ligand for preparing N doping Carbon Materials is concentrated mainly on imidazoles and its derivative.But these ligands often valency
Lattice costly, largely limit its extensive preparation, are unfavorable for industrialized production.Therefore, find cheap
With high N/C than ligand it is very crucial.
The content of the invention
The present invention is exactly to be asked to solve material N/C made from existing method than technology low, that ligand material cost is higher
A kind of topic, there is provided the preparation method of the high nitrogen doped Carbon Materials of low, the obtained material N/C higher of ligand material cost.
For this reason, method provided by the invention includes the following steps：Step 1：By molar concentration rate 1:(0.25~4) weighs
Hexa and metal salt, are then dissolved in solvent, react 0~48h at room temperature, are washed away not after filtering and with solvent
Reaction raw materials, then drying obtain hexa polymerization of olefin using catalyst polymer precursor；Step 2：Take and match somebody with somebody obtained by the step 1
Position polymer precursor, is progressively heated to 200~1000 DEG C in an inert atmosphere, when insulation 1~5 is small, pickling or not pickling it
After obtain high nitrogen doped Carbon Materials.
Preferably, in step 1, the metal salt for molysite, cadmium salt, cobalt salt, nickel salt, mantoquita, pink salt, vanadic salts, molybdenum salt or
One kind of titanate.
Preferably, in step 1, the solvent is water, in ethanol, hydrochloric acid, acetone, sulfuric acid, n,N-Dimethylformamide
It is a kind of.
Preferably, in step 2, the acid is hydrochloric acid, nitric acid, hydrogen peroxide or sulfuric acid.
The present invention can make full use of coordination polymer using hexa polymerization of olefin using catalyst polymer precursor as raw material
The high N/C ratios of stability and hexa, so as to prepare the Carbon Materials of high nitrogen-containing doping.Hexa is made
For a kind of raw material of industry, raw material is easy to get, cheap, and preparation process is simple, easily realizes large-scale production.
Brief description of the drawings
Fig. 1 is that the present invention is that gained is high nitrogen doped under hexa/800 DEG C of nitric acid copper coordination polymer carburizing temperature
Carbon Materials scanning electron microscope (SEM) photograph.
Fig. 2 is that the high nitrogen doped Carbon Materials of gained are saturating under hexa/800 DEG C of nitric acid copper coordination polymer carburizing temperature
Penetrate electron microscope.
Fig. 3 is respectively the high nitrogen doped Carbon Materials nitrogen element content change of gained at 600,700,800 and 900 DEG C for carburizing temperature
Change figure.
Fig. 4 is high nitrogen doped Carbon Materials obtained by 800 DEG C of carburizing temperature as the forthright again of anode material of lithium-ion battery
Can curve map.
Fig. 5 be carburizing temperature be respectively at 600,700,800 and 900 DEG C the high nitrogen doped Carbon Materials of gained in 100mA g-1
Voltage capacity curve map under current density.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and examples：
Embodiment 1
By 1.00g hexas, 1.00g Gerhardites (Cu (NO3)2·3H2O) be dissolved separately in 50ml without
It is admixed together after being dissolved completely under 400r/min stir speed (S.S.)s in water-ethanol, gained coordination polymer is sunk after reacting 1h
Form sediment and centrifuge, and washed for several times with absolute ethyl alcohol.Gained mixture is placed in heating, drying in convection oven, is pulverized
End.Then gained powder is placed in retort, being warming up to 200 DEG C under nitrogen protection with the heating rate of 5 DEG C/min cures 2
Hour.The copper particle in cured product is then removed with the mixed liquor of hydrogen peroxide and hydrochloric acid, then is again placed in carbonizing by sample
In stove, under nitrogen protection with the heating rate of 5 DEG C/min be warming up to 800 DEG C charing 2 it is small when, obtain high nitrogen doped Carbon Materials.
As shown in 1 scanning electron microscope of attached drawing (SEM) and 2 transmission electron microscope of attached drawing (TEM), obtained high nitrogen doped Carbon Materials by
The particle composition of 150nm.As shown in Figure 3, the nitrogen content that 800 DEG C of processing obtain high nitrogen doped Carbon Materials is 20.38at%.
Embodiment 2
Operating method is identical with embodiment 1, the difference is that temperature is 600 DEG C in carbonization process, when insulation 2 is small, obtains height
N doping Carbon Materials.
As shown in Figure 3, the nitrogen content that 600 DEG C of processing obtain high nitrogen doped Carbon Materials is 29.42at%.
Embodiment 3
Operating method is identical with embodiment 1, the difference is that temperature is 700 DEG C in carbonization process, when insulation 2 is small.
As shown in Figure 3, the nitrogen content that 700 DEG C of processing obtain high nitrogen doped Carbon Materials is 25.78at%.
Embodiment 4
Operating method is identical with embodiment 1, the difference is that temperature is 900 DEG C in carbonization process, when insulation 2 is small.
As shown in Figure 3, the nitrogen content that 900 DEG C of processing obtain high nitrogen doped Carbon Materials is 13.32at%.
Embodiment 5
By 14.00g hexas, 5.80g Nickelous nitrate hexahydrates (Ni (NO3)2·6H2O) 25ml is dissolved separately in go
It is admixed together after being dissolved completely under 400r/min stir speed (S.S.)s in ionized water, gained coordination polymer is sunk after reacting 1h
Form sediment and centrifuge, and washed for several times with acetone.Gained mixture is placed in heating, drying in convection oven, grind into powder.With
Gained powder is placed in retort afterwards, under nitrogen protection with the heating rate of 5 DEG C/min be warming up to 600 DEG C charing 2 it is small when.
Products therefrom is then obtained into high nitrogen doped Carbon Materials with nitric acid acidwashing 24h.
Embodiment 6
By 14.00g hexas, 5.80g cabaltous nitrate hexahydrates (Co (NO3)2·6H2O) 25ml is dissolved separately in go
It is admixed together after being dissolved completely under 400r/min stir speed (S.S.)s in ionized water, gained coordination polymer is sunk after reacting 1h
Form sediment and centrifuge, and washed for several times with acetone.Gained mixture is placed in heating, drying in convection oven, grind into powder.With
Gained powder is placed in retort afterwards, under nitrogen protection with the heating rate of 5 DEG C/min be warming up to 600 DEG C charing 2 it is small when.
Products therefrom is then obtained into high nitrogen doped Carbon Materials at 80 DEG C with nitric acid acidwashing 24h.
Embodiment 7
To provide sodium ion battery electrode material prepared by a kind of high nitrogen doped Carbon Materials.Quality percentage is pressed by following components
Than composition：High nitrogen doped Carbon Materials 80% in embodiment 1, acetylene black 10%, binding agent 10%.Use high nitrogen doped Carbon Materials
As anode material of lithium-ion battery, as shown in Figure 4, in 100mA g-1Current density it is lower 800 DEG C acquisition it is high nitrogen doped
Carbon Materials can obtain 254mAh g-1Reversible capacity, even in 5A g-1Current density under still keep 142mAh g-1's
Reversible capacity, shows good chemical property.
Comparative example 1
The high nitrogen doped Carbon Materials obtained using under different carbonization temperatures are used as anode material of lithium-ion battery.By following groups
Divide and form by mass percentage：High nitrogen doped Carbon Materials 80%, acetylene black 10%, binding agent 10%.As carbonization temperature is from 600
DEG C 900 DEG C are increased to, its nitrogen content is respectively 29.42,25.78,20.38,13.32at%.As shown in Figure 5, in 100mA
g-1Current density it is lower 600 DEG C acquisition high nitrogen doped Carbon Materials can obtain 303mAh g-1Reversible capacity, 700 DEG C are
288mAh g-1, 800 DEG C are 254mAh g-1, 900 DEG C are 189mAh g-1.Nitrogen content is higher, and chemical property is substantially better.
Presently preferred embodiments of the present invention is illustrated above, but the present invention is not limited to the embodiment,
Those skilled in the art can also make a variety of equivalent modifications or replacement on the premise of without prejudice to spirit of the invention,
These equivalent modifications or replacement are all contained in the application claim limited range.
Claims (4)
- A kind of 1. preparation method of high nitrogen doped Carbon Materials, it is characterized in that including the following steps：Step 1：By molar concentration rate 1:(0.25~4) weighs hexa and metal salt, is then dissolved in solvent In, 0~48h is reacted at room temperature, unreacting material is washed away after filtering and with solvent, and then drying obtains hexa basigamy Position polymer precursor；Step 2：Coordination polymer precursor obtained by taking the step 1, is progressively heated to 200~1000 in an inert atmosphere DEG C, when insulation 1~5 is small, high nitrogen doped Carbon Materials are obtained after pickling or not pickling.
- 2. the preparation method of high nitrogen doped Carbon Materials according to claim 1, it is characterised in that：It is described in the step 1 Metal salt is one kind of molysite, cadmium salt, cobalt salt, nickel salt, mantoquita, pink salt, vanadic salts, molybdenum salt or titanate.
- 3. the preparation method of high nitrogen doped Carbon Materials according to claim 1, it is characterised in that：It is described in the step 1 Solvent is water, one kind in ethanol, acetone, hydrochloric acid, sulfuric acid, N,N-dimethylformamide.
- 4. the preparation method of high nitrogen doped Carbon Materials according to claim 1, it is characterised in that：In the step 2, institute It is hydrochloric acid, nitric acid, hydrogen peroxide or sulfuric acid to state acid.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106894025A (en) * | 2017-04-14 | 2017-06-27 | 中国科学院海洋研究所 | The pickle of zero-g aircraft detection metallic material corrosion thing and application |
| CN109136979A (en) * | 2018-08-08 | 2019-01-04 | 东华大学 | The nitrogen-doped carbon composite material of hollow zinc doping cobalt oxide nickel coated and its preparation |
| CN110620229A (en) * | 2019-08-16 | 2019-12-27 | 华南师范大学 | Battery anode material, battery anode and lithium selenium battery |
| CN111943855A (en) * | 2018-03-29 | 2020-11-17 | 西南大学 | Preparation method of metal-doped cadmium metal organic complex, product and derivative thereof |
| CN112678796A (en) * | 2020-12-15 | 2021-04-20 | 大连工业大学 | Method for preparing porous carbon material with controllable structural morphology by aid of ball milling |
| CN114455569A (en) * | 2022-02-11 | 2022-05-10 | 齐鲁工业大学 | Phosphorus-doped nitrogen-rich porous carbon nanosheet and preparation method and application thereof |
| CN115304054A (en) * | 2022-09-16 | 2022-11-08 | 北京化工大学 | Preparation method of high-nitrogen-doped porous carbon nanosheet and application of high-nitrogen-doped porous carbon nanosheet in lithium-sodium ion battery |
| CN115974048A (en) * | 2023-03-09 | 2023-04-18 | 东莞理工学院 | Porous magnetic carbon material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110129675A1 (en) * | 2009-12-01 | 2011-06-02 | Samsung Electronics Co., Ltd. | Material including graphene and an inorganic material and method of manufacturing the material |
| CN103183330A (en) * | 2013-04-02 | 2013-07-03 | 中国矿业大学 | Controllable synthesis method for nitrogen and phosphorus co-doped graphitized carbon ball with hollow structure |
| CN103545523A (en) * | 2013-10-30 | 2014-01-29 | 北京化工大学 | Porous carbon microsphere, preparation method and lithium ion battery negative electrode material |
| CN105810914A (en) * | 2016-05-13 | 2016-07-27 | 中南大学 | Sulfur-doping porous carbon material of sodium ion battery and preparation method of sulfur-doping porous carbon material |
| CN106564868A (en) * | 2016-10-09 | 2017-04-19 | 上海应用技术大学 | Preparation method of nitrogen-doped porous carbon material |
-
2017
- 2017-11-23 CN CN201711183772.3A patent/CN107963620A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110129675A1 (en) * | 2009-12-01 | 2011-06-02 | Samsung Electronics Co., Ltd. | Material including graphene and an inorganic material and method of manufacturing the material |
| CN103183330A (en) * | 2013-04-02 | 2013-07-03 | 中国矿业大学 | Controllable synthesis method for nitrogen and phosphorus co-doped graphitized carbon ball with hollow structure |
| CN103545523A (en) * | 2013-10-30 | 2014-01-29 | 北京化工大学 | Porous carbon microsphere, preparation method and lithium ion battery negative electrode material |
| CN105810914A (en) * | 2016-05-13 | 2016-07-27 | 中南大学 | Sulfur-doping porous carbon material of sodium ion battery and preparation method of sulfur-doping porous carbon material |
| CN106564868A (en) * | 2016-10-09 | 2017-04-19 | 上海应用技术大学 | Preparation method of nitrogen-doped porous carbon material |
Cited By (11)
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|---|---|---|---|---|
| CN106894025A (en) * | 2017-04-14 | 2017-06-27 | 中国科学院海洋研究所 | The pickle of zero-g aircraft detection metallic material corrosion thing and application |
| CN111943855A (en) * | 2018-03-29 | 2020-11-17 | 西南大学 | Preparation method of metal-doped cadmium metal organic complex, product and derivative thereof |
| CN111943855B (en) * | 2018-03-29 | 2023-04-14 | 西南大学 | Preparation method of metal-doped cadmium metal organic complex, product and derivative thereof |
| CN109136979A (en) * | 2018-08-08 | 2019-01-04 | 东华大学 | The nitrogen-doped carbon composite material of hollow zinc doping cobalt oxide nickel coated and its preparation |
| CN110620229A (en) * | 2019-08-16 | 2019-12-27 | 华南师范大学 | Battery anode material, battery anode and lithium selenium battery |
| CN110620229B (en) * | 2019-08-16 | 2020-10-16 | 华南师范大学 | Battery anode material, battery anode and lithium selenium battery |
| CN112678796A (en) * | 2020-12-15 | 2021-04-20 | 大连工业大学 | Method for preparing porous carbon material with controllable structural morphology by aid of ball milling |
| CN114455569A (en) * | 2022-02-11 | 2022-05-10 | 齐鲁工业大学 | Phosphorus-doped nitrogen-rich porous carbon nanosheet and preparation method and application thereof |
| CN115304054A (en) * | 2022-09-16 | 2022-11-08 | 北京化工大学 | Preparation method of high-nitrogen-doped porous carbon nanosheet and application of high-nitrogen-doped porous carbon nanosheet in lithium-sodium ion battery |
| CN115974048A (en) * | 2023-03-09 | 2023-04-18 | 东莞理工学院 | Porous magnetic carbon material and preparation method and application thereof |
| CN115974048B (en) * | 2023-03-09 | 2024-03-19 | 东莞理工学院 | Porous magnetic carbon material and preparation method and application thereof |
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