CN108270008A - A kind of method that single-layer graphene is prepared based on the insertion stripping of molten alkali metal liquid - Google Patents
A kind of method that single-layer graphene is prepared based on the insertion stripping of molten alkali metal liquid Download PDFInfo
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- CN108270008A CN108270008A CN201810061273.5A CN201810061273A CN108270008A CN 108270008 A CN108270008 A CN 108270008A CN 201810061273 A CN201810061273 A CN 201810061273A CN 108270008 A CN108270008 A CN 108270008A
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- alkali metal
- layer graphene
- graphite
- stripping
- metal liquid
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
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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 methods for preparing single-layer graphene based on the insertion stripping of molten alkali metal liquid.The graphene nano material of this single layer structure is using graphite as presoma, using molten alkali metal as solvent, the preparation of single-layer graphene is realized by solvent heat.The present invention is mainly using under the protection of high-purity argon gas; utilize solvent-thermal method; alkali metal ion is embedded between graphite linings; obtain the single-layer graphene material of alkali metal insertion; then n-hexane, deionized water cleaning are passed sequentially through again; by techniques such as centrifugations, the graphene nano material of the single layer structure of high-purity has been prepared.The preparation process of the present invention is simple, of low cost, and prepared nano material has high-specific surface area, good electric conductivity.Structural stability and electrochemistry cycle performance have huge application potential in lithium secondary battery electrode negative material field.
Description
Technical field
The invention belongs to new energy nanometer energy storage material fields, relate generally to a kind of be inserted into based on molten alkali metal liquid and remove
The method for preparing single-layer graphene.
Background technology
21 century, the energy and environment have become the two principal themes of world today's sustainable development, in order to solve energy crisis
With this two big worlds problem of environmental pollution, various countries have put into huge fund and have greatly developed new and renewable energy.As new energy
Representative, lithium ion battery has that energy density is high, opens compared to the secondary cells such as Ni-MH battery, nickel-cadmium cell and lead-acid battery
The remarkable advantages such as road voltage is high, environmental-friendly, service life is long, and self discharge is small, security performance is superior, have been widely used for electronic
The fields such as automobile, portable electronic product, energy storage.In each assembly unit of lithium ion battery, electrode material is lithium ion battery
Key, performance quality directly determine the key performances such as capacity, energy density and the cycle life of lithium ion battery.Cause
This, develops high performance lithium ion battery electrode material, seems to the performance for improving lithium ion battery and is even more important.
Traditional lithium ion battery negative material is graphite cathode material, and lithium ion is embedded easily in carbon-coating and deviates to be formed
LiC6 intercalation compounds, but its specific capacity is relatively low, theoretically can only achieve 372mAh/g, it is impossible to meet high performance lithium ion battery
Requirement, in order to further improve the energy density of lithium ion battery and cycle life, need further to develop new cathode material
Material.
And graphene was sent out for the first time as a kind of novel carbon material in the scholar by Manchester universities of Britain in 2004
It is existing, be it is a kind of by single layer of carbon atom with SP2 hybridized orbits it is tightly packed into bi-dimensional cellular shape structure new carbon.Graphite
Alkene has high electron mobility, high theoretical specific surface area, high thermal conductivity, high theoretical lithium storage content and excellent mechanics
Performance, in electrode of solar battery material, super capacitor material, Heat Conduction Material, lithium ion battery electrode material and composite wood
Material etc. shows wide application prospect.Wherein the laminated structure of graphene provides storage lithium active sites, and interlamellar spacing is conducive to lithium
The diffusion of ion is a kind of excellent lithium storage materials.However the preparation method of grapheme material is more, performance difference is larger, main
To include mechanical stripping method, chemical oxidization method, crystal epitaxy method, chemical vapour deposition technique, organic synthesis method and carbon nanometer
Pipe stripping method etc..Although the above method can obtain graphene nano material, its is of high cost, complex process, poor controllability, closes
It is not high enough into graphene purity, the raising effect for storing up lithium performance is not obvious.Therefore by artificial improvement synthesis technology and
Its used presoma obtains the graphene nano sheet material of high-purity so as to improve storage lithium by the technique of simple possible
It can all need further to be studied.
In conclusion the synthesizing graphite alkene method mentioned in most of document or patent has all obtained stone to a certain extent
Black alkene nanometer sheet, improves its chemical property, so as to influence application and development of the graphene in terms of lithium electricity.But existing stone
Black alkene nanometer piece preparation method is all more complicated, and the graphene nano material specific surface area prepared is limited, electric conductivity
Difference, it is limited for improving the effect of its lithium storage performance.
