CN107706424B - Carbon nanotube conductive slurry, preparation method thereof and lithium ion battery - Google Patents
Carbon nanotube conductive slurry, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN107706424B CN107706424B CN201710914440.1A CN201710914440A CN107706424B CN 107706424 B CN107706424 B CN 107706424B CN 201710914440 A CN201710914440 A CN 201710914440A CN 107706424 B CN107706424 B CN 107706424B
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- carbon nanotubes
- tube diameters
- conductive paste
- nano tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a carbon nano tube conductive slurry, a preparation method thereof and a lithium ion battery. The carbon nano tube conductive slurry comprises the following components in percentage by mass of 100 percent: 0.5-10% of a conductive functional body; 0.1-5% of a dispersant; 85-97.5% of a solvent; the conductive functional body comprises a thick-caliber multi-wall carbon nano tube with the pipe diameter of 40-150 nm and a thin-caliber multi-wall carbon nano tube with the pipe diameter of 5-40 nm, the difference of the pipe diameters of the thick-caliber multi-wall carbon nano tube and the thin-caliber multi-wall carbon nano tube is not less than 20nm, the mass ratio of the thick-caliber multi-wall carbon nano tube to the thin-caliber multi-wall carbon nano tube is (8-2) - (2-8), and the pipe length of the thick-caliber multi-wall carbon nano tube and the thin-caliber multi-wall carbon nano tube. The carbon nanotube conductive slurry provided by the invention has the characteristics of uniform dispersion of carbon nanotubes, less sedimentation, no obvious layering, volume resistivity of about 50m omega cm, viscosity of less than 15000mPa & s, uniform conductive network and the like.
Description
Technical Field
The invention belongs to the technical field of conductive paste, and particularly relates to carbon nanotube conductive paste, a preparation method thereof and a lithium ion battery.
Background
The carbon nano tube is a one-dimensional tubular nano material formed by curling single-layer or multi-layer graphite, has higher electronic conductivity and lower consumption compared with the traditional conductive agent carbon black, acetylene black and the like, is favorable for improving the capacity of the battery, prolonging the cycle life of the battery and particularly improving the high-rate charge-discharge performance of the battery, and has attractive application prospect in the aspect of the conductive agent of the lithium ion power battery. As such, carbon nanotubes have become one of the major directions in the development of lithium ion battery conductive agents. In practical application, the carbon nanotubes are overlapped in a cross way to form a staggered network to transmit electrons, so that the conduction is realized, and in the network, the carbon nanotubes are contacted with each other, or the carbon nanotubes are compounded with other substances with conductive characteristics to be contacted with each other, so that the carbon nanotubes effectively improve the large-current discharge capacity of the battery.
However, due to the existence of strong van der waals force between the layers of the carbon nanotubes and the nature of large specific surface area and high aspect ratio of the carbon nanotubes, the carbon nanotubes are in an agglomerated form in many cases and are difficult to be uniformly dispersed in the material.
At present, chemical methods and physical methods are adopted in the market to disperse the carbon nanotubes. The chemical method is mainly to treat with strong oxidizing acid to obtain carbon nanotubes with good dispersibility, but the method can damage the structure of the carbon nanotubes and influence the conductivity of the carbon nanotubes. The physical method adopts ultrasonic treatment or ball mill dispersion, but the method has low production efficiency and poor dispersion effect. The current carbon nanotube conductive slurry used in a battery factory has a relatively high viscosity which is larger than 30000mPa & s, which causes inconvenience in subsequent processing and use, and the current solvent used for the carbon nanotube conductive slurry is N-methyl pyrrolidone, which has a large smell and strong irritation and can corrode human skin. And if the viscosity is less than 30000mPa.S, the problems of carbon nanotube sedimentation, slurry separation and delamination and the like can occur during standing.
Disclosure of Invention
Aiming at the problems of poor dispersing effect, sedimentation during standing, separation and layering and the like of the existing carbon nano tube conductive slurry, the invention provides the carbon nano tube conductive slurry and the preparation method thereof.
