CN114975974A - High-energy-density graphite composite material, preparation method thereof and lithium ion battery - Google Patents
High-energy-density graphite composite material, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN114975974A CN114975974A CN202210811545.5A CN202210811545A CN114975974A CN 114975974 A CN114975974 A CN 114975974A CN 202210811545 A CN202210811545 A CN 202210811545A CN 114975974 A CN114975974 A CN 114975974A
- Authority
- CN
- China
- Prior art keywords
- graphite composite
- composite material
- density graphite
- precursor material
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000010439 graphite Substances 0.000 title claims abstract description 42
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 66
- 239000002243 precursor Substances 0.000 claims abstract description 49
- 239000007789 gas Substances 0.000 claims abstract description 46
- 239000011331 needle coke Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 150000002367 halogens Chemical class 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000010000 carbonizing Methods 0.000 claims abstract description 12
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 11
- 239000010426 asphalt Substances 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 238000009832 plasma treatment Methods 0.000 claims abstract description 5
- 239000007773 negative electrode material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011669 selenium Substances 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007770 graphite material Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000007738 vacuum evaporation Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000009656 pre-carbonization Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- -1 Polyethylene Polymers 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013098 chemical test method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Abstract
The invention relates to a high-energy-density graphite composite material, a preparation method thereof and a lithium ion battery, and belongs to the technical field of lithium ion batteries. The preparation method of the high-energy density graphite composite material comprises the following steps: 1) uniformly mixing needle coke and asphalt, and pre-carbonizing to obtain a precursor material A; 2) carrying out oxygen plasma treatment on the precursor material A prepared in the step 1) to carry out surface pore-forming modification to obtain a precursor material B; 3) depositing a doping compound on the precursor material B prepared in the step 2) through physical vapor deposition treatment to obtain a doped precursor material C; 4) and (3) preserving the heat of the doped precursor material C prepared in the step 3) at a high temperature in a halogen gas atmosphere, and then carbonizing to obtain the material. According to the preparation method of the high-energy-density graphite composite material, the Sn, P and S materials are gasified and doped in the pores and the surface of the porous graphite, so that the specific capacity and the cycle performance of the porous graphite composite material are greatly improved.
Description
Technical Field
The invention relates to a high-energy-density graphite composite material, a preparation method thereof and a lithium ion battery, and belongs to the technical field of lithium ion batteries.
Background
With the great demand of lithium ion batteries in power batteries, the lithium ion batteries are required to have higher energy density, fast charging capability, service life, safety performance and lower price. The energy density of the lithium ion battery is an important factor influencing the application prospect of the power battery, and in order to improve the energy density of the power lithium battery, the energy density of the anode material and the energy density of the cathode material can be improved.
The improvement of the energy density of the negative electrode material is mainly to develop a novel negative electrode material, and the current commercialized negative electrode material mainly takes a graphite material as a main material, but the specific capacity and the compaction density of the negative electrode material are low, so that the improvement of the energy density of the negative electrode material is limited. The silicon-carbon material has higher specific capacity, but has deviation of cycle performance and cost which is several times of that of graphite.
The performance of the graphite material is mainly improved by improving the specific capacity, the compaction density and the first efficiency of the graphite material. At present, the method for improving the material compaction density and specific capacity mainly adopts a high-temperature integrated coating, bonding and carbonizing process, so that the surfaces of composite graphite particles bonded by core-shell structure primary particles with small particle sizes are arranged towards all directions, the internal pores of graphite are increased, and the specific capacity of the material can be improved to a certain extent. However, this approach has limited improvement in cycle performance of the anode material.
Disclosure of Invention
The invention provides a high-energy-density graphite composite material, a preparation method thereof and a lithium ion battery, which are used for simultaneously improving the specific capacity and the cycle performance of the graphite composite material.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a high-energy density graphite composite material comprises the following steps:
1) uniformly mixing needle coke and asphalt, and pre-carbonizing at 200-500 ℃ for 1-6h to obtain a precursor material A;
2) carrying out oxygen plasma treatment on the precursor material A prepared in the step 1) to carry out surface pore-forming modification to obtain a precursor material B;
3) depositing a doping compound on the precursor material B prepared in the step 2) through physical vapor deposition treatment to obtain a doped precursor material C; the doping compound is at least one of a tin-containing compound, a phosphorus-containing compound and a sulfur-containing compound;
4) and (3) preserving the heat of the doped precursor material C prepared in the step 3) for 1-6h at the temperature of 200-1100 ℃ in a halogen gas atmosphere, and then carbonizing the doped precursor material C for 1-6h at the temperature of 700-1100 ℃ in an inert atmosphere to obtain the material.
