CN114497507A - Quick-filling graphite composite material and preparation method thereof - Google Patents
Quick-filling graphite composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114497507A CN114497507A CN202210108862.0A CN202210108862A CN114497507A CN 114497507 A CN114497507 A CN 114497507A CN 202210108862 A CN202210108862 A CN 202210108862A CN 114497507 A CN114497507 A CN 114497507A
- Authority
- CN
- China
- Prior art keywords
- composite material
- graphite
- quick
- graphite composite
- charging
- 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
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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Abstract
The invention discloses a quick-filling graphite composite material and a preparation method thereof, wherein the quick-filling graphite composite material is of a core-shell structure, and a core is a complex comprising graphite with the particle size of 0.5-2 mu m and solid electrolyte powder; the shell comprises inorganic lithium salt, wherein the mass ratio of the shell is 1 wt% -10 wt%. According to the invention, the inner core of the quick-charging graphite composite material is doped with the solid electrolyte with high ionic conductivity, and the surface of the quick-charging graphite composite material is coated with the paraffin and the coupling agent thereof, so that the activation point of the quick-charging graphite composite material is improved, the ion transmission rate is improved, finally, the lithium molybdate with high density and high lithium ion conductivity is deposited on the outer layer of the quick-charging graphite composite material by an atomic vapor deposition method, and the power and the cycle performance of the quick-charging graphite composite material are improved.
Description
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, and particularly relates to a quick-charging graphite composite material and a preparation method thereof.
Background
With the improvement of the requirements of the lithium ion battery on energy density and quick charge performance thereof, the lithium ion battery cathode material is required to have high energy density, and the quick charge performance of the material is also improved. The current marketable negative electrode material mainly comprises artificial graphite, the actual specific capacity is about 355mAh/g, the charging rate is less than or equal to 5C, and the requirement of the next generation of high-energy-density quick-charging battery cannot be met. In order to improve the energy density and the quick charging performance of the graphite material, needle coke raw materials with small defect degree, high graphitization degree and small aggregate particle size are generally selected. However, the soft carbon/hard carbon is coated on the surface of the material, the soft carbon/hard carbon has low specific capacity (300mAh/g), the first efficiency is low (80-85%), the coating amount is 2-3%, and the energy density of the whole graphite composite material can be reduced. In order to improve the energy density and the quick charging performance of the graphite material, the coating material and the coating mode thereof need to be optimized and improved.
The atomic vapor deposition method is a new deposition mode, has the advantages of accurately controlling the deposition amount of the material, having high density, depositing oxides, lithiates, conductive agents and other substances with different conductivities according to requirements, achieving the best quick charging performance with the minimum deposition amount and improving the cycle performance of the material.
Disclosure of Invention
The invention aims to provide a quick-filling graphite composite material and a preparation method thereof, which can improve the energy density and the power performance of the graphite material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a quick-filling graphite composite material is of a core-shell structure, wherein a core is a composite body of graphite with the particle size of 0.5-2 mu m and solid electrolyte powder; the shell comprises inorganic lithium salt, wherein the mass ratio of the shell is 1 wt% -10 wt%.
Further, the graphite comprises a graphite semi-finished product formed by carbonizing petroleum coke powder and asphalt and amorphous carbon thereof.
Further, the mass ratio of the petroleum coke powder, the solid electrolyte and the asphalt is 100: 1-10: 1to 10.
Further, the solid electrolyte is one of Li7-xLaxZr2-xAxO12, Li1+ yAlyGe2-y (PO4)3, Li 3-2 zBzMO and LiZrO2, wherein A is selected from any one of Ta, Nb, Al, Ga, Mg, Ca, Sr and Ba, B is selected from one of Mg, Ca, Sr and Ba, and M is Cl or I; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1.
