CN107879336A - A kind of high electric property graphene nano piece preparation method and its graphene nanometer sheet - Google Patents
A kind of high electric property graphene nano piece preparation method and its graphene nanometer sheet Download PDFInfo
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- CN107879336A CN107879336A CN201711121230.3A CN201711121230A CN107879336A CN 107879336 A CN107879336 A CN 107879336A CN 201711121230 A CN201711121230 A CN 201711121230A CN 107879336 A CN107879336 A CN 107879336A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
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- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The present invention relates to technical field of graphene, discloses a kind of high electric property graphene nano piece preparation method.The present invention prepares graphene nanometer sheet this technique using wet grinding can significantly improve the chemical property of graphene nanometer sheet, its process is not only simple to operate, cost is low but also is easily enlarged productionization, and introduce graphene quantum dot and be used to improve dispersiveness as auxiliary agent, in mechanical milling process lamella can due to size reduce and mutually reunite cause store up lithium ability decline, therefore adding graphene quantum dot can effectively prevent mechanical milling process size from reducing the problem of storage lithium ability brought declines, while also contribute to stability.In addition, graphene quantum dot is easily recycled simultaneously, repeatable utilization is realized in environmentally safe, energy-conserving and environment-protective, and wherein graphene quantum dot addition is very few can not play scattered effect, and amount can cause reunion on the contrary greatly.
Description
Technical field
The present invention relates to technical field of graphene, is prepared more particularly, to a kind of high electric property graphene nanometer sheet
Method.
Background technology
Graphene, is a kind of carbon atom by sp2 hydridization bonding in the form of hexagon grid, the two dimension of the carbon formed
Planar monolayer structure, it is the allotrope of carbon.Graphene is the elementary cell for building other dimension carbon materials, when it is with bag
When the mode wrapped up in, wind and piled up changes, the fullerene, one-dimensional CNT and three-dimensional stone of zero dimension can be formed respectively
Ink.Graphene has good electricity-optics performance, mechanical property, heat-conductive characteristic and the migration of high electric charge carrier
Rate, while also outstanding mechanical strength and pliability.These properties of graphene, it is allowed to be rapidly become by numerous concerns
The focus of research.The graphene and its derivative handled by chemical modification is even more the material with specific function, available for crystalline substance
Body pipe, liquid-crystal apparatus, electrochemica biological sensor, ultracapacitor, fuel cell, solar cell etc..Ground past
During studying carefully, people generally prepare graphite with mechanical stripping method, chemical vapour deposition technique, epitaxial growth method, oxidation-reduction method etc.
Alkene.But these above-mentioned methods can not be used for being prepared on a large scale flawless high-quality graphene.For example, mechanical stripping method
Although zero defect high-quality graphene can be made in theory, the yield of gained graphene is very limited.And it is vapor-deposited
Although method can be used for preparing large-area graphene, its complex manufacturing, preparation condition are harsh, production cost is high and stone
The separation of black alkene film and shifting process are even more that difficulty is very big, so this method still has significant limitation.
Mechanical attrition method is not only simple to operate, economic and practical, and expense is readily applied in industrialization large-scale production,
Therefore the extensive new process for preparing few layer graphene and its composite is also suddenly become, studies ball-milling method at present to stone
The research of the Electrochemical Performances of black alkene nanometer sheet and report are less, and the present invention improves graphene nano by wet-grinding technology and relative device
The storage lithium performance of piece.
The content of the invention
The technical problems to be solved of the present invention are in view of the shortcomings of the prior art, to be expanded by low temperature prestripping
Graphene nanometer sheet, further improves the chemical property of expanded graphite alkene nanometer sheet using wet-grinding technology and relative device, and introduces graphite
Alkene quantum dot is as dispersant, there is provided a kind of cost is relatively low, yield is high, the high electric property graphene of energy scale industrial production
Nanometer piece preparation method.
The present invention also provides a kind of graphene nanometer sheet being prepared using the above method.