The particle size of the needle coke in the step 1) is 10-50 μm.
The mass ratio of the needle coke to the asphalt in the step 1) is 100: 15-25.
Cooling after pre-carbonization in the step 1), and carrying out ball milling.
Further, the temperature of the pre-carbonization in the step 1) is 200-300 ℃.
The vacuum degree of the oxygen plasma treatment in the step 2) is 0.1-1Torr, the flow of the introduced oxygen is 10-50sccm, the power is 60-140W, and the time is 1-10 min.
The doping compounds in the step 3) are SnO and P 2 O 5 、CS 2 At least one of (a).
And (3) introducing the gasified doping compound gas into the reactor for 5-60min at the flow rate of 1-50mL/min during physical vapor deposition in the step 3).
In the step 4), the halogen gas is at least one of fluorine gas, chlorine gas and bromine gas.
The flow rate of the halogen gas in the step 4) is 1-50 mL/min.
Preferably, the temperature in the step 4) is kept for 1-6h at 200-300 ℃ in a halogen gas atmosphere.
In the high energy density graphite composite material, the mass fraction of halogen and doping elements is 1-5 wt%. The doping element is at least one of Sn, P, S and Se.
According to the preparation method of the high-energy density graphite composite material, high-capacity Sn, P and S materials are gasified and doped in the pores and the surface of the porous graphite through a physical vapor deposition method, and the specific capacity of the porous graphite is improved. The vapor deposition method adopted by the application has the characteristics of good consistency, uniform doping, high density and the like, and can also improve the tap density and the cycle performance of the material. Furthermore, the surface of the material is modified by halogen gas, so that the defect degree of the surface of the material is reduced, and the first efficiency and the specific capacity of the material are improved. Meanwhile, halogen on the surface of the material forms-C-X-, so that the material has better compatibility with electrolyte, and the cycle and storage performance of the material are improved.
Drawings
Fig. 1 is an SEM image of a high energy density graphite composite material of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention easier to understand, the present invention will be described in detail with reference to specific embodiments.
Example 1
The preparation method of the high energy density graphite composite material of the embodiment comprises the following steps:
1) adding 100g of needle coke into a reaction kettle, crushing the needle coke to a particle size of 30 mu m, then adding 20g of petroleum asphalt, uniformly mixing, and pre-carbonizing the mixture for 3 hours at 350 ℃; cooling and ball-milling to obtain a precursor material A;
2) carrying out surface pore-forming modification on the carbon source precursor prepared in the step 1) by adopting an oxygen plasma technology to obtain a precursor material B; the specific parameters are as follows: the vacuum degree is 0.5Torr, the oxygen flow is 30sccm, the power is 100W, and the action time is 5 min;
3) transferring the precursor material B prepared in the step 2) into a tube furnace, and then carrying out physical vapor deposition (vacuum evaporation deposition) at 1100 ℃ and a vacuum degree of 2 x 10 -4 Vaporizing SnO under the Pa condition, introducing the vaporized gas into a tubular furnace, introducing the gas at a flow rate of 30mL/min for 30min, and stopping introducing the gas to obtain a SnO-doped precursor material C;
4) introducing chlorine gas into the SnO-doped precursor material C in a tubular furnace, heating to 250 ℃ under the condition of continuously introducing chlorine gas, and keeping the temperature for 3 hours, wherein the gas flow of the chlorine gas is 30 mL/min; and then heating to 950 ℃ under the inert atmosphere of argon gas for carbonization for 3 hours to obtain the carbon nano tube.
The high energy density graphite composite material of this example was prepared by the above method.