Furthermore, the invention also provides a lithium ion battery.
The invention is realized by the following steps:
the carbon nanotube conductive paste comprises the following components in percentage by mass of 100 percent:
0.5 to 10 percent of conductive functional body;
0.1 to 5 percent of dispersant;
85% -97.5% of solvent;
the conductive functional body is composed of multi-walled carbon nanotubes with thick tube diameters and thin tube diameters, wherein the tube diameters of the multi-walled carbon nanotubes with the thick tube diameters are 40 nm-150 nm, the tube diameters of the multi-walled carbon nanotubes with the thin tube diameters are 5 nm-40 nm, the difference value between the tube diameters of the multi-walled carbon nanotubes with the thick tube diameters and the tube diameters of the multi-walled carbon nanotubes with the thin tube diameters is larger than or equal to 20nm, the mass ratio of the multi-walled carbon nanotubes with the thick tube diameters to the multi-walled carbon nanotubes with the thin tube diameters is (8-2): 2-8), and the tube lengths of the multi-walled carbon nanotubes with the thick tube diameters and the thin tube diameters are 30.
Correspondingly, the preparation method of the carbon nanotube conductive paste at least comprises the following steps:
step S01, mixing a dispersing agent and a solvent to uniformly mix the dispersing agent and the solvent;
s02, adding a conductive functional body into the mixed solution obtained in the step S01 under the stirring condition, and performing pre-dispersion to obtain a premix;
and S03, grinding the premix to obtain the carbon nano tube conductive slurry.
Furthermore, the lithium ion battery comprises a negative electrode material and a positive electrode material, wherein the conductive agent of the negative electrode material or the positive electrode material is prepared from the carbon nanotube conductive paste or the carbon nanotube conductive paste prepared by the preparation method of the carbon nanotube conductive paste.
Compared with the prior art, the carbon nanotube conductive slurry provided by the invention has the characteristics that the carbon nanotubes are uniformly dispersed, the solid content change of upper and lower layers is small after standing for 90 days, the sedimentation is less, no obvious layering phenomenon exists, the volume resistivity is about 50m omega-cm, the viscosity is only 5000-15000 mPa & s, the conductive network is uniform, and the like. The functional electric conductor is a mixture of multi-walled carbon nanotubes with different pipe diameters, the prepared conductive paste has a good conductive network, so that the contact surfaces of the carbon nanotubes and the anode active material and the cathode active material of the lithium ion battery are wider, more conductive bridge channels are formed, and the conductivity of the lithium ion battery is further improved.
The preparation method of the carbon nanotube conductive paste provided by the invention has the advantages that the process is simple and feasible, the structure of the carbon nanotube is not damaged, the prepared carbon nanotube conductive paste has relatively low viscosity and excellent conductivity, the paste has good stability after standing for 3 months, the phenomenon of layering or separation does not occur, the property is stable and uniform, and the preparation method is suitable for large-scale industrial production.
The carbon nano tube conductive paste provided by the invention has the characteristics of low viscosity, good conductivity, no layering and no precipitation after standing and the like, so that when the carbon nano tube conductive paste is used as a conductive agent for a positive electrode material and a negative electrode material of a lithium ion battery, the preparation of the positive electrode material and the negative electrode material is time-saving and labor-saving, the conductivity of the obtained lithium ion battery is good, and the lithium ion battery can show excellent cycle performance.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM image of a conventional carbon nanotube conductive paste;
FIG. 2 is an SEM image of the carbon nanotube conductive paste prepared in example 7 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a carbon nano tube conductive slurry.
