CN109449419B - CNT-graphite composite active material for lithium ion battery and preparation method thereof - Google Patents

CNT-graphite composite active material for lithium ion battery and preparation method thereof Download PDF

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CN109449419B
CN109449419B CN201811308477.0A CN201811308477A CN109449419B CN 109449419 B CN109449419 B CN 109449419B CN 201811308477 A CN201811308477 A CN 201811308477A CN 109449419 B CN109449419 B CN 109449419B
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CN109449419A (en
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闫振忠
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Taizhou University
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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
    • H01M4/362—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a CNT-graphite composite active material for a lithium ion battery and a preparation method thereof, belonging to the technical field of lithium batteries. The CNT-graphite composite active material is a CNT-graphite material with CNT self-generated on the surface of graphite in situ, and the preparation method comprises the following steps: coating a layer of Ni (OH) on the surface of graphite2Granulating to obtain modified graphite; placing the modified graphite in an atmosphere furnace, heating and preserving heat to obtain CNT-graphite powder with CNT growing on the surface of the graphite; and (2) placing the CNT-graphite powder in acid liquor for acid treatment to remove Ni, and then cleaning with deionized water to obtain the CNT-graphite composite active material. The CNT-graphite composite active material has high conductivity and high charge-discharge rate when being applied to a lithium ion battery.

Description

CNT-graphite composite active material for lithium ion battery and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium batteries, and relates to a CNT-graphite composite active material for a lithium ion battery and a preparation method thereof.
Background
The lithium ion battery is a secondary battery (rechargeable battery), and with the development of the society, the application of the lithium ion battery is increasingly wide, and the requirements on the performance of the lithium ion battery are higher and higher.
Lithium ion batteries operate primarily by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, Li + is inserted and extracted back and forth between two electrodes: during charging, Li + is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. The lithium ion battery mainly comprises a positive pole piece, a negative pole piece, electrolyte and a diaphragm, wherein a positive active material is coated on the positive pole piece, a negative active material is coated on the negative pole piece, and the positive and negative active materials of the lithium ion battery are one of important factors determining the performance of the lithium ion battery. At present, graphite is taken as a main active material of the lithium ion battery cathode, but the charge-discharge multiplying power of the graphite taken as the active material of the lithium ion battery cathode is low and needs to be improved. In order to improve the electron conductivity of the negative electrode sheet, a conductive agent, such as CNT, is generally added to the negative electrode sheet. The conductive agent has fine particles and extremely high specific surface area, is easy to agglomerate in the slurry and is difficult to disperse. And the cost of the lithium ion battery is increased to a certain extent by adding a large amount of the conductive agent.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a CNT-graphite composite active material for a lithium ion battery, wherein the CNT-graphite composite active material is prepared by in-situ generation of CNT on the surface of graphite, and has high conductivity and high charge-discharge rate when being applied to the lithium ion battery.
The purpose of the invention can be realized by the following technical scheme:
a CNT-graphite composite active material for a lithium ion battery is a CNT-graphite material with in-situ generated CNT on a graphite surface.
The CNT-graphite material with the CNT self-generated on the surface of the graphite in situ is used as the lithium ion battery cathode active material, so that the electronic conductivity of the graphite in the charging and discharging processes can be fully improved, the specific surface area of the graphite is increased, the charging and discharging multiplying power of the graphite is improved, meanwhile, the addition amount of the cathode conductive agent in the manufacturing process of the lithium ion battery can be reduced, and the problem that the traditional method for directly adding the conductive agent is difficult to disperse is solved.
Preferably, the CNT grown on the graphite surface in the CNT-graphite material has a length of 1 μm to 3 μm and a diameter of 20nm to 70 nm.
Theoretically, the longer the CNT and the smaller the diameter of the CNT, the larger the specific gravity and the larger the specific surface area of the CNT in the CNT-graphite material, which is more favorable for improving the conductivity of the lithium ion battery. However, the specific surface area of the CNT-graphite material increases, and the amount of the binder used needs to be increased to stabilize the service life of the negative electrode, and excessive use of the binder adversely affects the performance of the lithium ion battery. Therefore, the invention comprehensively considers the porosity, thickness, multiplying power and capacity of the lithium ion battery cathode pole piece and other electrochemical properties, and controls the length of the CNT within 1-3 μm.
