CN111628175B - Conductive slurry based on carbon nano tube and preparation process thereof - Google Patents
Conductive slurry based on carbon nano tube and preparation process thereof Download PDFInfo
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- CN111628175B CN111628175B CN202010505051.5A CN202010505051A CN111628175B CN 111628175 B CN111628175 B CN 111628175B CN 202010505051 A CN202010505051 A CN 202010505051A CN 111628175 B CN111628175 B CN 111628175B
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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
Abstract
The invention discloses a conductive paste based on carbon nano tubes and a preparation process thereof, wherein the conductive paste is prepared by processing the following raw materials in parts by weight: 40-52 parts of active substance, 45-50 parts of solvent, 0.5-2 parts of binder, 0.5-1.3 parts of conductive agent and 1.5-3 parts of dispersant; according to the invention, the carbon nano tube is used as a conductive agent, the carbon nano tube is treated by concentrated sulfuric acid and concentrated nitric acid, the dispersibility of the carbon nano tube in substances such as a solvent and the like can be improved, impurities can be removed, then the carbon nano tube is used as a conductive agent to prepare conductive slurry, specifically, firstly, the surface treatment is carried out on an active substance to improve the dispersibility, the active substance and the conductive agent are uniformly dispersed by ball milling treatment, then, dispersion liquid is added into the active substance and the conductive agent, the active substance and the conductive agent are uniformly dispersed by ball milling to form uniformly dispersed slurry, and finally, the diluted slurry is stirred by a planetary stirrer to uniformly disperse the active substance and the conductive agent, so that the conductive slurry with the uniformly dispersed conductive agent is obtained.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to conductive slurry based on carbon nanotubes and a preparation process thereof.
Background
The lithium ion battery mainly comprises a positive plate, a negative plate and a diaphragm arranged between the positive plate and the negative plate, wherein the positive plate comprises a positive current collector and a positive diaphragm coated on the positive current collector, the negative plate comprises a negative current collector and a negative diaphragm coated on the negative current collector, the positive diaphragm and the negative diaphragm are formed by coating active slurry on the surface of the positive plate or the negative plate and then drying the active slurry, and the active slurry mainly comprises active substances, conductive agents and binders;
the carbon nano tube is a one-dimensional carbon nano material, has good electronic conductivity compared with the traditional conductive agent, and has less usage amount compared with the traditional conductive agent, so the energy density of the battery can be favorably improved.
Disclosure of Invention
The invention aims to provide a conductive paste based on carbon nanotubes and a preparation process thereof.
The technical problems to be solved by the invention are as follows:
the carbon nanotubes are easy to agglomerate and entangle, so that the carbon nanotubes cannot be uniformly dispersed, and the conductivity of the conductive paste is affected.
The purpose of the invention can be realized by the following technical scheme:
the conductive slurry based on the carbon nano tube is prepared by processing the following raw materials in parts by weight:
40-52 parts of active substance, 45-50 parts of solvent, 0.5-2 parts of binder, 0.5-1.3 parts of conductive agent and 1.5-3 parts of dispersant;
the binder is one of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose and polyacrylate;
the solvent is N-methyl pyrrolidone;
the dispersing agent is polyvinylpyrrolidone;
the active substance is one of lithium titanate, lithium nickel cobalt aluminum oxide, lithium nickel cobalt oxygen, lithium nickel cobalt manganese oxygen, cobalt lithium oxide and layered lithium manganate;
the preparation process of the conductive slurry based on the carbon nano tube comprises the following steps:
firstly, adding a binder and a dispersant into a solvent, stirring and mixing until the binder is dissolved to form a dispersion liquid for later use;
secondly, mixing active substances with absolute ethyl alcohol, adding the mixture into a ball milling tank, and wet milling for 2-6h at the rotating speed of 200-350r/min, wherein a layer of hydrophilic film can be formed on the surface of the lithium battery negative electrode material through mechanical shearing force, so that the hydrophilicity of the negative electrode material particles is improved, and the dispersion effect of the negative electrode material particles in water is improved;
thirdly, adding the conductive agent into a ball milling tank, wet-milling for 40-90min at the rotating speed of 240-540r/min to uniformly disperse the conductive agent and the active substance, supplementing the dispersion liquid prepared in the first step into the ball milling tank in the ball milling process, and keeping the mixed material of the conductive agent and the active substance in a slurry state, wherein the addition amount of the dispersion liquid is 20-50% of the total weight of the dispersion liquid;
and fourthly, adding the slurry obtained by the treatment in the previous step into the rest dispersion liquid, adding the mixture of the slurry and the dispersion liquid into a planetary stirrer, adjusting the revolution speed of the stirrer to be 25-30r/min and the rotation speed to be 450-plus-one 600r/min, continuously stirring for 5-10min, fully mixing the slurry obtained in the third step with the dispersion liquid, adjusting the rotation speed of the stirrer to be 1200-plus-one 1800r/min, keeping the revolution speed unchanged, continuously stirring for 60-95min to obtain mixed slurry, and finally removing bubbles generated by stirring through vacuum defoaming to obtain the conductive slurry based on the carbon nano tube.
