CN110357082A - A kind of graphene of alkali metal containing - Google Patents
A kind of graphene of alkali metal containing Download PDFInfo
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- CN110357082A CN110357082A CN201810312710.6A CN201810312710A CN110357082A CN 110357082 A CN110357082 A CN 110357082A CN 201810312710 A CN201810312710 A CN 201810312710A CN 110357082 A CN110357082 A CN 110357082A
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- alkali metal
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The present invention provides a kind of graphene of alkali metal containing, and the graphene of the alkali metal containing has 1-10 layers, and planar dimension is 0.1-500 μm, and containing a small amount of alkali metal or alkali metal compound, the quality of alkali metal accounts for the 0.01-10% of the graphene quality of the alkali metal containing.The present invention also proposes that the alkali metal containing graphene is preparing the application in lithium ion battery.Alkali metal containing graphene proposed by the present invention constitutes novel grapheme material with the alkali metal and two-dimentional graphite content that conductivity is high, redox normal potential is extremely low, and chemical property is further improved, and is adapted to the manufacture of high capacity lithium ion battery.
Description
Technical field
The invention belongs to carbon material preparation fields, and in particular to a kind of alkali metal containing graphene.
Background technique
Graphene is by single layer sp2Hydbridized carbon atoms rearrange, and have due to excellent physicochemical properties and answer extensively
Material.Its excellent physicochemical properties include unique two-dimensional structure, high conductivity and thermal conductivity, bigger serface,
High Young's model and high chemical stability etc..Unique single layer structure, excellent flexibility and superpower thermal conductivity,
The graphene made has relatively broad application in fields such as energy storage, catalysis, composite materials.
The preparation method of graphene mainly has method from bottom to top and from top to bottom method at present.Growth method from bottom to top,
Such as chemical vapor deposition method.The method of preparing graphene through chemical vapor deposition has preparation process harshness, energy consumption height, efficiency
The problems such as low, at high cost, limits the possibility that this method prepares graphene large-scale application.And chemical vapor deposition preparation
Graphene, the graphene especially quickly generated, due to being generally the graphene of multiphase nucleation preparation, so in the face of graphene
With a large amount of non-sp2Hydbridized carbon atoms, this strong influence electric conductivity of graphene.Method from top to bottom, such as liquid phase removing
Method and oxidation-reduction method etc..From graphite material, graphene is removed using the mechanical means such as such as ultrasound, shearing, is further passed through
Crossing separation, perhaps reduction acquisition graphene such methods generally require higher energy during the preparation process or generation environment is dirty
The waste of dye.Importantly, if being difficult to obtain the graphene of single layer using purely mechanic removing, if using oxidation-reduction method
Graphene is prepared with many defects, and there is a large amount of oxygen-containing functional group residual.
Therefore, for currently prepared graphene the characteristics of and the means for preparing graphene, exploitation low energy consumption, big rule
Mould, environmental protection, efficiently graphene preparation means obtain the graphite that New Energy plays its unique two-dimensional structure, excellent conductive characteristic
Alkene is of great significance to the application for realizing graphene.
Summary of the invention
For shortcoming existing for graphene prepared by current various means, the purpose of the present invention is to propose to one kind to contain
Alkali metal graphene, the graphene thickness is thin, and single layer rate is high, has and contains a small amount of alkali metal ion or alkali metal compound, no
Containing oxygen-containing Guan Nengtuan, the advantages that planar disfigurement is few, and conductivity is high.
Realize the technical solution of the object of the invention are as follows:
A kind of alkali metal containing graphene, the alkali metal containing graphene have 1-10 layers, and planar dimension is 0.1-500 μm, no
Containing oxygen-containing functional group, containing a small amount of alkali metal or alkali metal compound, the quality of alkali metal accounts for the alkali metal containing graphene matter
The 0.01-10% of amount.
Preferably, the alkali metal containing graphene has 1-5 layers, and planar dimension is 1-20 μm.
Further, the content of oxygen is less than 1wt% in the graphene of the alkali metal containing.
