CN108039475A - The preparation method and N of a kind of Graphite modify graphite modified new method and application - Google Patents
The preparation method and N of a kind of Graphite modify graphite modified new method and application Download PDFInfo
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- CN108039475A CN108039475A CN201711332001.6A CN201711332001A CN108039475A CN 108039475 A CN108039475 A CN 108039475A CN 201711332001 A CN201711332001 A CN 201711332001A CN 108039475 A CN108039475 A CN 108039475A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 172
- 239000010439 graphite Substances 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 230000004048 modification Effects 0.000 claims abstract description 30
- 238000012986 modification Methods 0.000 claims abstract description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000227 grinding Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- 239000007770 graphite material Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001529297 Coregonus peled Species 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Preparation method and N the present invention relates to a kind of Graphite modify graphite modified new method and application, comprise the following steps：Step 1：Black expanded graphite is made by graft process in native graphite；Step 2：Graphite is made by ball-grinding machine in the obtained black expanded graphite in the step 1；Step 3：By the Graphite and N, N ' dimethylformamide is uniformly mixed by ultrasonic disperse, obtain uniform Graphite N, N ' dimethylformamide mixed liquors；Step 4：N modification graphite is made by a step solvent-thermal method in the Graphite N that will be obtained in the step 3, N ' dimethylformamides mixed liquor.The beneficial effects of the invention are as follows：Can prepare with high coulombic efficiency, height ratio capacity, high magnification, suitable embedding lithium voltage N modification graphite materials, can large-scale application in power battery field.
Description
Technical field
The present invention relates to graphite modified Material Field, more particularly to a kind of preparation method of Graphite and N modification graphite
Modified new method and application.
Background technology
Since being produced with first lithium ion battery, native graphite is always most ripe commercial batteries negative material,
It is mainly used on portable electric appts.The structure of native graphite is carbon atom SP2Hydridization forms the netted planar structure of hexagonal,
Simply combined between net plane layer with Van der Waals power, interlamellar spacing is, between layers with ABAB (2H) or ABCABC
The way of stacking arrangement of (3R).Due to the structural integrity of graphite material, theoretical lithium storage content is 372mAh/g, is at present using most
More lithium ion battery negative materials.But with the development of electric automobile, in electric automobile field, due to in running car
The integration requirement of journey, the charging of automobile batteries and traveling process energy regenerating, what on-vehicle battery should with high capacity and well
Rate of charge performance.And graphite material can not be used as negative material to be suitable among power battery due to following four reason：
(1) since the perfect crystal structure of graphite causes Li to generate LiC with graphite material6Intercalation compound, its lithium storage content is only
372mAh/g can be reached；(2) due to the perfect crystal structure of graphite, lithium ion is difficult to be passed through from the basal plane of graphite linings, and can only
It is inserted into from diamond shaped positions (end face), the high rate during charging-discharging which results in graphite material is poor；(3) since graphite is perfectly brilliant
Body structure, can be inserted into graphite flake layer altogether during Lithium-ion embeding, organic solvent is inserted into quilt between graphite flake layer with solvent
Reduction, generation gas expansion cause graphite flake layer to peel off, therefore cause constantly destroying and regenerate so that electrolyte disappears for SEI
It is poor to consume excessive cycle life；(4) since the perfect crystal structure of graphite, the current potential of the embedding lithium of graphite are more electric close to analysis lithium than relatively low
Position, Li dendrite can be deposited on electrode surface during high current charge-discharge, puncture membrane, easily trigger safety issue.
But the huge reserves of native graphite and cheap price, attract people and it is studied, to pass through
Change native graphite obtains structural change, and it stores up lithium performance, its performance is reached power battery requirement, can widely apply in power
Among battery.
Chemical method and Physical are broadly divided into graphite modified method at present.Wherein chemical method mainly passes through surface oxidation
Method destroy native graphite structure.The oxidation that Peled reports to graphite progress appropriateness can improve its electrochemistry
Energy.This has introduced nanometer micropore and passage mainly due to oxidation in graphite surface, while yet forms both one layer of fine and close oxidation
Layer.The formation of nanometer micropore and passage can increase the embedded quantity of lithium ion, and the formation of fine and close oxide layer can then be reduced
The decomposition of electrolyte.Therefore, its reversible capacity, the coulombic efficiency and cycle performance that circulate first.But this method pair
The influence of intercalation potential is very little can't to improve large current charge analysis lithium problem.Physical mainly passes through ball milling native graphite
Method go to destroy the structure of graphite, Dai et al. is reported can effectively improve modified stone by carrying out ball milling to native graphite
Black capacity, high current high rate performance and raising removal lithium embedded platform.But primary product prepared by this method is graphene, its
Specific surface area is high, coulombic efficiency is low first and this method reaction time long when small (generally higher than 48), to equipment requirement
Compare high (high energy ball mill).