The carbon nano tube conductive slurry comprises the following components in percentage by mass of 100 percent:
0.5 to 10 percent of conductive functional body;
0.1 to 5 percent of dispersant;
85% -97.5% of solvent;
the conductive functional body is composed of multi-walled carbon nanotubes with thick tube diameters and thin tube diameters, wherein the tube diameters of the multi-walled carbon nanotubes with the thick tube diameters are 40 nm-150 nm, the tube diameters of the multi-walled carbon nanotubes with the thin tube diameters are 5 nm-40 nm, the difference value between the tube diameters of the multi-walled carbon nanotubes with the thick tube diameters and the tube diameters of the multi-walled carbon nanotubes with the thin tube diameters is larger than or equal to 20nm, the mass ratio of the multi-walled carbon nanotubes with the thick tube diameters to the multi-walled carbon nanotubes with the thin tube diameters is (8-2): 2-8), and the tube lengths of the multi-walled carbon nanotubes with the thick tube diameters and the thin tube diameters are 30.
The carbon nanotube conductive paste of the present invention is further explained below.
In any embodiment, the conductive paste mainly contains carbon nanotubes, and the conductive paste is prevented from agglomerating as shown in fig. 1 by the combination of the carbon nanotubes with different tube diameters.
Preferably, the mass ratio of the thick-caliber multi-walled carbon nanotubes to the thin-caliber multi-walled carbon nanotubes is 4: 6-6: 4. Under the mixture ratio, the obtained carbon nano tube conductive slurry has no agglomeration phenomenon as shown in figure 1, and has no obvious slurry layering and no carbon nano tube precipitation problem after standing for 3 months.
In the present invention, the dispersant is mainly used to disperse the carbon nanotubes in the solvent. Preferably, the dispersant is at least one of polyvinylpyrrolidone, polyvinyl alcohol, a polyoxy acrylate copolymer, polyvinylidene fluoride, polyethylene glycol octyl phenyl ether, a polyoxyethylene polyoxypropylene block copolymer, sodium carboxymethyl cellulose, sodium dodecyl sulfate and sodium dodecyl sulfate.
Preferably, the solvent is one or more of methyl 3-methoxypropionate, ethylene glycol diacetate and propylene glycol diacetate. The selected solvents belong to novel environment-friendly solvents, have very low odor, are medium-boiling-point solvents, and have very small irritation and corrosiveness on human skin.
Further preferably, on the premise that the mass ratio of the thick-caliber multi-walled carbon nanotubes to the thin-caliber multi-walled carbon nanotubes is 4: 6-6: 4, the solvent is prepared from 3-methoxypropionic acid methyl ester, ethylene glycol diacetate and propylene glycol diacetate according to the mass ratio of 1: 1: 1, and mixing. Under the conditions, the carbon nanotubes in the obtained carbon nanotube conductive slurry are fully dispersed to form a three-dimensional netted conductive grid as shown in fig. 2; importantly, after standing for 3 months, the solid content of the upper layer and the lower layer of the slurry changes by less than 0.6%, the layering is extremely tiny, the precipitation phenomenon does not occur, the volume resistivity is only 46 +/-1 m omega-cm, the viscosity change rate is not more than 60%, and the property is stable.
The carbon nanotube conductive slurry provided by the embodiment of the invention has the characteristics that the carbon nanotubes are uniformly dispersed, the solid content change of the upper layer and the lower layer is small when the carbon nanotube conductive slurry is kept still for 90 days, the sedimentation is less, the obvious layering phenomenon does not exist, the volume resistivity is about 50m omega cm, the viscosity is only 5000-15000 mPa & s, the conductive network is uniform, and the like. And because the functional electric conductor is a mixture of multi-walled carbon nanotubes with different pipe diameters, the obtained conductive paste has a good conductive network, so that the contact surfaces of the carbon nanotubes and the anode active material and the cathode active material of the lithium ion battery are wider, more conductive bridge channels are formed, and the conductivity of the anode and the cathode of the lithium ion battery is further improved.
The invention further provides a preparation method of the carbon nano tube conductive slurry on the premise of providing the carbon nano tube conductive slurry.
In one embodiment, the method for preparing the carbon nanotube conductive paste at least comprises the following steps:
step S01, mixing a dispersing agent and a solvent to uniformly mix the dispersing agent and the solvent;
s02, adding a conductive functional body into the mixed solution obtained in the step S01 under the stirring condition, and performing pre-dispersion to obtain a premix;
and S03, grinding the premix to obtain the carbon nano tube conductive slurry.