Invention content
The purpose of the present invention is to solve the shortcomings of the prior art and defect, provide and a kind of be inserted into based on molten alkali metal liquid
The method that stripping prepares single-layer graphene, preparation method of the invention is novel, and low manufacture cost, preparation process is simple, becomes most
It is possible that efficiently prepare the method for single-layer graphene nanometer sheet.
The present invention adopts the following technical scheme that realization：
A kind of method for preparing single-layer graphene based on the insertion stripping of molten alkali metal liquid, specifically includes following steps：
Step S1：Reaction vessel of the autoclave as solvent heat is chosen, the autoclave includes stainless steel autoclave body
And the polytetrafluoroethylliner liner of 30ml；
Step S2：Alkali metal and graphite precursor mixture is configured, gained homogeneous mixture is transferred to above-mentioned autoclave
In, as solvent thermal reaction predecessor；
Step S3：Using solvent thermal reaction, the alkali metal got well will be configured and graphite precursor mixture is filled at high temperature under high pressure
Divide reaction, after the completion of reaction, by adding in n-hexane into reaction solution, be centrifugally separating to obtain the mono-layer graphite of alkali metal insertion
Alkene；
Step S4：The single-layer graphene of alkali metal insertion is prepared to the list of high-purity through deionized water centrifugation cleaning
Layer graphene nanometer sheet.
Further, alkali metal is configured in the step S2 and the specific method of graphite precursor mixture is：In gloves
In case, by the protection of high-purity argon gas, the alkali metal of certain mass is weighed, then adds in graphitic carbon to it, then by stirring,
Mixed uniformly precursor mixture is formed, then the precursor mixture is transferred in 30ml polytetrafluoroethylliner liners,
Stainless steel cauldron interior sealing is good.
Preferably, high-purity argon gas purity used is 99.999% in the glove box, alkali metal used is lithium（High purity lithium
Piece）Or sodium（High pure sodium piece）, the alkali metal quality weighed is 1-3g, and the graphite quality weighed is 0.1-0.3g, and the two stirring is mixed
The conjunction time is 20-30min.
Further, the specific method of single-layer graphene that alkali metal insertion is obtained in the step S3 is：It will be configured
The autoclave equipped with alkali metal and graphite precursor mixture be transferred in air dry oven, it is molten at a certain temperature
Agent thermal response for a period of time after, treat its natural cooling, by adding in n-hexane, be then centrifuged for detaching, obtain alkali metal insertion
Single-layer graphene.
Preferably, by the autoclave equipped with alkali metal/graphite precursor mixture in air dry oven solvent heat
Temperature for 100 DEG C -150 DEG C, the time of solvent heat is 24-72h, and after its natural cooling, the amount for adding in n-hexane is 15-
30ml, centrifugation rate 8000r/min, centrifugation time 30min, it is 3-5 to repeat eccentric cleaning separation circulation technology number
It is secondary.
Further, the individual layer stone of high-purity is prepared in the step S4 by organic solvent centrifugation cleaning
The specific method of black alkene nanometer sheet is：The single-layer graphene that obtained alkali metal is embedded in is transferred in beaker, is slowly added to
Ionized water, discovery have bubble generation, after the reaction was complete after it, are centrifuged at a high speed several times by centrifuge, obtain mono-layer graphite
Alkene nanometer sheet.
Preferably, the deionized water added in is 20-40ml, centrifugation rate 8000r/min, centrifugation time 30min,
It is 3-5 times to repeat eccentric cleaning separation circulation technology number, obtains the single-layer graphene of high-purity.
Compared with prior art, the beneficial effects of the present invention are：
The present invention provides a kind of method for preparing single-layer graphene based on the insertion stripping of molten alkali metal liquid, this method can fill
Divide using high capacity characteristics of the graphene in terms of lithium ion battery, prepare the lithium using graphene nano material as charge and discharge electric material
Ion battery cathode material；The present invention is utilized under the protection of high-purity argon gas first, and graphitic carbon and alkali metal are blended in one
It rises, by the effect of solvent heat, between alkali metal ion is embedded into graphite linings, so as to form the mono-layer graphite of alkali metal insertion
Alkene nano material then by purifying decontamination, obtains the graphene nanometer sheet of high-purity, this method is of low cost, technique letter
It is single, obtain the single-layer graphene nanometer sheet of high storage lithium performance.