Another object of the present invention is to provide a method for preparing a CNT-graphite composite active material for a lithium ion battery, the method comprising the steps of,
s1, coating a layer of Ni (OH) on the surface of graphite2Granulating to obtain modified graphite;
s2, placing the modified graphite in an atmosphere furnace, heating and preserving heat to obtain CNT-graphite powder with CNT growing on the surface of the graphite;
and S3, placing the CNT-graphite powder in acid liquor for acid treatment to remove Ni, and then washing with deionized water to obtain the CNT-graphite composite active material.
The invention relates to a method for preparing graphite by using Ni (OH) on the surface of graphite2Coating of the particles, thereby catalyzing the graphite surface CGrowth of NT, Ni (OH) during heating2Decomposing into NiO, reacting with carbon atoms to reduce into Ni, and growing CNT on the graphite surface by using solid graphite as carbon source.
Preferably, in the step S1, the graphite is firstly ultrasonically cleaned in absolute ethyl alcohol for 20min to 40min, and then the absolute ethyl alcohol is filtered to remove. The purpose is to remove impurities in graphite and improve the affinity of graphite and aqueous solution.
Preferably, Ni (OH) in the step S12The particle size of the particles is 20nm-70 nm.
The invention controls Ni (OH)2The particle size in turn controls the diameter of the CNTs. Metallic Ni can catalyze the growth of CNT on the surface of graphite, the size of metallic Ni determines the diameter of CNT, and Ni (OH)2The particle size of the precursor of metallic Ni determines the size of the Ni particles.
Preferably, the modified graphite in step S1 is prepared by co-precipitation method, wherein the graphite surface is coated with a layer of ni (oh)2And (3) granules.
Preferably, the modified graphite is prepared in step S1 by mixing graphite and Ni (NO)3)2Preparing the solution into suspension at a ratio of 4.5g/L-5.5g/L, adding NaOH solution to pH 7.5-8.0, standing, removing supernatant, and washing with anhydrous ethanol to obtain Ni (OH)2Vacuum drying graphite turbid body to obtain nano Ni (OH)2Particle-coated modified graphite particles.
Preferably, the Ni (NO)3)2The concentration of the solution is 0.03mol/L-0.6 mol/L.
Preferably, the standing time is 22-26 h.
Preferably, the concentration of the NaOH solution is 0.4mol/L to 0.5 mol/L.
Preferably, the NaOH solution is added dropwise.
Preferably, the number of times of washing with absolute ethanol is three.
Ni(NO3)2Molar concentration of the solution affects the final Ni (OH)2Particle size, the instantThe invention controls Ni (NO)3)2Molar concentration of solution Ni (OH)2The particle size of the particles is controlled within 20nm-70 nm.
Preferably, the heating and heat preservation process in the step S2 is to heat to 600-850 ℃ at a heating rate of 14-16 ℃/min under the protection of inert gas atmosphere, and preserve heat for 1-2 h.
The invention controls the length of CNT to be 1-3 μm by controlling the heating speed, temperature and holding time in the holding process.
Preferably, the inert gas is argon.
Preferably, the acid solution in step S3 is 4.5 wt.% to 5.5 wt.% HCl solution.
Preferably, the acidic treatment in step S3 is ultrasonic treatment in acid liquor for 2.5-3.5 h.