The content of the invention
The technical problems to be solved by the invention are directed at present to the various drawbacks of process for modifying natural graphite, there is provided one
The preparation method and N of kind Graphite modify graphite modified new method and application, and ball milling stone is made by one step graft process of ball milling
Ink, and Graphite is modified by N element, prepare with high coulombic efficiency, height ratio capacity, high magnification, suitable embedding lithium voltage
N modification graphite materials, can large-scale application in power battery field.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
According to an aspect of the present invention, there is provided a kind of preparation method of Graphite, comprises the following steps：
Step 1：Black expanded graphite is made by graft process in native graphite；
Step 2：Graphite is made by ball-grinding machine in the obtained black expanded graphite in the step 1.
Based on the above technical solutions, the present invention can also be improved as follows.
Further：The graft process in the step 1 concretely comprises the following steps, and native graphite is added in the concentrated sulfuric acid and is stirred
0.8h to 1.6h is mixed, persulfate is then added and continues to stir 0.3h to 0.8h, stops that temperature is heated to 30 DEG C extremely after stirring
60 DEG C and reacted, the time of reaction is 8h to 12h, is washed with water, and filtering, then dries, obtain black expanded graphite.
Further：The particle size of the native graphite is 32 mesh, 50 mesh, 80 mesh, 100 mesh, 200 mesh, 325 mesh, 500 mesh
In one or more.
Further：The specific method of the step 2 is to put the obtained black expanded graphite in the step 1
Enter in ball-grinding machine, inert gas is filled with into ball-grinding machine, for replacing the air in ball-grinding machine, in turning for ball-grinding machine
Speed is ball milling 1h to 10h under 800r/min to 1400r/min, and Graphite is made.
Further：The inert gas being filled with ball-grinding machine is argon gas or neon.
According to another aspect of the present invention, there is provided a kind of ball according to made from a kind of preparation method of Graphite
Application of the grinding stone ink as negative electrode of lithium ion battery.
According to another aspect of the present invention, there is provided a kind of N modifies graphite modified new method, comprises the following steps：
Step 3：By the Graphite and N, N '-dimethyl formamide is uniformly mixed by ultrasonic disperse, is obtained uniformly
Graphite-N, N '-dimethyl formamide mixed liquor；
Step 4：Graphite-the N that will be obtained in the step 3, N '-dimethyl formamide mixed liquor pass through one
N modification graphite is made in step solvent-thermal method.
Based on the above technical solutions, the present invention can also be improved as follows.
Further：The specific method of the step 3 is that the Graphite is added to N, N '-dimethyl formamide
In, using ultrasonic disperse 10min to 120min, by the Graphite and N, N '-dimethyl formamide is uniformly mixed, and is obtained
Even Graphite-N, N '-dimethyl formamide mixed liquor.
Further：A step solvent-thermal method in the step 4 concretely comprises the following steps, the institute that will be obtained in the step 3
Graphite-N is stated, N '-dimethyl formamide mixed liquor is transferred in reaction kettle, and is sealed and be placed in baking oven, at 120 DEG C extremely
2h to 24h is reacted at a temperature of 200 DEG C, the reaction product N that will be obtained, N '-dimethyl formamide is cleaned with water, then 60
DEG C to 8h to 16h is dried in vacuo at a temperature of 120 DEG C, N modification graphite is made.
According to another aspect of the present invention, there is provided a kind of N according to made from a kind of N modifies graphite modified new method
Application of the modification graphite as negative electrode of lithium ion battery.
The beneficial effects of the invention are as follows：Graphite is made by one step graft process of ball milling, and passes through a step solvent-thermal method,
N element modification Graphite is introduced in Graphite, so as to reduce the specific surface area of Graphite, improves the head of Graphite
Secondary coulombic efficiency, prepare with high coulombic efficiency, height ratio capacity, high magnification, suitable embedding lithium voltage N modification graphite materials
Material, can be used as negative material be applied to power battery among, can large-scale application in power battery field.