In order to better understand the preparation method, the preparation method is further explained below.
In step S01, the dispersant and the solvent are mixed, so that the preparation time of the slurry can be saved, and the carbon nanotubes can be uniformly dispersed in the mixed solution formed by the dispersant and the solvent. When the dispersant and the solvent are mixed, the stirring speed is 3000 r/min-5000 r/min, and the stirring time is 5 s-30 s.
In step S02, when the mixed solution of the carbon nano tube, the dispersant and the solvent is pre-dispersed, the stirring speed is 5000r/min to 8000r/min, and the stirring time is 10min to 20min, thus obtaining the premix.
In step S03, the grinding process is performed by sanding, and the sanding time is 1min to 120 min. Specifically, a sand mill is used for sanding, and the conductive slurry containing a plurality of spherical or strip-shaped carbon nanotube aggregates with the particle size of 5-20 microns is obtained through sanding of the sand mill.
More specifically, the sand mill is a turbine type sand mill, and in the sanding process, the rotating speed of the sand mill is controlled to be 500-2500 r/min.
The grinding medium in the sand mill is any one or more of zirconium dioxide beads, zirconium silicate beads, aluminum dioxide beads and steel balls, and the particle size of the grinding medium is 0.5-3.0 mm.
The preparation method of the carbon nanotube conductive paste provided by the invention has the advantages that the process is simple and feasible, the structure of the carbon nanotube is not damaged, the prepared carbon nanotube conductive paste has relatively low viscosity and excellent conductivity, the paste has good stability after standing for 3 months, the phenomenon of layering or separation does not occur, the property is stable and uniform, and the preparation method is suitable for large-scale industrial production.
Correspondingly, the invention further provides the lithium ion battery.
In an embodiment, the lithium ion battery includes a negative electrode material and a positive electrode material, and the conductive agent of the negative electrode material or the positive electrode material is made of the carbon nanotube conductive paste or the carbon nanotube conductive paste prepared by the preparation method of the carbon nanotube conductive paste.
Other positive electrode materials, negative electrode materials, separators and electrolytes of the lithium ion battery are well known in the art, and a detailed description thereof is omitted for brevity.
The carbon nano tube conductive paste provided by the invention has the characteristics of low viscosity, good conductivity, no layering and no precipitation after standing and the like, so that when the carbon nano tube conductive paste is used as a conductive agent for a positive electrode material and a negative electrode material of a lithium ion battery, the preparation of the positive electrode material and the negative electrode material is time-saving and labor-saving, the conductivity of the obtained lithium ion battery is good, and the lithium ion battery can show excellent cycle performance.
In order to better explain the technical solution of the present invention, the following description is made with reference to a plurality of specific examples.
Example 1
A carbon nanotube conductive paste comprises the following components:
wherein the diameter of the thin-caliber multi-walled carbon nanotube is 5-40 nm, and the length of the thin-caliber multi-walled carbon nanotube is 30-100 mu m; the diameter of the thick-diameter multi-wall carbon nano tube is 60-150 nm, and the length of the tube is 30-100 mu m.
The preparation method of the carbon nano tube conductive slurry comprises the following steps:
(1) adding 9.35kg of methyl 3-methoxypropionate as a solvent carrier into a 15L container, and adding 0.15kg of polyvinylpyrrolidone as a dispersant;
(2) fully dissolving polyvinylpyrrolidone into 3-methoxy methyl propionate by using a high-speed stirrer under the condition of 5000r/min to obtain a mixed solution;
(3) adding 0.2kg of thin-caliber multi-walled carbon nanotubes and 0.3kg of thick-caliber multi-walled carbon nanotubes into the dissolved mixed solution, and stirring for 20min under the condition that the rotating speed of a stirrer is 5000r/min to obtain pre-dispersed slurry;
(4) and adding the pre-dispersed slurry into a turbine sand mill, wherein ball milling beads of the turbine sand mill are zirconia beads with the diameter of 1.5mm, and grinding for 3 hours at 2200r/min to obtain the carbon nano tube conductive slurry.