Compared with the prior art, the invention has the following beneficial effects:
the CNT-graphite material with the CNT self-generated on the surface of the graphite in situ is used as the negative electrode active material of the lithium ion battery, so that the electronic conductivity of the graphite in the charging and discharging process is fully improved, the charging and discharging multiplying power of the graphite is improved, meanwhile, the addition amount of a negative electrode conductive agent in the manufacturing process of the lithium ion battery can be reduced, and the problem that the traditional method for directly adding the conductive agent is difficult to disperse is avoided. By firstly forming a layer of Ni (OH) on the surface of graphite2And the size of the generated CNT is effectively controlled through a specific heat preservation and ignition process, so that the performance of the generated negative active material is controlled.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1
The CNT-graphite composite active material for a lithium ion battery in this example was prepared according to the following steps:
(1) ultrasonically cleaning 2.5g of graphite in absolute ethyl alcohol for 30min, then filtering to remove the absolute ethyl alcohol, and adding the cleaned graphite into 500mL of 0.03mol/L Ni (NO)3)2In solutionMagnetically stirring for 10min to form suspension, then continuously stirring and dropwise adding 0.45mol/L NaOH solution until the pH value is 7.8, standing for 24h, removing supernatant, and washing with anhydrous ethanol for three times to obtain stable Ni (OH)2Vacuum drying graphite turbid body to obtain nano Ni (OH)2Particle-coated modified graphite particles, nano-ni (oh)2The particle size of the particles is 20nm-30 nm;
(2) placing the modified graphite in an atmosphere furnace, heating to 730 ℃ at a heating speed of 15 ℃/min under the protection of argon, and preserving heat for 1.6h to grow CNT on the surface of the graphite, thereby preparing CNT-graphite powder, wherein the length of the CNT is 1.8-2.3 μm, and the diameter of the CNT is 20-30 nm;
(3) and (2) placing the CNT-graphite powder in 5.0 wt.% HCl solution for ultrasonic treatment for 3h to remove Ni, and then cleaning with deionized water for three times to obtain the CNT-graphite composite active material.
Example 2
Unlike example 1, the amount of graphite used in step (1) was 2.8g, and Ni (NO) was used3)2The concentration of the solution was 0.45mol/L, and the rest was the same as in example 1.
Produced nano Ni (OH)2Modified graphite particles coated with particles of Nano Ni (OH)2The particle size of the particles is 40nm-60 nm; in the prepared CNT-graphite powder, the length of the CNT is 1.8-2.5 μm, and the diameter is 40-60 nm;
example 3
Unlike example 1, the amount of graphite used in step (1) was 3.0g, and Ni (NO) was used3)2The concentration of the solution was 0.6mol/L, and the rest was the same as in example 1.
Produced nano Ni (OH)2Modified graphite particles coated with particles of Nano Ni (OH)2The particle size of the particles is 50nm-70 nm; in the prepared CNT-graphite powder, the length of the CNT is 1.9-2.6 μm, and the diameter is 50-70 nm;
example 4
The difference from example 1 was that the heating rate of the modified graphite in step (2) in the atmosphere furnace was 14 ℃/min, and the other steps were the same as in example 1.
The length of CNT in the prepared CNT-graphite material is 2.0 μm-3.0 μm, and the diameter is 20nm-30 nm.
Example 5
The heating rate of the modified graphite in the step (2) in the atmosphere furnace was 16 ℃/min, which was different from example 1, and the same as example 1.
The length of CNT in the prepared CNT-graphite material is 1.2 mu m-2.0 mu m, and the diameter is 20nm-30 nm.
Example 6
The difference from example 1 is that the temperature of the modified graphite in step (2) in the atmosphere furnace was 600 ℃ and the other steps were the same as example 1.
The length of CNT in the prepared CNT-graphite material is 1.5-2.2 μm, and the diameter is 20-30 nm.
Example 7
The difference from example 1 is that the modified graphite in step (2) was held at 850 ℃ in an atmosphere furnace, and the rest was the same as example 1.
The length of CNT in the prepared CNT-graphite material is 2.0-2.6 μm, and the diameter is 20nm-30 nm.
Comparative example 1
The heat preservation temperature of the modified graphite in the atmosphere furnace in the step (2) is 590 ℃, the heat preservation time is 50min, and the rest is the same as that of the embodiment 1.
The obtained CNT-graphite material had poor quality and impurities due to the lack of orientation of CNTs.
Comparative example 2
The heat preservation temperature of the modified graphite in the step (2) in the atmosphere furnace is 870 ℃, the heat preservation time is 2 hours, and the rest is the same as that of the embodiment 1.
The prepared CNT-graphite material has more CNT impurities.
Comparative example 3
In the prior art, conventional graphite and a conductive agent CNT are adopted as a negative active material.
The performance of lithium ion batteries manufactured using the negative active materials of examples 1 to 7 of the present invention and comparative examples 1 to 3 was compared, and the comparison results are shown in table 1.
Table 1: comparison of cell Performance in examples 1 to 7 and comparative examples 1 to 3
Figure BDA0001854338340000061
Figure BDA0001854338340000071
In conclusion, the CNT-graphite composite active material for the lithium ion battery is prepared by the method for growing the CNT on the surface of the graphite in situ, so that the specific surface area of the graphite is effectively increased, and the electronic conductivity and the charge-discharge rate of the graphite are improved.
The amount of graphite in example 1 of the present invention may also be 2.25g (i.e., graphite and Ni (NO)3)2The ratio of the solution was 4.5g/L), 2.75g (i.e., graphite and Ni (NO)3)2The ratio of the solution is 5.5g/L) and any value between 2.25g and 2.75 g; the concentration of the NaOH solution can be any value between 0.4mol/L, 0.5mol/L and 0.4mol/L to 0.5 mol/L; the pH value adjusted after adding the NaOH solution can be any value between 7.5, 8.0 and 7.5 to 8.0; the heat preservation time of the modified graphite in the atmosphere furnace can be any value between 1h, 2h and 1h to 2 h; finally prepared nano Ni (OH)2Modified graphite particles coated with particles of Nano Ni (OH)2The particle size of the particles is 20nm-70nm, the length of CNT in the prepared CNT-graphite material is 2.0 μm-2.6 μm, the diameter of CNT is 20nm-70nm, the capacity of the lithium ion battery prepared by the cathode active material is 3.8Ah-4.1Ah, the energy density is 146Wh/kg-151Wh/kg, the internal resistance is 28m omega-32 m omega, and the discharge capacity retention rate is 83.5% -86.0% after 1000 cycles of 1C/1C.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (7)

1. A preparation method of a CNT-graphite composite active material for a lithium ion battery is characterized in that the CNT-graphite composite active material is a CNT-graphite material with in-situ generated CNT on the graphite surface;
the method for preparing the CNT-graphite composite active material for the lithium ion battery comprises the following steps,
s1, uniformly coating a layer of Ni (OH) on the surface of the graphite by a coprecipitation method2Preparing particles into modified graphite, specifically, mixing graphite with Ni (NO)3)2Preparing the solution into suspension at a ratio of 4.5g/L-5.5g/L, adding NaOH solution to pH 7.5-8.0, standing, removing supernatant, and washing with anhydrous ethanol to obtain Ni (OH)2Vacuum drying graphite turbid body to obtain nano Ni (OH)2Particle-coated modified graphite particles;
s2, placing the modified graphite in an atmosphere furnace, heating and preserving heat to obtain CNT-graphite powder with CNT growing on the surface of the graphite;
and S3, placing the CNT-graphite powder in acid liquor for acid treatment to remove Ni, and then washing with deionized water to obtain the CNT-graphite composite active material.
2. The method of preparing a CNT-graphite composite active material for a lithium ion battery according to claim 1, wherein CNTs grown on a graphite surface in the CNT-graphite material have a length of 1 μm to 3 μm and a diameter of 20nm to 70 nm.
3. The method of claim 1, wherein the step S1 comprises adding Ni (OH)2The particle size of the particles is 20nm-70 nm.
4. The method of claim 1, wherein the Ni (NO) is selected from the group consisting of Ni, and Ni3)2Concentration of the solutionIs 0.03mol/L to 0.6 mol/L.
5. The method of claim 1, wherein the heating and maintaining in step S2 is performed by heating to 600 ℃ to 850 ℃ at a heating rate of 14 ℃/min to 16 ℃/min under the protection of an inert gas atmosphere, and maintaining the temperature for 1h to 2 h.
6. The method of preparing the CNT-graphite composite active material for a lithium ion battery according to claim 1, wherein the acid solution in the step S3 is 4.5 wt.% to 5.5 wt.% HCl solution.
7. The method of preparing the CNT-graphite composite active material for the lithium ion battery according to claim 1, wherein the acidic treatment in the step S3 is an ultrasonic treatment in an acid solution for 2.5 to 3.5 hours.
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