Wherein, the alkali metal containing graphene conductive rate is greater than 300Scm-1, specific surface area is greater than 200m2·g-1。
It is highly preferred that the specific surface area is 400m2·g-1-2000m2·g-1。
Wherein, the alkali metal is lithium, sodium, potassium, rubidium, caesium, one of francium or a variety of.
The preparation method preparation of this field always can be used in alkali metal containing graphene proposed by the present invention.Here, proposing one
The preferred preparation method of kind.
The alkali metal containing graphene, is prepared by following steps:
(1) in inert environments, graphite-like raw material and alkali metal are mixed, obtain uniformly mixed graphite-like carbon
Material-alkali metal composite material, and stood in inert environments, make that metal intercalation reaction occurs, until composite material is by black
Become golden yellow；
(2) resulting composite material is put into the liquid medium that can be reacted and is reacted, remove intercalation object,
By shaking or removing, clean, separate, grapheme material is obtained.
Wherein, step (1) alkali metal is the alloy of one or more of lithium, sodium, potassium；The graphite-like is former
Material is natural or artificial graphite, specially graphite paper, graphite powder, crystalline flake graphite, expanded graphite, spherical graphite, Gao Ding
To one of pyrolytic graphite etc. or a variety of.
The inert environments are argon atmosphere, helium atmosphere, are stood in inert environments to sample and become golden yellow, stood
Time is in 10h or more.
Wherein, in step (2), the liquid medium be water, methanol, ethyl alcohol, propyl alcohol, n-butanol, ethylene glycol, formic acid,
One of acetic acid, propionic acid, hydrochloric acid are a variety of.
Alkali metal containing graphene of the present invention in the application of battery, catalytic field, including but not limited to electrocondution slurry,
Graphene combination electrode material etc..
The invention has the following advantages over the prior art:
Alkali metal containing graphene proposed by the present invention has oxygen-containing functional group few, and two-dimensional structure is complete, only containing a small amount of
Alkali metal, thus it is conductive high the advantages that, be adapted to lithium battery electrocondution slurry, combination electrode material etc. application.
The present invention further uses lithium or other high activity alkali metals and intercalation occurs for graphite carbon material mixing
To prepare this grapheme material；It can be carried out under the conditions ofs room temperature, air etc. in the preparation process of its later period graphene, be suitble to work
Industry large scale preparation graphene, more valuable electrode material is provided to lithium ion battery industry.
Detailed description of the invention
Fig. 1 is the electromicroscopic photograph of 1 alkali metal containing graphene of embodiment.
Fig. 2 is the atomic force photo of 1 alkali metal containing graphene of embodiment.
Fig. 3 is the atomic force photo of 2 alkali metal containing graphene of embodiment.
Fig. 4 is the content table of the XPS full spectrogram and each element of 1 alkali metal containing graphene of embodiment.
Specific embodiment
Illustrate technical solution of the present invention below by way of specific embodiment.It should be understood that mention one of the present invention or
Multiple steps do not repel before and after the combination step that there is also between other methods and step or these specifically mentioned steps
Other methods and step can also be inserted into.It should also be understood that these examples are merely to illustrate the present invention rather than the limitation present invention
Range.Unless otherwise indicated, the number of various method steps is only to identify the purpose of various method steps, rather than limit each method
Arrangement order or limit practical range of the invention, relativeness is altered or modified, in no substantial technological content alteration
Under conditions of, it also can be considered the enforceable scope of the present invention.
Raw material employed in embodiment and instrument do not have specific limitation to its source, buy in market or according to this
In field prepared by conventional method known to technical staff.
Embodiment 1:
The alkali metal containing graphene of the present embodiment is prepared by the following method:
(1) natural graphite powder and lithium metal are mixed in inert environments argon gas with the ratio of mass ratio 6:1, is first led to
Cross roll-in lithium and graphite powder roll-in is uniform, be subsequently placed in ar gas environment 10 hours, mixture by black transitions at golden yellow,
The single order intercalation of lithium has occurred in graphite at this time.