According to the invention, firstly, inorganic active substances are subjected to surface treatment to improve the dispersibility of the active substances, and long-time ball milling treatment can avoid agglomeration of the active substances, so that the active substances and the conductive agent are uniformly dispersed, then, a dispersion liquid taking N-methyl pyrrolidone as a solvent is added into the active substances, and ball milling is carried out to form uniformly dispersed slurry of the active substances and the conductive agent in the dispersion liquid, and finally, the diluted slurry is stirred by a planetary stirrer to uniformly disperse the active substances and the conductive agent, so that the conductive slurry with the uniformly dispersed conductive agent is obtained.
The preparation method of the conductive agent comprises the following steps:
adding carbon nanotubes into deionized water, performing ultrasonic dispersion to obtain a carbon nanotube dispersion liquid, and adding mixed acid into the carbon nanotube dispersion liquid, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid is 3:1, the mass fraction of the carbon nanotubes in the carbon nanotube dispersion liquid is 5-16%, and the volume ratio of the carbon nanotube dispersion liquid to the mixed acid is 1: 3-6;
filtering and separating the carbon nanotubes in the previous step every 2-3h, adding the carbon nanotubes into mixed acid to enable the mixed acid to completely immerse the carbon nanotubes, performing ultrasonic dispersion treatment on the carbon nanotubes at intervals in the soaking process, filtering and separating the carbon nanotubes after replacing the mixed acid for 8-12 times to obtain the carbon nanotubes, circularly washing the carbon nanotubes to be neutral through deionized water, and drying the carbon nanotubes to obtain a conductive agent;
in the step, the carbon nano tube is treated by concentrated sulfuric acid and concentrated nitric acid, so that oxygen-containing polar groups such as hydroxyl, carboxyl and the like are grafted on the surface of the carbon nano tube, and thus the dispersibility of the carbon nano tube in substances such as a solvent and the like can be improved, impurities can be removed, and the activity of the carbon nano tube can be improved;
the invention has the beneficial effects that:
the invention takes carbon nano-tubes as a conductive agent, treats the carbon nano-tubes by concentrated sulfuric acid and concentrated nitric acid, leads the surface of the carbon nano-tubes to be grafted with oxygen-containing polar groups such as hydroxyl, carboxyl and the like, thus improving the dispersibility of the carbon nano-tubes in substances such as solvents and the like, simultaneously removing impurities and improving the activity of the carbon nano-tubes, then takes the carbon nano-tubes as the conductive agent to prepare conductive slurry, concretely, firstly carries out surface treatment on inorganic active substances to improve the dispersibility of the active substances, can avoid agglomeration of the active substances by long-time ball milling treatment, leads the active substances and the conductive agent to be uniformly dispersed, then adds dispersion liquid taking N-methyl pyrrolidone as the solvent into the active substances, ball-mills to form uniformly dispersed slurry of the active substances and the conductive agent in the dispersion liquid, and finally stirs the diluted slurry by a planetary stirrer, the active material and the conductive agent are uniformly dispersed, and thus the conductive paste with the uniformly dispersed conductive agent is obtained.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The conductive slurry based on the carbon nano tube is prepared by processing the following raw materials in parts by weight:
46 parts by weight of active substance, 50 parts by weight of solvent, 1.7 parts by weight of binder, 1 part by weight of conductive agent and 1.3 parts by weight of dispersant;
the binder is polyvinylidene fluoride;
the solvent is N-methyl pyrrolidone;
the dispersing agent is polyvinylpyrrolidone;
the active substance is lithium titanate.
The preparation process of the conductive slurry based on the carbon nano tube is characterized by comprising the following steps of:
firstly, adding a binder and a dispersant into a solvent, stirring and mixing until the binder is dissolved to form a dispersion liquid for later use;
secondly, mixing the active substance with absolute ethyl alcohol, adding the mixture into a ball milling tank, and wet-milling the mixture for 2 to 6 hours at the rotating speed of 300 r/min;
adding a conductive agent into a ball milling tank, carrying out wet milling for 60min at the rotating speed of 300r/min to uniformly disperse the conductive agent and the active substance, supplementing the dispersion liquid prepared in the first step into the ball milling tank in the ball milling process, and keeping the mixed material of the conductive agent and the active substance in a slurry state, wherein the addition amount of the dispersion liquid is 40% of the total weight of the dispersion liquid;
and fourthly, adding the slurry obtained by the treatment in the previous step into the rest dispersion liquid, adding the mixture of the slurry and the dispersion liquid into a planetary stirrer, adjusting the revolution speed of the stirrer to be 30r/min and the rotation speed to be 600r/min, continuously stirring for 8min to fully mix the slurry obtained in the third step with the dispersion liquid, adjusting the rotation speed of the stirrer to be 1200r/min, keeping the revolution speed unchanged, continuously stirring for 80min to obtain mixed slurry, and finally removing bubbles generated by stirring through vacuum defoaming to obtain the conductive slurry based on the carbon nano tubes.
The preparation method of the conductive agent comprises the following steps:
adding carbon nanotubes into deionized water, performing ultrasonic dispersion to obtain a carbon nanotube dispersion liquid, and adding mixed acid into the carbon nanotube dispersion liquid, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid is 3:1, the mass fraction of the carbon nanotubes in the carbon nanotube dispersion liquid is 7%, and the volume ratio of the carbon nanotube dispersion liquid to the mixed acid is 1: 4;
filtering and separating the carbon nano tube in the previous step every 2h, adding the carbon nano tube into the mixed acid to enable the mixed acid to completely immerse the carbon nano tube, performing ultrasonic dispersion treatment on the carbon nano tube at intervals in the soaking process, filtering and separating to obtain the carbon nano tube after changing the mixed acid for 12 times, circularly washing the carbon nano tube to be neutral through deionized water, and drying the carbon nano tube to obtain the conductive agent
Example 2
The conductive slurry based on the carbon nano tube is prepared by processing the following raw materials in parts by weight:
50 parts of active substance, 48 parts of solvent, 0.7 part of binder, 1.2 parts of conductive agent and 2.1 parts of dispersant;
the binder is one of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose and polyacrylate;
the solvent is N-methyl pyrrolidone;
the dispersing agent is polyvinylpyrrolidone;
the active substance is one of lithium titanate, lithium nickel cobalt aluminum oxide, lithium nickel cobalt oxygen, lithium nickel cobalt manganese oxygen, cobalt lithium oxide and layered lithium manganate.
The preparation process of the conductive slurry based on the carbon nano tube is characterized by comprising the following steps of:
firstly, adding a binder and a dispersant into a solvent, stirring and mixing until the binder is dissolved to form a dispersion liquid for later use;
secondly, mixing the active substance with absolute ethyl alcohol, adding the mixture into a ball milling tank, and wet-milling for 4 hours at the rotating speed of 300 r/min;
thirdly, adding the conductive agent into a ball milling tank, carrying out wet milling for 60min at the rotating speed of 480r/min to uniformly disperse the conductive agent and the active substance, supplementing the dispersion liquid prepared in the first step into the ball milling tank in the ball milling process, and keeping the mixed material of the conductive agent and the active substance in a slurry state, wherein the addition amount of the dispersion liquid is 40% of the total weight of the dispersion liquid;
and fourthly, adding the slurry obtained by the treatment in the previous step into the rest dispersion liquid, adding the mixture of the slurry and the dispersion liquid into a planetary stirrer, adjusting the revolution speed of the stirrer to be 30r/min and the rotation speed to be 480r/min, continuously stirring for 10min to fully mix the slurry obtained in the third step with the dispersion liquid, adjusting the rotation speed of the stirrer to be 1600r/min, keeping the revolution speed unchanged, continuously stirring for 90min to obtain mixed slurry, and finally removing bubbles generated by stirring through vacuum defoaming to obtain the conductive slurry based on the carbon nano tubes.
The preparation method of the conductive agent comprises the following steps:
adding carbon nanotubes into deionized water, performing ultrasonic dispersion to obtain a carbon nanotube dispersion liquid, and adding a mixed acid into the carbon nanotube dispersion liquid, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid is 3:1, the mass fraction of the carbon nanotubes in the carbon nanotube dispersion liquid is 12%, and the volume ratio of the carbon nanotube dispersion liquid to the mixed acid is 1: 6;
filtering and separating the carbon nano tube in the previous step every 2h, adding the carbon nano tube into the mixed acid to enable the mixed acid to completely immerse the carbon nano tube, performing ultrasonic dispersion treatment on the carbon nano tube at intervals in the soaking process, filtering and separating to obtain the carbon nano tube after changing the mixed acid for 12 times, circularly washing the carbon nano tube to be neutral through deionized water, and drying the carbon nano tube to obtain the conductive agent
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.
Claims (1)
1. The conductive slurry based on the carbon nano tube is prepared by processing the following raw materials in parts by weight:
40-52 parts of active substance, 45-50 parts of solvent, 0.5-2 parts of binder, 0.5-1.3 parts of conductive agent and 1.5-3 parts of dispersant;
the binder is one of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose and polyacrylate;
the solvent is N-methyl pyrrolidone;
the dispersing agent is polyvinylpyrrolidone;
the active substance is one of lithium titanate, lithium nickel cobalt aluminum oxide, lithium nickel cobalt oxygen, lithium nickel cobalt manganese oxygen, cobalt lithium oxide and layered lithium manganate;
the preparation process of the conductive paste based on the carbon nano tube comprises the following steps:
firstly, adding a binder and a dispersant into a solvent, stirring and mixing until the binder is dissolved to form a dispersion liquid for later use;
secondly, mixing the active substance with absolute ethyl alcohol, adding the mixture into a ball milling tank, and wet milling for 2-6h at the rotating speed of 200-350 r/min;
thirdly, adding the conductive agent into a ball milling tank, wet-milling for 40-90min at the rotating speed of 240-540r/min to uniformly disperse the conductive agent and the active substance, supplementing the dispersion liquid prepared in the first step into the ball milling tank in the ball milling process, and keeping the mixed material of the conductive agent and the active substance in a slurry state, wherein the addition amount of the dispersion liquid is 20-50% of the total weight of the dispersion liquid;
fourthly, adding the slurry obtained by the previous step into the rest dispersion liquid, adding the mixture of the slurry and the dispersion liquid into a planetary mixer, adjusting the revolution speed of the mixer to be 25-30r/min and the rotation speed to be 450-plus-material 600r/min, continuously stirring for 5-10min, fully mixing the slurry obtained in the third step with the dispersion liquid, adjusting the rotation speed of the mixer to be 1200-plus-material 1800r/min, keeping the revolution speed unchanged, continuously stirring for 60-95min to obtain mixed slurry, and finally removing bubbles generated by stirring through vacuum defoaming to obtain the conductive slurry based on the carbon nano tube;
the preparation method of the conductive agent comprises the following steps:
adding carbon nanotubes into deionized water, performing ultrasonic dispersion to obtain a carbon nanotube dispersion liquid, and adding mixed acid into the carbon nanotube dispersion liquid, wherein the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed acid is 3:1, the mass fraction of the carbon nanotubes in the carbon nanotube dispersion liquid is 5-16%, and the volume ratio of the carbon nanotube dispersion liquid to the mixed acid is 1: 3-6;
and (2) filtering and separating the carbon nanotube dispersion liquid in the previous step every 2-3h, adding the carbon nanotube dispersion liquid into the mixed acid to enable the mixed acid to completely immerse the carbon nanotubes, performing ultrasonic dispersion treatment on the carbon nanotubes at intervals in the soaking process, filtering and separating to obtain the carbon nanotubes after replacing the mixed acid for 8-12 times, circularly washing the carbon nanotubes to be neutral through deionized water, and drying the carbon nanotubes to obtain the conductive agent.
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| CN106611855A (en) * | 2015-10-22 | 2017-05-03 | 郑州比克电池有限公司 | Polymer lithium ion battery and positive electrode slurry therefor |
| CN106876715B (en) * | 2017-03-30 | 2020-03-17 | 湖北金泉新材料有限责任公司 | Carbon nanotube-containing anode slurry, preparation method and application thereof |
| CN107482220B (en) * | 2017-06-23 | 2020-07-14 | 深圳市德方纳米科技股份有限公司 | Conductive carbon slurry for lithium ion battery and preparation method and application thereof |
| CN107611375A (en) * | 2017-08-21 | 2018-01-19 | 深圳拓邦股份有限公司 | A kind of preparation method of lithium ion battery anode glue size |
| CN109167068B (en) * | 2018-09-17 | 2020-09-01 | 醒狮科技投资有限公司 | Lithium battery positive electrode slurry and processing technology thereof |
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