CN115881895A - Amorphous carbon negative electrode material and preparation method and application thereof - Google Patents
Amorphous carbon negative electrode material and preparation method and application thereof Download PDFInfo
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- 229910003481 amorphous carbon Inorganic materials 0.000 title claims abstract description 74
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 36
- 239000010439 graphite Substances 0.000 claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 29
- 238000000498 ball milling Methods 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims description 41
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 230000007547 defect Effects 0.000 abstract description 16
- 238000003860 storage Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 230000037303 wrinkles Effects 0.000 abstract description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- -1 functionalization Chemical compound 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses an amorphous carbon negative electrode material and a preparation method and application thereof, wherein the preparation method of the amorphous carbon negative electrode material comprises the following steps: and (4) ball-milling the graphite to obtain the amorphous carbon negative electrode material. The amorphous carbon negative electrode material is applied to the lithium ion battery as the lithium ion battery negative electrode material, the defects added on the surface of the amorphous carbon negative electrode material comprise an edge structure, surface wrinkles and rich oxygen end groups, active sites are provided for the redox reaction of lithium ions, the increase of the density of the surface defects improves the storage capacity of lithium, and the specific capacity and the cycling stability of the material are further improved.
Description
Technical Field
The invention belongs to the technical field of amorphous carbon negative electrode materials, and particularly relates to an amorphous carbon negative electrode material and a preparation method and application thereof.
Background
With the continuous development of secondary batteries, rechargeable lithium ion batteries with high energy density, stable charge and discharge platforms, wide working temperature range, low self-discharge rate and long cycle stability are important candidates for many types of batteries, and energy storage technologies represented by lithium ion batteries play an important role in the field of energy supply at present. The lithium ion secondary battery not only well meets the fast and changeable development requirements of electronic products, but also has wider application prospect in high-end fields such as hybrid electric vehicles, military affairs, aerospace and the like.
The choice and improvement of electrode materials is critical to the durability and reliability of lithium ion batteries. Taking the lithium ion battery cathode as an example, since the first generation of son y lithium ion battery was commercialized in 1991, graphitic carbon is still mainly used as a cathode material of the lithium ion battery. As a negative electrode, graphite has a long cycle life and relatively low cost. Due to Li + LiC embedded in the layered structure of graphite material to form 6 Corresponding to a Li to C ratio of 1 between graphite layers, the theoretical capacity of commercial bulk graphite is limited (372 mAh/g). Therefore, the surface modification of graphite to improve the charge and discharge performance is a problem to be solved urgently.
Modification is an effective way to increase the capacity of carbon materials. The modification of graphite is mainly carried out from the following two aspects: the change of crystal structure and the change of surface property. Modification routes to graphite can be found in the literature, including oxidation, fluorination, coating, and doping. Several methods, such as graphite edge functionalization, graphite oxide chemical derivatization, and chemical vapor deposition, have been applied to surface modification of carbon-based materials to improve lithium storage performance. Although graphene can be prepared using a chemical deposition method, this method is not conducive to large-scale production due to cost and technical challenges. Furthermore, exfoliation of graphite into graphene involves hazardous oxidants, such as HNO 3 Or H 2 SO 4 And the process is cumbersome. And the corrosive chemical oxidation method can cause serious damage to the surface of the graphite substrate due to the introduction of a large amount of chemical substances. Therefore, it is important to develop an environmentally friendly and simple method for obtaining a negative electrode material for a commercial graphite lithium battery having higher lithium storage performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of an amorphous carbon negative electrode material. The preparation method has the advantages of simple process, wide raw material source, suitability for large-scale industrial production and the like.
Another object of the present invention is to provide an amorphous carbon anode material obtained by the above preparation method.
The invention also aims to provide the application of the amorphous carbon negative electrode material as a negative electrode material of a lithium ion battery in the lithium ion battery.
The purpose of the invention is realized by the following technical scheme.
A preparation method of an amorphous carbon anode material comprises the following steps: and ball-milling graphite to obtain the amorphous carbon negative electrode material.
In the technical scheme, the ball milling time is 1-4 h, and the ball milling speed is 1000-1200 r/min.
In the technical scheme, the ratio of the grinding balls and graphite of the ball mill is (10-20): 1.
The amorphous carbon anode material obtained by the preparation method.
The amorphous carbon negative electrode material is applied to the lithium ion battery as the negative electrode material of the lithium ion battery.
In the above technical solution, the preparation method of the negative electrode of the lithium ion battery comprises: and uniformly mixing the amorphous carbon negative electrode material, the binder, the conductive agent and the solvent to obtain slurry, coating the slurry on a copper foil current collector by adopting a coating method, and drying in a vacuum environment to obtain the negative electrode.
In the technical scheme, the solvent is N-methyl pyrrolidone.
In the technical scheme, the ratio of the amorphous carbon negative electrode material to the binder to the conductive agent is (7-8) to 1 (1-2) in parts by mass.
In the technical scheme, the drying temperature is 80-100 ℃, and the drying time is 12-24 h.
In the above technical solution, the conductive agent is acetylene black, and the binder is PVDF.
In the above technical solution, the positive electrode of the lithium ion battery is a metal lithium sheet.
In the technical scheme, the concentration of the amorphous carbon negative electrode material in the slurry is 70-80 wt%.
Compared with the prior art, the invention has the advantages that:
1) The method for preparing the amorphous carbon material with controllable surface defect density by using the commercial graphite as the raw material and performing high-energy ball milling treatment has the advantages of simple operation, wide raw material, low cost, good repeatability, no complex chemical reaction or toxic chemical reagent, environmental friendliness, obvious economic benefit and benefit for industrial production.
2) The amorphous carbon negative electrode material provided by the invention takes commercial graphite as a raw material, the spacing between graphite sheet layers is enlarged after high-energy ball milling, the amorphous carbon negative electrode material with controllable defect density is obtained by controlling the ball milling time, the defects added on the surface of the amorphous carbon negative electrode material comprise edge structures, surface wrinkles and abundant oxygen end groups, active sites are provided for the redox reaction of lithium ions, the lithium storage capacity is improved by increasing the density of the surface defects, and the specific capacity and the cycling stability of the material are further improved.
Drawings
Fig. 1 is an XRD pattern of the amorphous carbon anode material prepared in example 1;
FIG. 2 is an SEM image of an amorphous carbon anode material prepared in example 1;
fig. 3 is a Raman graph of the amorphous carbon anode material prepared in example 1;
fig. 4 is a graph showing the results of performance tests of a CR 2032-type button cell assembled from the amorphous carbon anode material prepared in example 1;
fig. 5 is an XRD pattern of the amorphous carbon anode material prepared in example 2;
FIG. 6 is an SEM image of an amorphous carbon anode material prepared in example 2;
fig. 7 is a Raman chart of an amorphous carbon anode material prepared in example 2;
fig. 8 is a graph of performance test results of CR2032 type button cell assembled from the amorphous carbon anode material prepared in example 2;
fig. 9 is an XRD pattern of the amorphous carbon anode material prepared in example 3;
FIG. 10 is an SEM image of an amorphous carbon anode material prepared in example 3;
fig. 11 is a Raman chart of an amorphous carbon anode material prepared in example 3;
fig. 12 is a graph showing the results of performance tests of a CR 2032-type button cell assembled from the amorphous carbon anode material prepared in example 3;
fig. 13 is an XRD pattern of the amorphous carbon anode material prepared in example 4;
FIG. 14 is an SEM photograph of an amorphous carbon anode material prepared in example 4;
fig. 15 is a Raman chart of an amorphous carbon anode material prepared in example 4;
fig. 16 is a graph showing the results of performance tests on CR2032 type button cells assembled from the amorphous carbon anode material prepared in example 4;
FIG. 17 is an XRD pattern of commercial graphite of comparative example 1;
fig. 18 is an SEM image of commercial graphite in comparative example 1;
FIG. 19 is a Raman plot of the commercial graphite of comparative example 1;
fig. 20 is a graph showing the results of performance tests on CR 2032-type button cells obtained in comparative example 1.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Commercial graphite (P15X) was purchased from duochem; polyvinylidene fluoride (PVDF, AR), copper foil current collector and acetylene black were purchased from Shenzhenjac Jingzhida, inc.; n-methyl pyrrolidone (NMP, AR) was purchased from Sinopharm.
The XRD test model is as follows: ARL Equisox 3000 using Cu K alpha 1 radiation, france
The model of the SEM test instrument is as follows: quanta FEG, USA
The model of the Raman testing instrument is as follows: HORIBA JOBIN YVON s.a.s., france
The model of the blue test instrument is as follows: land CT2001A, china
The high-energy ball mill has the following types: MSK-SFM-3, china
Example 1
A preparation method of an amorphous carbon anode material comprises the following steps: in a 100ml corundum ball milling tank, 1g of commercial graphite is ball milled for 1h at the rotating speed of 1200r/min to obtain the amorphous carbon anode material, wherein the ratio of ball milled grinding balls to graphite is 20.
Example 2
A preparation method of an amorphous carbon anode material comprises the following steps: in a 100ml corundum ball milling tank, 1g of commercial graphite is ball milled for 2h at the rotating speed of 1200r/min to obtain the amorphous carbon anode material, wherein the ratio of ball milled grinding balls to graphite is 20.
Example 3
A preparation method of an amorphous carbon anode material comprises the following steps: in a 100ml corundum ball milling tank, 1g of commercial graphite is ball milled for 3h at the rotating speed of 1200r/min to obtain the amorphous carbon anode material, wherein the ratio of ball milled grinding balls to graphite is 20.
Example 4
A preparation method of an amorphous carbon anode material comprises the following steps: in a 100ml corundum ball milling tank, 1g of commercial graphite is ball milled for 4h at the rotating speed of 1200r/min to obtain the amorphous carbon negative electrode material, wherein the ratio of ball milled grinding balls to graphite is 20.
The amorphous carbon negative electrode material can be used as a lithium ion battery negative electrode material to be applied to a lithium ion battery.
The preparation method of the negative electrode of the lithium ion battery comprises the following steps: uniformly mixing the amorphous carbon negative electrode material, the binder, the conductive agent and N-methyl pyrrolidone (NMP) in examples 1-4, fully grinding to obtain black pasty slurry, coating the slurry on a copper foil current collector by adopting a coating method, and drying in a vacuum oven at 80 ℃ for 12h in a vacuum environment to remove the N-methyl pyrrolidone, so as to obtain a negative electrode, wherein the conductive agent is acetylene black, the binder is PVDF, the ratio of the amorphous carbon negative electrode material, the binder and the conductive agent is 8.
The cathode is assembled into a CR2032 button cell: the positive electrode is a metal lithium sheet, and the electrolyte is LiPF 6 Mixture of ethylene carbonate and diethyl carbonate, liPF in electrolyte 6 At a concentration of 1M, a volume ratio of ethylene carbonate to diethyl carbonate of 1.
Comparative example 1
The preparation method of the cathode comprises the following steps: the preparation method comprises the following steps of uniformly mixing commercial graphite, a binder, a conductive agent and N-methyl pyrrolidone (NMP), fully grinding to obtain black pasty slurry, coating the slurry on a copper foil current collector by adopting a coating method, and drying for 12 hours in a vacuum oven at 80 ℃ in a vacuum environment to remove the N-methyl pyrrolidone, so as to obtain a negative electrode, wherein the conductive agent is acetylene black, the binder is PVDF, the ratio of an amorphous carbon negative electrode material to the binder to the conductive agent is 8, and the concentration of the amorphous carbon negative electrode material in the slurry is 80wt%.
The cathode is assembled into a CR2032 button cell: the positive electrode is a metal lithium sheet, and the electrolyte is LiPF 6 Mixture of ethylene carbonate and diethyl carbonate, liPF in electrolyte 6 1M, a volume ratio of ethylene carbonate to diethyl carbonate of 1.
Fig. 1 is an XRD pattern of amorphous carbon anode material obtained in example 1. It can be seen from the figure that the intensity of the diffraction peak of the obtained material is reduced, which indicates that the crystallinity of the material is reduced and the material is in an amorphous state.
Fig. 2 is an SEM image of the amorphous carbon anode material obtained in example 1. The resulting material is seen to be scaly.
Fig. 3 is a Raman graph of the amorphous carbon anode material obtained in example 1. 1350cm can be seen from the figure -1 A defect (D) peak representing a disordered vibration peak of the carbon material and 1580cm -1 Where represents sp 2 G peak of in-plane vibration of carbon atom, intensity ratio (I) of D band to G band of amorphous structure of sample D /I G ) It is demonstrated to represent the defect density of the carbon material. From the figure, I can be seen D /I G The value was 0.81.
Fig. 4 is a graph showing the results of performance tests of a CR 2032-type button cell assembled from the amorphous carbon anode material obtained in example 1. It can be seen from the figure that the negative electrode of the lithium ion battery prepared by the embodiment has good electrochemical performance: under the current density of 0.2A/g, the coulombic efficiency of the first loop is 52%, the discharge capacity of the first loop is 757.6mAh/g, and the capacity is maintained at 404.1mAh/g after 200 cycles of circulation.
Fig. 5 is an XRD pattern of the amorphous carbon anode material obtained in example 2. It can be seen from the figure that the intensity of the diffraction peak of the obtained material is reduced, which indicates that the crystallinity of the material is reduced and the material is in an amorphous state.
Fig. 6 is an SEM image of the amorphous carbon anode material obtained in example 2. It can be seen from the figure that the resulting material is in the form of a non-uniform block.
Fig. 7 is a Raman chart of an amorphous carbon anode material obtained in example 2. 1350cm can be seen from the figure -1 A defect (D) peak representing a disordered vibration peak of the carbon material and 1580cm -1 Where represents sp 2 G peak of in-plane vibration of carbon atom, strength ratio of D band to G band (I) of amorphous structure of sample D /I G ) It is demonstrated to represent the defect density of the carbon material. From the figure, I can be seen D /I G The value was 1.15.
Fig. 8 is a graph of the performance test results of CR2032 type button cell assembled from the amorphous carbon anode material obtained in example 2. It can be seen from the figure that the negative electrode of the lithium ion battery prepared by the embodiment has good electrochemical performance: under the current density of 0.2A/g, the coulombic efficiency of the first circle is 56%, the discharge capacity of the first circle is 828.3mAh/g, and after 200 circles of circulation, the capacity is kept to be 451.3mAh/g.
Fig. 9 is an XRD pattern of amorphous carbon anode material obtained in example 3. It can be seen from the figure that the intensity of the diffraction peak of the obtained material is reduced, which indicates that the crystallinity of the material is reduced and the material is in an amorphous state.
Fig. 10 is an SEM image of an amorphous carbon negative electrode material obtained in example 3. It can be seen from the figure that the resulting material is in the form of a uniform mass.
Fig. 11 is a Raman chart of an amorphous carbon anode material obtained in example 3. 1350cm can be seen from the figure -1 A defect (D) peak representing a disordered vibration peak of the carbon material and 1580cm -1 Where represents sp 2 G peak of in-plane vibration of carbon atom, intensity ratio (I) of D band to G band of amorphous structure of sample D /I G ) Proof is used to represent the defect density of the carbon material. From the figure, I can be seen D /I G The value was 1.38.
Fig. 12 is a graph of the performance test results of CR2032 button cell assembled from the amorphous carbon anode material obtained in example 3. It can be seen from the figure that the negative electrode of the lithium ion battery prepared by the embodiment has good electrochemical performance: under the current density of 0.2A/g, the first-turn coulombic efficiency is 76%, the first-turn discharge capacity is 1118.6mAh/g, and the capacity is kept at 622.5mAh/g after 200-turn circulation.
Fig. 13 is an XRD pattern of amorphous carbon anode material obtained in example 4. The resulting material is seen to have a reduced diffraction peak intensity, indicating that the crystallinity of the material is reduced and the material is amorphous.
Fig. 14 is an SEM image of an amorphous carbon anode material obtained in example 4. It can be seen from the figure that the resulting material portions are in the form of agglomerated masses.
Fig. 15 is a Raman graph of an amorphous carbon anode material obtained in example 4. 1350cm can be seen from the figure -1 A defect (D) peak representing a disordered vibration peak of the carbon material and 1580cm -1 Where represents sp 2 In-plane vibration of carbon atomsDynamic G peak, amorphous structure of sample from intensity ratio of D band to G band (I) D /I G ) It is demonstrated to represent the defect density of the carbon material. From the figure, I can be seen D /I G The value was 1.30.
Fig. 16 is a graph of the performance test results of CR2032 button cell assembled from the amorphous carbon negative electrode material obtained in example 4. It can be seen from the figure that the negative electrode of the lithium ion battery prepared in the example has good electrochemical performance: under the current density of 0.2A/g, the coulombic efficiency of the first circle is 59%, the discharge capacity of the first circle is 1007.3mAh/g, and after 200 circles of circulation, the capacity is kept at 482.1mAh/g.
Fig. 17 is an XRD pattern of the commercial graphite of comparative example 1. From the figure, it can be seen that the diffraction peak intensity of the commercial graphite is strong, which indicates that the crystallinity of the material is good and the material is in a crystalline state.
Fig. 18 is an SEM image of the commercial graphite in comparative example 1. It can be seen that the material is in the form of a large sized block.
Fig. 19 is a Raman graph of the commercial graphite in comparative example 1. The G peak of the material is obviously stronger than the D peak, and the I peak can be seen from the figure D /I G The value is only 0.64, indicating that the material has few surface defects.
Fig. 20 is a graph of the results of performance tests of comparative example 1 assembled into CR2032 type button cells. It can be seen from the figure that the negative electrode of the lithium ion battery prepared by the comparative example has lower capacity electrochemical performance: under the current density of 0.2A/g, the coulombic efficiency of the first circle is 44%, the discharge capacity of the first circle is 400.5mAh/g, and after 200 circles of circulation, the capacity is maintained at 289.4mAh/g.
The invention being thus described by way of example, it should be understood that any simple alterations, modifications or other equivalent alterations as would be within the skill of the art without the exercise of inventive faculty, are within the scope of the invention.
Claims (10)
1. A preparation method of an amorphous carbon negative electrode material is characterized by comprising the following steps: and (3) carrying out ball milling on graphite to obtain the amorphous carbon negative electrode material.
2. The preparation method of claim 1, wherein the ball milling time is 1-4 h, and the rotation speed of the ball milling is 1000-1200 r/min.
3. The preparation method according to claim 1 or 2, characterized in that the ratio of the ball-milled grinding balls to the graphite is (10-20): 1 in parts by mass.
4. An amorphous carbon anode material obtained by the production method according to claim 1.
5. Use of the amorphous carbon negative electrode material of claim 4 as a negative electrode material for a lithium ion battery in a lithium ion battery.
6. The application of claim 5, wherein the preparation method of the negative electrode of the lithium ion battery is as follows: and uniformly mixing the amorphous carbon negative electrode material, the binder, the conductive agent and the solvent to obtain slurry, coating the slurry on a copper foil current collector by adopting a coating method, and drying in a vacuum environment to obtain the negative electrode.
7. Use according to claim 5, characterized in that the solvent is N-methylpyrrolidone, the conductive agent is acetylene black and the binder is PVDF.
8. The use according to claim 5, characterized in that the ratio of the amorphous carbon negative electrode material, the binder and the conductive agent is (7-8): 1 (1-2), and the concentration of the amorphous carbon negative electrode material in the slurry is 70-80 wt%.
9. Use according to claim 5, wherein the drying temperature is between 80 and 100 ℃ and the drying time is between 12 and 24 hours.
10. The use of claim 5, wherein the positive electrode of the lithium ion battery is a metallic lithium sheet.
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| CN108054024A (en) * | 2017-12-22 | 2018-05-18 | 湖南工业大学 | A kind of application of mixed expanded graphite as lithium-ion capacitor negative material |
| CN110061237A (en) * | 2019-04-25 | 2019-07-26 | 广东工业大学 | A kind of amorphous carbon cell negative electrode material and its preparation method and application |
| WO2020013718A1 (en) * | 2018-07-13 | 2020-01-16 | Uniwersytet Warszawski | Method of manufacture of carbonaceous material for anode mass of lithium ion cell as well as material obtained using this method, and method of manufacture lithium ion cell anode using said material and anode obtained thereby |
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- 2021-09-27 CN CN202111138806.3A patent/CN115881895A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811759A (en) * | 2014-02-20 | 2014-05-21 | 深圳市贝特瑞新能源材料股份有限公司 | Modification method of natural graphite ball-milling machinery and modified natural graphite anode material |
| CN108054024A (en) * | 2017-12-22 | 2018-05-18 | 湖南工业大学 | A kind of application of mixed expanded graphite as lithium-ion capacitor negative material |
| WO2020013718A1 (en) * | 2018-07-13 | 2020-01-16 | Uniwersytet Warszawski | Method of manufacture of carbonaceous material for anode mass of lithium ion cell as well as material obtained using this method, and method of manufacture lithium ion cell anode using said material and anode obtained thereby |
| CN110061237A (en) * | 2019-04-25 | 2019-07-26 | 广东工业大学 | A kind of amorphous carbon cell negative electrode material and its preparation method and application |
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