Brief description of the drawings
Fig. 1 is the Graphite XRD diagram of the different Ball-milling Times of the present invention；
Fig. 2 schemes for ball milling 2h graphite TEM of the present invention；
Fig. 3 is ball milling 2h graphite first charge-discharge figure of the present invention；
Fig. 4 is ball milling 20h graphite first charge-discharge figure of the present invention；
Fig. 5 schemes for N modifications graphite XPS of the present invention；
Fig. 6 is Graphite of the present invention (BMEG) and N modifications graphite (ND-BMEG) BET curve comparison figures；
Fig. 7 is N modifications graphite first charge-discharge figure of the present invention.
Embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
A kind of preparation method of Graphite, comprises the following steps：
Step 1：Native graphite will be added to stirring 0.8h to 1.6h in the concentrated sulfuric acid, persulfate is then added and continue to stir
0.3h to 0.8h to be mixed, temperature is heated to 30 DEG C to 60 DEG C after stopping stirring and is reacted, the time of reaction is 8h to 12h,
It is washed with water, filters, then dry, obtain black expanded graphite；
Step 2：The obtained black expanded graphite in the step 1 is put into ball-grinding machine, to ball-grinding machine
Inert gas is inside filled with, is 800r/min to 1400r/min in the rotating speed of ball-grinding machine for replacing the air in ball-grinding machine
Lower ball milling 1h to 10h, is made Graphite.
The particle size of native graphite in the step 1 for 32 mesh, 50 mesh, 80 mesh, 100 mesh, 200 mesh, 325 mesh,
One or more in 500 mesh.
The quality of native graphite is 1g to 16g in the step 1, and the volume of the concentrated sulfuric acid is 5ml to 80ml.
Dry temperature is 60 DEG C to 120 DEG C in the step 1, and the dry time is 8h to 16h.
The quality of persulfate in the step 1 is 0.5g to 8g, is preferably 5g in the following embodiments.
The inert gas being filled with the step 2 in ball-grinding machine is argon gas or neon, in following embodiment
In, it is preferably argon gas.
Different Ball-milling Time graphite XRD (X-ray diffraction, X-ray diffraction) figures are as shown in Figure 1, ball milling 2h stones
Black TEM (Transmission electron microscope, transmission electron microscope) figure is as shown in Figure 2.
A kind of Graphite according to made from a kind of preparation method of Graphite is born as lithium ion battery
The application of pole；Ball milling 2h graphite first charge-discharge figures are as shown in figure 3, its coulombic efficiency (Initial coulombic first
Efficiency, ICE) it is 77.8%；Ball milling 20h graphite first charge-discharge figures are as shown in figure 4, its coulombic efficiency (ICE) first
For 56.8%.
It is graphite modified that a kind of Graphite described according to made from a kind of preparation method of Graphite carries out N modifications
New method, it is characterised in that comprise the following steps：
Step 3：The Graphite is added to N, in N '-dimethyl formamide, using ultrasonic disperse 10min extremely
120min, by the Graphite and N, N '-dimethyl formamide is uniformly mixed, and obtains uniform Graphite-N, N '-diformazan
Base formamide mixed liquor；
Step 4：Graphite-the N that will be obtained in the step 3, N '-dimethyl formamide mixed liquor are transferred to
In reaction kettle, and seal and be placed in baking oven, 2h to 24h, the reaction product that will be obtained are reacted at a temperature of 120 DEG C to 200 DEG C
With N, N '-dimethyl formamide is cleaned with water, and 8h to 16h is then dried in vacuo at a temperature of 60 DEG C to 120 DEG C, and obtained N is repaiied
Adorn modified graphite.
A kind of N modifications graphite according to made from a kind of N modifies graphite modified new method is as lithium ion
The application of battery cathode；N modification graphite first charge-discharge figures are as shown in Figure 7.
N modifies graphite XPS (X-ray photoelectron spectroscopy, X-ray photoelectron spectroscopic analysis) figure
As shown in figure 5, wherein (a) is the full spectrograms of XPS, (b) is the fine spectrograms of Graphite C1s, and (c) is modified Graphite C1s essences for N
Thin spectrogram, (d) are modified the fine spectrograms of Graphite N1s for N.
Graphite (BMEG) and N modifications Graphite (ND-BMEG) BET curve comparison figures are as shown in Figure 6.
Illustrated below in conjunction with specific embodiment.