(2) above-mentioned golden yellow composite material is taken out from inert environments, is put into the HCl solution of 0.05M, graphite interleaves
The lithium metal of layer is quickly reacted with hydrochloric acid and water, and graphite is expanded and is lifted off of, is dispersed in dilute hydrochloric acid.After the reaction was completed
Solution is ultrasonically treated one hour, is then cleaned repeatedly with the dilute hydrochloric acid of 0.05M and water.It is finally separating, is dried to obtain graphene.
Gained alkali metal containing graphene planes size is 1-4 microns (as shown in Fig. 1), which is
1nm or so (as shown in Fig. 2), for the number of plies less than 5 layers, amount containing lithium is 0.77wt%, and oxygen-containing is 0.32wt% (referring to fig. 4).This
The conductivity of the graphene of alkali metal containing is about 500Scm-1, specific surface area 600m2·g-1。
Embodiment 2:
The alkali metal containing graphene of the present embodiment is prepared by the following method:
(1) crystalline flake graphite and lithium metal are mixed in inert environments argon gas with the ratio of mass ratio 8:1, is first passed through
Roll-in is uniform by lithium and graphite powder roll-in, is subsequently placed in ar gas environment 15 hours, and mixture is by black transitions at golden yellow (it
After always remain as golden yellow), the single order intercalation of lithium has occurred in graphite at this time.
(2) above-mentioned golden yellow composite material is taken out from inert environments, is put into ethyl alcohol, the lithium metal of intercalation between graphite
It quickly expands and is lifted off of with ethanol synthesis, graphite, dispersion is in ethanol.Solution is ultrasonically treated one after the reaction was completed
Hour, then cleaned repeatedly with the dilute hydrochloric acid of 0.05M and water.It is finally separating, is dried to obtain graphene.
The graphene size is 2-8 microns (shown in attached drawing 3), which is 3nm or so (such as 3 institute of attached drawing
Show), for the number of plies less than 10 layers, amount containing lithium is 1.20wt%, and oxygen-containing is 0.48wt.%.This alkali metal containing graphene conductive rate is about
450S·cm-1, specific surface area 550m2·g-1。
Embodiment 3:
The alkali metal containing graphene of the present embodiment is prepared by the following method:
(1) by expanded graphite (99.9%) and lithium metal-sodium (mass ratio 1:1) in inert environments argon gas with mass ratio 3:
1 ratio is mixed, and it is uniform by lithium and graphite powder roll-in to first pass through roll-in, is subsequently placed in ar gas environment 10 hours, is mixed
Object by black transitions at golden yellow (always remaining as golden yellow) later, and the single order intercalation of lithium has occurred in graphite at this time.
(2) above-mentioned golden yellow composite material is taken out from inert environments, is put into the HCl solution of 0.05M, graphite interleaves
The lithium metal of layer is quickly reacted with hydrochloric acid and water, and graphite is expanded and is lifted off of, is dispersed in dilute hydrochloric acid.After the reaction was completed
Solution is ultrasonically treated one hour, is then cleaned repeatedly with the dilute hydrochloric acid of 0.05M and water.It is finally separating, is dried to obtain graphene.
The graphene size is 0.5-2 microns, which is 1nm or so, and the number of plies is less than 5 layers, amount containing lithium
For 2.0wt%, oxygen-containing is 0.7wt.%.This alkali metal containing graphene conductive rate is 430Scm-1, specific surface area 520m2
g-1。
Above example is only that a specific embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, those skilled in the art can also do numerous modifications and variations on the basis of existing technology, not depart from design of the present invention
Under the premise of spirit, all variations and modifications that this field ordinary engineering and technical personnel makes technical solution of the present invention,
It should fall within the scope of protection determined by the claims of the present invention.
Claims (10)
1. a kind of graphene of alkali metal containing, which is characterized in that the graphene of the alkali metal containing has 1-10 layers, and planar dimension is
0.1-500 μm, containing a small amount of alkali metal or alkali metal compound, the quality of alkali metal accounts for the graphene quality of the alkali metal containing
0.01-10%.