The purpose of the present invention is achieved by the following technical programs：
A kind of high electric property graphene nano piece preparation method is provided, comprised the following steps：
S1. oxidation crystalline flake graphite is prepared：Crystalline flake graphite and sodium nitrate are added separately in the concentrated sulfuric acid, keeping below 20 DEG C
It is gradually added into KMnO simultaneously 4, keep low temperature to stir 1~2h, temperature is then risen into 35~40 DEG C of stirring 30min, then by temperature
65~80 DEG C are risen to, and hydrogen peroxide is added dropwise into solution, keeps 40min, by being centrifuged repeatedly and filtration washing, then vacuum is done
It is dry, obtain aoxidizing crystalline flake graphite；
S2. prestripping：Step S1 is obtained into oxidation crystalline flake graphite to be placed in heating furnace, temperature is increased to 260~305 from room temperature
DEG C, programming rate is 9.0 DEG C/min, and keeps being passed through inert gas with 3000ml/min；
S3. peel off：The product that step S2 is obtained is peeled off using the further liquid phase of wet grinding, using ethanol as milling atmosphere, simultaneously
Graphene quantum dot is added as auxiliary agent, ratio of grinding media to material is 400~600:1, graphene quantum dot addition is that expanded graphite alkene is received
The 4%~8% of rice piece concentration, ball milling is carried out by planetary ball mill, rotating speed is 400~600r/min, and the time is 4~6h, ball
The suspension being prepared after mill is 10000rpm by rotating speed, and graphene nanometer sheet suspension is obtained after centrifuging 20min.
Wherein, graphene quantum dot described in step S3 reaches recycling by press filtration recovery.
The present invention prepares graphene nanometer sheet this technique using wet grinding can significantly improve the electricity of graphene nanometer sheet
Chemical property, its process is not only simple to operate, cost is low but also is easily enlarged productionization, and introduces graphene quantum
Point as auxiliary agent be used for improve dispersiveness, in mechanical milling process lamella can due to size reduce and mutually reunite cause store up lithium energy
Power declines, therefore adds asking for the storage lithium ability decline that graphene quantum dot can effectively prevent the reduction of mechanical milling process size from bringing
Topic, while also contribute to stability.In addition, graphene quantum dot is easily recycled simultaneously, environmentally safe, energy-saving ring
Protect, realize repeatable utilization, wherein graphene quantum dot addition is very few can not play scattered effect, and amount can cause greatly on the contrary
Reunite.
Preferably, crystalline flake graphite carbon content more than 99% described in step S1, the mesh of the mesh of particle diameter 100~200.
Preferably, washing described in step S1 refers to that remaining uses deionized water first using the HCL using 5%.
Preferably, crystalline flake graphite and KMnO described in step S1 4Mass ratio be 1:3.
Preferably, hydrogen peroxide concentration described in step S1 is 20%, and the volume ratio with solution is 1：2.
Preferably, inert atmosphere described in step S2 is Ar gas.
Preferably, Ball-milling Time described in step S3 is 5h, Ball-milling Time 500r/min.
Preferably, ratio of grinding media to material described in step S3 is 500:1.
Preferably, the addition of graphene quantum dot described in step S3 is the 8% of swollen crystalline flake graphite concentration.
The present invention also provides a kind of graphene nanometer sheet being prepared using the above method, and initial charge specific capacity is
1230mAh/g, discharge capacity specific capacity after 20 cycles is 573mAh/g, and coulombic efficiency is held in more than 99%.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention carries out oxygen using cheap crystalline flake graphite as raw material, using low, medium and high temperature three phases to crystalline flake graphite
Change, can effectively control the side reaction in crystalline flake graphite oxidizing process to occur, and then improve the oxidizability of crystalline flake graphite.
Oxidation crystalline flake graphite is placed and carries out Low Temperature Heat Treatment under an inert atmosphere by the present invention, compared to high-temperature expansion cost more
It is low, it is adapted to commercial Application, in the presence of Ar gas, triggers the fast decoupled of oxygen-containing functional group by low temperature, compared to pyroreaction
Oxygen content and defect are less, obtain that expanded graphite alkene nanometer sheet is aobvious to possess two-dimensional crystallinity after stripping, are received to improve graphene
The electric property of rice piece, further using ball-milling technology.
The present invention prepares graphene nanometer sheet this technique using wet grinding can significantly improve the electricity of graphene nanometer sheet
Chemical property, when current density is 1000mA/g, discharge capacity can be brought up to after 20 cycles from 237mAh/g
573mAh/g, and the cycle stability of graphene nanometer sheet can also be improved, after ball milling coulombic efficiency be held in 99% with
On.