Embodiment 1, the preparation method and N of a kind of Graphite modify graphite modified new method and application, specifically include as
Lower step：
Step 1：10g specifications are added in the 50ml concentrated sulfuric acids for the native graphite of 50 mesh, 1h is stirred at room temperature, adds 5g
30min is stirred after ammonium persulfate, stops stirring, reactor is transferred in the baking oven that temperature is 40 DEG C, keeps the temperature 10h, then will
The graphite expanded adds water washing and filters, and acid-base value is washed till as neutrality, then in the drying in oven 12h that temperature is 80 DEG C；
Step 2：Take 2g expanded graphites to be placed in ball grinder, add 14g abrading-balls, argon gas is filled with into ball grinder, for putting
The air changed the shuttle in grinding jar, after sealing ball grinder, is placed on high speed ball mill, the ball milling 2h in the case where rotating speed is 1400r/min,
Ball milling 2h graphite (BMEG-2h) is made；
Step 3：Electrode slice is made in above-mentioned ball milling 2h graphite (BMEG-2h), tests its half-cell performance；
Step 4：0.5g ball milling 2h graphite (BMEG-2h) powder is taken, is distributed to 50mlN, in N '-dimethyl formamide, is used
Power is the Ultrasound Instrument ultrasonic disperse 2h of 500W, obtains uniform ball milling 2h graphite (BMEG-2h)-N, N '-dimethyl formamide
Dispersion liquid；
Step 5：Above-mentioned dispersion soln is transferred in reaction kettle, reacts 6h at 150 DEG C, with N, N '-dimethyl formamide
Reaction product is cleaned with water, and vacuum drying 12h at 80 DEG C, is made N modification graphite；
Step 6：Electrode slice is made in above-mentioned N modifications graphite, tests its half-cell performance.
Embodiment 2, the preparation method and N of a kind of Graphite modify graphite modified new method and application, specifically include as
Lower step：
Step 1：10g specifications are added in the 50ml concentrated sulfuric acids for the native graphite of 50 mesh, 1h is stirred at room temperature, adds 5g
30min is stirred after ammonium persulfate, stops stirring, reactor is transferred in the baking oven that temperature is 40 DEG C, is kept the temperature 10h, will expand
Good graphite adds water washing and filters, and acid-base value is washed till as neutrality, then in the drying in oven 12h that temperature is 80 DEG C；
Step 2：Take 2g expanded graphites to be placed in ball grinder, add 14g abrading-balls, argon gas is filled with into ball grinder, for putting
The air changed the shuttle in grinding jar, after sealing ball grinder, is placed on high speed ball mill, the ball milling in the case where rotating speed is 1400r/min
10h, is made ball milling 10h graphite (BMEG-10h)；
Step 3：Electrode slice is made in above-mentioned ball milling 10h graphite (BMEG-10h), tests its half-cell performance；
Step 4：0.5g ball milling 10h graphite (BMEG-10h) powder is taken, is distributed to 50mlN, in N '-dimethyl formamide,
The Ultrasound Instrument ultrasonic disperse 2h for being 500W with power, obtains uniform ball milling 10h graphite (BMEG-10h)-N, N '-dimethyl first
Acid amides dispersion liquid；
Step 5：Above-mentioned dispersion soln is transferred in reaction kettle, reacts 12h at 150 DEG C, with N, N '-dimethyl formyl
Amine and water clean reaction product, and vacuum drying 12h at 80 DEG C, is made N modification graphite；
Step 6：Electrode slice is made in above-mentioned N modifications graphite, tests its half-cell performance.
Embodiment 3, the preparation method and N of a kind of Graphite modify graphite modified new method and application, specifically include as
Lower step：
Step 1：10g specifications are added in the 50ml concentrated sulfuric acids for the native graphite of 80 mesh, 1h is stirred at room temperature, adds 5g
Ammonium persulfate stirs 30min, stops stirring, reactor is transferred in the baking oven that temperature is 40 DEG C, keeps the temperature 10h, will expand
Graphite add water washing and filter, be washed till acid-base value as neutrality, be then 80 DEG C of drying in oven 12h in temperature；
Step 2：Take 2g expanded graphites to be placed in ball grinder, add 14g abrading-balls, argon gas is filled with into ball-grinding machine, is used for
The air in ball-grinding machine is replaced, after sealing ball grinder, is placed on high speed ball mill, the ball milling in the case where rotating speed is 800r/min
8h, obtains ball milling 8h graphite (BMEG-8h)；
Step 3：Electrode slice is made in above-mentioned ball milling 8h graphite (BMEG-8h), tests its half-cell performance；
Step 4：0.5g ball milling 8h graphite (BMEG-8h) powder is taken, is distributed to 50mlN, in N '-dimethyl formamide, is used
Power is the Ultrasound Instrument ultrasonic disperse 2h of 500W, obtains uniform ball milling 8h graphite (BMEG-8h)-N, N '-dimethyl formamide
Dispersion liquid；
Step 5：Above-mentioned dispersion soln is transferred in reaction kettle, reacts 6h at 200 DEG C, with N, N '-dimethyl formamide
Reaction product is cleaned with water, and vacuum drying 12h at 80 DEG C, is made N modification graphite；
Step 6：Electrode slice is made in above-mentioned N modifications graphite, tests its half-cell performance.
Embodiment 4, the preparation method and N of a kind of Graphite modify graphite modified new method and application, specifically include as
Lower step：
Step 1：10g specifications are added in the 50ml concentrated sulfuric acids for the native graphite of 80 mesh, 1h is stirred at room temperature, adds 5g
30min is stirred after ammonium persulfate, stops stirring, reactor is transferred in the baking oven that temperature is 40 DEG C, is kept the temperature 10h, will expand
Good graphite adds water washing and filters, and acid-base value is washed till as neutrality, then in the drying in oven 12h that temperature is 80 DEG C；
Step 2：Take 2g expanded graphites to be placed in ball grinder, add 14g abrading-balls, argon gas is filled with into ball grinder, for putting
The air changed the shuttle in grinding jar, after sealing ball grinder, is placed on high speed ball mill, the ball milling 10h in the case where rotating speed is 800r/min,
Ball milling 10h graphite (BMEG-10h) is made；
Step 3：Electrode slice is made in above-mentioned ball milling 10h graphite (BMEG-10h), tests its half-cell performance；
Step 4：0.5g ball milling 10h graphite (BMEG-10h) powder is taken, is distributed to 50mlN, in N '-dimethyl formamide,
The Ultrasound Instrument ultrasonic disperse 2h for being 500W with power, obtains uniform ball milling 10h graphite (BMEG-10h)-N, N '-dimethyl first
Acid amides dispersion liquid；
Step 5：Above-mentioned dispersion soln is transferred in reaction kettle, reacts 6h at 120 DEG C, with N, N '-dimethyl formamide
Reaction product is cleaned with water, and vacuum drying 12h at 80 DEG C, is made N modification graphite；
Step 6：Electrode slice is made in above-mentioned N modifications graphite, tests its half-cell performance.
Embodiment 5, the preparation method and N of a kind of Graphite modify graphite modified new method and application, specifically include as
Lower step：
Step 1：10g specifications are added in the 50ml concentrated sulfuric acids for the native graphite of 50 mesh, 1h is stirred at room temperature, adds 5g
30min is stirred after ammonium persulfate, stops stirring, reactor is transferred in the baking oven that temperature is 40 DEG C, is kept the temperature 10h, will expand
Good graphite adds water washing and filters, and acid-base value is washed till as neutrality, then in the drying in oven 12h that temperature is 80 DEG C；
Step 2：Take 2g expanded graphites to be placed in ball grinder, add 14g abrading-balls, argon gas is filled with into ball grinder, for putting
The air changed the shuttle in grinding jar, after sealing ball grinder, is placed on high speed ball mill, the ball milling in the case where rotating speed is 1050r/min
10h, is made ball milling 10h graphite (BMEG-10h)；
Step 3：Electrode slice is made in above-mentioned ball milling 10h graphite, tests its half-cell performance；
Step 4：0.5g ball milling 10h powdered graphites are taken, are distributed to 50mlN, in N '-dimethyl formamide, are with power
The Ultrasound Instrument ultrasonic disperse 2h of 500W, obtains uniform ball milling 10h graphite-N, N '-dimethyl formamide dispersion liquid；
Step 5：Above-mentioned dispersion soln is transferred in reaction kettle, reacts 12h at 160 DEG C, with N, N '-dimethyl formyl
Amine and water clean reaction product, and vacuum drying 10h at 80 DEG C, is made N modification graphite；
Step 6：Electrode slice is made in above-mentioned N modifications graphite, tests its half-cell performance.
By embodiment one, into embodiment five, manufactured electrode slice carries out charge-discharge test, tests its half-cell performance, real
The charge-discharge performance for applying manufactured electrode slice in example five is best.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of Graphite, it is characterised in that comprise the following steps：
Step 1：Black expanded graphite is made by graft process in native graphite；
Step 2：Graphite is made by ball-grinding machine in the obtained black expanded graphite in the step 1.
A kind of 2. preparation method of Graphite according to claim 1, it is characterised in that：It is described slotting in the step 1
Layer method concretely comprises the following steps, and native graphite is added 0.8h to 1.6h is stirred in the concentrated sulfuric acid, then adds persulfate and continues to stir
0.3h to 0.8h to be mixed, temperature is heated to 30 DEG C to 60 DEG C after stopping stirring and is reacted, the time of reaction is 8h to 12h,
It is washed with water, filters, then dry, obtain black expanded graphite.
A kind of 3. preparation method of Graphite according to claim 2, it is characterised in that：The particle diameter of the native graphite is big
Small is the one or more in 32 mesh, 50 mesh, 80 mesh, 100 mesh, 200 mesh, 325 mesh, 500 mesh.
A kind of 4. preparation method of Graphite according to claim 1, it is characterised in that：The specific method of the step 2
For the obtained black expanded graphite in the step 1 is put into ball-grinding machine, indifferent gas is filled with into ball-grinding machine
Body, for replacing the air in ball-grinding machine, ball-grinding machine rotating speed be 800r/min to 1400r/min under ball milling 1h extremely
10h, is made Graphite.
A kind of 5. preparation method of Graphite according to claim 4, it is characterised in that：It is filled with described in ball-grinding machine
Inert gas is argon gas or neon.
6. a kind of Graphite described according to made from a kind of any preparation method of Graphite of claim 1 to 5 is made
For the application of negative electrode of lithium ion battery.
7. a kind of Graphite according to made from a kind of claim 1 to 5 any preparation method of Graphite into
Row N modifies graphite modified new method, it is characterised in that comprises the following steps：
Step 3：By the Graphite and N, N '-dimethyl formamide is uniformly mixed by ultrasonic disperse, obtains uniform ball
Grinding stone ink-N, N '-dimethyl formamide mixed liquor；
Step 4：Graphite-the N that will be obtained in the step 3, N '-dimethyl formamide mixed liquor are molten by a step
The hot legal system of agent obtains N modification graphite.
8. a kind of N modifies graphite modified new method according to claim 7, it is characterised in that：The specific side of the step 3
Method is, the Graphite is added to N, in N '-dimethyl formamide, using ultrasonic disperse 10min to 120min, will described in
Graphite and N, N '-dimethyl formamide are uniformly mixed, and obtain uniform Graphite-N, the mixing of N '-dimethyl formamide
Liquid.
9. a kind of N modifies graphite modified new method according to claim 7, it is characterised in that：A step in the step 4
Solvent-thermal method concretely comprises the following steps, the Graphite-N that will be obtained in the step 3, N '-dimethyl formamide mixed liquor
It is transferred in reaction kettle, and seals and be placed in baking oven, 2h to 24h is reacted at a temperature of 120 DEG C to 200 DEG C, it is anti-by what is obtained
Product N is answered, N '-dimethyl formamide is cleaned with water, and 8h to 16h, system are then dried in vacuo at a temperature of 60 DEG C to 120 DEG C
Obtain N modification graphite.
Make 10. a kind of N a kind of according to claim 7 modifies the N modifications graphite made from graphite modified new method
For the application of negative electrode of lithium ion battery.
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| CN1884059A (en) * | 2005-06-24 | 2006-12-27 | 南京理工大学 | Process for preparing expandable micropowder graphite |
| CN101348251A (en) * | 2008-09-01 | 2009-01-21 | 武汉理工大学 | Method for preparing graphite nanosheet using high-energy ball mill |
| CN102034975A (en) * | 2010-11-15 | 2011-04-27 | 中国科学院青岛生物能源与过程研究所 | Nitrogen-doped graphite carbon serving as anode material of lithium ion battery, and preparation method and application thereof |
| CN103803539A (en) * | 2014-02-17 | 2014-05-21 | 上海交通大学 | Nitrogen-doped graphene oxide material and preparation method thereof |
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|---|---|---|---|---|
| CN1884059A (en) * | 2005-06-24 | 2006-12-27 | 南京理工大学 | Process for preparing expandable micropowder graphite |
| CN101348251A (en) * | 2008-09-01 | 2009-01-21 | 武汉理工大学 | Method for preparing graphite nanosheet using high-energy ball mill |
| CN102034975A (en) * | 2010-11-15 | 2011-04-27 | 中国科学院青岛生物能源与过程研究所 | Nitrogen-doped graphite carbon serving as anode material of lithium ion battery, and preparation method and application thereof |
| CN103803539A (en) * | 2014-02-17 | 2014-05-21 | 上海交通大学 | Nitrogen-doped graphene oxide material and preparation method thereof |
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