2. the graphene of alkali metal containing according to claim 1, which is characterized in that the graphene of the alkali metal containing has 1-
5 layers, planar dimension is 1-20 μm.
3. the graphene of alkali metal containing according to claim 1, which is characterized in that oxygen in the graphene of the alkali metal containing
Content be less than 1wt%.
4. the graphene of alkali metal containing according to claim 1, which is characterized in that the graphene of the alkali metal containing is led
Electric rate is greater than 300Scm-1, specific surface area is greater than 200m2·g-1。
5. the graphene of alkali metal containing according to claim 4, which is characterized in that the specific surface area is 400m2·g-1-
2000m2·g-1。
6. the graphene of alkali metal containing according to claim 1, which is characterized in that the alkali metal be lithium, sodium, potassium,
One of rubidium, caesium, francium are a variety of.
7. the graphene of alkali metal containing according to claim 1-6, which is characterized in that the alkali metal containing graphite
Alkene is prepared by following steps:
(1) in the atmosphere not reacted with alkali metal, graphite-like raw material and alkali metal are mixed, it is equal to obtain mixing
Even graphite carbon material-alkali metal composite material, and stood in the atmosphere that do not reacted with alkali metal, insert generation alkali metal
Layer reaction, until composite material becomes golden yellow by black；
(2) resulting composite material is put into the liquid medium that can be reacted and is reacted, remove intercalation object, passed through
Concussion or removing, cleaning, separation, obtain the graphene of alkali metal containing.
8. the graphene of alkali metal containing according to claim 7, which is characterized in that in step (1), the alkali metal is
One or more of lithium, sodium, potassium, rubidium, caesium, francium；The graphite-like raw material are natural or artificial graphite, preferably
Graphite paper, graphite powder, crystalline flake graphite, mesophase pitch carbosphere, expanded graphite, spherical graphite, in highly oriented pyrolytic graphite
It is one or more；
The atmosphere that do not react with alkali metal includes one of argon gas, helium, hydrogen etc. or a variety of, anti-not with alkali metal
It is stood in the atmosphere answered to sample and becomes golden yellow, time of repose is in 10h or more.
9. alkali metal containing graphene according to claim 7, which is characterized in that in step (2), the liquid medium is
One of water, methanol, ethyl alcohol, propyl alcohol, n-butanol, ethylene glycol, formic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid are a variety of.
10. any one of the claim 1-9 alkali metal containing graphene is in the application of battery, catalytic field.
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| CN201810312710.6A CN110357082A (en) | 2018-04-09 | 2018-04-09 | A kind of graphene of alkali metal containing |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114408916A (en) * | 2021-12-16 | 2022-04-29 | 广东邦普循环科技有限公司 | Expanded graphite and preparation method thereof |
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| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN103626165A (en) * | 2012-08-28 | 2014-03-12 | 海洋王照明科技股份有限公司 | Graphene preparation method |
| CN104003372A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof |
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- 2018-04-09 CN CN201810312710.6A patent/CN110357082A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN103626165A (en) * | 2012-08-28 | 2014-03-12 | 海洋王照明科技股份有限公司 | Graphene preparation method |
| CN104003372A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114408916A (en) * | 2021-12-16 | 2022-04-29 | 广东邦普循环科技有限公司 | Expanded graphite and preparation method thereof |
| WO2023109192A1 (en) * | 2021-12-16 | 2023-06-22 | 广东邦普循环科技有限公司 | Expanded graphite and preparation method therefor |
| CN114408916B (en) * | 2021-12-16 | 2023-07-07 | 广东邦普循环科技有限公司 | Expanded graphite and preparation method thereof |
| GB2617006A (en) * | 2021-12-16 | 2023-09-27 | Guangdong Brunp Recycling Technology Co Ltd | Expanded graphite and preparation method therefor |
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Application publication date: 20191022 |