Example 2
The preparation method of the high energy density graphite composite material of the embodiment comprises the following steps:
1) adding 100g of needle coke into a reaction kettle, crushing the needle coke until the particle size is 10 mu m, then adding 20g of coal-based asphalt, uniformly mixing, and pre-carbonizing the mixture at 500 ℃ for 6 hours; cooling and ball-milling to obtain a precursor material A;
2) carrying out surface pore-forming modification on the carbon source precursor prepared in the step 1) by adopting an oxygen plasma technology to obtain a precursor material B; the specific parameters are as follows: the vacuum degree is 0.1Torr, the oxygen flow is 10sccm, the power is 60W, and the action time is 10 min;
3) transferring the precursor material B prepared in the step 2) into a tube furnace, and then carrying out physical vapor deposition (vacuum evaporation deposition) at 400 ℃ and a vacuum degree of 1 × 10 -4 Under the condition of Pa, adding P 2 O 5 Vaporizing, introducing vaporized gas into a tubular furnace at flow rate of 1mL/min for 60min, and stopping introducing gas to obtain P 2 O 5 A doped precursor material C;
4) will P 2 O 5 Introducing fluorine gas into the doped precursor material C in a tubular furnace, heating to 200 ℃ under the condition of continuously introducing the fluorine gas, and preserving the temperature for 6 hours, wherein the gas flow of the fluorine gas is 1 mL/min; and then heating to 700 ℃ under the inert atmosphere of argon gas for carbonization for 6 hours to obtain the carbon nano tube.
The high energy density graphite composite material of this example was prepared by the above method.
Example 3
The preparation method of the high energy density graphite composite material of the embodiment comprises the following steps:
1) adding 100g of needle coke into a reaction kettle, crushing the needle coke until the particle size is 50 mu m, then adding 20g of petroleum asphalt, uniformly mixing, and pre-carbonizing the mixture for 1h at 200 ℃; cooling and ball-milling to obtain a precursor material A;
2) carrying out surface pore-forming modification on the carbon source precursor prepared in the step 1) by adopting an oxygen plasma technology to obtain a precursor material B; the specific parameters are as follows: the vacuum degree is 1Torr, the oxygen flow is 50sccm, the power is 140W, and the action time is 1 min;
3) transferring the precursor material B prepared in the step 2) into a tube furnace, and then carrying out physical vapor deposition (vacuum evaporation deposition) at 200 ℃ and a vacuum degree of 1 × 10 -4 Under Pa, adding CS 2 Carrying out steamDissolving, introducing the vaporized gas into a tube furnace at a flow rate of 50mL/min for 5min, and stopping introducing gas to obtain CS 2 A doped precursor material C;
4) to connect CS 2 Introducing bromine gas into the doped precursor material C in a tube furnace, heating to 300 ℃ under the condition of continuously introducing the bromine gas, and keeping the temperature for 1h, wherein the gas flow of the bromine gas is 50 mL/min; and then heating to 1100 ℃ under the inert atmosphere of argon gas for carbonization for 1h to obtain the carbon nano tube.
The high energy density graphite composite material of this example was prepared by the above method.
Example 4
The preparation method of the high energy density graphite composite material of the embodiment comprises the following steps:
1) adding 100g of needle coke into a reaction kettle, crushing the needle coke until the particle size is 30 mu m, then adding 20g of petroleum asphalt, uniformly mixing, and pre-carbonizing the mixture for 3 hours at 350 ℃; cooling and ball-milling to obtain a precursor material A;
2) carrying out surface pore-forming modification on the carbon source precursor prepared in the step 1) by adopting an oxygen plasma technology to obtain a precursor material B; the specific parameters are as follows: the vacuum degree is 0.5Torr, the oxygen flow is 30sccm, the power is 100W, and the action time is 5 min;
3) transferring the precursor material B prepared in the step 2) into a tube furnace, and then carrying out physical vapor deposition (vacuum evaporation) at 750 ℃ and 1 × 10 vacuum degree -4 Under Pa, SeO 2 Vaporizing, introducing the vaporized gas into a tubular furnace, introducing the gas at a flow rate of 30mL/min for 30min, and stopping introducing the gas to obtain a doped precursor material C;
4) will be SeO 2 Transferring the doped precursor material C into a tubular furnace, introducing fluorine gas, heating to 250 ℃ under the condition of continuously introducing the fluorine gas, and preserving the temperature for 3 hours, wherein the gas flow of the fluorine gas is 30 mL/min; and then heating to 950 ℃ under the inert atmosphere of argon gas for carbonization for 3 hours to obtain the carbon nano tube.
