CN114094097A - Preparation method of long-life high-power graphite composite material - Google Patents

Preparation method of long-life high-power graphite composite material Download PDF

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CN114094097A
CN114094097A CN202010858031.6A CN202010858031A CN114094097A CN 114094097 A CN114094097 A CN 114094097A CN 202010858031 A CN202010858031 A CN 202010858031A CN 114094097 A CN114094097 A CN 114094097A
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composite material
carbon
polyaniline
graphite
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徐军红
陈和平
陈玉
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LUOYANG YUEXING NEW ENERGY TECHNOLOGY CO LTD
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • 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
    • H01M4/362—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 belongs to the field of graphite cathode materials, and particularly relates to a preparation method of a long-life high-power graphite composite material. The preparation method of the graphite composite material comprises the following steps: 1) preparing polyaniline on a carbon nano tube by adopting an electrochemical deposition method on a conductive matrix with the carbon nano tube growing on the surface, and removing the conductive matrix to obtain a carbon nano tube/polyaniline composite material; 2) carrying out hydrothermal reaction on the carbon nano tube/polyaniline composite material, a water-soluble organic carbon source and water under the action of an acid catalyst, and filtering to obtain a solid carbon nano tube/polyaniline/hydrothermal carbon composite material; 3) and uniformly mixing the hard carbon-coated graphite, the solid carbon nanotube/polyaniline/hydrothermal carbon composite material and an acid solution, and then spraying and drying. The graphite composite material prepared by the method has the advantages that the core is graphite, and the shell is of a double-layer structure, so that the cycle and power performance of the material can be effectively improved.

Description

Preparation method of long-life high-power graphite composite material
Technical Field
The invention belongs to the field of graphite cathode materials, and particularly relates to a preparation method of a long-life high-power graphite composite material.
Background
With the improvement of the requirements of the market on the quick charge and the cycle mileage of the lithium ion battery, the negative electrode material used by the lithium ion battery is required to have excellent quick charge and power performance while having high energy density.
The power type artificial graphite used in the current market mainly comprises inner core graphite and soft carbon or hard carbon coated on the surface of the inner core graphite, lithium ions are mainly transmitted through the soft carbon or the hard carbon on the surface of a material in the charging and discharging process, electron transmission is mainly transmitted through a copper foil current collector, the whole is obtained, the ion transmission performance of the material can be improved, but the electron transmission is not improved. In combination, the power performance and cycle performance of existing hard carbon-coated graphite composites are still unsatisfactory.
Disclosure of Invention
The invention aims to provide a preparation method of a long-life high-power graphite composite material, which has good power performance and cycle performance.
In order to achieve the purpose, the technical scheme of the long-life high-power graphite composite material is as follows:
a preparation method of a long-life high-power graphite composite material comprises the following steps:
1) preparing polyaniline on a carbon nano tube by adopting an electrochemical deposition method on a conductive matrix with the carbon nano tube growing on the surface, and removing the conductive matrix to obtain a carbon nano tube/polyaniline composite material;
2) carrying out hydrothermal reaction on the carbon nano tube/polyaniline composite material, a water-soluble organic carbon source and water under the action of an acid catalyst, and filtering to obtain a solid carbon nano tube/polyaniline/hydrothermal carbon composite material; the temperature of the hydrothermal reaction is 120-200 ℃;
3) and uniformly mixing the hard carbon-coated graphite, the solid carbon nanotube/polyaniline/hydrothermal carbon composite material and an acid solution, and then spraying and drying.
According to the preparation method of the long-life high-power graphite composite material, the core is graphite, the shell is of a double-layer structure, and in the double-layer structure, the hard carbon layer on the inner side can improve the insertion and extraction rate of lithium ions in the charging and discharging process and improve the quick charging and cycle performance; the solid carbon nanotube/polyaniline/hydrothermal carbon layer on the outer side can exert the characteristics of the carbon nanotube/polyaniline double-layer capacitor, the power performance of the material is improved, the characteristics of porosity and stable bonding of hydrothermal carbon are further cooperated, and the cycle and power performance of the material can be effectively improved.
