CN112436139A - Preparation method of three-dimensional composite conductive agent - Google Patents
Preparation method of three-dimensional composite conductive agent Download PDFInfo
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- CN112436139A CN112436139A CN201910786132.4A CN201910786132A CN112436139A CN 112436139 A CN112436139 A CN 112436139A CN 201910786132 A CN201910786132 A CN 201910786132A CN 112436139 A CN112436139 A CN 112436139A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of a three-dimensional composite conductive agent, which comprises the following steps: s1: adding pyrrole monomer into hydrochloric acid solution, and then adding carbon nano tube into the solution for cooling and ultrasonic treatment; s2: adding ammonium persulfate into the hydrochloric acid solution for cooling, adding into the solution prepared by S1, and stirring; s3: dispersing graphene oxide in deionized water, performing ultrasonic treatment, stirring, adding the solution prepared in S2, heating for reaction, cleaning for several times, and drying to obtain a conductive agent; s4: and carrying out high-temperature heat treatment and crushing to obtain the three-dimensional conductive agent. The polypyrrole is coated on the carbon nanotube, and then the graphene is grafted on the carbon nanotube to form a stable three-dimensional structure, so that the risk of agglomeration of a conductive agent in the homogenization process of the positive electrode and the negative electrode of the lithium ion battery is reduced, and the polypyrrole is reduced and carbonized by high-temperature heat treatment, so that the conductivity of the positive electrode and the negative electrode is effectively improved, and the electrical property of the lithium ion battery is improved; meanwhile, the process requirement and the production difficulty are reduced.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery conductive agents, and particularly relates to a preparation method of a three-dimensional composite conductive agent.
Background
The carbon nano tube and the graphene belong to carbon materials with extremely excellent conductivity. The carbon nano tube is generally used as a lithium ion battery conductive agent to improve the conductivity of a battery pole piece due to the excellent conductivity of the carbon nano tube, and meanwhile, the carbon nano tube can form a network structure in a long-range due to the larger one-dimensional average tube diameter ratio, so that an active material is firmly grabbed, the bonding stability among the active materials is improved, and the flexibility of the pole piece is also enhanced. Graphene is a two-dimensional honeycomb-shaped carbon material formed by close packing of single-layer carbon atoms, and has attracted much attention due to its ultrahigh electron mobility, thermal conductivity, excellent electron conductivity, and mechanical properties. If the carbon nano tube and the graphene are directly compounded, the prepared conductive agent slurry is easily agglomerated, and the use is affected.
However, at present, when the positive and negative electrode plates of the lithium ion battery are prepared, a plurality of conductive agents with different dimensions are generally compounded, and the method can theoretically form a three-dimensional conductive network structure, so that the conductivity of the lithium ion battery is more excellent, but the method has the risk of conductive particle agglomeration, has high process requirements and increases the production difficulty. Therefore, a conductive agent with a three-dimensional structure needs to be developed, and the conductive agent can be directly added as a lithium ion positive and negative electrode plate conductive agent without compounding various conductive agents, so that the conductivity of the electrode plate and the electrical property of a lithium ion battery are improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a three-dimensional composite conductive agent, aiming at reducing the risk of agglomeration of the conductive agent in the homogenization process of a positive electrode and a negative electrode of a lithium ion battery, improving the conductivity of the positive electrode and the negative electrode, and improving the electrical property of the lithium ion battery.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
a preparation method of a three-dimensional composite conductive agent comprises the following steps:
s1: adding pyrrole monomer into 1M hydrochloric acid solution, then adding carbon nano tube into the solution, and cooling to 0-10 ℃ and carrying out ultrasonic treatment for 30-90 min;
s2: adding ammonium persulfate into a 1M hydrochloric acid solution, cooling the solution to 0-10 ℃, adding the solution into the solution prepared in S1, stirring for 1-5 h, repeatedly washing with deionized water and methanol for several times, precipitating and drying;
s3: dispersing graphene oxide in deionized water, performing ultrasonic treatment for 1-2 hours, stirring for 5-15 hours to obtain a graphene dispersion liquid, then adding the solution prepared in S2, heating to 100-150 ℃, reacting for 1-5 hours, cleaning for several times, and drying to obtain a conductive agent;
s4: and (3) under the protection of inert gas, heating the conductive agent prepared in the step (S3) to a certain temperature at the speed of 2-5 ℃/min, keeping for 1-3 h, and then crushing to obtain the three-dimensional composite conductive agent.
The carbon nano tube has an average tube diameter of 0.1-0.5 nm and a length of 1-100 μm. Furthermore, the carbon nano tube has an average tube diameter of 0.1-0.3 nm and a length of 1-80 μm.
The graphene is a graphene microchip, and the sheet diameter is less than 50 mu m. The graphene is further characterized in that the graphene is a graphene micro-sheet, and the sheet diameter is less than 40 μm.
The concentration of the graphene dispersion liquid is 0.5-2 mg/mL. Further, the concentration of the graphene dispersion liquid is 0.5-1.5 mg/mL.
The mass ratio of the carbon nano tube to the graphene is 1-5: 1. Further, the mass ratio of the carbon nano tube to the graphene is 1-3: 1.
The temperature rise temperature is 500-1500 ℃. Further, the temperature rise temperature is 800-1200 ℃.
The three-dimensional composite conductive agent is prepared by the preparation method of the three-dimensional composite conductive agent.
The invention has the beneficial effects that: the polypyrrole is coated on the carbon nanotube, and then the graphene is grafted on the carbon nanotube to form a stable three-dimensional structure, so that the risk of agglomeration of a conductive agent in the homogenization process of the anode and the cathode of the lithium ion battery can be reduced, and the polypyrrole can be reduced and carbonized by high-temperature heat treatment, so that the conductivity of the anode and the cathode pole pieces can be effectively improved, and the electrical property of the lithium ion battery can be improved; meanwhile, the process requirement and the production difficulty are reduced.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and the description in this section is only exemplary and explanatory and should not be construed as limiting the scope of the present invention in any way.
Example 1:
s1: adding pyrrole monomer into 1M 50mL hydrochloric acid solution, then adding 1g of carbon nanotube into the solution, and cooling to 0 ℃ and carrying out ultrasound for 60 min;
s2: adding ammonium persulfate into 1M 50mL hydrochloric acid solution, cooling the solution to 0 ℃, adding the solution into the solution prepared in S1, stirring for 2h, repeatedly washing with deionized water and methanol for several times, precipitating and drying;
s3: dispersing 1g of graphene oxide in deionized water, performing ultrasonic treatment for 1 hour, stirring for 12 hours to obtain a graphene dispersion solution, then adding the solution prepared in S2, heating to 130 ℃, reacting for 3 hours, cleaning and drying for several times to obtain a conductive agent;
s4: and (3) under the protection of inert gas, heating the conductive agent prepared in the step (S3) to 1200 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, and then crushing to obtain the three-dimensional composite conductive agent.
Example 2:
s1: adding pyrrole monomer into 1M 50mL hydrochloric acid solution, then adding 3g carbon nano tube into the solution, and cooling to 0 ℃ and carrying out ultrasonic treatment for 60 min;
s2: adding ammonium persulfate into 1M 50mL hydrochloric acid solution, cooling the solution to 0 ℃, adding the solution into the solution prepared in S1, stirring for 2h, repeatedly washing with deionized water and methanol for several times, precipitating and drying;
s3: dispersing 1g of graphene oxide in deionized water, performing ultrasonic treatment for 1 hour, stirring for 12 hours to obtain a graphene dispersion solution, then adding the solution prepared in S2, heating to 130 ℃, reacting for 3 hours, cleaning and drying for several times to obtain a conductive agent;
s4: and (3) under the protection of inert gas, heating the conductive agent prepared in the step (S3) to 1200 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, and then crushing to obtain the three-dimensional composite conductive agent.
Example 3:
s1: adding pyrrole monomer into 1M 50mL hydrochloric acid solution, then adding 5g carbon nano tube into the solution, and cooling to 0 ℃ and carrying out ultrasonic treatment for 60 min;
s2: adding ammonium persulfate into 1M 50mL hydrochloric acid solution, cooling the solution to 0 ℃, adding the solution into the solution prepared in S1, stirring for 2h, repeatedly washing with deionized water and methanol for several times, precipitating and drying;
s3: dispersing 1g of graphene oxide in deionized water, performing ultrasonic treatment for 1 hour, stirring for 12 hours to obtain a graphene dispersion solution, then adding the solution prepared in S2, heating to 130 ℃, reacting for 3 hours, cleaning and drying for several times to obtain a conductive agent;
s4: and (3) under the protection of inert gas, heating the conductive agent prepared in the step (S3) to 1200 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, and then crushing to obtain the three-dimensional composite conductive agent.
Example 4:
s1: adding pyrrole monomer into 1M 50mL hydrochloric acid solution, then adding 3g carbon nano tube into the solution, and cooling to 0 ℃ and carrying out ultrasonic treatment for 60 min;
s2: adding ammonium persulfate into 1M 50mL hydrochloric acid solution, cooling the solution to 0 ℃, adding the solution into the solution prepared in S1, stirring for 2h, repeatedly washing with deionized water and methanol for several times, precipitating and drying;
s3: dispersing 1g of graphene oxide in deionized water, performing ultrasonic treatment for 1 hour, stirring for 12 hours to obtain a graphene dispersion solution, then adding the solution prepared in S2, heating to 130 ℃, reacting for 3 hours, cleaning and drying for several times to obtain a conductive agent;
s4: and (3) under the protection of inert gas, heating the conductive agent prepared in the step (S3) to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, and then crushing to obtain the three-dimensional composite conductive agent.
Example 4:
s1: adding pyrrole monomer into 1M 50mL hydrochloric acid solution, then adding 3g carbon nano tube into the solution, and cooling to 0 ℃ and carrying out ultrasonic treatment for 60 min;
s2: adding ammonium persulfate into 1M 50mL hydrochloric acid solution, cooling the solution to 0 ℃, adding the solution into the solution prepared in S1, stirring for 2h, repeatedly washing with deionized water and methanol for several times, precipitating and drying;
s3: dispersing 1g of graphene oxide in deionized water, performing ultrasonic treatment for 1 hour, stirring for 12 hours to obtain a graphene dispersion solution, then adding the solution prepared in S2, heating to 130 ℃, reacting for 3 hours, cleaning and drying for several times to obtain a conductive agent;
s4: and (3) under the protection of inert gas, heating the conductive agent prepared in the step (S3) to 1500 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, and then crushing to obtain the three-dimensional composite conductive agent.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (6)
1. The preparation method of the three-dimensional composite conductive agent is characterized by comprising the following steps of:
s1: adding pyrrole monomer into 1M hydrochloric acid solution, then adding carbon nano tube into the solution, and cooling to 0-10 ℃ and carrying out ultrasonic treatment for 30-90 min;
s2: adding ammonium persulfate into a 1M hydrochloric acid solution, cooling the solution to 0-10 ℃, adding the solution into the solution prepared in S1, stirring for 1-5 h, repeatedly washing with deionized water and methanol for several times, precipitating and drying;
s3: dispersing graphene oxide in deionized water, performing ultrasonic treatment for 1-2 hours, stirring for 5-15 hours to obtain a graphene dispersion liquid, then adding the solution prepared in S2, heating to 100-150 ℃, reacting for 1-5 hours, cleaning for several times, and drying to obtain a conductive agent;
s4: and (3) under the protection of inert gas, heating the conductive agent prepared in the step (S3) to a certain temperature at the speed of 2-5 ℃/min, keeping for 1-3 h, and then crushing to obtain the three-dimensional composite conductive agent.
2. The method for preparing a three-dimensional composite conductive agent according to claim 1, wherein the carbon nanotubes have an average diameter of 0.1 to 0.5nm and a length of 1 to 100 μm.
3. The method of claim 1, wherein the graphene is a graphene platelet, and the platelet diameter is less than 50 μm.
4. The method for preparing the three-dimensional composite conductive agent according to claim 1, wherein the concentration of the graphene dispersion liquid is 0.5-2 mg/mL.
5. The method for preparing the three-dimensional composite conductive agent according to claim 1, wherein the mass ratio of the carbon nanotube to the graphene is 1-5: 1.
6. The method for preparing the three-dimensional composite conductive agent according to claim 1, wherein the temperature rise is 500-1500 ℃.
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