The high energy density graphite composite material of this example was prepared by the above method.
Example 5
The preparation method of the high energy density graphite composite material of the embodiment is different from the embodiment 4 in that, in the step 3), the precursor material B prepared in the step 2) is transferred into a tube furnace, and then physical vapor deposition is carried out at the temperature of 150 ℃ and the vacuum degree of 1 × 10 -4 Under the Pa condition, the mass ratio of 1:1 is CS 2 、SeS 2 And (3) vaporizing, introducing the vaporized gas into the tubular furnace, introducing the gas at a flow rate of 30mL/min for 30min, and stopping introducing the gas to obtain a doped precursor material C.
Otherwise, the same as in example 4.
Comparative example
The preparation method of the graphite composite material of the present comparative example includes the steps of:
1) adding 100g of needle coke into a reaction kettle, crushing the needle coke until the particle size is 30 mu m, adding 20g of petroleum asphalt, uniformly mixing, pre-carbonizing the mixture at 250 ℃ for 3 hours, and performing ball milling treatment to obtain a carbon source precursor;
2) heating the carbon source precursor prepared in the step 1) to 950 ℃ in an argon inert atmosphere, preserving heat for 3 hours, naturally cooling to room temperature, and crushing to obtain the carbon source precursor.
Examples of the experiments
1) SEM test
The composite material prepared in example 1 was subjected to SEM test, and the results are shown in fig. 1.
As can be seen from FIG. 1, the obtained composite material has secondary particles with a particle size of 10-20 μm and uniform size distribution.
2) Physical and chemical testing
The powder conductance, specific surface area, graphitization degree and trace element content (Sn, P, S and Se) of the composite material prepared in the examples 1-5 are tested according to the test method in the national standard GB/T-243354-2019 graphite cathode material for lithium ion batteries, and the test results are shown in Table 1.
3) Button cell test
The composite materials prepared in examples 1to 5 and comparative example were used as negative active materials to assemble button cells, respectively, as follows:
and adding LA132 binder, conductive agent SP and solvent deionized water into the negative electrode material, stirring and mixing uniformly to prepare negative electrode slurry, coating the negative electrode slurry on copper foil, drying, rolling and cutting to prepare a negative electrode sheet. The weight ratio of the negative electrode material, the LA132 binder, the SP conductive agent and the deionized water is 95:4:1: 220.
The metal lithium sheet is taken as a counter electrode, a Polyethylene (PE) film is taken as a diaphragm, and the electrolyte is LiPF with the concentration of 1.3mol/L 6 The solution, solvent was obtained by mixing EC and DEC in a volume ratio of 1:1, and button cells were assembled in an argon-filled glove box.
The prepared button cell is respectively arranged on a Wuhan blue electricity CT2001A type cell tester, and is charged and discharged at 0.1C multiplying power, the charging and discharging voltage range is 0.005V to 2.0V, the first discharge capacity and the first discharge efficiency are measured, and the proportion of the 3C multiplying power discharge capacity to the 0.2C multiplying power discharge capacity is measured.
The test results are shown in table 1:
TABLE 1 Properties of composites of examples 1-5 and comparative examples
As can be seen from Table 1, the discharge capacities of the composite anode materials prepared in examples 1to 5 were significantly higher than those of the comparative examples; the reason may be that the graphite material is doped with high-capacity Sn/P/S/Se elements to improve the specific capacity of the material, Se also has a catalytic effect to improve the specific capacity of the material, and the halogen gas is modified to reduce the surface defects of the material and improve the first efficiency of the material; meanwhile, the specific surface area of the material is increased through halogen modification, the contact area of the electrolyte and the material is increased, the impedance is reduced, and the rate capability is improved.