The present invention improves the chemical property of graphene nanometer sheet by ball-milling technology, and its process not only operates letter
List, cost is low and is easily enlarged productionization, and introduces graphene quantum dot and be used to improve dispersiveness as auxiliary agent, in ball
During mill lamella can due to size reduce and mutually reunite cause store up lithium ability decline, therefore add graphene quantum dot energy
Effectively prevent mechanical milling process size from reducing the problem of storage lithium ability brought declines, while also contribute to stability.In addition,
Graphene quantum dot is easily recycled simultaneously, environmentally safe, energy-conserving and environment-protective, realizes repeatable utilize.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Following examples are only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
The present invention uses crystalline flake graphite as raw material, carbon content more than 99%, the mesh of the mesh of particle diameter 100~200, using low temperature, medium temperature
Crystalline flake graphite is aoxidized with high temperature three phases, can effectively control the side reaction in crystalline flake graphite oxidizing process to send out
It is raw, and then improve the oxidizability of crystalline flake graphite.
Oxidation crystalline flake graphite is placed and carries out Low Temperature Heat Treatment under an inert atmosphere by the present invention, compared to high-temperature expansion cost more
It is low, it is adapted to commercial Application, in the presence of Ar gas, triggers the fast decoupled of oxygen-containing functional group by low temperature, compared to pyroreaction
Oxygen content and defect are less, obtain that expanded graphite alkene nanometer sheet is aobvious to possess two-dimensional crystallinity after stripping, mainly by about 10 layers also
Former graphene oxide composition, in order to improve the electric property of graphene nanometer sheet, further using ball-milling technology.
The present invention prepares graphene nanometer sheet this technique using wet grinding can significantly improve the electricity of graphene nanometer sheet
Chemical property, when current density is 1000mA/g, discharge capacity can be brought up to after 20 cycles from 237mAh/g
573mAh/g, and the cycle stability of graphene nanometer sheet can also be improved, after ball milling coulombic efficiency be held in 99% with
On.
The present invention improves the chemical property of graphene nanometer sheet by ball-milling technology, and its process not only operates letter
List, cost is low and is easily enlarged productionization, and introduces graphene quantum dot and be used to improve dispersiveness as auxiliary agent, in ball
During mill lamella can due to size reduce and mutually reunite cause store up lithium ability decline, therefore add graphene quantum dot energy
Effectively prevent mechanical milling process size from reducing the problem of storage lithium ability brought declines, while also contribute to stability.
In addition, graphene quantum dot is easily recycled simultaneously, environmentally safe, energy-conserving and environment-protective, repeatable utilization is realized, its
Middle graphene quantum dot addition is very few can not to play scattered effect, and amount can cause reunion on the contrary greatly.
Integrated artistic of the present invention is simple, and graphite flake layer is destroyed less, it is possible to achieve industrialized mass production, obtains
The graphene nanometer sheet of high quality.
Embodiment 1
The present embodiment provides a kind of preparation method of expanded graphite alkene nanometer sheet, comprises the following steps：
S1. oxidation crystalline flake graphite is prepared：Crystalline flake graphite and sodium nitrate are added separately in the concentrated sulfuric acid, keeping below 20 DEG C
It is gradually added into KMnO simultaneously 4, low temperature stirring 1h is kept, temperature is then risen into 35 DEG C of stirring 30min, then temperature is risen to 65
DEG C, and hydrogen peroxide is added dropwise, keeps 40min, by being centrifuged repeatedly and filtration washing, be then dried in vacuo, obtain aoxidizing scale stone
Ink；
S2. prestripping：Step S1 is obtained into oxidation crystalline flake graphite to be placed in heating furnace, temperature is increased to 260~305 from room temperature
DEG C, programming rate is 9.0 DEG C/min, and keeps being passed through Ar gas with 3000ml/min, obtains expanded graphite alkene nanometer sheet, described swollen
Swollen 235 times, 441 ㎡ of specific surface area/g of graphene nanometer sheet expansion multiple, is mainly made up of about 10 layers of redox graphene.
Wherein, crystalline flake graphite carbon content more than 99% described in step S1, the mesh of particle diameter 100, the washing refer to use first
Using 5% HCL, remaining uses deionized water, the crystalline flake graphite and KMnO 4Mass ratio be 1:3, the hydrogen peroxide concentration
For 20%, the volume ratio with solution is 1：2.Inert atmosphere described in step S2 is nitrogen atmosphere.
The expanded graphite alkene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out electrochemistry
It can test, discharge capacity specific capacity after 20 cycles is 178mAh/g.
Embodiment 2
The present embodiment provides a kind of preparation method of expanded graphite alkene nanometer sheet, comprises the following steps：
S1. oxidation crystalline flake graphite is prepared：Crystalline flake graphite and sodium nitrate are added separately in the concentrated sulfuric acid, keeping below 20 DEG C
It is gradually added into KMnO simultaneously 4, low temperature stirring 2h is kept, temperature is then risen into 40 DEG C of stirring 30min, then temperature is risen to 80
DEG C, and hydrogen peroxide is added dropwise, keeps 40min, by being centrifuged repeatedly and filtration washing, be then dried in vacuo, obtain aoxidizing scale stone
Ink；
S2. prestripping：Step S1 will be obtained aoxidizing crystalline flake graphite and be placed in heating furnace, temperature is increased to 260 from room temperature~
305 DEG C, programming rate is 9.0 DEG C/min, and keeps being passed through Ar gas with 3000ml/min, obtains expanded graphite alkene nanometer sheet, institute
300 times, 497 ㎡ of specific surface area/g of expanded graphite alkene nanometer sheet expansion multiple is stated, mainly by about 10 layers of redox graphene
Composition.
Wherein, crystalline flake graphite carbon content more than 99% described in step S1, the mesh of particle diameter 200, the washing refer to use first
Using 5% HCL, remaining uses deionized water, the crystalline flake graphite and KMnO 4Mass ratio be 1:3, the hydrogen peroxide concentration
For 20%, the volume ratio with solution is 1：2.Inert atmosphere described in step S2 is nitrogen atmosphere.
The expanded graphite alkene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out electrochemistry
It can test, discharge capacity specific capacity after 20 cycles is 234mAh/g.
In order to further prepare low Sheet Graphite alkene nanometer sheet, the present invention continues to the expanded graphite alkene nanometer sheet
Peeled off, the expanded graphite alkene nanometer sheet conduct of high expansioning multiple, high-specific surface area that preferred embodiment 2 is prepared is former
Material.
Embodiment 3
The present embodiment provides a kind of high electric property graphene nano piece preparation method, comprises the following steps：
S3. peel off：The product that embodiment 2 is obtained is peeled off using the further liquid phase of wet grinding, is placed in agate filling, Ran Houjia
Enter agate ball, using ethanol as milling atmosphere, while add graphene quantum dot and play peptizaiton as auxiliary agent, ratio of grinding media to material is
400:1, graphene quantum dot addition is the 4% of expanded graphite alkene nanometer sheet concentration, and ball milling is carried out by planetary ball mill,
Rotating speed is 400r/min, time 4h, and the suspension being prepared after ball milling is 10000rpm by rotating speed, after centrifuging 20min
Graphene nanometer sheet suspension stably dispersing is obtained, concentration 6.8mg/ml, the graphene nanometer sheet dispersion liquid is stood two
The moon does not observe precipitation.Wherein described graphene quantum dot reaches recycling by press filtration recovery.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, discharge capacity specific capacity after 20 cycles is 453mAh/g, and coulombic efficiency is held in 97.2%.
Embodiment 4
The present embodiment is substantially the same manner as Example 3, and difference is, graphene quantum dot addition expanded graphite in step S3
The 6% of alkene nanometer sheet concentration, graphene nanometer sheet concentration reaches 8.4mg/ml in dispersion liquid.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, discharge capacity specific capacity after 20 cycles is 467mAh/g, and coulombic efficiency is held in 97.7%.
Embodiment 4
The present embodiment is substantially the same manner as Example 3, and difference is, graphene quantum dot addition expanded graphite in step S3
The 8% of alkene nanometer sheet concentration, graphene nanometer sheet concentration reaches 9.8mg/ml in dispersion liquid.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, discharge capacity specific capacity after 20 cycles is 489mAh/g, and coulombic efficiency is held in 98.1%.
Embodiment 5
The present embodiment is substantially the same manner as Example 3, and difference is, graphene quantum dot addition expanded graphite in step S3
The 10% of alkene nanometer sheet concentration.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, discharge capacity specific capacity after 20 cycles is 474mAh/g, and coulombic efficiency is held in 97.6%.The present embodiment is due to stone
Black alkene quantum dot addition is excessive, lamella can be caused to reunite so as to influence to store up lithium performance.
Embodiment 6
The present embodiment is substantially the same manner as Example 4, and difference is, ratio of grinding media to material is 500 in step S3:1.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, discharge capacity specific capacity after 20 cycles is 497mAh/g, and coulombic efficiency is held in 98.3%.
Embodiment 7
The present embodiment is substantially the same manner as Example 6, and difference is, ratio of grinding media to material is 600 in step S3:1.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, discharge capacity specific capacity after 20 cycles is 488mAh/g, and coulombic efficiency is held in 98.1%, illustrated with ratio of grinding media to material
Increase, the chemical property of graphene nanometer sheet first rises to be declined afterwards, main reason is that the addition of sample is very little, can be led
Sample is caused to be bonded on agate pot surface, inwall and ball milling, and as ratio of grinding media to material increases, the reduction of lamella size causes to roll into a ball
The larger particle of granularity is polymerized to, this can make it that diffusion of the electrolyte inside it is not improved well.
Embodiment 8
The present embodiment is substantially the same manner as Example 6, and difference is, rotating speed is 500r/min in step S3.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, discharge capacity specific capacity after 20 cycles is 508mAh/g, and coulombic efficiency is held in 98.7%.
Embodiment 9
The present embodiment is substantially the same manner as Example 8, and difference is, rotating speed is 600r/min in step S3.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, discharge capacity specific capacity after 20 cycles is 502mAh/g, and coulombic efficiency is held in 98.4%.
The present embodiment increases to 800r/min with rotating speed, and graphene film interlayer sends folding and reunited again, causes to store up lithium
Ability decline.
Embodiment 10
The present embodiment is substantially the same manner as Example 8, and difference is, Ball-milling Time is 5h in step S3.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, discharge capacity specific capacity after 20 cycles is 513mAh/g, and coulombic efficiency is held in 98.9%.
Embodiment 11
The present embodiment is substantially the same manner as Example 10, and difference is, Ball-milling Time is 6h in step S3.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, discharge capacity specific capacity after 20 cycles is 513mAh/g, and coulombic efficiency is held in 98.9%, and the present embodiment is with ball
There are a large amount of curlings in time consuming increase lamella edge, and lamella is reunited again, causes the ability for storing up lithium to decline.
Embodiment 12
The present embodiment provides a kind of high electric property graphene nano piece preparation method, comprises the following steps：
S3. peel off：The product that embodiment 2 is obtained is peeled off using the further liquid phase of wet grinding, is placed in agate filling, Ran Houjia
Enter agate ball, using ethanol as milling atmosphere, while add graphene quantum dot and play peptizaiton as auxiliary agent, ratio of grinding media to material is
500:1, graphene quantum dot addition is the 10% of expanded graphite alkene nanometer sheet concentration, and ball milling is carried out by planetary ball mill,
Rotating speed is 500r/min, time 5h, and the suspension being prepared after ball milling is 10000rpm by rotating speed, after centrifuging 20min
Graphene nanometer sheet suspension stably dispersing is obtained, concentration 10.1mg/ml, the graphene dispersing solution is stood two months and not seen
Observe precipitation.Wherein described graphene quantum dot reaches recycling by press filtration recovery.
The graphene nanometer sheet that the present embodiment is prepared is used for the negative material of lithium battery, carries out chemical property survey
Examination, initial charge specific capacity is 1230mAh/g, and discharge capacity specific capacity after 20 cycles is 573mAh/g, and coulombic efficiency is equal
It is maintained at more than 99%.
Comparative example 1
This comparative example is substantially the same manner as Example 1, and difference is, graphene quantum dot is not added in step S3.
The concentration that this comparative example obtains is 6mg/ml graphene nanometer sheet dispersion liquid, and contrast is uneven, subregion piece
Layer is thicker, does not peel away the translucency extreme difference for causing lamella completely, and the graphene nanometer sheet dispersion liquid stands two hours or so
Just it was observed that precipitation.The graphene nanometer sheet that this comparative example is prepared is used for the negative material of lithium battery, carries out electrochemistry
Performance test, discharge capacity specific capacity after 20 cycles is 341mAh/g.
Claims (10)
1. a kind of high electric property graphene nano piece preparation method, it is characterised in that comprise the following steps：
S1. oxidation crystalline flake graphite is prepared：Crystalline flake graphite and sodium nitrate are added separately in the concentrated sulfuric acid, keeping below 20 DEG C
It is gradually added into KMnO simultaneously 4, keep low temperature to stir 1~2h, temperature is then risen into 35~40 DEG C of stirring 30min, then by temperature
65~80 DEG C are risen to, and hydrogen peroxide is added dropwise into solution, keeps 40min, by being centrifuged repeatedly and filtration washing, then vacuum is done
It is dry, obtain aoxidizing crystalline flake graphite；
S2. prestripping：Step S1 is obtained into oxidation crystalline flake graphite to be placed in heating furnace, temperature is increased to 260~305 from room temperature
DEG C, programming rate is 9.0 DEG C/min, and keeps being passed through inert gas with 3000ml/min；
S3. peel off：The product that step S2 is obtained is peeled off using the further liquid phase of wet grinding, using ethanol as milling atmosphere, simultaneously
Graphene quantum dot is added as auxiliary agent, ratio of grinding media to material is 400~600:1, graphene quantum dot addition is that expanded graphite alkene is received
The 4%~8% of rice piece concentration, ball milling is carried out by planetary ball mill, rotating speed is 400~600r/min, and the time is 4~6h, ball
The suspension being prepared after mill is 10000rpm by rotating speed, and graphene nanometer sheet suspension is obtained after centrifuging 20min；
Wherein, graphene quantum dot described in step S3 reaches recycling by press filtration recovery.
2. high electric property graphene nano piece preparation method according to claim 1, it is characterised in that described in step S1
Crystalline flake graphite carbon content more than 99%, the mesh of the mesh of particle diameter 100~200.
3. high electric property graphene nano piece preparation method according to claim 1, it is characterised in that described in step S1
Washing refers to that remaining uses deionized water first using the HCL using 5%.
4. high electric property graphene nano piece preparation method according to claim 1, it is characterised in that described in step S1
Crystalline flake graphite and KMnO 4Mass ratio be 1:3.
5. high electric property graphene nano piece preparation method according to claim 1, it is characterised in that described in step S1
Hydrogen peroxide concentration is 20%, and the volume ratio with solution is 1：2.
6. high electric property graphene nano piece preparation method according to claim 1, it is characterised in that described in step S2
Inert atmosphere is Ar gas.
7. high electric property graphene nano piece preparation method according to claim 1, it is characterised in that described in step S3
Ball-milling Time is 5h, Ball-milling Time 500r/min.
8. high electric property graphene nano piece preparation method according to claim 1, it is characterised in that described in step S3
Ratio of grinding media to material is 500:1.
9. high electric property graphene nano piece preparation method according to claim 1, it is characterised in that described in step S3
The addition of graphene quantum dot is the 8% of swollen crystalline flake graphite concentration.
10. the stone that the high electric property graphene nano piece preparation method according to claim 1~9 any one is prepared
Black alkene nanometer sheet.
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Cited By (2)
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| CN113277503A (en) * | 2021-05-28 | 2021-08-20 | 常州第六元素材料科技股份有限公司 | Preparation method of reduced graphene oxide and graphene heat-conducting film |
| CN115520858A (en) * | 2022-04-28 | 2022-12-27 | 宁波大学 | Preparation method of nitrogen-doped single-layer graphene |
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| CN101870466A (en) * | 2010-05-20 | 2010-10-27 | 北京化工大学 | Preparation method of electrode material graphene nanometer sheet and electrode sheet prepared therefrom |
| CN102730667A (en) * | 2011-04-08 | 2012-10-17 | 安炬科技股份有限公司 | Method for preparing monolayer graphite |
| CN103935999A (en) * | 2014-05-09 | 2014-07-23 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene |
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| CN101870466A (en) * | 2010-05-20 | 2010-10-27 | 北京化工大学 | Preparation method of electrode material graphene nanometer sheet and electrode sheet prepared therefrom |
| CN102730667A (en) * | 2011-04-08 | 2012-10-17 | 安炬科技股份有限公司 | Method for preparing monolayer graphite |
| CN103935999A (en) * | 2014-05-09 | 2014-07-23 | 中国科学院上海微***与信息技术研究所 | Preparation method of graphene |
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| CN113277503A (en) * | 2021-05-28 | 2021-08-20 | 常州第六元素材料科技股份有限公司 | Preparation method of reduced graphene oxide and graphene heat-conducting film |
| CN115520858A (en) * | 2022-04-28 | 2022-12-27 | 宁波大学 | Preparation method of nitrogen-doped single-layer graphene |
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