Further, the composite also comprises an additive, the additive is paraffin and/or stearic acid, and the mass sum ratio of the additive to the petroleum coke powder, the solid electrolyte and the asphalt is 1-5: 100.
further, the composite also comprises a silane coupling agent, and the mass sum ratio of the silane coupling agent to the graphite, the petroleum coke powder, the solid electrolyte and the asphalt is 1-5: 100.
further, the silane coupling agent is one or more of 3-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diethylenetriaminepropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane and gamma-aminopropylmethyldiethoxysilane.
A preparation method of a quick-filling graphite composite material comprises the following steps:
according to the mass ratio of 100: 1-10: weighing and grinding petroleum coke powder with the particle size of 0.5-2 mu m, solid electrolyte and asphalt 1-10, introducing oxidizing mixed gas, heating to 800-1200 ℃, preserving heat for 1-6 hours, and crushing to obtain a graphite precursor composite material A;
adding an additive into the graphite precursor composite material A obtained in the step S1, uniformly dispersing, adding a silane coupling agent, uniformly dispersing again, and performing spray drying to obtain a graphite precursor composite material B; wherein the mass ratio of the graphite precursor composite material A to the additive to the silane coupling agent is 100: 1-5: 1-5;
and forming a lithium molybdate deposition layer with uniform thickness on the surface of the graphite precursor composite material B layer by an atomic vapor deposition method, and cooling to room temperature after completing cyclic deposition to obtain the graphite composite material coated with lithium molybdate.
Further, the additive is prepared into an additive solution with the mass concentration of 1-10 wt%.
Further, the deposition step of the step S3 is to inject lithium molybdate for 0.5 seconds; purging with nitrogen for 60 seconds; introducing an oxygen source for 5 seconds; purging with nitrogen for 5 seconds; introducing water for 0.03 second; purging with nitrogen for 50 seconds; the circulation is started for 100-200 circles from 5 seconds of introducing the oxygen source.
The invention has the beneficial effects that:
1) the surface of the graphite precursor composite material A is coated with paraffin and/or stearic acid, so that the surface of the graphite precursor composite material A can be activated, the silane coupling agent can be used for bonding the graphite precursor composite materials A, the bonding force between the materials is improved, the paraffin and/or stearic acid are firstly added for activating the surface of the graphite precursor composite material A, the silane coupling agent is added after activation, so that the surfaces of the graphite precursor composite materials A are bonded to form aggregates, the expansion of the materials is reduced, and the phenomena of pulverization, falling and the like of the materials in the circulating process cannot occur.
2) The invention utilizes the atomic vapor deposition technology to enable the molybdenum source and the oxygen source to form the lithium molybdate deposition layer with uniform thickness on the surface of the graphite precursor composite material B. On one hand, the obtained lithium molybdate deposition layer can keep the stability of the electrode material structure, and effectively prevent the corrosion of electrolyte and the structural change after multiple charging and discharging; on the other hand, the obtained lithium molybdate deposition layer can work on the surface of the negative electrode material stably for a long time, and the separation and falling of a coating layer caused by volume change of an electrode active material in the charging and discharging process are effectively avoided; the coating of the lithium molybdate material can construct an ion channel on the surface of the cathode material, so that the transmission of lithium ions is accelerated, a vacancy is provided for the lithium ions which cannot be inserted into crystal lattices, the utilization rate of the lithium ions is improved, and the electrochemical performance of the electrode material is improved; meanwhile, sufficient lithium ions are provided in the lithium molybdate charging and discharging process, and the power and the cycle performance of the material are improved.
3) The solid electrolyte is doped in the core of the quick-charging graphite composite material, and by means of the characteristics of strong lithium ion conductivity and stable structure, the diffusion rate of lithium ions in the charging and discharging process is improved, and the power performance is improved.