4) Pouch cell testing
The graphite composite negative electrode materials prepared in examples 1to 5 and comparative examples are used as negative electrode active materials respectively, a binder, a conductive agent and a solvent are added into the negative electrode active materials, stirring and mixing are carried out uniformly to prepare negative electrode slurry, the negative electrode slurry is coated on copper foil, and negative electrode sheets are prepared by drying, rolling and cutting. The binder is LA132 binder, the conductive agent is SP conductive agent, the solvent is secondary distilled water, and the weight ratio of the negative electrode active material, the SP conductive agent, the LA132 binder and the secondary distilled water is 95:1:4: 220.
With ternary materials (LiNi) 1/3 Co 1/3 Mn 1/3 O 2 ) Adding a binder, a conductive agent and a solvent into the positive active material, uniformly stirring and mixing to prepare positive slurry, coating the positive slurry on an aluminum foil, drying, rolling and cutting to prepare a positive plate; the binder is PVDF, the conductive agent is SP, and the solvent is N-methylpyrrolidone. The weight ratio of the positive electrode material, the conductive agent, the binder and the solvent is 93:3:4: 140.
LiPF at a concentration of 1.3mol/L 6 The solution is an electrolyte, wherein the solvent is obtained by mixing EC and DEC in a volume ratio of 1:1, and celegard2400 is a diaphragm, so that the 2Ah flexible package battery is prepared.
a. Rate capability test
The charging and discharging voltage range is 2.8-4.2V, the testing temperature is 25 +/-3.0 ℃, the charging is respectively carried out at 1.0C, 2.0C, 3.0C and 5.0C, the discharging is carried out at 1.0C, the constant current ratio and the temperature of the battery under different charging modes are tested, and the results are shown in Table 2:
TABLE 2 Rate Properties of composites of examples 1-5 and comparative examples
As can be seen from Table 2, the rate charging performance of the soft-package battery is obviously superior to that of a comparative example, the charging time is short, and the composite negative electrode material has good quick charging performance. The reason may be that the battery has a porous core and is doped with metal/nonmetal elements to improve the compatibility of the material and the electrolyte, reduce the impedance and the compatibility of the surface halogen and the electrolyte, and improve the dynamic performance, so that the constant current ratio of the battery is improved, namely the quick charge performance is improved.
b. Cycle performance test
The following experiment was performed on the pouch batteries manufactured using the negative electrode materials of examples 1to 5 and comparative example: the capacity retention rate was measured by performing 100, 300, and 500 charge-discharge cycles in sequence at a charge-discharge rate of 2C/2C and a voltage range of 2.8-4.2V, and the results are shown in Table 3:
TABLE 3 cyclability of lithium ion batteries made from composites of examples 1-5 and comparative examples
As can be seen from table 3, the cycle performance of the lithium ion battery prepared from the composite negative electrode material prepared by the invention is obviously better than that of the comparative example in each stage, which may be caused by doping halogen elements on the graphite surface to reduce the transmission path and improve the rate performance of lithium ions, and simultaneously reducing the expansion of the porous core structure to improve the stability of the cycle structure of the material, thereby improving the cycle performance.
Claims (10)
1. A preparation method of a high-energy-density graphite composite material is characterized by comprising the following steps:
1) uniformly mixing needle coke and asphalt, and pre-carbonizing at 200-500 ℃ for 1-6h to obtain a precursor material A;
2) carrying out oxygen plasma treatment on the precursor material A prepared in the step 1) to carry out surface pore-forming modification to obtain a precursor material B;
3) depositing a doping compound on the precursor material B prepared in the step 2) through physical vapor deposition treatment to obtain a doped precursor material C; the doping compound is at least one of a tin-containing compound, a phosphorus-containing compound, a sulfur-containing compound and a selenium-containing compound;
4) and (3) preserving the heat of the doped precursor material C prepared in the step 3) for 1-6h at the temperature of 200-1100 ℃ in a halogen gas atmosphere, and then carbonizing the doped precursor material C for 1-6h at the temperature of 700-1100 ℃ in an inert atmosphere to obtain the material.
2. The method for preparing a high energy density graphite composite material according to claim 1, wherein the particle size of the needle coke in step 1) is 10 to 50 μm.
3. The method for preparing the high energy density graphite composite material according to claim 1, wherein the mass ratio of the needle coke to the pitch in the step 1) is 100: 15-25.