Example 2
A carbon nanotube conductive paste comprises the following components:
wherein the diameter of the thin-caliber multi-walled carbon nanotube is 5-40 nm, and the length of the thin-caliber multi-walled carbon nanotube is 30-100 mu m; the diameter of the thick-diameter multi-wall carbon nano tube is 60-150 nm, and the length of the tube is 30-100 mu m.
The preparation method of the carbon nano tube conductive slurry comprises the following steps:
(1) 4.675kg of methyl 3-methoxypropionate and 4.675kg of ethylene glycol diacetate as solvent carriers were charged in a 15L vessel, to which 0.15kg of polyvinylpyrrolidone as a dispersant was added;
(2) fully dissolving polyvinylpyrrolidone into 3-methoxy methyl propionate and ethylene glycol diacetate by using a high-speed stirrer under the condition of 5000r/min to obtain a mixed solution;
(3) adding 0.2kg of thin-caliber multi-walled carbon nanotubes and 0.3kg of thick-caliber multi-walled carbon nanotubes into the dissolved mixed solution, and stirring for 20min under the condition that the rotating speed of a stirrer is 5000r/min to obtain pre-dispersed slurry;
(4) and adding the pre-dispersed slurry into a turbine sand mill, wherein ball milling beads of the turbine sand mill are zirconia beads with the diameter of 1.5mm, and grinding for 3 hours at 2200r/min to obtain the carbon nano tube conductive slurry.
Example 3
A carbon nanotube conductive paste comprises the following components:
wherein the diameter of the thin-caliber multi-walled carbon nanotube is 5-40 nm, and the length of the thin-caliber multi-walled carbon nanotube is 30-100 mu m; the diameter of the thick-diameter multi-wall carbon nano tube is 60-150 nm, and the length of the tube is 30-100 mu m.
The preparation method of the carbon nano tube conductive slurry comprises the following steps:
(1) 4.675kg of methyl 3-methoxypropionate and 4.675kg of propylene glycol diacetate as solvent carriers were charged in a 15L vessel, to which 0.15kg of polyvinylpyrrolidone as a dispersant was added;
(2) fully dissolving polyvinylpyrrolidone into methyl 3-methoxypropionate and propylene glycol diacetate by using a high-speed stirrer under the condition of 5000r/min to obtain a mixed solution;
(3) adding 0.2kg of thin-caliber multi-walled carbon nanotubes and 0.3kg of thick-caliber multi-walled carbon nanotubes into the dissolved mixed solution, and stirring for 20min under the condition that the rotating speed of a stirrer is 5000r/min to obtain pre-dispersed slurry;
(4) and adding the pre-dispersed slurry into a turbine sand mill, wherein ball milling beads of the turbine sand mill are zirconia beads with the diameter of 1.5mm, and grinding for 3 hours at 2200r/min to obtain the carbon nano tube conductive slurry.
Since the preparation methods of the present invention are basically the same, and the small changes in the stirring speed and the stirring time do not greatly affect the performance of the carbon nanotube conductive paste, the formulations of the carbon nanotube conductive pastes of examples 1 to 12 and comparative examples 1 to 4 are listed in table 1 to save space.
TABLE 1 formulation of carbon nanotube conductive paste for examples 1-12 and comparative examples 1-4
In order to verify the properties of the carbon nanotube conductive pastes prepared in examples 1 to 12 and comparative examples 1 to 4, the following tests were performed on the products prepared in examples 1 to 12 and comparative examples 1 to 4:
(1) and testing solid content, fineness, appearance and viscosity, wherein the testing comprises the steps of preparing the solid content after standing for 1 day and standing for 3 months to obtain the solid content of an upper layer and a lower layer, specifically, after standing for 1 day, testing the solid content, sealing and storing the solid content by using a bottle, and then standing the solid content in an indoor common environment for 3 months. And when the conductive paste is placed for 3 months, measuring the fineness of the conductive paste, and observing whether a solution is separated out from the surface, the solid contents of the upper layer and the lower layer and the viscosity. Specific results are shown in table 2;
(2) and (3) volume resistivity test: the test was carried out according to the standard method of GB/T33818-2017, and the test results are shown in Table 2.
TABLE 2 tables of Performance data of the carbon nanotube conductive pastes of examples 1 to 12 and comparative examples 1 to 4
As can be seen from tables 1 and 2:
(1) in examples 1, 4 and 5, after standing for 3 months, the obtained carbon nanotube conductive paste is easy to slightly precipitate under the conditions of two multi-wall carbon nanotubes with different tube diameters and addition of a single solvent, the solid content change rate of an upper layer and a lower layer is between 1.4% and 6.5%, the viscosity change rate is about 200%, and the volume resistivity is more than 56m omega cm;
(2) in examples 7, 9, and 11, in the case of two multi-walled carbon nanotubes with different tube diameters and three solvents, after standing for 3 months, the solid content change rates of the upper layer and the lower layer are both less than 0.6%, the viscosity change rate is both less than 60%, and the volume resistivity is less than 50m Ω · cm, the performance of the carbon nanotube conductive paste is more superior to other performances, and SEM scanning is performed on the carbon nanotube conductive paste obtained in example 7, specifically as shown in fig. 2, it can be seen from fig. 2 that the coarse and fine multi-walled carbon nanotubes are uniformly dispersed and do not agglomerate;
(3) in the examples 2 and 3, under the condition that two kinds of multi-wall carbon nanotubes with different tube diameters and two kinds of solvents are added, after standing for 3 months, the solid content change rate of the upper layer and the lower layer is between 5.6% and 10%, the viscosity change rate is more than 200%, and the volume resistivity is more than 56m omega cm;
(3) in examples 6 and 8, under the condition that the input amount of two multi-walled carbon nanotubes with different tube diameters is the same and one or two solvents are added, after standing for 3 months, the solid content change rate of the upper layer and the lower layer is between 4.7% and 6.7%, a precipitation phenomenon exists, the viscosity change rate is within 150% to 200%, and the volume resistivity is more than 50m omega.cm;
(4) in examples 2, 3 and 10, under the condition that two kinds of multi-wall carbon nanotubes with different tube diameters are added and two kinds of solvents are added, after standing for 3 months, the solid content change rate of the upper layer and the lower layer is between 5.6% and 10%, the viscosity change rate is about 200%, and the volume resistivity is more than 56m omega cm;
(5) compared with examples 7, 9 and 11 and 12, in the case of two kinds of multi-wall carbon nanotubes with different tube diameters and two kinds of solvents, after standing for 3 months, the solid content change rate of the upper layer and the lower layer of the examples 7, 9 and 11 is less than 0.6%, no precipitation exists, the viscosity change rate is less than 60%, the volume resistivity is less than 50m omega.cm, while the volume resistivity of the example 12 is more than 50m omega.cm, and the solid content is more than 1.0% although no precipitation exists;
(6) in comparative examples 1-4, under the condition of single-caliber multi-wall carbon nano-tubes and the addition of a single solvent, after standing for 3 months, the solid content change rate of the upper layer and the lower layer is between 5.6% and 10%, the viscosity change rate is about 200%, and the volume resistivity is greater than 56m omega.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A carbon nanotube conductive paste, characterized in that: the carbon nano tube conductive slurry comprises the following components in percentage by mass of 100 percent:
0.5 to 10 percent of conductive functional body;
0.1 to 5 percent of dispersant;
85% -97.5% of solvent;
the conductive functional body consists of multi-walled carbon nanotubes with thick tube diameters and thin tube diameters, wherein the tube diameters of the multi-walled carbon nanotubes with the thick tube diameters are 40 nm-150 nm, the tube diameters of the multi-walled carbon nanotubes with the thin tube diameters are 5 nm-40 nm, the difference value between the tube diameters of the multi-walled carbon nanotubes with the thick tube diameters and the tube diameters of the multi-walled carbon nanotubes with the thin tube diameters is more than or equal to 20nm, and the tube lengths of the multi-walled carbon nanotubes with the thick tube diameters and the thin tube diameters are 30 mu m-100 mu m; the mass ratio of the large-caliber multi-walled carbon nanotubes to the small-caliber multi-walled carbon nanotubes is 4: 6-6: 4, and the solvent is prepared from 3-methoxypropionic acid methyl ester, ethylene glycol diacetate and propylene glycol diacetate according to the mass ratio of 1: 1: 1, and mixing.
2. The carbon nanotube conductive paste of claim 1, wherein: the dispersing agent is at least one of polyvinylpyrrolidone, polyvinyl alcohol, a polyoxyethylene acrylate copolymer, polyvinylidene fluoride, polyethylene glycol octyl phenyl ether, a polyoxyethylene polyoxypropylene block copolymer, sodium carboxymethylcellulose, sodium dodecyl sulfate and sodium dodecyl sulfate.
3. A method for preparing the carbon nanotube conductive paste according to any one of claims 1 to 2, wherein: at least comprises the following steps:
step S01, mixing a dispersing agent and a solvent to uniformly mix the dispersing agent and the solvent;
s02, adding a conductive functional body into the mixed solution obtained in the step S01 under the stirring condition, and performing pre-dispersion to obtain a premix;
and S03, grinding the premix to obtain the carbon nano tube conductive slurry.
4. The method for preparing the carbon nanotube conductive paste according to claim 3, wherein: the grinding treatment mode is sanding, and the sanding time is 1-120 min.
5. The method for producing the carbon nanotube conductive paste according to any one of claims 3 to 4, wherein: the grinding medium for grinding is any one or more of zirconium dioxide beads, zirconium silicate beads, aluminum dioxide beads and steel balls, and the particle size of the grinding medium is 0.5-3.0 mm.
6. A lithium ion battery comprises a negative electrode material and a positive electrode material, and is characterized in that: the conductive agent of the negative electrode material or the positive electrode material is prepared from the carbon nanotube conductive paste of any one of claims 1 to 2 or the carbon nanotube conductive paste prepared by the preparation method of the carbon nanotube conductive paste of any one of claims 3 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710914440.1A CN107706424B (en) | 2017-09-30 | 2017-09-30 | Carbon nanotube conductive slurry, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710914440.1A CN107706424B (en) | 2017-09-30 | 2017-09-30 | Carbon nanotube conductive slurry, preparation method thereof and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107706424A CN107706424A (en) | 2018-02-16 |
| CN107706424B true CN107706424B (en) | 2021-05-07 |
Family
ID=61175680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710914440.1A Active CN107706424B (en) | 2017-09-30 | 2017-09-30 | Carbon nanotube conductive slurry, preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107706424B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111028982A (en) * | 2018-10-10 | 2020-04-17 | 东北林业大学 | Preparation method of carbon nano tube conductive slurry |
| CN110380016A (en) * | 2019-06-04 | 2019-10-25 | 深圳烯湾科技有限公司 | Carbon nanotube aqueous slurry, carbon nanotube silicon carbon material and preparation method thereof |
| CN110343270A (en) * | 2019-07-05 | 2019-10-18 | 深圳烯湾科技有限公司 | A kind of preparation method of carbon nanotube anti-static material, slurry and film and film |
| CN110473653B (en) * | 2019-07-26 | 2021-01-05 | 深圳烯湾科技有限公司 | High-carbon-content carbon nanotube conductive slurry and preparation method thereof |
| CN110491546A (en) * | 2019-07-26 | 2019-11-22 | 深圳烯湾科技有限公司 | Carbon nanotube conducting slurry and preparation method thereof |
| CN110600741B (en) * | 2019-08-29 | 2020-10-30 | 厦门劦能科技有限公司 | Production process of lithium battery anode composite conductive slurry |
| CN112161900B (en) * | 2020-09-23 | 2022-12-09 | 东莞瑞泰新材料科技有限公司 | Method for rapidly measuring anti-settling property of graphene slurry |
| CN113035407B (en) * | 2021-02-27 | 2023-07-07 | 河南克莱威纳米碳材料有限公司 | Carbon nano tube compound conductive slurry for lithium ion battery and preparation method thereof |
| CN113571256A (en) * | 2021-07-22 | 2021-10-29 | 哈尔滨万鑫石墨谷科技有限公司 | Aqueous carbon nanotube slurry and preparation method and application thereof |
| CN114122403A (en) * | 2021-11-19 | 2022-03-01 | 江苏海基新能源股份有限公司 | Lithium ion battery anode slurry, anode plate and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1588679A (en) * | 2004-08-09 | 2005-03-02 | 深圳市纳米港有限公司 | Lithium ion secondary cell positive pole material and its preparing method |
| CN106229032A (en) * | 2016-08-03 | 2016-12-14 | 深圳市三顺中科新材料有限公司 | A kind of composite conducting slurry of lithium ion battery plus-negative plate and preparation method thereof |
-
2017
- 2017-09-30 CN CN201710914440.1A patent/CN107706424B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1588679A (en) * | 2004-08-09 | 2005-03-02 | 深圳市纳米港有限公司 | Lithium ion secondary cell positive pole material and its preparing method |
| CN106229032A (en) * | 2016-08-03 | 2016-12-14 | 深圳市三顺中科新材料有限公司 | A kind of composite conducting slurry of lithium ion battery plus-negative plate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107706424A (en) | 2018-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107706424B (en) | Carbon nanotube conductive slurry, preparation method thereof and lithium ion battery | |
| CN112331380B (en) | Composite conductive slurry and preparation method and application thereof | |
| CN106207094B (en) | A kind of lithium battery graphene conductive slurry and preparation method thereof | |
| CN102195032B (en) | Method for preparing lithium ion battery pole pieces | |
| CN110970620B (en) | Preparation method of high-stability graphene/carbon nanotube composite conductive slurry | |
| CN107492661B (en) | Graphene lithium battery conductive slurry and preparation method thereof | |
| CN109216700A (en) | A kind of lithium ion battery combined conductive agent and preparation method thereof | |
| CN109962240A (en) | Method for preparing anode slurry for lithium carbon fluoride battery with carbon nanotube as conductive agent | |
| WO2017031943A1 (en) | Method for preparing negative electrode paste for high-capacity silica-powder-doped lithium battery | |
| WO2016169289A1 (en) | Method for preparing lithium ion battery negative electrode slurry | |
| CN108963227A (en) | Conducting polymer coated Si composite carbon nanometer tube negative electrode material and its preparation method and application | |
| CN113035407B (en) | Carbon nano tube compound conductive slurry for lithium ion battery and preparation method thereof | |
| CN112803025B (en) | Preparation method of single-walled carbon nanotube conductive slurry, lithium ion battery negative electrode material and preparation method thereof | |
| CN110350161B (en) | Preparation method of silicon-carbon negative electrode precursor | |
| WO2017032166A1 (en) | Preparation method for lithium battery negative-electrode slurry doped with tin powder | |
| CN112186140B (en) | Silicon-based active composite conductive slurry applied to silicon-carbon cathode and cathode slurry mixing method | |
| CN107768637A (en) | A kind of preparation method of porous graphene/carbon nanotube lithium sulphur positive electrode | |
| CN112151801A (en) | Lithium ion battery anode slurry and preparation method thereof | |
| CN108091878A (en) | A kind of preparation method of lithium-sulfur cell graphene carbon nanotube composite conducting skeleton | |
| CN105591082A (en) | Nano sheet-shaped lithium titanate and multi-wall carbon nano tube composite material and preparation method thereof | |
| CN108511760A (en) | A kind of lithium battery conductive agent and preparation method thereof | |
| CN106450326B (en) | A kind of high dispersive graphene conductive powder and its application in lithium battery | |
| CN108878888A (en) | A kind of anode slice of lithium ion battery | |
| CN108511692A (en) | A kind of lithium ion cell electrode and preparation method thereof | |
| CN109713308B (en) | CNT-containing aqueous lithium battery slurry and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |