CN108039475B - Preparation method of ball-milled graphite, novel N-modified graphite modification method and application - Google Patents
Preparation method of ball-milled graphite, novel N-modified graphite modification method and application Download PDFInfo
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- CN108039475B CN108039475B CN201711332001.6A CN201711332001A CN108039475B CN 108039475 B CN108039475 B CN 108039475B CN 201711332001 A CN201711332001 A CN 201711332001A CN 108039475 B CN108039475 B CN 108039475B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 239000010439 graphite Substances 0.000 title claims abstract description 120
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 119
- 238000002715 modification method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 43
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 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
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 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
- 238000009830 intercalation Methods 0.000 abstract description 11
- 230000002687 intercalation Effects 0.000 abstract description 11
- 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
- 238000004729 solvothermal method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000001132 ultrasonic dispersion Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 11
- 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
- 239000000843 powder Substances 0.000 description 8
- 238000011049 filling Methods 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001529297 Coregonus peled Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
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- 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
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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
- H01M4/13—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
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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
- H01M4/13—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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a preparation method of ball-milled graphite, a novel method for modifying N-modified graphite and application, comprising the following steps of: the method comprises the following steps: preparing black expanded graphite from natural graphite by an intercalation method; step two: preparing the black expanded graphite prepared in the first step into ball-milled graphite through ball-milling equipment; step three: uniformly mixing the ball-milled graphite and N, N '-dimethylformamide through ultrasonic dispersion to obtain a uniform ball-milled graphite-N, N' -dimethylformamide mixed solution; step four: and (3) preparing the ball-milled graphite-N, N' -dimethylformamide mixed solution obtained in the third step into N modified graphite by a one-step solvothermal method. The invention has the beneficial effects that: the N modified graphite material with high coulombic efficiency, high specific capacity, high multiplying power and suitable lithium intercalation voltage can be prepared, and can be applied to the field of power batteries in a large scale.
Description
Technical Field
The invention relates to the field of graphite modified materials, in particular to a preparation method of ball-milled graphite, a novel method for modifying N-modified graphite and application.
Background
With the generation of the first lithium ion battery, natural graphite has been the most mature cathode material of commercial batteries, and is mainly used in portable electronic devices. The structure of natural graphite is carbon atom SP2The hybrid forms a hexagonal net-shaped planar structure, the net-shaped planar layers are only combined by Van der Waals force, and the interlayer spacing is
The layers are arranged in a stacking mode of ABAB (2H) or ABCABC (3R). Because the graphite material has a complete structure, the theoretical lithium storage capacity is 372mAh/g, and the graphite material is the most applied lithium ion battery cathode material at present. However, with the development of electric vehicles, in the field of electric vehicles, due to the comprehensive requirements of the mileage of the vehicle, the charging of the vehicle battery and the energy recovery during the driving process, the vehicle-mounted battery should have high capacity and good charging rate performance. Graphite materials are not suitable for use in power batteries for four reasons: (1) li can only generate LiC with graphite materials due to the perfect crystal structure of graphite6The lithium storage capacity of the intercalation compound can only reach 372 mAh/g; (2) due to the perfection of graphiteIn the crystal structure of (2), lithium ions hardly penetrate through the basal plane of the graphite layer and can only be inserted from a diamond position (end face), so that the large-current charge-discharge performance of the graphite material is poor; (3) because of the perfect crystal structure of graphite, a solvent is co-inserted into graphite sheets in the lithium ion intercalation process, an organic solvent is inserted between the graphite sheets to be reduced, and the generated gas expands to cause the graphite sheets to be peeled off, so that the continuous damage and regeneration of SEI are caused, and the electrolyte is excessively consumed, and the cycle life is poor; (4) because of the perfect crystal structure of graphite, the potential ratio of graphite lithium intercalation is close to the lithium precipitation potential, lithium dendrite can be deposited on the electrode surface in the process of heavy current charging and discharging, and the diaphragm is punctured, thus easily causing the safety problem.
However, the huge reserves and the low price of the natural graphite attract people to research the natural graphite, so that the lithium storage performance of the natural graphite is changed by changing the structure of the natural graphite, the performance of the natural graphite meets the requirements of power batteries, and the natural graphite can be widely applied to the power batteries.
The current methods for modifying graphite are mainly divided into chemical methods and physical methods. Wherein the chemical method mainly destroys the structure of the natural graphite by a surface oxidation method. Peled reports that moderate oxidation of graphite can improve its electrochemical performance. This is mainly due to the fact that the oxidation introduces nano-micropores and channels on the graphite surface and forms a compact oxide layer at the same time. The formation of nano-pores and channels can increase the intercalation amount of lithium ions, and the formation of a dense oxide layer can reduce the decomposition of the electrolyte. Thus, its reversible capacity, first cycle coulombic efficiency, and cycle performance. However, the method has little influence on the lithium intercalation potential and cannot improve the problem of lithium precipitation caused by high-current charging. The physical method mainly destroys the structure of the graphite by a method of ball milling natural graphite, and Dai et al report that the ball milling of natural graphite can effectively improve the capacity and the large current rate capability of modified graphite and improve the lithium-intercalation-deintercalation platform. However, the main product prepared by the method is graphene, the specific surface area is high, the first coulombic efficiency is low, the reaction time of the method is long (generally more than 48 hours), and the requirement on equipment is high (high-energy ball mill).
Disclosure of Invention
The invention aims to solve the technical problems of various defects of the conventional natural graphite modification method, and provides a preparation method of ball-milled graphite, a novel N-modified graphite modification method and application thereof.
The technical scheme for solving the technical problems is as follows:
according to one aspect of the present invention, there is provided a method for preparing ball-milled graphite, comprising the steps of:
the method comprises the following steps: preparing black expanded graphite from natural graphite by an intercalation method;
step two: and (3) preparing the black expanded graphite prepared in the step one into ball-milled graphite through ball-milling equipment.
On the basis of the technical scheme, the invention can be further improved as follows.
Further: the intercalation method in the first step comprises the specific steps of adding natural graphite into concentrated sulfuric acid, stirring for 0.8-1.6 h, adding persulfate, continuously stirring for 0.3-0.8 h, heating to 30-60 ℃ after stirring is stopped, reacting for 8-12 h, washing with water, filtering, and drying to obtain black expanded graphite.
Further: the particle size of the natural graphite is one or more of 32 meshes, 50 meshes, 80 meshes, 100 meshes, 200 meshes, 325 meshes and 500 meshes.
Further: and the specific method of the second step is that the black expanded graphite prepared in the first step is placed into ball milling equipment, inert gas is filled into the ball milling equipment for replacing air in the ball milling equipment, and ball milling is carried out for 1 to 10 hours at the rotating speed of the ball milling equipment of 800 to 1400r/min, so as to prepare the ball milled graphite.
Further: the inert gas filled into the ball milling equipment is argon or neon.
According to another aspect of the invention, the invention provides application of the ball-milled graphite prepared by the preparation method of the ball-milled graphite as a negative electrode of a lithium ion battery.
According to another aspect of the present invention, there is provided a novel method for modifying N-modified graphite, comprising the steps of:
step three: uniformly mixing the ball-milled graphite and N, N '-dimethylformamide through ultrasonic dispersion to obtain a uniform ball-milled graphite-N, N' -dimethylformamide mixed solution;
step four: and (3) preparing the ball-milled graphite-N, N' -dimethylformamide mixed solution obtained in the third step into N modified graphite by a one-step solvothermal method.
On the basis of the technical scheme, the invention can be further improved as follows.
Further: adding the ball-milled graphite into N, N ' -dimethylformamide, dispersing for 10min to 120min by using ultrasonic, and uniformly mixing the ball-milled graphite and the N, N ' -dimethylformamide to obtain a uniform ball-milled graphite-N, N ' -dimethylformamide mixed solution.
Further: the one-step solvothermal method in the fourth step comprises the specific steps of transferring the ball-milled graphite-N, N '-dimethylformamide mixed solution obtained in the third step into a reaction kettle, sealing and placing the reaction kettle in an oven, reacting for 2 hours to 24 hours at the temperature of 120 ℃ to 200 ℃, washing the obtained reaction product with N, N' -dimethylformamide and water, and then drying in vacuum for 8 hours to 16 hours at the temperature of 60 ℃ to 120 ℃ to obtain the N modified graphite.
According to another aspect of the invention, the application of the N modified graphite prepared by the novel N modified graphite modification method as the negative electrode of the lithium ion battery is provided.
The invention has the beneficial effects that: the ball-milling graphite is prepared by a ball-milling one-step intercalation method, and N element is introduced into the ball-milling graphite to modify the ball-milling graphite by a one-step solvothermal method, so that the specific surface area of the ball-milling graphite is reduced, the first coulombic efficiency of the ball-milling graphite is improved, and the N modified graphite material with high coulombic efficiency, high specific capacity, high multiplying power and suitable lithium intercalation voltage is prepared, can be used as a negative electrode material to be applied to power batteries and can be applied to the field of power batteries on a large scale.
Drawings
FIG. 1 is an XRD pattern of the ball milled graphite of the present invention at different ball milling times;
FIG. 2 is a TEM image of ball-milled 2h graphite according to the present invention;
FIG. 3 is a graph of the first charging and discharging of graphite after ball milling for 2h according to the present invention;
FIG. 4 is a graph of the first charging and discharging of graphite after ball milling for 20h according to the present invention;
FIG. 5 is an XPS plot of N-modified graphite according to the present invention;
FIG. 6 is a graph comparing BET curves of ball milled graphite (BMEG) and N modified graphite (ND-BMEG) in accordance with the present invention;
FIG. 7 is a first charge-discharge diagram of the N-modified graphite of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
A preparation method of ball-milled graphite comprises the following steps:
the method comprises the following steps: adding natural graphite into concentrated sulfuric acid, stirring for 0.8 to 1.6 hours, then adding persulfate, continuously stirring for 0.3 to 0.8 hour, stopping stirring, heating to 30 to 60 ℃ and reacting for 8 to 12 hours, washing with water, filtering, and drying to obtain black expanded graphite;
step two: and (2) putting the black expanded graphite prepared in the step one into ball milling equipment, filling inert gas into the ball milling equipment for replacing air in the ball milling equipment, and performing ball milling for 1 to 10 hours at the rotating speed of the ball milling equipment of 800 to 1400r/min to prepare the ball milled graphite.
The particle size of the natural graphite in the first step is one or more of 32 meshes, 50 meshes, 80 meshes, 100 meshes, 200 meshes, 325 meshes and 500 meshes.
In the first step, the mass of the natural graphite is 1g to 16g, and the volume of the concentrated sulfuric acid is 5ml to 80 ml.
The drying temperature in the first step is 60-120 ℃, and the drying time is 8-16 h.
The mass of the persulfate in the first step is 0.5g to 8g, and in the following examples, it is preferably 5 g.
The inert gas filled into the ball milling equipment in the second step is argon or neon, and in the following embodiments, argon is preferred.
The XRD (X-ray diffraction) pattern of graphite with different ball-milling times is shown in figure 1, and the TEM (Transmission electron microscope) pattern of ball-milled 2h graphite is shown in figure 2.
The ball-milled graphite prepared by the preparation method of the ball-milled graphite is applied as a negative electrode of a lithium ion battery; the graph of the first charge-discharge of the ball-milled 2h graphite is shown in FIG. 3, and the first coulombic efficiency (ICE) of the graphite is 77.8%; the graph of the first charge-discharge of the graphite after ball milling for 20h is shown in FIG. 4, and the first coulombic efficiency (ICE) of the graphite is 56.8%.
A novel method for modifying graphite by N modification of ball-milled graphite prepared by the preparation method of the ball-milled graphite is characterized by comprising the following steps:
step three: adding the ball-milled graphite into N, N ' -dimethylformamide, dispersing for 10min to 120min by using ultrasonic, and uniformly mixing the ball-milled graphite and the N, N ' -dimethylformamide to obtain a uniform ball-milled graphite-N, N ' -dimethylformamide mixed solution;
step four: transferring the ball-milled graphite-N, N '-dimethylformamide mixed solution obtained in the third step into a reaction kettle, sealing and placing the reaction kettle in an oven, reacting for 2h to 24h at the temperature of 120 ℃ to 200 ℃, washing the obtained reaction product with N, N' -dimethylformamide and water, and then drying in vacuum for 8h to 16h at the temperature of 60 ℃ to 120 ℃ to obtain the N modified graphite.
The N modified graphite prepared by the novel N modified graphite modification method is used as a lithium ion battery cathode; the first charge-discharge diagram of the N-modified graphite is shown in fig. 7.
An XPS (X-ray photoelectron spectroscopy) diagram of the N-modified graphite is shown in FIG. 5, wherein (a) is an XPS full spectrum, (b) is a milled graphite C1s fine spectrum, (C) is an N-modified milled graphite C1s fine spectrum, and (d) is an N-modified milled graphite N1s fine spectrum.
A comparison of BET curves for ball-milled graphite (BMEG) and N-modified ball-milled graphite (ND-BMEG) is shown in FIG. 6.
The following description is given with reference to specific examples.
the method comprises the following steps: adding 10g of natural graphite with the specification of 50 meshes into 50ml of concentrated sulfuric acid, stirring for 1h at room temperature, adding 5g of ammonium persulfate, stirring for 30min, stopping stirring, transferring the reactor into a drying oven with the temperature of 40 ℃, preserving heat for 10h, then adding water into the expanded graphite, washing and filtering, washing until the pH value is neutral, and then drying for 12h in the drying oven with the temperature of 80 ℃;
step two: placing 2g of expanded graphite in a ball milling tank, adding 14g of grinding balls, filling argon into the ball milling tank for replacing air in the ball milling tank, sealing the ball milling tank, placing the ball milling tank on a high-speed ball mill, and carrying out ball milling for 2 hours at the rotating speed of 1400r/min to obtain graphite (BMEG-2 hours) subjected to ball milling for 2 hours;
step three: preparing the graphite (BMEG-2h) subjected to ball milling for 2h into an electrode plate, and testing the performance of the half cell;
step four: taking 0.5g of ball-milled 2h graphite (BMEG-2h) powder, dispersing the powder into 50ml of N, N '-dimethylformamide, and ultrasonically dispersing the powder for 2h by using an ultrasonic instrument with the power of 500W to obtain uniform ball-milled 2h graphite (BMEG-2h) -N, N' -dimethylformamide dispersion liquid;
step five: transferring the dispersion solution into a reaction kettle, reacting for 6 hours at 150 ℃, washing a reaction product with N, N' -dimethylformamide and water, and drying for 12 hours in vacuum at 80 ℃ to obtain N modified graphite;
step six: and (3) preparing the N modified graphite into an electrode plate, and testing the performance of the half-cell.
the method comprises the following steps: adding 10g of natural graphite with the specification of 50 meshes into 50ml of concentrated sulfuric acid, stirring for 1h at room temperature, adding 5g of ammonium persulfate, stirring for 30min, stopping stirring, transferring the reactor into a drying oven with the temperature of 40 ℃, preserving heat for 10h, adding water into the expanded graphite, washing and filtering the graphite until the pH value is neutral, and drying the graphite in the drying oven with the temperature of 80 ℃ for 12 h;
step two: placing 2g of expanded graphite in a ball milling tank, adding 14g of grinding balls, filling argon into the ball milling tank for replacing air in the ball milling tank, sealing the ball milling tank, placing the ball milling tank on a high-speed ball mill, and carrying out ball milling for 10 hours at the rotating speed of 1400r/min to obtain graphite (BMEG-10 hours) subjected to ball milling for 10 hours;
step three: preparing the graphite (BMEG-10h) subjected to ball milling for 10h into an electrode plate, and testing the performance of the half cell;
step four: taking 0.5g of graphite (BMEG-10h) powder subjected to ball milling for 10h, dispersing the graphite powder into 50ml of N, N '-dimethylformamide, and ultrasonically dispersing the graphite powder for 2h by using an ultrasonic instrument with the power of 500W to obtain uniform graphite (BMEG-10h) -N, N' -dimethylformamide dispersion liquid subjected to ball milling for 10 h;
step five: transferring the dispersion solution into a reaction kettle, reacting for 12 hours at 150 ℃, washing a reaction product with N, N' -dimethylformamide and water, and drying for 12 hours at 80 ℃ in vacuum to prepare N modified graphite;
step six: and (3) preparing the N modified graphite into an electrode plate, and testing the performance of the half-cell.
Embodiment 3, a preparation method of ball-milled graphite, a new method for modifying N-modified graphite and an application thereof, specifically comprising the following steps:
the method comprises the following steps: adding 10g of natural graphite with the specification of 80 meshes into 50ml of concentrated sulfuric acid, stirring for 1h at room temperature, adding 5g of ammonium persulfate, stirring for 30min, stopping stirring, transferring the reactor into a drying oven with the temperature of 40 ℃, preserving heat for 10h, adding water into expanded graphite, washing and filtering until the pH value is neutral, and drying for 12h in the drying oven with the temperature of 80 ℃;
step two: placing 2g of expanded graphite in a ball milling tank, adding 14g of milling balls, filling argon into ball milling equipment for replacing air in the ball milling equipment, sealing the ball milling tank, placing the ball milling tank on a high-speed ball mill, and performing ball milling for 8 hours at the rotating speed of 800r/min to obtain graphite (BMEG-8 hours) subjected to ball milling for 8 hours;
step three: preparing the graphite (BMEG-8h) subjected to ball milling for 8h into an electrode plate, and testing the performance of the half cell;
step four: taking 0.5g of ball-milled 8h graphite (BMEG-8h) powder, dispersing the powder into 50ml of N, N '-dimethylformamide, and ultrasonically dispersing the powder for 2h by using an ultrasonic instrument with the power of 500W to obtain uniform ball-milled 8h graphite (BMEG-8h) -N, N' -dimethylformamide dispersion liquid;
step five: transferring the dispersion solution into a reaction kettle, reacting for 6 hours at 200 ℃, washing a reaction product with N, N' -dimethylformamide and water, and drying for 12 hours in vacuum at 80 ℃ to obtain N modified graphite;
step six: and (3) preparing the N modified graphite into an electrode plate, and testing the performance of the half-cell.
Embodiment 4, a preparation method of ball-milled graphite, a new method for modifying N-modified graphite and an application thereof, specifically comprising the following steps:
the method comprises the following steps: adding 10g of natural graphite with the specification of 80 meshes into 50ml of concentrated sulfuric acid, stirring for 1h at room temperature, adding 5g of ammonium persulfate, stirring for 30min, stopping stirring, transferring the reactor into a drying oven with the temperature of 40 ℃, preserving heat for 10h, adding water into the expanded graphite, washing and filtering the graphite until the pH value is neutral, and drying the graphite in the drying oven with the temperature of 80 ℃ for 12 h;
step two: placing 2g of expanded graphite in a ball milling tank, adding 14g of grinding balls, filling argon into the ball milling tank for replacing air in the ball milling tank, sealing the ball milling tank, placing the ball milling tank on a high-speed ball mill, and carrying out ball milling for 10 hours at the rotating speed of 800r/min to obtain graphite (BMEG-10 hours) subjected to ball milling for 10 hours;
step three: preparing the graphite (BMEG-10h) subjected to ball milling for 10h into an electrode plate, and testing the performance of the half cell;
step four: taking 0.5g of graphite (BMEG-10h) powder subjected to ball milling for 10h, dispersing the graphite powder into 50ml of N, N '-dimethylformamide, and ultrasonically dispersing the graphite powder for 2h by using an ultrasonic instrument with the power of 500W to obtain uniform graphite (BMEG-10h) -N, N' -dimethylformamide dispersion liquid subjected to ball milling for 10 h;
step five: transferring the dispersion solution into a reaction kettle, reacting for 6 hours at 120 ℃, washing a reaction product with N, N' -dimethylformamide and water, and drying for 12 hours at 80 ℃ in vacuum to prepare N modified graphite;
step six: and (3) preparing the N modified graphite into an electrode plate, and testing the performance of the half-cell.
Embodiment 5, a preparation method of ball-milled graphite, a new method for modifying N-modified graphite and an application thereof, specifically comprising the following steps:
the method comprises the following steps: adding 10g of natural graphite with the specification of 50 meshes into 50ml of concentrated sulfuric acid, stirring for 1h at room temperature, adding 5g of ammonium persulfate, stirring for 30min, stopping stirring, transferring the reactor into a drying oven with the temperature of 40 ℃, preserving heat for 10h, adding water into the expanded graphite, washing and filtering the graphite until the pH value is neutral, and drying the graphite in the drying oven with the temperature of 80 ℃ for 12 h;
step two: placing 2g of expanded graphite in a ball milling tank, adding 14g of milling balls, filling argon into the ball milling tank for replacing air in the ball milling tank, sealing the ball milling tank, placing the ball milling tank on a high-speed ball mill, and carrying out ball milling for 10 hours at the rotating speed of 1050r/min to obtain graphite (BMEG-10 hours) subjected to ball milling for 10 hours;
step three: preparing the graphite subjected to ball milling for 10 hours into an electrode plate, and testing the performance of the half cell;
step four: taking 0.5g of graphite powder subjected to ball milling for 10h, dispersing the graphite powder into 50ml of N, N '-dimethylformamide, and ultrasonically dispersing for 2h by using an ultrasonic instrument with the power of 500W to obtain a uniform graphite-N, N' -dimethylformamide dispersion liquid subjected to ball milling for 10 h;
step five: transferring the dispersion solution into a reaction kettle, reacting for 12 hours at 160 ℃, washing a reaction product with N, N' -dimethylformamide and water, and drying for 10 hours in vacuum at 80 ℃ to obtain N modified graphite;
step six: and (3) preparing the N modified graphite into an electrode plate, and testing the performance of the half-cell.
The electrode sheets manufactured in examples one to five were subjected to charge and discharge experiments to test the half-cell performance thereof, and the electrode sheet manufactured in example five had the best charge and discharge performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. A method for modifying graphite by N modification of ball milling graphite is characterized by comprising the following steps:
the method comprises the following steps: adding natural graphite into concentrated sulfuric acid, stirring for 0.8-1.6 h, adding persulfate, continuously stirring for 0.3-0.8 h, stopping stirring, heating to 30-60 ℃ for reaction for 8-12 h, washing with water, filtering, and drying to obtain black expanded graphite;
step two: preparing the black expanded graphite prepared in the first step into ball-milled graphite through ball-milling equipment;
step three: adding ball-milled graphite into N, N ' -dimethylformamide, dispersing for 10min to 120min by using ultrasonic, and uniformly mixing the ball-milled graphite and the N, N ' -dimethylformamide to obtain uniform ball-milled graphite-N, N ' -dimethylformamide mixed solution;
step four: transferring the ball-milled graphite-N, N '-dimethylformamide mixed solution obtained in the third step into a reaction kettle, sealing and placing the reaction kettle in an oven, reacting for 2h to 24h at the temperature of 120 ℃ to 200 ℃, washing the obtained reaction product with N, N' -dimethylformamide and water, and then drying in vacuum for 8h to 16h at the temperature of 60 ℃ to 120 ℃ to obtain the N modified graphite.
2. The method for modifying graphite through N modification of ball milling graphite according to claim 1, wherein the method comprises the following steps: the particle size of the natural graphite is one or more of 32 meshes, 50 meshes, 80 meshes, 100 meshes, 200 meshes, 325 meshes and 500 meshes.
3. The method for modifying graphite through N modification of ball milling graphite according to claim 1, wherein the method comprises the following steps: and the specific method of the second step is that the black expanded graphite prepared in the first step is placed into ball milling equipment, inert gas is filled into the ball milling equipment for replacing air in the ball milling equipment, and ball milling is carried out for 1 to 10 hours at the rotating speed of the ball milling equipment of 800 to 1400r/min, so as to prepare the ball milled graphite.
4. The method for modifying graphite through N modification of ball milling graphite according to claim 3, wherein the method comprises the following steps: the inert gas filled into the ball milling equipment is argon or neon.
5. The application of the N modified graphite prepared by the N modified graphite modification method according to claim 1 as a negative electrode of a lithium ion battery.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2017
- 2017-12-13 CN CN201711332001.6A patent/CN108039475B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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