4. The method for preparing a high energy density graphite composite material according to claim 1, wherein the degree of vacuum in the oxygen plasma treatment in the step 2) is 0.1to 1Torr, the flow of the introduced oxygen is 10 to 50sccm, the power is 60 to 140W, and the time is 1to 10 min.
5. The method for preparing the high energy density graphite composite material according to any one of claims 1to 4, wherein the doping compound in the step 3) is SnO or P 2 O 5 、CS 2 、SeO、SeS 2 At least one of (1).
6. The method for preparing the high energy density graphite composite material according to claim 1, wherein the gasified doping compound gas is introduced at a flow rate of 1-50mL/min for 5-60min during the physical vapor deposition in the step 3).
7. The method for preparing the high energy density graphite composite material according to claim 1, wherein the halogen gas in the step 4) is at least one of fluorine gas, chlorine gas and bromine gas.
8. The method for preparing a high energy density graphite composite material according to claim 7, wherein the flow rate of the halogen gas in the step 4) is 1to 50 mL/min.
9. A high energy density graphite composite material produced by the production method as set forth in claim 1.
10. A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the negative electrode comprises a negative electrode current collector and a negative electrode material layer arranged on the surface of the negative electrode current collector, the negative electrode material layer comprises a negative electrode active material, and the negative electrode active material is the high-energy-density graphite composite material disclosed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210811545.5A CN114975974A (en) | 2022-07-11 | 2022-07-11 | High-energy-density graphite composite material, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210811545.5A CN114975974A (en) | 2022-07-11 | 2022-07-11 | High-energy-density graphite composite material, preparation method thereof and lithium ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114975974A true CN114975974A (en) | 2022-08-30 |
Family
ID=82969667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210811545.5A Pending CN114975974A (en) | 2022-07-11 | 2022-07-11 | High-energy-density graphite composite material, preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114975974A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594164A (en) * | 2022-10-11 | 2023-01-13 | 安徽清能碳再生科技有限公司（Cn） | Intelligent control system of lithium battery negative electrode carbon material production and preparation system |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101465424A (en) * | 2008-12-29 | 2009-06-24 | 武汉市力诚科技有限公司 | Powder carbon element composite material for lithium ion battery cathode and preparation method thereof |
| CN101887967A (en) * | 2010-06-18 | 2010-11-17 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN101958414A (en) * | 2010-10-21 | 2011-01-26 | 武汉工程大学 | Method for preparing anode of lithium sulfur battery |
| US20120225352A1 (en) * | 2011-03-01 | 2012-09-06 | Ali Abouimrane | Electrode materials for rechargeable batteries |
| CN103943860A (en) * | 2014-04-25 | 2014-07-23 | 焦作聚能能源科技有限公司 | Negative pole material for lithium ion power and energy storage battery, as well as preparation method and battery thereof |
| CN106058189A (en) * | 2016-07-19 | 2016-10-26 | 天津师范大学 | Method for synthesizing high-capacity anode material of lithium ion battery |
| CN107623116A (en) * | 2017-09-22 | 2018-01-23 | 苏州海旭新材料科技有限公司 | A kind of composite cathode material of lithium ion battery and preparation method thereof |
| CN109686948A (en) * | 2018-12-26 | 2019-04-26 | 辽宁工程技术大学 | A kind of preparation method of lithium-sulfur battery composite cathode material |
| KR20200101247A (en) * | 2019-02-19 | 2020-08-27 | 숭실대학교산학협력단 | Ni2P CARBON COMPOSITE NEGATIVE ACTIVE MATERIAL FOR LITHIUM ION BATTERY AND METHOD FOR MANUFACTURING THE SAME |
| CN113921784A (en) * | 2021-09-29 | 2022-01-11 | 湖北亿纬动力有限公司 | Negative electrode material and preparation method and application thereof |
| CN114497506A (en) * | 2022-01-29 | 2022-05-13 | 辽宁中宏能源新材料股份有限公司 | Hard carbon-inorganic lithium salt composite electrode material and preparation method and application thereof |
-
2022
- 2022-07-11 CN CN202210811545.5A patent/CN114975974A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101465424A (en) * | 2008-12-29 | 2009-06-24 | 武汉市力诚科技有限公司 | Powder carbon element composite material for lithium ion battery cathode and preparation method thereof |
| CN101887967A (en) * | 2010-06-18 | 2010-11-17 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN101958414A (en) * | 2010-10-21 | 2011-01-26 | 武汉工程大学 | Method for preparing anode of lithium sulfur battery |
| US20120225352A1 (en) * | 2011-03-01 | 2012-09-06 | Ali Abouimrane | Electrode materials for rechargeable batteries |
| CN103943860A (en) * | 2014-04-25 | 2014-07-23 | 焦作聚能能源科技有限公司 | Negative pole material for lithium ion power and energy storage battery, as well as preparation method and battery thereof |
| CN106058189A (en) * | 2016-07-19 | 2016-10-26 | 天津师范大学 | Method for synthesizing high-capacity anode material of lithium ion battery |
| CN107623116A (en) * | 2017-09-22 | 2018-01-23 | 苏州海旭新材料科技有限公司 | A kind of composite cathode material of lithium ion battery and preparation method thereof |
| CN109686948A (en) * | 2018-12-26 | 2019-04-26 | 辽宁工程技术大学 | A kind of preparation method of lithium-sulfur battery composite cathode material |
| KR20200101247A (en) * | 2019-02-19 | 2020-08-27 | 숭실대학교산학협력단 | Ni2P CARBON COMPOSITE NEGATIVE ACTIVE MATERIAL FOR LITHIUM ION BATTERY AND METHOD FOR MANUFACTURING THE SAME |
| CN113921784A (en) * | 2021-09-29 | 2022-01-11 | 湖北亿纬动力有限公司 | Negative electrode material and preparation method and application thereof |
| CN114497506A (en) * | 2022-01-29 | 2022-05-13 | 辽宁中宏能源新材料股份有限公司 | Hard carbon-inorganic lithium salt composite electrode material and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594164A (en) * | 2022-10-11 | 2023-01-13 | 安徽清能碳再生科技有限公司（Cn） | Intelligent control system of lithium battery negative electrode carbon material production and preparation system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022166007A1 (en) | Three-dimensional silicon-carbon composite material and preparation method therefor | |
| CN114447305B (en) | Multi-carbon-based quick-charge anode composite material and preparation method thereof | |
| WO2022166059A1 (en) | Boron-doped resin-coated artificial graphite material | |
| CN109037643B (en) | High-capacity high-compaction graphite composite material and preparation method thereof | |
| CN115714170B (en) | Preparation method of high-energy-density quick-charge anode material | |
| CN113889594A (en) | Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material | |
| CN113764646B (en) | High-energy-density quick-charging graphite composite material and preparation method thereof | |
| CN114975974A (en) | High-energy-density graphite composite material, preparation method thereof and lithium ion battery | |
| CN113889595A (en) | Preparation method of solid electrolyte coated graphite composite material | |
| CN114122392B (en) | High-capacity quick-charging graphite composite material and preparation method thereof | |
| CN114655951B (en) | Preparation method of lithium ion battery cathode material | |
| CN115566170A (en) | Preparation method of high-energy-density quick-charging lithium ion battery cathode material | |
| CN113594461B (en) | Carbon-silicon composite material and preparation method and application thereof | |
| CN115714177A (en) | Silicon-carbon composite material and preparation method thereof | |
| CN115275166A (en) | Long-life graphite composite material and preparation method thereof | |
| CN115566167A (en) | Silicon-based composite material prepared by gaseous atomization method and preparation method | |
| CN114864897A (en) | Quick-charging graphite composite material and preparation method thereof | |
| CN115020682A (en) | Preparation method of high-energy-density quick-charging graphite cathode material | |
| CN114497507A (en) | Quick-filling graphite composite material and preparation method thereof | |
| CN115172680A (en) | High-capacity high-rate lithium ion battery and preparation method thereof | |
| CN115332496B (en) | Preparation method of silica composite material for lithium ion battery | |
| CN115472809B (en) | Preparation method of graphite composite material with high first efficiency | |
| CN115954476A (en) | Quick-charging negative electrode material, preparation method thereof and lithium ion battery | |
| CN117342552A (en) | Quick-charging graphite composite material, preparation method thereof and battery | |
| CN116525805A (en) | High-power silicon-based composite anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |