CN108461753B - Carbon nanotube conductive agent slurry for lithium ion battery cathode material and preparation method thereof - Google Patents
Carbon nanotube conductive agent slurry for lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN108461753B CN108461753B CN201810137678.2A CN201810137678A CN108461753B CN 108461753 B CN108461753 B CN 108461753B CN 201810137678 A CN201810137678 A CN 201810137678A CN 108461753 B CN108461753 B CN 108461753B
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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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- 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 lithium ion batteries, and relates to carbon nano tube conductive agent slurry for a lithium ion battery cathode and a preparation method thereof. The active carbon is added into the conductive agent slurry, so that the dispersibility of the carbon nano tube is facilitated, the active carbon is dispersed in the negative electrode material, the adsorption capacity of the negative electrode of the lithium ion battery to the electrolyte is facilitated, and the diffusion path of ions is reduced; the negative electrode film forming agent is added into the conductive agent slurry, so that the formation of a surface SEI film of the negative electrode during charging and discharging is facilitated.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to conductive slurry for a lithium ion battery cathode.
Background
The negative electrode material is an important factor influencing the energy density of the lithium ion battery, the porosity is the most critical factor determining the performance of the negative electrode material, and the negative electrode material with high porosity can adsorb more lithium ions, so that the energy density of the lithium ion battery is improved. In order to avoid the influence of concentration polarization, the electrode is required to have an optimal pore structure. In order to ensure the high-current discharge capacity of the battery, the electronic conductivity and the ionic conductivity of the electrode must be optimal, and the low-resistance electrode material has important significance on the power density of the lithium ion battery.
The intrinsic conductivity of the negative electrode material is not very high, and the negative electrode material of a general commercial lithium ion battery is doped with a conductive agent. The characteristics of the conductive agent affect the size and shape of pores between the electrode active particles. In addition, the electrolyte absorption capacity of the conductive agent also influences the permeation of the electrolyte into the electrode, the electrode density is increased, the electrical contact among particles is improved, and the resistance of the electrode can be improved. Carbon nanotubes can form a conductive network in the electrode material, which is the most desirable condition of a conductive structure. The carbon nano tube is used as a conductive agent, so that the electrical contact among electrode material particles can be optimized, the contact between an electrode and a current collector is improved, and the mesh structure formed by the carbon nano tube in the electrode material can lock electrode active material particles and enhance the contact among the electrode materials.
The specific surface area of the activated carbon can reach 3000m at most2A specific surface area of the graphite anode material is only 3.5m2/g-6m2The active carbon is doped in the conductive agent of the negative electrode material of the lithium battery, so that the dispersibility of the electrode material in slurry is facilitated, the electrode holding capacity of the lithium battery to electrolyte in the use process can be improved, the ion diffusion path is shortened, and the adsorption capacity of the negative electrode to lithium ions is increased, which is a key factor influencing the high-current charge and discharge performance of the battery.
The chemical composition, structure, texture, stability, etc. of the solid electrolyte interface (SEI film) formed on the carbon negative electrode are critical in determining the compatibility of the carbon negative electrode/electrolyte of the lithium ion battery, and the SEI film determines the performance of the battery, such as reversible capacity, storage life, cycle life, and safety. The formation of the SEI film results from the decomposition of the electrolyte during charging. The stable SEI film not only minimizes the irreversible capacity of the battery and ensures the energy density, but also is beneficial to the cycle stability, the rate capability and the safety performance of the battery. In addition, an effective SEI film should also be able to inhibit electrochemical exfoliation of graphite due to co-intercalation of solvated lithium. Unstable solvated lithium intercalation compounds are decomposed in electrochemical reactions as short-term intermediates, which can generate gases in the graphite layers and ion microcracks, causing exfoliation of the graphite structure lamellae and destruction of the particles. Electrochemical exfoliation of graphite can cause decomposition of the graphite structure, ultimately leading to cell failure. Exfoliation easily occurs in graphite materials of high crystallinity, particularly in the case where the electrolyte contains propylene carbonate as a solvent.
The negative electrode film forming agent can form a stable SEI film on the surface of a negative electrode of a lithium ion battery, wherein ethylene carbonate (VC) is the first developed electrolyte solvent and has extremely high relative dielectric constantConstant (epsilon)r= 127), good conductivity can be improved. The addition of a small amount of VC, which can be a typical negative electrode film-forming additive, can suppress the generation of gas, obtain high cycle efficiency at the time of first charge, and also suppress the decomposition of a readily reducible solvent such as trimethyl phosphate (TMP).
The carbon nano tube can form a stable conductive network in an electrode material, the high compactibility of the carbon nano tube is beneficial to improving the electrode density, the DBP adsorption capacity of the carbon nano tube is low, a small amount of binder is adopted, the electrode can achieve proper mechanical strength, the thermal conductivity of the carbon nano tube is very high, and the thermal dispersion is beneficial to a power type battery. In addition, the excessively high crushing force does not cause the breakage of particles, compared to the graphite conductive agent.
Graphite is anisotropic, and the small ionic size and complex agglomerate structure of the graphite conductive agent, carbon black, used in the market results in a low compacted density of the negative electrode material.
Disclosure of Invention
The invention aims to solve the problems and provides carbon nano tube conductive agent slurry for a lithium ion battery cathode material and a preparation method thereof.
The technical scheme adopted by the invention is as follows: a carbon nanotube conductive agent slurry for a lithium ion battery cathode material and a preparation method thereof are provided, the carbon nanotube conductive agent slurry for the lithium ion battery cathode material is characterized in that: the weight ratio of the components is as follows:
85% -90% of N-methylpyrrolidone (NMP);
3% -6% of Carbon Nanotubes (CNTs);
5% -10% of Activated Carbon (AC);
1-2% of polyvinylpyrrolidone (PVP);
1% -2% of ethylene carbonate (VC). (accurate value)
A preparation method of carbon nano tube conductive agent slurry for a lithium ion battery cathode material comprises the following steps:
step (1): in the whole slurry preparation process, the moisture is strictly controlled, the indoor humidity is regulated to be below 15%, used equipment and instruments are fully dried, and N-methylpyrrolidone (NMP) is fully used for cleaning;
step (2): weighing NMP, adding into a stirring tank, adding polyvinylpyrrolidone (PVP) in the stirring process, turning on ultrasonic waves, adding ethylene carbonate (VC) after fully dissolving, and fully dissolving;
and (3): adding activated carbon powder, stirring for 30min, then adding Carbon Nanotubes (CNTs), stirring at a high speed, and transferring the composite slurry into a sand mill device after the carbon material is fully infiltrated;
and (4): adjusting the rotation speed of the sand mill to 1000r/min, grinding for 8-10h, and controlling the temperature to be not too high in the grinding process and keeping the temperature below 50 ℃.
The particle size of the active carbon is 5-10 mu m, and the specific surface area is 2000m2More than g.
The carbon nano tube is one or a mixture of a multi-wall carbon nano tube, a single-wall carbon nano tube and an array carbon nano tube.
The polyvinylpyrrolidone is a nonionic high molecular compound, the lipophilic group of the polyvinylpyrrolidone is provided by a hydrophobic compound containing active hydrogen, the hydrophilic group of the polyvinylpyrrolidone is provided by a low molecular compound of an ether group and a free hydroxyl group, and the addition amount of the polyvinylpyrrolidone is generally 0.5-5.0% (turbidity point value).
The negative electrode film-forming additive is ethylene carbonate, ethylene carbonate, styrene carbonate, catechol carbonate, methyl amino carbonate, ethyl amino carbonate, vinyl acetate, acrylonitrile and 2-cyanofuran, and sulfite compounds, such as ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite and other assistants.
The sand mill can be a vertical sand mill, a horizontal sand mill, a double-cone rod type sand mill or a basket type sand mill, and the used dispersion medium is zirconia balls with the grain diameter of 1.0mm-1.5 mm.
The stirring tank may be a propeller stirrer, a turbine stirrer or an anchor stirrer.
Compared with the prior art, the invention has the following advantages: (1) the invention adopts the carbon nano tube as the conductive agent, has good conductivity, and can form a conductive network in the cathode material to enhance the bonding strength between the cathode materials. (2) The invention adds the activated carbon which can absorb the electrolyte in the cathode material, thereby shortening the diffusion path of electrolyte molecules, reducing the polarization resistance and improving the high-current charge and discharge performance of the lithium battery monomer. (3) The negative electrode film forming agent is added to promote the electrolyte to form a stable SEI film on the surface of the negative electrode material, so that the electrochemical performance of the lithium battery is improved, and the service life of the lithium battery is prolonged.
Drawings
FIG. 1 is an SEM image of a 400nm negative electrode conductive paste of the present invention.
Fig. 2 is an SEM image of the negative electrode conductive paste of the present invention at 300 nm.
FIG. 3 is a SEM image of 1 μm of the negative electrode conductive paste of the present invention.
Detailed Description
The first scheme is as follows:
step (1), firstly, opening a dehumidifier, adjusting the indoor humidity to be below 15%, fully drying the used equipment and instruments, and cleaning the equipment and instruments by using NMP;
step (2): weighing 925g of NMP, adding into a stirring tank, adding 3g of PVP in the stirring process, turning on ultrasonic waves, adding 2g of VC after fully dissolving, and fully dissolving;
and (3): adding 20g of activated carbon powder while stirring, stirring for 30min, then adding 50g of CNTs, stirring at a high speed, and transferring the composite slurry into a sand mill device after the carbon material is fully infiltrated;
and (4): and (3) adjusting the rotation speed of the sand mill to 1000r/min, grinding for 10h, and keeping the temperature of a bin of the sand mill below 40 ℃ by using a water cooling machine.
The conductive paste was measured to have a moisture content of 2937ppm, a particle size of 8 μm and a viscosity of 10570 mPa.s.
Scheme II:
step (1), firstly, opening a dehumidifier, adjusting the indoor humidity to be below 15%, fully drying the used equipment and instruments, and cleaning the equipment and instruments by using NMP;
step (2): weighing 930g of NMP, adding into a stirring tank, adding 3g of PVP in the stirring process, turning on ultrasonic waves, adding 2g of VC after fully dissolving, and fully dissolving;
and (3): adding 15g of activated carbon powder while stirring, stirring for 30min, then adding 50g of CNTs, stirring at a high speed, and transferring the composite slurry into a sand mill device after the carbon material is fully infiltrated;
and (4): and (3) adjusting the rotation speed of the sand mill to 1000r/min, grinding for 10h, and keeping the temperature of a bin of the sand mill below 40 ℃ by using a water cooling machine.
The conductive paste was found to have a moisture content of 3347ppm, a particle size of 12 μm and a viscosity of 13470 mPa.s.
Claims (8)
1. A preparation method of carbon nano tube conductive agent slurry for a lithium ion battery cathode material is characterized by comprising the following steps of: the carbon nano tube conductive agent slurry for preparing the cathode material of the lithium ion battery comprises the following components in percentage by weight:
85% -90% of N-methylpyrrolidone (NMP);
3% -6% of Carbon Nanotubes (CNTs);
5% -10% of Activated Carbon (AC);
1-2% of polyvinylpyrrolidone (PVP);
1% -2% of ethylene carbonate (VC).
2. The preparation method of the carbon nanotube conductive agent slurry for the lithium ion battery negative electrode material according to claim 1, characterized by comprising the following steps:
step (1): in the whole slurry preparation process, the moisture is strictly controlled, the indoor humidity is regulated to be below 15%, used equipment and instruments are fully dried, and N-methyl pyrrolidone is fully used for cleaning;
step (2): weighing N-methylpyrrolidone (NMP), adding into a stirring tank, adding polyvinylpyrrolidone (PVP) during stirring, turning on ultrasonic waves, adding ethylene carbonate (VC) after fully dissolving, and fully dissolving;
and (3): adding activated carbon powder, stirring for 30min, then adding Carbon Nanotubes (CNTs), stirring at a high speed, and transferring the composite slurry into a sand mill device after the carbon material is fully infiltrated;
and (4): adjusting the rotation speed of the sand mill to 1000r/min, grinding for 8-10h, and controlling the temperature to be not too high in the grinding process and keeping the temperature below 50 ℃.
3. The preparation method of the carbon nanotube conductive agent slurry for the lithium ion battery negative electrode material according to claim 2, characterized in that: the particle size of the active carbon is 5-10 μm, and the specific surface area is more than 2000m 2/g.
4. The preparation method of the carbon nanotube conductive agent slurry for the lithium ion battery negative electrode material according to claim 2, characterized in that: the carbon nano tube is one or a mixture of a multi-wall carbon nano tube, a single-wall carbon nano tube and an array carbon nano tube.
5. The preparation method of the carbon nanotube conductive agent slurry for the lithium ion battery negative electrode material according to claim 2, characterized in that: the polyvinylpyrrolidone is a nonionic high molecular compound, the lipophilic group of the polyvinylpyrrolidone is provided by a hydrophobic compound containing active hydrogen, the hydrophilic group of the polyvinylpyrrolidone is provided by a low molecular compound of an ether group and a free hydroxyl group, and the addition amount of the polyvinylpyrrolidone is 0.5-5.0 percent of the cloud point value.
6. The preparation method of the carbon nanotube conductive agent slurry for the lithium ion battery negative electrode material according to claim 2, characterized in that: the negative electrode film forming additive is more than one of ethylene carbonate, ethylene carbonate, styrene carbonate, catechol carbonate, methyl amino carbonate, amino ethyl carbonate, vinyl acetate, acrylonitrile, 2-cyanofuran and sulfite compounds.
7. The preparation method of the carbon nanotube conductive agent slurry for the lithium ion battery negative electrode material according to claim 2, characterized in that: the sand mill is any one of a vertical sand mill, a horizontal sand mill, a double-cone rod type sand mill and a basket type sand mill, and the used dispersion medium is zirconia balls with the grain diameter of 1.0mm-1.5 mm.
8. The preparation method of the carbon nanotube conductive agent slurry for the lithium ion battery negative electrode material according to claim 2, characterized in that: the stirring tank is a propeller stirrer, a turbine stirrer or an anchor stirrer.
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| CN111697226B (en) * | 2020-06-23 | 2022-05-17 | 内蒙古中科四维热管理材料有限公司 | Preparation method of oily conductive agent slurry and electrode plate and assembly method of battery |
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| CN102709523A (en) * | 2012-06-13 | 2012-10-03 | 湖南丰源业翔晶科新能源股份有限公司 | Process for dispersing carbon nanotubes in electroconductive adhesive of lithium ion battery |
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Address after: 330000 No.278 luozhu Road, Xiaolan economic and Technological Development Zone, Nanchang County, Nanchang City, Jiangxi Province Patentee after: Jiangxi Nanotechnology Research Institute Address before: 330200 building 15, Xiaolan innovation and entrepreneurship base, No. 266, Huiren Avenue, Xiaolan economic and Technological Development Zone, Nanchang City, Jiangxi Province Patentee before: NANCHANG INSTITUTE, SUZHOU INSTITUTE OF NANO-TECH AND NANO-BIONICS, CAS |
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Effective date of registration: 20211208 Address after: 330000 No.278 luozhu Road, Xiaolan economic and Technological Development Zone, Nanchang County, Nanchang City, Jiangxi Province Patentee after: Nanchang Zhongke Yucheng Technology Development Co.,Ltd. Address before: 330000 No.278 luozhu Road, Xiaolan economic and Technological Development Zone, Nanchang County, Nanchang City, Jiangxi Province Patentee before: Jiangxi Nanotechnology Research Institute |
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Effective date of registration: 20211228 Address after: 330000 No.278 luozhu Road, Xiaolan economic and Technological Development Zone, Nanchang County, Nanchang City, Jiangxi Province Patentee after: Nanchang Xinsu nano material Co.,Ltd. Address before: 330000 No.278 luozhu Road, Xiaolan economic and Technological Development Zone, Nanchang County, Nanchang City, Jiangxi Province Patentee before: Nanchang Zhongke Yucheng Technology Development Co.,Ltd. |