Drawings
Fig. 1 is an SEM image of a fast-charging graphite composite material prepared in example 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of a quick-filling graphite composite material comprises the following steps:
step S1, weighing and mixing 100g of petroleum coke powder with the particle size of 1 mu m, 5g of Li6.5La0.5Zr1.5Nb0.5O12 and 5g of petroleum asphalt, grinding in a ball mill for 24 hours, transferring into a tubular furnace, introducing argon inert gas to remove air in the tube, introducing chlorine mixed gas (volume ratio, chlorine: argon is 1: 10), heating to 1000 ℃, preserving heat for 3 hours, and crushing to obtain a graphite precursor composite material A;
s2, adding 3g of paraffin wax additive into 100ml of carbon tetrachloride solution to prepare an additive solution with the mass concentration of 3 wt%, then adding 100g of the graphite precursor composite material A obtained in the step S1, ultrasonically dispersing uniformly, then adding 3g of 3-aminopropyltriethoxysilane, and carrying out spray drying to obtain a graphite precursor composite material B;
and S3, placing the graphite precursor composite material B obtained in the step S2 into a reaction chamber by an atomic vapor deposition method, vacuumizing the chamber, keeping the pressure of 0.1toor, and raising the temperature to 200 ℃. And lithium molybdate was deposited according to the following procedure: s31, introducing lithium salt for 0.5 second; s32, purging with nitrogen for 60 seconds; s33, introducing an oxygen source for 5 seconds; s34, purging with nitrogen for 5 seconds; s35, introducing water for 0.03 second; s36, purging with nitrogen for 50 seconds; s37, 150 cycles from step S31. And forming lithium molybdate deposition layers with uniform thickness on the surface of the graphite precursor composite material B layer by layer, and cooling to room temperature after completing the cyclic deposition to obtain the lithium molybdate coated quick-charging graphite composite material.
Example 2
A preparation method of a quick-filling graphite composite material comprises the following steps:
step S1, weighing and mixing 100g of petroleum coke powder with the particle size of 0.5 mu m, 1g of Li1.5Al0.5Ge1.5(PO4)3 and 1g of petroleum asphalt, grinding the mixture in a ball mill for 24 hours, transferring the mixture to a tubular furnace, introducing argon inert gas to remove air in the tube, introducing fluorine gas mixed gas (volume ratio, fluorine gas: argon gas is 1: 10), heating to 800 ℃, keeping the temperature for 6 hours, and crushing to obtain a graphite precursor composite material A;
step S2, adding 1g of stearic acid additive into 100ml of N-methyl pyrrolidone to prepare an additive solution with the mass concentration of 1 wt%, then adding 100g of the graphite precursor composite material A obtained in the step S1, ultrasonically dispersing uniformly, adding 1g of gamma-aminopropyltrimethoxysilane, dispersing uniformly, and performing spray drying to obtain a graphite precursor composite material B;
and S3, placing the graphite precursor composite material B obtained in the step S2 into a reaction chamber by an atomic vapor deposition method, vacuumizing the chamber, keeping the pressure of 0.1toor, and raising the temperature to 150 ℃. And lithium molybdate was deposited according to the following procedure: s31, introducing lithium salt for 0.5 second; s32, purging with nitrogen for 60 seconds; s33, introducing an oxygen source for 5 seconds; s34, purging with nitrogen for 5 seconds; s35, introducing water for 0.03 second; s36, purging with nitrogen for 50 seconds; s37, 200 cycles are repeated from step S31. And forming lithium molybdate deposition layers with uniform thickness on the surface of the graphite precursor composite material B layer by layer, and cooling to room temperature after completing the cyclic deposition to obtain the lithium molybdate coated quick-charging graphite composite material.
Example 3
A preparation method of a quick-filling graphite composite material comprises the following steps:
step S1, weighing 100g of petroleum coke powder with the particle size of 2 mu m and 10g of LiMg in a mixing manner0.5Adding CLO and 10g of petroleum asphalt into a grinding machine, grinding for 24 hours, transferring into a tube furnace, introducing argon inert gas to remove air in the tube, introducing oxygen mixed gas (volume ratio, oxygen: argon is 1: 10), heating to 1200 ℃, preserving heat for 1 hour, and crushing to obtain a graphite precursor composite material A;
s2, adding 5g of paraffin additive into 50ml of cyclohexane organic solvent to prepare an additive solution with the mass concentration of 10 wt%, then adding 100g of the graphite precursor composite material A obtained in the S1, ultrasonically dispersing uniformly, then adding 5g of gamma-diethylenetriaminepropylmethyldimethoxysilane, dispersing uniformly, and carrying out spray drying to obtain a graphite precursor composite material B;
and S3, placing the graphite precursor composite material B obtained in the step S2 into a reaction chamber by an atomic vapor deposition method, vacuumizing the chamber, keeping the pressure of 0.1toor, and raising the temperature to 250 ℃. And lithium molybdate was deposited according to the following procedure: s31, introducing lithium salt for 0.5 second; s32, purging with nitrogen for 60 seconds; s33, introducing an oxygen source for 5 seconds; s34, purging with nitrogen for 5 seconds; s35, introducing water for 0.03 second; s36, purging with nitrogen for 50 seconds; s37, 100 cycles from step S31. And forming lithium molybdate deposition layers with uniform thickness on the surface of the graphite precursor composite material B layer by layer, and cooling to room temperature after completing cyclic deposition to obtain the lithium molybdate-coated quick-charging graphite composite material.
According to the invention, the inner core of the quick-charging graphite composite material is doped with the solid electrolyte with high ionic conductivity, and the surface of the quick-charging graphite composite material is coated with the paraffin and the coupling agent thereof, so that the activation point of the quick-charging graphite composite material is improved, the ion transmission rate is improved, finally, the lithium molybdate with high density and high lithium ion conductivity is deposited on the outer layer of the quick-charging graphite composite material by an atomic vapor deposition method, and the power and the cycle performance of the quick-charging graphite composite material are improved.
Comparative example
Weighing 100g of petroleum coke powder with the particle size of 1 mu m and 5g of petroleum asphalt, grinding in a ball mill for 24h, then transferring to a tubular furnace, introducing argon inert gas to remove air in the tube, then heating to 1000 ℃ under the atmosphere of argon, preserving heat for 3h, and crushing to obtain the graphite composite material. And then adding 100ml of 5% lithium molybdate carbon tetrachloride flux, and carrying out spray drying to obtain the lithium molybdate coated graphite composite material.
Examples of the experiments
1 test of physical and chemical Properties
1.1 SEM test
The SEM test was performed on the rapid graphite composite material prepared in example 1, and the test results are shown in fig. 1.
As can be seen from FIG. 1, the rapidly-filled graphite composite material prepared in example 1 has a spheroidal structure, uniform size and a particle size of 10-15 μm.
1.2 powder conductivity test
The quick-charging graphite composite materials prepared in the examples 1to 3 and the graphite composite material prepared in the comparative example are taken to be subjected to powder conductivity test, and the powder conductivity test method comprises the following steps: the graphite composite materials prepared in examples 1to 3 and the graphite composite material prepared in the comparative example were pressed into a bulk structure on a powder compaction densitometer under a pressure of 2T, and then a four-probe tester was used to perform a powder conductivity test, with the test results shown in table 1.
1.3 tap Density, specific surface area test
Similarly, the tap density is tested according to GB/T2433and 2019 graphite cathode materials for lithium ion batteries, and the test result of the specific surface area is shown in Table 1.
1.4 coating integrity test
And testing the integrity of the lithium molybdate coated on the surface of the core of the quick-charging graphite composite material by XPS.
TABLE 1
| Item | Example 1 | Example 2 | Example 3 | Comparative example |
| Conductivity (S/cm) | 4.13 | 4.01 | 3.81 | 1.84 |
| Tap density (g/cm)3) | 1.11 | 1.09 | 1.03 | 0.90 |
| Specific surface area (m)2/g) | 1.56 | 1.48 | 1.45 | 1.12 |
| Degree of coating integrity | 98.9％ | 98.6％ | 97.9％ | 86.9％ |
As can be seen from Table 1, the conductivity of the lithium molybdate-coated rapid graphite composite material prepared by the atomic vapor deposition method of the invention is obviously higher than that of the comparative example, and the reasons for this are as follows: the surface of the quick-charging graphite composite material is coated with lithium molybdate with higher conductivity, so that the transmission rate of ions/electrons is improved; the outermost dense carbon layer also contributes to the improvement of electron conductivity. Meanwhile, the lithium molybdate coated on the surface of the material has the characteristics of high density, large density and the like, so that the tap density of the quick-charging graphite composite material is obviously improved.
2 button cell test
Button cells a1, a2, a3 and b1 were assembled by using the quick-charging graphite composite materials prepared in examples 1to 3 and the graphite composite material prepared in comparative example as negative electrode materials. The assembling method comprises the following steps: respectively adding a binder, a conductive agent and a solvent into the quick-charging graphite composite material prepared in the examples 1-3 and the graphite composite material prepared in the comparative example, stirring and pulping, then coating the slurry on a copper foil, and drying and rolling to prepare a negative plate; the binder is LA132 binder, the conductive agent is SP, and the solvent is secondary distilled water. The proportion of each component is as follows: and (3) anode material: SP: LA 132: 95g of secondary distilled water: 1 g: 4 g: 220 mL; the electrolyte is LiPF6/EC+DEC(LiPF6In a concentration of1.2mol/L, the volume ratio of EC to DEC is 1:1), a metal lithium sheet is taken as a counter electrode, and a diaphragm adopts a Polyethylene (PE), polypropylene (PP) or polyethylene propylene (PEP) composite film. The button cell is assembled in a glove box filled with argon, electrochemical performance test is carried out on a Wuhan blue electricity CT2001A type cell tester, the charging and discharging voltage range is 0.005V-2.0V, the charging and discharging multiplying power is 0.1C, the specific capacity of the button cell under the multiplying power of 3C is tested, and the test result is shown in table 2.
TABLE 2
As can be seen from table 2, the first discharge capacity and the first charge-discharge efficiency of the lithium ion battery prepared by using the rapid graphite composite material prepared in examples 1to 3 of the present invention as the negative electrode material are significantly higher than those of the comparative example, and the reasons for this are as follows: the lithium molybdate composite material is coated on the outer surface of the graphite core of the quick-charging graphite composite material, and the characteristic of high lithium ion conductivity of lithium molybdate is utilized to accelerate the intercalation and deintercalation of lithium ions, reduce the irreversible capacity loss of the material and improve the first efficiency; meanwhile, lithium molybdate improves the lithium ion conductivity and improves the rate capability of the button cell.
3 pouch cell testing
Preparing a negative pole piece by using the quick-charging graphite composite material prepared in the examples 1-3 and the graphite composite material prepared in the comparative example as negative pole materials; with ternary materials (LiNi)1/3Co1/3Mn1/3O2) As a positive electrode material, LiPF6Solution (solvent EC + DEC, volume ratio 1:1, LiPF)6The concentration of (1.3 mol/L) as an electrolyte and celegard2400 as a diaphragm, and 5Ah soft package batteries A1, A2, A3 and B1 are prepared. And then testing the cycle performance, the rate performance and the expansion performance of the soft package battery in different states.
Cycle performance test conditions: the charging and discharging current is 1C/1C, the voltage range is 2.8-4.2V, and the cycle times are 500 times.
Multiplying power performance test conditions: the charging multiplying power is 1C/3C/5C/8C, and the discharging multiplying power is 1C; the voltage range is 2.8-4.2V.
The test results are shown in tables 3 and 4.
TABLE 3
As can be seen from table 3, the cycle performance of the pouch cells prepared using the rapid graphite composites prepared in examples 1-3 was better than the comparative examples for the following reasons: in the aspect of 1C/1C rate cycle performance, the lithium molybdate coating layer deposited on the surface of the graphite core of the rapid graphite filling composite material prepared in examples 1to 3 by the atomic vapor deposition method and the core containing the solid electrolyte with a stable structure both improve the characteristic of stable structure of the material and improve the cycle performance.
TABLE 4
As can be seen from table 4, the pouch cells prepared from the rapid graphite composite materials prepared in examples 1to 3 had better constant current ratios, which are the following reasons: the lithium molybdate with high density is coated on the surface of the graphite core of the quick-charging graphite composite material, so that the lithium ion intercalation and deintercalation rate of the material in the multiplying power charging process is improved, and the multiplying power charging performance is improved.
The foregoing is only a preferred embodiment of the present invention, and many variations in the detailed description and the application range can be made by those skilled in the art without departing from the spirit of the present invention, and all changes that fall within the protective scope of the invention are therefore considered to be within the scope of the invention.
Claims (10)
1. The quick-filling graphite composite material is characterized by being of a core-shell structure and comprising an inner core and a shell coated on the surface of the inner core, wherein the inner core is a composite body of graphite with the particle size of 0.5-2 mu m and solid electrolyte powder; the shell comprises inorganic lithium salt, wherein the mass ratio of the shell is 1 wt% -10 wt%.
2. The rapid-filling graphite composite material according to claim 1, wherein the graphite comprises a graphite semi-finished product formed by carbonizing petroleum coke powder and pitch and amorphous carbon thereof.
3. The quick-filling graphite composite material according to claim 2, wherein the mass ratio of the petroleum coke powder, the solid electrolyte and the asphalt is 100: 1-10: 1to 10.
4. The rapid-charging graphite composite material according to claim 1, wherein the solid electrolyte is Li7- xLaxZr2-xAxO12、Li1+yAlyGe2-y(PO4)3、Li3–2zBzMO、LiZrO2Wherein A is selected from any one of Ta, Nb, Al, Ga, Mg, Ca, Sr and Ba, B is selected from one of Mg, Ca, Sr and Ba, and M is Cl or I; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and z is more than or equal to 0 and less than or equal to 1.
5. The quick-filling graphite composite material according to any one of claims 1to 4, wherein the composite body further comprises an additive, the additive is paraffin and/or stearic acid, and the mass sum ratio of the additive to the petroleum coke powder, the solid electrolyte and the asphalt is 1-5: 100.
6. the quick-filling graphite composite material according to claim 5, wherein the composite body further comprises a silane coupling agent, and the mass sum ratio of the silane coupling agent to the graphite, the petroleum coke powder, the solid electrolyte and the asphalt is 1-5: 100.
7. the rapid-charging graphite composite material according to claim 6, wherein the silane coupling agent is one or more of 3-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-diethylenetriaminopropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, and gamma-aminopropylmethyldiethoxysilane.
8. The preparation method of the quick-filling graphite composite material is characterized by comprising the following steps:
according to the mass ratio of 100: 1-10: weighing and grinding petroleum coke powder with the particle size of 0.5-2 mu m, solid electrolyte and asphalt 1-10, introducing oxidizing mixed gas, heating to 800-1200 ℃, preserving heat for 1-6 hours, and crushing to obtain a graphite precursor composite material A;
adding an additive into the graphite precursor composite material A, uniformly dispersing, adding a silane coupling agent, uniformly dispersing again, and spray-drying to obtain a graphite precursor composite material B; wherein the mass ratio of the graphite precursor composite material A to the additive to the silane coupling agent is 100: 1-5: 1-5;
and forming a lithium molybdate deposition layer with uniform thickness on the surface of the graphite precursor composite material B layer by an atomic vapor deposition method, and cooling to room temperature after completing cyclic deposition to obtain the graphite composite material coated with lithium molybdate.
9. The preparation method of the quick-charging graphite composite material as claimed in claim 1, wherein the additive is prepared into an additive solution with a mass concentration of 1-10 wt%.
10. The method for preparing the rapid-charging graphite composite material according to claim 9, wherein the depositing step is to inject lithium molybdate for 0.5 seconds; purging with nitrogen for 60 seconds; introducing an oxygen source for 5 seconds; purging with nitrogen for 5 seconds; introducing water for 0.03 second; purging with nitrogen for 50 seconds; and circulating for 100-200 circles from 0.5 second of introducing the lithium molybdate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210108862.0A CN114497507A (en) | 2022-01-29 | 2022-01-29 | Quick-filling graphite composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210108862.0A CN114497507A (en) | 2022-01-29 | 2022-01-29 | Quick-filling graphite composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114497507A true CN114497507A (en) | 2022-05-13 |
Family
ID=81476248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210108862.0A Pending CN114497507A (en) | 2022-01-29 | 2022-01-29 | Quick-filling graphite composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114497507A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116005030A (en) * | 2023-01-09 | 2023-04-25 | 杰瑞新能源科技有限公司 | Cobalt-based composite material, preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104091937A (en) * | 2014-07-18 | 2014-10-08 | 深圳市振华新材料股份有限公司 | Lithium titanate-coated surface-treated graphite negative electrode material, preparation method and application of negative electrode material |
| CN105576209A (en) * | 2016-02-04 | 2016-05-11 | 中南大学 | High-capacity silicon-based anode material for lithium ion battery and preparation method thereof, and lithium ion battery |
| CN106532053A (en) * | 2016-12-22 | 2017-03-22 | 上海杉杉科技有限公司 | Graphite anode material for lithium ion batteries and preparation method thereof |
| CN109888229A (en) * | 2019-03-01 | 2019-06-14 | 中山市华舜科技有限责任公司 | A kind of preparation method of the lithium ion battery negative material based on lithium titanate coated graphite composite material |
| CN110745819A (en) * | 2019-10-25 | 2020-02-04 | 哈尔滨工业大学 | Method for modifying surface of graphite material by using silane coupling agent, lithium ion battery cathode and preparation method thereof |
| CN111509198A (en) * | 2019-01-31 | 2020-08-07 | 贝特瑞新材料集团股份有限公司 | Core-shell structure composite material, preparation method thereof and application thereof in lithium ion battery |
| WO2021109965A1 (en) * | 2019-12-04 | 2021-06-10 | 华为技术有限公司 | Lithium ion battery electrode material and preparation method therefor |
| CN113540416A (en) * | 2021-07-08 | 2021-10-22 | 洛阳月星新能源科技有限公司 | Solid electrolyte coated graphite composite material, preparation method and application thereof, and lithium ion battery |
| CN113594459A (en) * | 2021-07-26 | 2021-11-02 | 常州烯源谷新材料科技有限公司 | Composite negative electrode material with multilayer structure and preparation method and application thereof |
| CN113764646A (en) * | 2021-09-15 | 2021-12-07 | 河北坤天新能源科技有限公司 | High-energy-density quick-charging graphite composite material and preparation method thereof |
| CN113889594A (en) * | 2020-07-02 | 2022-01-04 | 洛阳月星新能源科技有限公司 | Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material |
-
2022
- 2022-01-29 CN CN202210108862.0A patent/CN114497507A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104091937A (en) * | 2014-07-18 | 2014-10-08 | 深圳市振华新材料股份有限公司 | Lithium titanate-coated surface-treated graphite negative electrode material, preparation method and application of negative electrode material |
| CN105576209A (en) * | 2016-02-04 | 2016-05-11 | 中南大学 | High-capacity silicon-based anode material for lithium ion battery and preparation method thereof, and lithium ion battery |
| CN106532053A (en) * | 2016-12-22 | 2017-03-22 | 上海杉杉科技有限公司 | Graphite anode material for lithium ion batteries and preparation method thereof |
| CN111509198A (en) * | 2019-01-31 | 2020-08-07 | 贝特瑞新材料集团股份有限公司 | Core-shell structure composite material, preparation method thereof and application thereof in lithium ion battery |
| CN109888229A (en) * | 2019-03-01 | 2019-06-14 | 中山市华舜科技有限责任公司 | A kind of preparation method of the lithium ion battery negative material based on lithium titanate coated graphite composite material |
| CN110745819A (en) * | 2019-10-25 | 2020-02-04 | 哈尔滨工业大学 | Method for modifying surface of graphite material by using silane coupling agent, lithium ion battery cathode and preparation method thereof |
| WO2021109965A1 (en) * | 2019-12-04 | 2021-06-10 | 华为技术有限公司 | Lithium ion battery electrode material and preparation method therefor |
| CN113889594A (en) * | 2020-07-02 | 2022-01-04 | 洛阳月星新能源科技有限公司 | Preparation method of boron-doped lithium lanthanum zirconate-coated graphite composite material |
| CN113540416A (en) * | 2021-07-08 | 2021-10-22 | 洛阳月星新能源科技有限公司 | Solid electrolyte coated graphite composite material, preparation method and application thereof, and lithium ion battery |
| CN113594459A (en) * | 2021-07-26 | 2021-11-02 | 常州烯源谷新材料科技有限公司 | Composite negative electrode material with multilayer structure and preparation method and application thereof |
| CN113764646A (en) * | 2021-09-15 | 2021-12-07 | 河北坤天新能源科技有限公司 | High-energy-density quick-charging graphite composite material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116005030A (en) * | 2023-01-09 | 2023-04-25 | 杰瑞新能源科技有限公司 | Cobalt-based composite material, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105895879B (en) | Fluorine-doped carbon-coated positive electrode composite material and preparation method and application thereof | |
| CN109390563B (en) | Modified lithium iron phosphate positive electrode material, preparation method thereof, positive plate and lithium secondary battery | |
| CN108054378A (en) | Lithium battery composite positive pole with nucleocapsid and preparation method thereof | |
| CN112420999B (en) | Phosphorus-based negative electrode material with coating structure and preparation method and application thereof | |
| CN112310359B (en) | Negative electrode active material and secondary battery | |
| CN110931781A (en) | Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material | |
| CN112467111A (en) | Conductive carbon substrate loaded graphene aerogel composite electrode and preparation method thereof | |
| CN114447305A (en) | Multi-element carbon-based rapid-charging negative electrode composite material and preparation method thereof | |
| CN113555539A (en) | High-energy-density quick-charging graphite composite negative electrode material, preparation method thereof and lithium ion battery | |
| US6972134B2 (en) | Method of preparing positive active material for rechargeable lithium batteries | |
| CN114300671B (en) | Graphite composite negative electrode material and preparation method and application thereof | |
| CN115072703A (en) | Composite negative electrode material and preparation method and application thereof | |
| CN114497507A (en) | Quick-filling graphite composite material and preparation method thereof | |
| CN115020682B (en) | Preparation method of high-energy-density quick-charging graphite cathode material | |
| CN114937770B (en) | Double-layer lithium ion conductor coated modified lithium cobalt oxide positive electrode material, preparation method thereof, lithium ion battery and electric equipment | |
| CN115275168A (en) | High-rate lithium ion battery negative electrode material and preparation method thereof | |
| CN114122392B (en) | High-capacity quick-charging graphite composite material and preparation method thereof | |
| CN113594461B (en) | Carbon-silicon composite material and preparation method and application thereof | |
| CN114864897A (en) | Quick-charging graphite composite material and preparation method thereof | |
| CN109638233A (en) | A kind of solid state ionic conductor and lithium-rich manganese base material combination electrode and lithium ion battery | |
| CN115275166A (en) | Long-life graphite composite material and preparation method thereof | |
| CN114975974A (en) | High-energy-density graphite composite material, preparation method thereof and lithium ion battery | |
| CN115207304A (en) | Graphite cathode composite material, preparation method thereof and lithium ion battery | |
| CN109309228B (en) | Positive electrode active material, preparation method, positive electrode and high-specific-energy power battery | |
| CN109244434B (en) | A kind of GaP@C composite and preparation method thereof and the application in cathode of lithium battery |
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 |