Description of the drawings
Fig. 1 is blocky graphite；
Fig. 2 is that the single-layer graphene of alkali metal insertion obtained after responseless alkali metal is removed by eccentric cleaning；
Fig. 3 is by adding in deionized water, then detaches removal alkali metal ion, obtained mono-layer graphite by eccentric cleaning
Alkene；
Description of the drawings：1 is mono-layer graphite, 2 alkali metal ions.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and embodiments.
Embodiment 1
A kind of method that single-layer graphene is prepared based on the insertion stripping of molten alkali metal liquid, the specific steps are：
（1）In glove box under high-purity argon gas protection, 0.1g graphitic carbons are weighed, add it to 30ml polytetrafluoroethyl-ne alkene reactions
In kettle, 1.5g lithium pieces are then weighed, are transferred into the polytetrafluoroethylliner liner equipped with graphite, then uniformly mixing is stirred by it
20min is mixed, is sealed, obtains precursor mixture, wherein Fig. 1 is blocky graphite structure；
（2）The reaction kettle of the 30ml is transferred in air dry oven, solvent thermal reaction for 24 hours, treats its natural cooling at 120 DEG C
Afterwards, which is transferred in beaker, adds in 30ml n-hexanes to it, then centrifuged by 50ml centrifuge tubes, centrifuged
Rate 8000r/min, centrifugation time 30min have centrifuged and then secondary using n-hexane, 3 are cleaned using same method
It is secondary, remove extra unreacted lithium metal, after cleaning is completed, obtain the graphene nanometer sheet of the lithium insertion of individual layer, Fig. 2 is lithium
Embedded single-layer graphene structure, wherein 1 is single-layer graphene, 2 be the lithium ion between embedded graphene layer；
（3）By step（2）In obtain lithium ion insertion single-layer graphene, be transferred in beaker, thereto add in 30ml go
Ionized water, it can be seen that have bubble generation, after the reaction was complete after it, remove extra lithium ion again by centrifuging, obtain
To single-layer graphene nanometer sheet, centrifugation rate 8000r/min, centrifugation time 30min are cleaned again using same method
Twice, the single-layer graphene nanometer sheet of high-purity, the single-layer graphene structure that Fig. 3 is are obtained.
Embodiment 2
A kind of method that single-layer graphene is prepared based on the insertion stripping of molten alkali metal liquid, the specific steps are：
（1）In glove box under high-purity argon gas protection, 0.15g graphitic carbons are weighed, it is anti-to add it to 30ml polytetrafluoroethylene (PTFE)
It answers in kettle, then weighs 2g lithium pieces, be transferred into the polytetrafluoroethylene (PTFE) that graphite is housed, be then mixed uniformly, sealing
It is good, precursor mixture is obtained, Fig. 1 is blocky graphite structure；
（2）The reaction kettle of the 30ml is transferred in air dry oven, the solvent thermal reaction 48h at 120 DEG C treats its natural cooling
Afterwards, which is transferred in beaker, adds in 30ml n-hexanes to it, then centrifuged by 50ml centrifuge tubes, centrifuged
Rate 8000r/min, centrifugation time 30min have been centrifuged and then secondary several using the cleaning of same method using n-hexane
It is secondary, remove extra unreacted lithium metal, after cleaning is completed, obtain the graphene nanometer sheet of the lithium ion insertion of individual layer, Fig. 2
For the single-layer graphene structure of lithium ion insertion, wherein 1 is single-layer graphene, 2 be the lithium ion of embedded interlayer；
（3）By step（2）Obtain lithium ion insertion single-layer graphene, be transferred in beaker, thereto add in 30ml go from
Sub- water, it can be seen that have bubble generation, after the reaction was complete after it, remove extra lithium ion again by centrifuging, obtain
Single-layer graphene nanometer sheet, centrifugation rate 8000r/min, centrifugation time 30min clean two again using same method
It is secondary, obtain the single-layer graphene nanometer sheet of high-purity, the single-layer graphene structure that Fig. 3 is.
Embodiment 3
A kind of method that single-layer graphene is prepared based on the insertion stripping of molten alkali metal liquid, the specific steps are：
（1）In glove box under high-purity argon gas protection, 0.2g graphitic carbons are weighed, add it to 30ml polytetrafluoroethyl-ne alkene reactions
In kettle, 3g sodium pieces are then weighed, are transferred into the polytetrafluoroethylene (PTFE) equipped with graphite, are then mixed uniformly, sealing
It is good, precursor mixture is obtained, wherein Fig. 1 is blocky graphite structure；
（2）The reaction kettle of the 30ml is transferred in air dry oven, the solvent thermal reaction 72h at 130 DEG C treats its natural cooling
Afterwards, which is transferred in beaker, adds in 30ml n-hexanes to it, then centrifuged by 50ml centrifuge tubes, centrifuged
Rate 8000r/min, centrifugation time 30min have been centrifuged and then secondary several using the cleaning of same method using n-hexane
It is secondary, remove the complete sodium block of extra unreacted, after cleaning is completed, obtain the graphene nanometer sheet of the sodium insertion of individual layer, Fig. 2 is sodium
Embedded single-layer graphene structure, wherein 1 be single-layer graphene, 2 sodium ion between intercalated layered；
（3）By step（2）The obtained single-layer graphene of sodium insertion, is transferred in beaker, adds in 30ml deionized waters thereto,
It can be seen that there is bubble generation, after the reaction was complete after it, remove extra sodium ion again by centrifuging, obtain individual layer stone
Black alkene nanometer sheet, centrifugation rate 8000r/min, centrifugation time 30min using same method are cleaned twice, obtained again
To the single-layer graphene nanometer sheet of high-purity, Fig. 3 is single-layer graphene structure.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (8)
- A kind of 1. method that single-layer graphene is prepared based on the insertion stripping of molten alkali metal liquid, it is characterised in that：Including following step Suddenly：1）Alkali metal and graphite precursor mixture are prepared, precursor mixture is transferred in autoclave；2）Autoclave is transferred in air dry oven, using solvent thermal reaction, makes precursor mixture in high temperature and pressure Lower fully reaction a period of time；3）It after the completion of reaction, treats its natural cooling, n-hexane is added in into reaction system, be centrifugally separating to obtain alkali metal insertion Single-layer graphene；4）Deionized water is slowly added into the single-layer graphene of alkali metal insertion, after complete reaction, is centrifuged cleaning The single-layer graphene nanometer sheet of high-purity is made in process.
- 2. the method according to claim 1 that single-layer graphene is prepared based on the insertion stripping of molten alkali metal liquid, feature It is：Step 1）Described in alkali metal and graphite precursor mixture in, the mass ratio of alkali metal and graphite is：1-3:0.1- 0.3。
- 3. the method according to claim 1 or 2 for preparing single-layer graphene based on the insertion stripping of molten alkali metal liquid, special Sign is：Step 1）Described in alkali metal be lithium or sodium.
- 4. the method according to claim 1 or 2 for preparing single-layer graphene based on the insertion stripping of molten alkali metal liquid, special Sign is：Step 1）Described in alkali metal and the preparation method of graphite precursor mixture be：In glove box, by high-purity The protection of argon gas weighs a certain amount of alkali metal and a certain amount of graphite respectively, and alkali metal and graphite are mixed by stirring It is even, form precursor mixture.
- 5. the method according to claim 4 that single-layer graphene is prepared based on the insertion stripping of molten alkali metal liquid, feature It is：The time that is stirred of alkali metal and graphite is 20-30min.
- 6. the method according to claim 1 or 2 for preparing single-layer graphene based on the insertion stripping of molten alkali metal liquid, special Sign is：Step 2）The temperature of middle solvent thermal reaction is：100 DEG C -150 DEG C, the reaction time is：24-72h.
- 7. the method according to claim 1 or 2 for preparing single-layer graphene based on the insertion stripping of molten alkali metal liquid, special Sign is：Step 3）The dosage of middle n-hexane is 15-30ml, centrifugation rate 8000r/min, centrifugation time 30min, is repeated Centrifugal separation process 3-5 times.
- 8. the method according to claim 1 or 2 for preparing single-layer graphene based on the insertion stripping of molten alkali metal liquid, special Sign is：Step 4）The dosage of middle deionized water is 20-40ml, centrifugation rate 8000r/min, centrifugation time 30min, is weighed Centrifugation cleaning 3-5 times again.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701187A (en) * | 2011-07-13 | 2012-10-03 | 华东理工大学 | Preparation method of graphene and graphene prepared by same |
| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN103971947A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Preparation method for graphene-ionic liquid composite materials and preparation method for supercapacitor |
-
2018
- 2018-01-23 CN CN201810061273.5A patent/CN108270008A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701187A (en) * | 2011-07-13 | 2012-10-03 | 华东理工大学 | Preparation method of graphene and graphene prepared by same |
| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN103971947A (en) * | 2013-01-28 | 2014-08-06 | 海洋王照明科技股份有限公司 | Preparation method for graphene-ionic liquid composite materials and preparation method for supercapacitor |
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Application publication date: 20180710 |