In step 1), the preparation of the conductive substrate with the carbon nanotubes grown on the surface can refer to the prior art. The conductive aggregate is preferably a copper foil. Specifically, catalyst powder is uniformly spread on the surface of the copper foil substrate, and then the carbon nano tube is vertically grown on the surface of the copper foil substrate by a chemical vapor deposition method.
When the conductive matrix with the carbon nano tubes growing on the surface is prepared. The catalyst can be selected from transition metal powder with the particle size of 100-500 nm. Typical transition metals are nickel, iron, cobalt, and the like. The working gas adopted by the chemical vapor deposition method is a carbon source gas, and the carbon source gas can be one of methane, acetylene and ethylene. The temperature of the chemical vapor deposition method can be set to 700-900 ℃, and the time can be set to 7-10 h. The introduction rate of the carbon source gas may be set to 1-50 ml/min.
When preparing polyaniline by an electrochemical deposition method, one of a cyclic voltammetry method, a constant voltage method and a constant current method can be adopted. The preparation of polyaniline by electrochemical deposition is carried out in hydrochloric acid solution of aniline. In the hydrochloric acid solution of aniline, the concentration of aniline is 0.1mol/L, and the mass fraction of the hydrochloric acid solution is 1%. When cyclic voltammetry is adopted, the voltage range is-2V, the scanning speed is 1mV/s, and the number of scanning cycles is 5 weeks. When a constant voltage method is adopted, the voltage is 2V, and the time is 1 h. When a constant current method is adopted, the current is 10mA/cm2The time is 1 h. The polyaniline prepared by the method has good deposition rate and can improve the conductivity of the material.
According to the carbon nanotube/polyaniline composite material prepared by the method, the carbon nanotubes vertically grow and are in a cluster structure, then polyaniline can be formed among the carbon nanotubes more easily by aniline, and the carbon nanotubes and the polyaniline are uniformly compounded.
In the step 2), the mass ratio of the water-soluble organic carbon source to the carbon nano tube/polyaniline composite material is 100 (10-30). Preferably, the water-soluble organic carbon source is one or more than two of rhamnose, furfural, furfuryl alcohol, malic acid and tartaric acid. The mass fraction of the organic carbon source aqueous solution formed by the water-soluble organic carbon source and water is preferably 1-10%. In the step, the acid catalyst is an acid solution with the molar concentration of 1-10mol/L, and the acid solution can be one of a hydrochloric acid solution, a phosphoric acid solution and a nitric acid solution. The amount of 10g of water-soluble organic carbon source used was 10 to 50ml of the acid catalyst. In this step, an acid catalyst is used to accelerate the reaction process and improve the conductivity of the material.
In the step 2), the time of the hydrothermal reaction is 1-12 h.
In step 3), the hard carbon-coated graphite may be prepared by the prior art. Preferably, the hard carbon-coated graphite is prepared by a method comprising the steps of: mixing graphite with 1-10% phenolic resin solution, filtering, and carbonizing at 500-900 deg.C. The carbonization time is 12-48 h. The amount of 100g graphite and the corresponding phenolic resin solution is 60-100 ml.
In the step 3), the acid solution is 1-5% by mass of hydrochloric acid solution, and the mass of 1000ml of the hydrochloric acid solution corresponding to the solid carbon nanotube/polyaniline/hydrothermal carbon composite material is 1-5 g. During the spray drying process, the addition of a hydrochloric acid solution can improve the electronic conductivity of the material.
Preferably, in the step 3), the mass ratio of the carbon nanotube/polyaniline/hydrothermal carbon composite material to the graphite in the hard carbon-coated graphite is (1-5): 100.
The graphite composite material prepared by the method has a core-shell structure, wherein the core is graphite, the shell is of a double-layer structure, and the hard carbon layer and the carbon nano tube/polyaniline/hydrothermal carbon layer are sequentially arranged from inside to outside. The carbon nano tube/polyaniline/hydrothermal carbon composite material is coated on the surface of the hard carbon, has the characteristics of high electronic conductivity, strong structural stability and the like, and can obviously improve the cycle and power performance of the material.
Drawings
Fig. 1 is an SEM image of a carbon nanotube/polyaniline/hydrothermal carbon composite material prepared in example 1 of the present invention;
fig. 2 is an SEM image of the graphite composite material prepared in example 1 of the present invention.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings. In the following examples, the particle size of the artificial graphite was (5-12) μm.
First, a specific embodiment of the preparation method of the long-life high-power graphite composite material
Example 1
The preparation method of the long-life high-power graphite composite material comprises the following steps:
1) preparing a carbon nano tube/polyaniline composite material: uniformly spreading 10g of iron catalyst powder with the particle size of 200nm on the surface of a copper foil in a tube furnace, then introducing argon inert gas to discharge air in the tube, introducing carbon source gas methane (the introduction rate is 10ml/min), heating to 800 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 8h, stopping introducing the methane gas, introducing the inert gas, and naturally cooling to room temperature to obtain the carbon nano tube growing on the copper foil.
The method comprises the following steps of taking a copper foil with carbon nano tubes growing on the surface as a working electrode, saturated calomel as a reference electrode and a platinum electrode as a counter electrode, and depositing polyaniline on the surface of the working electrode by a cyclic voltammetry method in 500ml of 0.1mol/L aniline aqueous solution, wherein the cyclic voltammetry method comprises the following process parameters: the voltage is-2 to 2V, the scanning speed is 1mV/s, and the scanning is carried out for 5 weeks. And then washing and drying, and removing the copper foil by adopting an ultrasonic vibration mode to obtain the carbon nano tube/polyaniline composite material.
2) Preparing a carbon nano tube/polyaniline/hydrothermal carbon composite material: adding 10g of furfural into 200ml of deionized water to prepare an organic carbon source aqueous solution with the mass fraction of 5%, placing the organic carbon source aqueous solution into a high-pressure reaction kettle, then adding 3g of carbon nano tube/polyaniline material, adding 10ml of hydrochloric acid solution with the concentration of 5mol/L as a catalyst, uniformly dispersing, carrying out hydrothermal reaction for 6h at 150 ℃, filtering, and drying to obtain the carbon nano tube/polyaniline/hydrothermal carbon composite material.
3) Preparing a graphite composite material: mixing 100g of artificial graphite with 60ml of phenolic resin solution with the mass fraction of 5%, filtering, drying, carbonizing at 700 ℃ for 24h, and naturally cooling to room temperature to obtain the hard carbon-coated graphite. Adding the hard carbon-coated graphite into 1000ml of dilute hydrochloric acid solution with the mass fraction of 3%, adding 1g of carbon nano tube/polyaniline/hydrothermal carbon composite material, uniformly mixing, and performing spray drying to obtain the composite material.
The graphite composite material obtained in the embodiment has a core-shell structure, the core is graphite, the shell is of a double-layer structure, and the hard carbon layer and the carbon nanotube/polyaniline/hydrothermal carbon layer are sequentially arranged from inside to outside.
Example 2
The preparation method of the long-life high-power graphite composite material comprises the following steps:
1) preparing a carbon nano tube/polyaniline composite material: uniformly spreading 10g of nickel catalyst powder with the particle size of 100nm on the surface of a copper foil in a tube furnace, then introducing argon inert gas to discharge air in the tube, introducing carbon source gas acetylene (the introduction rate is 1.0ml/min), raising the temperature to 700 ℃ at the temperature rise rate of 1 ℃/min, preserving the temperature for 8h, stopping introducing the acetylene gas, introducing argon, and naturally cooling to the room temperature to obtain the carbon nano tube growing on the copper foil.
The method comprises the following steps of taking a copper foil with carbon nano tubes growing on the surface as a working electrode, saturated calomel as a reference electrode and a platinum electrode as a counter electrode, and depositing polyaniline on the surface of the working electrode in 500ml of 0.1mol/L aniline aqueous solution by a constant current method, wherein the constant current method comprises the following process parameters: current density: 10mA/cm2And the time is 1 h. And then washing and drying, and removing the copper foil by adopting ultrasonic vibration to obtain the carbon nano tube/polyaniline composite material.
2) Preparing a carbon nano tube/polyaniline/hydrothermal carbon composite material: adding 10g of malic acid into 1000ml of deionized water to prepare an organic carbon source aqueous solution with the mass fraction of 1%, placing the organic carbon source aqueous solution into a high-pressure reaction kettle, then adding 1g of carbon nano tube/polyaniline material, adding 50ml of phosphoric acid solution with the concentration of 5mol/L as a catalyst, uniformly dispersing, carrying out hydrothermal reaction at 120 ℃ for 12h, filtering, and drying to obtain the carbon nano tube/polyaniline/hydrothermal carbon composite material.
3) Preparing a graphite composite material: mixing 100g of artificial graphite with 100ml of phenolic resin solution with the mass fraction of 5%, filtering, drying, carbonizing at 700 ℃ for 24h, and naturally cooling to room temperature to obtain the hard carbon-coated graphite. Adding the hard carbon-coated graphite into 1000ml of a 1% dilute hydrochloric acid solution, adding 5g of the carbon nanotube/polyaniline/hydrothermal carbon composite material, uniformly mixing, and performing spray drying to obtain the composite material.
The graphite composite material obtained in the embodiment has a core-shell structure, the core is graphite, the shell is of a double-layer structure, and the hard carbon layer and the carbon nanotube/polyaniline/hydrothermal carbon layer are sequentially arranged from inside to outside.
Example 3
The preparation method of the long-life high-power graphite composite material comprises the following steps:
1) preparing a carbon nano tube/polyaniline composite material: uniformly spreading 10g of cobalt catalyst powder with the particle size of 500nm on the surface of a copper foil in a tube furnace, then introducing argon inert gas to discharge air in the tube, introducing carbon source gas ethylene (the introduction rate is 50ml/min), heating to 900 ℃ at the heating rate of 10 ℃/min, preserving the heat for 8 hours, stopping introducing the ethylene gas, introducing argon, and naturally cooling to room temperature to obtain the carbon nano tube growing on the copper foil.
The method comprises the following steps of taking a copper foil with carbon nano tubes growing on the surface as a working electrode, saturated calomel as a reference electrode and a platinum electrode as a counter electrode, and depositing polyaniline on the surface of the working electrode by a constant pressure method in 500ml of 0.1mol/L aniline aqueous solution, wherein the constant pressure method comprises the following process parameters: voltage: 2V and time 1 h. And then washing and drying, and removing the copper foil by adopting ultrasonic vibration to obtain the carbon nano tube/polyaniline composite material.
2) Preparing a carbon nano tube/polyaniline/hydrothermal carbon composite material: adding 10g of tartaric acid into 100ml of deionized water to prepare an organic carbon source aqueous solution with the mass fraction of 10%, placing the organic carbon source aqueous solution into a high-pressure reaction kettle, then adding 1g of carbon nano tube/polyaniline material, adding 20ml of nitric acid solution with the concentration of 5mol/L as a catalyst, uniformly dispersing, carrying out hydrothermal reaction for 1h at 200 ℃, filtering and drying to obtain the carbon nano tube/polyaniline/hydrothermal carbon composite material.
3) Preparing a graphite composite material: mixing 100g of artificial graphite with 100ml of phenolic resin solution with the mass fraction of 1%, filtering, drying, carbonizing at 900 ℃ for 12h, and naturally cooling to room temperature to obtain the hard carbon coated graphite. Adding the hard carbon-coated graphite into 1000ml of dilute hydrochloric acid solution with the mass fraction of 3%, adding 5g of carbon nano tube/polyaniline/hydrothermal carbon composite material, uniformly mixing, and performing spray drying to obtain the composite material.
The graphite composite material obtained in the embodiment has a core-shell structure, the core is graphite, the shell is of a double-layer structure, and the hard carbon layer and the carbon nanotube/polyaniline/hydrothermal carbon layer are sequentially arranged from inside to outside.
Second, comparative example
The graphite composite material of the comparative example is prepared by adding 100g of artificial graphite into 100ml of a phenolic resin solution with the mass fraction of 1%, filtering, drying, carbonizing at 900 ℃ for 12h, and naturally cooling to room temperature to obtain the hard carbon-coated graphite.
Third, Experimental example
Experimental example 1
SEM test was performed on the carbon nanotube/polyaniline/hydrothermal carbon composite material prepared in step 2) of example 1, and the result is shown in fig. 1.
As can be seen from fig. 1, the carbon nanotubes vertically grow and are integrated into an integral structure by polyaniline and hydrothermal carbon polymerization.
SEM test was performed on the graphite composite material prepared in step 3) of example 1, and the result is shown in fig. 2.
As can be seen from FIG. 2, the obtained graphite composite material was in the form of irregular particles having a particle size of about 10 to 15 μm.
Experimental example 2
The specific surface area, tap density and powder conductivity of the graphite composite materials of examples 1 to 3 and comparative example were tested in this experimental example, and the specific detection method was performed according to the regulations of GB/T-2433sa 2009 lithium ion battery graphite-based negative electrode material, and the results are shown in table 1.
TABLE 1 physicochemical Properties of examples and comparative examples
Examples of the invention Specific surface area (m)2/g) Tap density (g/cm)3) Powder conductivity (S/cm)
Example 1 1.93 1.12 3.81
Example 2 1.88 1.11 3.79
Example 3 1.68 1.09 3.75
Comparative example 1.32 0.94 1.62
As can be seen from the results in table 1, the graphite composite materials of the examples had larger specific surface areas, tap densities, and powder conductivities. The larger specific surface area is beneficial to improving the electrochemical reaction efficiency. The higher tap density is beneficial to the compact accumulation of the powder, and is beneficial to improving the energy density, reducing the internal resistance and improving the rate capability. The higher powder conductivity is beneficial to the improvement of the rate capability and the power performance of the battery.
Experimental example 3
The graphite composite materials of examples 1 to 3 and comparative example were used as negative electrode materials to fabricate button cells, and the first discharge capacity and the first efficiency were tested.
The button cell manufacturing process comprises the following steps: weighing 9g of graphite negative electrode material, 0.5g of conductive agent SP and 0.5g of LA132 binder, adding the materials into 220ml of deionized water, uniformly stirring, coating the mixture on a copper foil to prepare a membrane, and then taking a lithium sheet as a negative electrode, a celegard2400 as a membrane and an electrolyte as LiPF6Solution (solute of 1mol/L LiPF6The solvents are Ethylene Carbonate (EC) and diethyl carbonate (DMC) in a weight ratio of 1:1, and the button cell is assembled in a glove box with oxygen and water contents lower than 0.1 ppm.
The button cell was mounted on a blue tester, charged and discharged at a rate of 0.1C, with a voltage range of 0.05V to 2.0V, and stopped after 3 weeks of cycling. The test results are shown in table 2.
TABLE 2 Performance testing of button cells
Example numbering First discharge capacity (mAH/g) First efficiency (%)
Example 1 357.5 94.2
Example 2 356.4 94.1
Example 3 356.7 93.9
Comparative example 351.8 92.1
As can be seen from the results in table 2, the button cell using the graphite composite material of the embodiment is a comparative example in terms of the first efficiency and the first discharge capacity, and the reason is that the case uses the carbon nanotube, polyaniline, and carbon composite structure with high conductivity, which is beneficial to increasing the electron transfer rate during the charge and discharge processes, thereby facilitating the gram capacity of the material to be exerted.
Experimental example 4
In the experimental example, the graphite composite materials of examples 1 to 3 and the comparative example are used as negative electrode materials to manufacture the soft package battery, and the cycle performance, the rate performance and the power performance of the soft package battery are tested.
Manufacturing the soft package battery: the negative electrode slurry formulation of parameter experiment example 3 was prepared into a negative electrode sheet using a ternary material (LiNi)1/3Co1/3Mn1/3O2) As the positive electrode, LiPF6The solution (concentration is 1.3mol/L, the solvent is EC + DEC, the volume ratio is 1:1) is used as electrolyte, and celegard2400 is used as a diaphragm to prepare the 5Ah flexible package battery.
4.1 cycle Performance test
And carrying out cycle test on the soft package lithium ion battery under the conditions that the charge and discharge voltage is 2.8-4.2V, the temperature is 25 +/-3.0 ℃ and the charge and discharge multiplying power is 1C/1C, wherein the test results are shown in Table 3.
Table 3 cycle performance of pouch cells using the graphite composite materials of examples and comparative examples
Examples Initial capacity retention (%) Capacity retention rate (%). about 500 times Capacity retention ratio (%). 1000 times
Example 1 100 97.3 95.1
Example 2 100 97.1 94.9
Example 3 100 96.7 94.3
Comparative example 100 92.1 88.9
As can be seen from the results of table 3, the pouch cells using the graphite composite material of the examples exhibited better cycle performance at each stage than the comparative examples. The reason is that the shell is made of a carbon nano tube, polyaniline and hydrothermal carbon composite material, wherein the carbon nano tube and the polyaniline are compounded to remarkably improve the electron conduction rate of the material, the hydrothermal carbon has a hole structure and good mechanical property, the liquid retention performance and the structural stability of the material can be improved, meanwhile, the hydrothermal carbon has good compatibility with electrolyte, and the material shows good cycle performance as a result of synergistic effect of the three.
4.2 multiplying power and power discharge performance test
Charging rate performance test conditions: the charging and discharging voltage is 2.5-4.2V, the temperature is 25 +/-3.0 ℃, the discharging multiplying power is 1.0C, and the charging multiplying power is 1.0C, 2.0C, 3.0C and 5.0C.
Discharge power performance: the product of the capacities with different discharge multiplying factors (the charge multiplying factor is 1.0C) and the median voltage is the power.
The rate performance and power performance results are shown in tables 4 and 5, respectively.
Table 4 rate performance of pouch cells using graphite composite materials of examples and comparative examples
Figure BDA0002647060010000071
Table 5 rate performance of pouch cells using graphite composite materials of examples and comparative examples
Figure BDA0002647060010000072
Figure BDA0002647060010000081
As can be seen from the results in tables 4 and 5, the coating layer of the material shell of the embodiment has a composite structure of polyaniline, carbon nanotube and hydrothermal carbon, and during the charging and discharging process, depending on the higher specific surface area, the double electric layer effect can be generated, which is beneficial to increasing the electron transmission rate in the material, so that the power performance of the material can be improved, and thus the rate charging performance can be improved.

Claims (8)

1. A preparation method of a long-life high-power graphite composite material is characterized by comprising the following steps:
1) preparing polyaniline on a carbon nano tube by adopting an electrochemical deposition method on a conductive matrix with the carbon nano tube growing on the surface, and removing the conductive matrix to obtain a carbon nano tube/polyaniline composite material;
2) carrying out hydrothermal reaction on the carbon nano tube/polyaniline composite material, a water-soluble organic carbon source and water under the action of an acid catalyst, and filtering to obtain a solid carbon nano tube/polyaniline/hydrothermal carbon composite material; the temperature of the hydrothermal reaction is 120-200 ℃;
3) and uniformly mixing the hard carbon-coated graphite, the solid carbon nanotube/polyaniline/hydrothermal carbon composite material and an acid solution, and then spraying and drying.
2. The preparation method of the long-life high-power graphite composite material as claimed in claim 1, wherein in the step 2), the mass ratio of the water-soluble organic carbon source to the carbon nanotube/polyaniline composite material is 100 (10-30).
3. The preparation method of the long-life high-power graphite composite material as claimed in claim 2, wherein the water-soluble organic carbon source is one or more of rhamnose, furfural, furfuryl alcohol, malic acid and tartaric acid.
4. The method for preparing the long-life high-power graphite composite material as claimed in any one of claims 1 to 3, wherein the hydrothermal reaction time in step 2) is 1 to 12 hours.
5. The method for preparing a long-life high-power graphite composite material as claimed in claim 1, wherein in the step 3), the hard carbon-coated graphite is prepared by a method comprising the steps of: mixing graphite with 1-10% phenolic resin solution, filtering, and carbonizing at 500-900 deg.C.
6. The method for preparing the long-life high-power graphite composite material as claimed in claim 5, wherein the carbonization time is 12 to 48 hours.
7. The method for preparing the long-life high-power graphite composite material as claimed in claim 1, wherein in the step 3), the acid solution is 1-5% by mass of hydrochloric acid solution, and 1000ml of the hydrochloric acid solution is 1-5g by mass of the solid carbon nanotube/polyaniline/hydrothermal carbon composite material.
8. The method for preparing the long-life high-power graphite composite material as claimed in any one of claims 1 and 5 to 7, wherein in the step 3), the mass ratio of the carbon nanotube/polyaniline/hydrothermal carbon composite material to the graphite in the hard carbon-coated graphite is (1-5): 100.
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