CN106229156B - A kind of preparation method of two-dimentional silicon-carbon nitrogen nano-material for energy stores - Google Patents
A kind of preparation method of two-dimentional silicon-carbon nitrogen nano-material for energy stores Download PDFInfo
- Publication number
- CN106229156B CN106229156B CN201610749411.XA CN201610749411A CN106229156B CN 106229156 B CN106229156 B CN 106229156B CN 201610749411 A CN201610749411 A CN 201610749411A CN 106229156 B CN106229156 B CN 106229156B
- Authority
- CN
- China
- Prior art keywords
- source
- silicon
- nitrogen
- carbon
- dimentional
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
A kind of preparation method of two-dimentional silicon-carbon nitrogen nano-material for energy stores, includes the following steps：（1）Silicon source, carbon source and nitrogen source are configured to mixed-powder；（2）By mixed-powder electron tubes type reaction in furnace；（3）Reaction product is put into ball milling in ball mill；（4）It will be washed to neutrality again after product after ball milling aqueous slkali soaking, obtains two-dimentional silicon-carbon nitrogen nanometer sheet.This method is using silicon source, carbon source, nitrogen source ternary object as raw material; it is cheap and easy to get; reaction condition facilitates controllable; the equipment needed is fairly simple; each component ratio is controllable in product, and the various parameters in reaction process are easy to be monitored and controlled, it is easy to accomplish low cost is produced in enormous quantities; it can be inherently eliminated pollution, be conducive to environmental protection.
Description
Technical field
Can be used for energy using ternary object (silicon source, carbon source, nitrogen source) as raw material high-temperature calcination preparation the present invention relates to a kind of
The method for measuring the two-dimentional silicon-carbon nitrogen nanometer sheet of storage art, belongs to two-dimentional silicon-carbon nitrogen nano-material preparing technical field.
Background technology
With the rise that graphene is studied, two-dimensional material is increasingly valued by people with its distinctive property.At this
In a little two-dimensional materials, the carbon nitrogen (graphitic carbon nitride) that nonmetalloid is constituted, since its excellent heat is steady
Qualitative, chemical stability, unique optical characteristics, electrology characteristic and environment friendly are increasingly paid close attention to by people.For example, carbon
Nitrogen has been successfully applied to catalysis and field of energy conversion (Shaowen as a kind of novel visible optical semiconductor catalyst
Cao, et al, Polymeric Photocatalysts Based on Graphitic Carbon Nitride,
Adv.Mater.2015,27,2150–2176).However, have the shortcomings that electronics conduction efficiency is low in carbon nitrogen, which has limited
Application of this nonmetallic two-dimensional material of carbon nitrogen in the energy stores such as lithium electricity and super electricity etc..Therefore how research obtains high energy
The two-dimentional nonmetallic materials of amount storage are a research hotspots of Material Field.
At the same time, researcher has found that many siliceous materials all have good electronic conductivity energy, especially silicon
Carbon nitrogen (SiCN) material has prodigious application prospect due to its good electric property and stability in energy storage field.Exactly
Based on the broad prospect of application of silicon-carbon nitrogen, scientists have carried out extensive research to the synthesis of silicon-carbon nitrogen, and obtain
Fruitful progress.
So far, most common preparation method is that the silicon of three-dimensional structure (3D) is prepared using the calcining of silane imine polymer
Carbon-nitrogen material.Compared to three-dimensional structure, two-dimensional material has more because of its larger specific surface area and efficient electron transmission performance
Good application value, however there has been no the preparation methods about two-dimentional silicon-carbon nitrogen nanometer sheet at present.
Therefore, develop it is a kind of it is easy to operate, can low cost, high yield obtain the larger two-dimentional silicon-carbon nitrogen of specific surface area
Nanometer sheet is of great significance.
Invention content
The present invention for existing silicon-carbon nitrogen material technology of preparing in terms of preparing two-dimentional silicon-carbon nitrogen nano-material it is existing not
Foot, provides a kind of preparation method of the two-dimentional silicon-carbon nitrogen nano-material for energy stores, to realize two-dimentional silicon-carbon nitrogen nanometer
The low cost of piece is prepared on a large scale.
The preparation method of the two-dimentional silicon-carbon nitrogen nano-material for energy stores of the present invention, includes the following steps：
(1) silicon source, carbon source and nitrogen source are configured to mixed-powder；
(2) mixed-powder is placed in vacuum tube furnace, is reacted 1~24 hour at 600 DEG C~1200 DEG C；
(3) reaction product is put into ball milling 2~8 hours in ball mill；
(4) it by after the aqueous slkali soaking 1~24 hour of the product after ball milling, then is washed to washing lotion and is in neutrality (pH value 7),
Obtain two-dimentional silicon-carbon nitrogen nanometer sheet.
Silicon source in step (1) is elemental silicon, silica, silicic acid, silicate or siliceous organic matter.
Nitrogen source in step (1) is lithium nitride, sodium azide, urea, dicyandiamide or melamine.
Carbon source in step (1) is graphite, glucose or citric acid.
The molar ratio of nitrogen source and carbon source is 1 in step (1):5-5:1, silicon source molal quantity is the sum of carbon source and nitrogen source molal quantity
0.1%-10%.
The mixed-powder of step (1) is that freeze-drying process obtains after silicon source, carbon source and nitrogen source are dissolved in the water together,
Or ground and mixed uniformly obtains.
Vacuum tube furnace reaches reaction temperature with 1 DEG C/min~10 DEG C/min of heating rate in step (2).
Reaction in step (2) is synthesis under normal pressure under nitrogen or argon, or in relative pressure is -0.1MPa
It is reacted under the vacuum condition of~-0.001Mpa.
The sodium hydroxide solution or potassium hydroxide solution that aqueous slkali in step (4) is concentration 1mol/L~10mol/L.
The method of the present invention is using ternary object (silicon source, carbon source, nitrogen source) as raw material, and raw material is cheap and easy to get, reaction condition side
It can control, the equipment needed is fairly simple, and each component ratio is controllable in product, it is easy to accomplish low cost is produced in enormous quantities.
The invention has the advantages that：
1. at low cost.Raw materials used is common chemical reagent or industrial chemicals, and operation sequence is simple, is conducive to improve production
Rate reduces cost.
2, the various parameters in reaction process (temperature, pressure, ratio etc.) are easy to be monitored and controlled, and can be easier to study
Reaction mechanism finds out the influence factor of most critical, as early as possible process for stabilizing condition.
3, low in the pollution of the environment, it can be inherently eliminated pollution, be conducive to environmental protection.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture of two-dimentional silicon-carbon nitrogen nanometer sheet prepared by the present invention.
Fig. 2 is the XRD diagram piece of two-dimentional silicon-carbon nitrogen nanometer sheet prepared by the present invention.
Fig. 3 is the EDS pictures of two-dimentional silicon-carbon nitrogen nanometer sheet prepared by the present invention.
Fig. 4 is the two-dimentional silicon-carbon nitrogen nanometer sheet of the invention prepared in ultracapacitor field cyclic voltammetry figure.
Specific implementation mode
Embodiment 1
(1) sodium metasilicate 1g, glucose 4.5g, urea 4.5g are weighed.Wherein the molar ratio of nitrogen source and carbon source is 3:1, silicon source
Molal quantity is the 3.5% of the sum of carbon source and nitrogen source molal quantity.Then three kinds of substances are placed in 100mL beakers, 80mL water is added
Middle stirring and dissolving.By solution freeze-drying process, mixed-powder is obtained.
(2) mixed-powder is put into ceramic boat, is placed in tube furnace.Under nitrogen atmosphere protection, with 8 DEG C/min
Rate is warming up to 1000 DEG C, and insulation reaction 8 hours.
(3) calcining gained reaction product is put into ball milling 2 hours in ball mill.
(4) product for obtaining ball milling is impregnated 16 hours with the sodium hydroxide solution of concentration 5mol/L, then uses deionized water
It is washed till neutral to get to silicon doped carbon nitrogen.
The scanning electron microscopic picture of two dimension silicon-carbon nitrogen nanometer sheet manufactured in the present embodiment is as shown in Figure 1, XRD diagram piece such as Fig. 2 institutes
Show, EDS pictures are as shown in figure 3, the results are shown in Figure 4 in ultracapacitor field cyclic voltammetry.
Embodiment 2
As described in Example 1, the difference is that：Sodium metasilicate is substituted with butadienyl triethoxysilane in step (1)
As silicon source.
Embodiment 3
As described in Example 1, the difference is that：Sodium metasilicate is substituted as silicon source using silicic acid in step (1).
Embodiment 4
As described in Example 1, the difference is that：Urea is substituted as nitrogen source using lithium nitride in step (1).
Embodiment 5
As described in Example 1, the difference is that：Sodium metasilicate 3.1g, glucose 18g, urea 1.2g in step (1).Its
The molar ratio of middle nitrogen source and carbon source is 1:5, silicon source molal quantity is the 9% of the sum of carbon source and nitrogen source molal quantity.
Embodiment 6
As described in Example 1, the difference is that：Sodium metasilicate 0.17g, glucose 18g, urea 30g in step (1).Its
The molar ratio of middle nitrogen source and carbon source is 5:1, silicon source molal quantity is the 0.1% of the sum of carbon source and nitrogen source molal quantity.
Embodiment 7
As described in Example 1, the difference is that：600 DEG C are warming up to 1 DEG C/min of rate in step (2), and is protected
Temperature reaction 24 hours.
Embodiment 8
As described in Example 1, the difference is that：In step (2) 1200 DEG C are warming up to 10 DEG C/min of rate, and
Insulation reaction 1 hour.
Embodiment 9
As described in Example 1, the difference is that：It is in the vacuum environment that relative degree of vacuum is -0.1Mpa in step (2)
Lower reaction.
Embodiment 10
As described in Example 1, the difference is that：It is to protect synthesis under normal pressure in argon gas atmosphere in step (2).
Embodiment 11
As described in Example 1, the difference is that：Ball-milling Time is set as 6 hours in step (3).
Embodiment 12
As described in Example 1, the difference is that：Ball-milling Time is set as 8 hours in step (3).
Embodiment 13
As described in Example 1, the difference is that：In step (4) soaked in the sodium hydroxide solution of concentration 1mol/L
Bubble 24 hours.
Embodiment 14
As described in Example 1, the difference is that：In step (4) soaked in the sodium hydroxide solution of concentration 10mol/L
Bubble 1 hour.
Embodiment 15
As described in Example 1, the difference is that：It is in the potassium hydroxide solution of a concentration of 8mol/L in step (4)
It impregnates 8 hours.
Embodiment 16
(1) silica 0.32g, citric acid 8.1g, dicyandiamide 1.2g are weighed.Wherein the molar ratio of nitrogen source and carbon source is 1:
3, silicon source molal quantity is the 10% of the sum of carbon source and nitrogen source molal quantity.Three kinds of substance ground and mixeds are uniform.
(2) obtained powder is put into ceramic boat, is placed in tube furnace.Relative degree of vacuum is the vacuum ring of -0.05Mpa
Under border, 800 DEG C are warming up to 6 DEG C/min, and insulation reaction 16 hours.
(3) calcining gained reaction product is put into ball milling 4 hours in ball mill.
(4) product for obtaining ball milling is impregnated 20 hours with the sodium hydroxide solution of 3mol/L, then be washed with deionized water to
It is neutral, you can to obtain silicon doped carbon nitrogen.
Embodiment 17
As described in Example 16, the difference is that：Silica is replaced as silicon source using elemental silicon in step (1).
Embodiment 18
As described in Example 16, the difference is that：Citric acid is substituted as carbon source using graphene in step (1).
Embodiment 19
As described in Example 16, the difference is that：Dicyandiamide is substituted as nitrogen source using sodium azide in step (1).
Embodiment 20
As described in Example 16, the difference is that：Dicyandiamide is substituted as nitrogen source using melamine in step (1).
Embodiment 21
As described in Example 16, the difference is that：Silica 0.1g in step (1), citric acid 1.8g, dicyandiamide
3.3g.Wherein, the molar ratio of nitrogen source and carbon source is 4:1, silicon source molal quantity is the 3.2% of the sum of carbon source and nitrogen source molal quantity.
Embodiment 22
As described in Example 16, the difference is that：It is in the vacuum that relative degree of vacuum is -0.001Mpa in step (2)
Under environment, 700 DEG C are warming up to 4 DEG C/min, and insulation reaction 20 hours.
Claims (4)
1. a kind of preparation method of two-dimentional silicon-carbon nitrogen nano-material for energy stores, characterized in that include the following steps：
（1）Silicon source, carbon source and nitrogen source are configured to mixed-powder；
（2）Mixed-powder is placed in vacuum tube furnace, is reacted 1~24 hour at 600 DEG C~1200 DEG C；
（3）Reaction product is put into ball milling 2~8 hours in ball mill；
（4）It after the aqueous slkali soaking 1~24 hour of the product after ball milling, then is washed to washing lotion and is in neutrality, pH 7 obtains two
Tie up silicon-carbon nitrogen nanometer sheet；
The step（1）In silicon source be elemental silicon, silica, silicic acid or silicate；The step（1）In nitrogen source be nitrogen
Change lithium, sodium azide, urea, dicyandiamide or melamine；The step（1）In carbon source be graphite, glucose or citric acid；
The step（1）The molar ratio of middle nitrogen source and carbon source is 1:5-5:1, silicon source molal quantity is the sum of carbon source and nitrogen source molal quantity
0.1%-10%；
The step（1）Mixed-powder be that freeze-drying process obtains after silicon source, carbon source and nitrogen source are dissolved in the water together,
Or ground and mixed uniformly obtains.
2. the preparation method for the two-dimentional silicon-carbon nitrogen nano-material of energy stores as described in claim 1, characterized in that institute
State step（2）Middle vacuum tube furnace reaches reaction temperature with 1 DEG C/min~10 DEG C/min of heating rate.
3. the preparation method for the two-dimentional silicon-carbon nitrogen nano-material of energy stores as described in claim 1, characterized in that institute
State step（2）In reaction be synthesis under normal pressure under nitrogen or argon, or relative pressure be -0.1MPa~-
It is reacted under the vacuum condition of 0.001Mpa.
4. the preparation method for the two-dimentional silicon-carbon nitrogen nano-material of energy stores as described in claim 1, characterized in that institute
State step（4）In aqueous slkali be concentration 1mol/L~10mol/L sodium hydroxide solution or potassium hydroxide solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610749411.XA CN106229156B (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of two-dimentional silicon-carbon nitrogen nano-material for energy stores |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610749411.XA CN106229156B (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of two-dimentional silicon-carbon nitrogen nano-material for energy stores |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106229156A CN106229156A (en) | 2016-12-14 |
| CN106229156B true CN106229156B (en) | 2018-08-03 |
Family
ID=57555965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610749411.XA Active CN106229156B (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of two-dimentional silicon-carbon nitrogen nano-material for energy stores |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106229156B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107068996B (en) * | 2017-02-27 | 2019-10-25 | 陕西六元碳晶股份有限公司 | A kind of continuous preparation method of silicon-carbon nitrogen composite material |
| CN107400852A (en) * | 2017-07-31 | 2017-11-28 | 广东海洋大学 | A kind of silicon-carbon nitroblue light luminescent film and preparation method thereof |
| CN110544590B (en) * | 2018-05-29 | 2021-05-04 | 中国海洋大学 | Nitrate-assisted synthesized nitrogen-doped nano carbon sheet and sodium storage application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104103807A (en) * | 2013-04-12 | 2014-10-15 | 华为技术有限公司 | Silicon-carbon composite anode material, preparation method thereof and lithium ion battery |
| CN104909351A (en) * | 2015-06-02 | 2015-09-16 | 上海应用技术学院 | Nitrogen-doped mesoporous carbon sphere nanomaterial and preparation method thereof |
-
2016
- 2016-08-29 CN CN201610749411.XA patent/CN106229156B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104103807A (en) * | 2013-04-12 | 2014-10-15 | 华为技术有限公司 | Silicon-carbon composite anode material, preparation method thereof and lithium ion battery |
| CN104909351A (en) * | 2015-06-02 | 2015-09-16 | 上海应用技术学院 | Nitrogen-doped mesoporous carbon sphere nanomaterial and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Three-dimensional polymer-derived ceramic/graphene paper as a Li-ion battery and supercapacitor electrode;L. David等;《RSC Advances》;20160527;第6卷;第53894–53902页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106229156A (en) | 2016-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103950923B (en) | A kind of novel method preparing high-quality Graphene | |
| CN105329876B (en) | A kind of preparation method of boron, nitrogen co-doped carbon quantum dot | |
| CN104801244A (en) | Method for preparing three-dimensional graphene-copper nanowire composite aerogel | |
| CN106229156B (en) | A kind of preparation method of two-dimentional silicon-carbon nitrogen nano-material for energy stores | |
| CN102698774B (en) | Hydrothermal preparation method for single-layer MoS2 and graphene composite nano material | |
| CN103449496A (en) | Nano cerium oxide and preparation method thereof | |
| CN107185576A (en) | A kind of preparation method of carbonitride/graphene composite material of three-dimensional structure | |
| CN103214878A (en) | Preparation method of graphite type carbon nitride-ionic liquid composite material | |
| CN102989497B (en) | Mesoporous graphite type carbon nitride/nitrogen-doped graphene composite material and preparation method thereof | |
| CN106744744A (en) | The preparation method and products therefrom of a kind of cellular graphite phase carbon nitride nano material of cobalt doped | |
| CN103157461A (en) | Nanometer photocatalyst bismuth tungstate and preparation method thereof | |
| CN108855187A (en) | A kind of fluorine richness boron carbon nitrogen catalysis material and its application in efficiently reduction carbon dioxide | |
| CN107837816A (en) | Fe2O3/g‑C3N4Compound system and preparation method and application | |
| CN113772637B (en) | Nanocomposite integrating heat conduction and wave absorption and preparation method thereof | |
| CN102583353B (en) | Hydrothermal method for preparing graphene | |
| CN105350113A (en) | Preparation method of nitride carbon nanofibers and obtained product | |
| CN105502370B (en) | A kind of solid-phase reduction process of graphene oxide | |
| CN107649153A (en) | A kind of method that solvent-thermal method prepares BiOCl photochemical catalysts | |
| CN106000390A (en) | Method for preparation of Bi2O3/BiTaO4 composite photocatalyst by molten salt technique | |
| CN104043471A (en) | Preparation method of graphene/Ta3N5 composite photo-catalyst | |
| CN106976854B (en) | A method of preparing carbon material | |
| CN102500360A (en) | Method for preparing mesoporous tungsten oxide/carbon composite conductive materials | |
| CN110627049A (en) | Preparation method and application of graphene-loaded black phosphorus quantum dot | |
| CN108675339A (en) | A kind of preparation method of the glomerate zinc cadmium sulphur solid-solution material of rodlike self assembly | |
| CN103539090B (en) | High orientation arrayed carbon nitride nanorod array and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 |