CN110634591B - Conductive paste, preparation method and application thereof, and battery - Google Patents

Conductive paste, preparation method and application thereof, and battery Download PDF

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CN110634591B
CN110634591B CN201910931424.2A CN201910931424A CN110634591B CN 110634591 B CN110634591 B CN 110634591B CN 201910931424 A CN201910931424 A CN 201910931424A CN 110634591 B CN110634591 B CN 110634591B
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conductive material
minimally invasive
carbonaceous
conductive
carbonaceous conductive
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CN110634591A (en
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马力
马贺然
王滨
周建辉
杨永旺
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Anhui Xinminhui New Material Technology Co ltd
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Xinao Graphene Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses conductive paste, a preparation method and application thereof, and a battery, relates to the technical field of batteries, and aims to reduce the viscosity of the conductive paste and solve the problem of performance reduction of the battery caused by adding excessive viscosity modifier in the preparation process. The preparation method of the conductive paste provided by the invention comprises the following steps: providing a carbonaceous conductive material, wherein the carbonaceous conductive material at least comprises carbon nano tubes; forming defects on the tube wall of the carbon nano tube included in the carbon conductive material to obtain the minimally invasive carbon conductive material; the conductive slurry is prepared by taking minimally invasive carbonaceous conductive materials as conductive agents. The invention is used for batteries.

Description

Conductive paste, preparation method and application thereof, and battery
Technical Field
The invention relates to the technical field of batteries, in particular to conductive paste, a preparation method and application thereof and a battery.
Background
A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. The material has the characteristics of higher energy density, good cycle performance, no memory effect and the like, and becomes the focus of attention of researchers in recent years. Among them, the positive electrode material of the lithium ion battery is generally transition metal oxide or transition metal phosphate, and the conductivity of the transition metal oxide or transition metal phosphate is low, so in order to improve the conductivity of the lithium ion battery, a conductive agent must be added in the electrode preparation process.
At present, in order to improve the energy density, rate capability, cycle life and other properties of a lithium ion battery, a carbon nanotube with a large specific surface area and a high purity is generally selected to prepare a conductive slurry. However, when the carbon nanotubes with large specific surface area and high purity are used as raw materials to prepare the conductive paste, the viscosity of the conductive paste is extremely high, and a large amount of viscosity modifier needs to be added, thereby causing the performance of the lithium ion battery to be reduced.
Disclosure of Invention
The invention aims to provide conductive paste, a preparation method and application thereof and a battery, so as to reduce the viscosity of the conductive paste and solve the problem of performance reduction of the battery caused by adding excessive viscosity regulator in the preparation process.
In order to achieve the above object, the present invention provides a method for preparing conductive paste, comprising: providing a carbonaceous conductive material, wherein the carbonaceous conductive material at least comprises carbon nanotubes; forming defects on the tube wall of the carbon nano tube included in the carbonaceous conductive material to obtain a minimally invasive carbonaceous conductive material; and preparing the conductive slurry by using the minimally invasive carbonaceous conductive material as a conductive agent.
Compared with the prior art, in the preparation method of the conductive paste provided by the invention, before the conductive paste is prepared by using the carbonaceous conductive material comprising the carbon nano tubes, the tube walls of the carbon nano tubes contained in the carbonaceous conductive material are damaged, so that the tube walls of the carbon nano tubes form local defects, and the minimally invasive carbonaceous conductive material is obtained. Therefore, the tube wall of the carbon nano tube contained in the minimally invasive carbonaceous conductive material forms local defects, and the local defects are presented in the form of wall holes on the tube wall of the carbon nano tube. When the wall of the carbon nanotube has the wall hole, the liquid entering the carbon nanotube can flow out from the wall hole of the side wall, so that the liquid absorption of the carbon nanotube is reduced, and therefore, compared with the viscosity of the conductive paste prepared from the carbon nanotube paste with larger specific surface area and higher purity, the viscosity of the conductive paste prepared from the minimally invasive carbonaceous conductive material containing the carbon nanotube with the wall hole as the conductive agent is lower. In addition, since the specific surface area of the carbon nanotubes having wall holes is reduced and the van der waals force between the carbon nanotubes having wall holes is low as compared with the carbon nanotubes having no wall holes, the viscosity of the conductive paste prepared using the minimally invasive carbonaceous conductive material containing the carbon nanotubes having wall holes as a conductive agent is low as compared with the viscosity of the conductive paste prepared using the carbon nanotube paste having a large specific surface area and a high purity.
Therefore, in the preparation method of the conductive paste provided by the embodiment of the invention, the liquid absorption property of the carbon nanotubes contained in the minimally invasive carbonaceous conductive material is lower, the van der waals force between the carbon nanotubes contained in the minimally invasive carbonaceous conductive material is lower, and the problem of viscosity increase of the conductive paste caused by adding the carbon nanotubes with larger specific surface area and higher purity can be effectively relieved.
In addition, in the preparation method of the conductive paste provided by the invention, the liquid absorption of the carbon nanotubes contained in the minimally invasive carbonaceous conductive material is low, and the van der waals force between the carbon nanotubes is low, so that in the process of preparing the conductive paste by using the minimally invasive carbonaceous conductive material as a conductive agent, the components of the conductive paste can be added at one time in the grinding process, the viscosity of the conductive paste can be kept stable in the grinding process, and the phenomenon that the viscosity obviously rises along with the deepening of the grinding degree can not occur in the grinding process, therefore, all the materials to be ground can be added and ground at one time, more than half of grinding time can be saved compared with the existing grinding method, and the grinding efficiency is high.
The invention also provides conductive paste which is prepared by the preparation method of the conductive paste.
Compared with the prior art, the beneficial effects of the conductive paste provided by the invention are the same as those of the preparation method of the conductive paste provided by the technical scheme, and are not repeated herein.
The invention also provides application of the conductive paste in a battery.
Compared with the prior art, the beneficial effect of the application of the conductive paste in the battery provided by the invention is the same as that of the preparation method of the conductive paste provided by the technical scheme, and the detailed description is omitted here.
The invention also provides a battery comprising the conductive paste.
Compared with the prior art, the beneficial effects of the battery provided by the invention are the same as those of the preparation method of the conductive paste provided by the technical scheme, and the details are not repeated herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a flowchart of a method for preparing conductive paste according to an embodiment of the present invention;
fig. 2 is a second flowchart of a method for preparing conductive paste according to an embodiment of the present invention;
fig. 3 is a third flowchart of a method for preparing conductive paste according to an embodiment of the present invention;
fig. 4 is a fourth flowchart of a method for preparing conductive paste according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
With the obvious and outstanding energy and environmental problems, the development of electric vehicles is imperative. Among them, the lithium ion battery has a higher energy density and a higher specific power, and is recognized as the most promising power battery for electric vehicles. At present, compared with the traditional conductive agents such as conductive carbon black and the like, the carbon nano tube has excellent conductivity and higher length-diameter ratio, higher electronic conductivity can be achieved by using lower amount in the lithium ion battery, the energy density of the battery is improved, and the cycle life of the battery is prolonged, so that the carbon nano tube is an ideal conductive agent.
However, when a carbon nanotube having a relatively small specific surface area is used as a conductive agent, the contact area of the carbon nanotube with an active material in an electrode is small, limiting the transfer of electrons between the active material and the carbon nanotube; in addition, when the carbon nanotubes with relatively high metal impurity content are used as the conductive agent, the service life and safety of the lithium ion battery are affected. Based on this, in the preparation process of the lithium ion battery, carbon nanotubes with large specific surface area and high purity are generally adopted as the conductive agent.
However, as the specific surface area of the carbon nanotube is increased and the purity of the carbon nanotube is improved, the difficulty in preparing the carbon nanotube conductive paste is greatly increased. Specifically, when the carbon nanotubes with large specific surface area and high purity are used as raw materials to prepare the conductive paste, the viscosity of the conductive paste is extremely high, so that the conductive paste is difficult to disperse uniformly, a large amount of viscosity modifier needs to be added, irreversible chemical reaction is easy to occur in the charging and discharging process of the battery, the performance of the lithium ion battery is reduced, and the requirements of the power battery cannot be met. In addition, because the viscosity of the conductive paste is extremely high and the viscosity is obviously increased along with the increase of the grinding degree, the carbon nanotubes need to be put into the conductive paste in batches in the grinding process, and after each batch is put into the conductive paste, the conductive paste needs to be ground until the viscosity of the conductive paste is stably reduced and then the rest batches of the conductive paste are continuously put into the conductive paste; and finally, after the carbon nano tubes are completely added, continuously grinding and dispersing until the parameters of fineness, viscosity and the like of the conductive slurry meet the discharging requirement, so that the grinding efficiency is low, and the method is not suitable for industrial production.
In view of the above problems, embodiments of the present invention provide a conductive paste, a preparation method and an application thereof, and a battery, which reduce the viscosity of the conductive paste on the premise of ensuring that the conductivity of the conductive paste is not reduced, solve the problem of performance reduction of the battery caused by adding an excessive viscosity modifier in the preparation process, and avoid the phenomenon that the viscosity is obviously increased along with the deepening of the grinding degree in the grinding process, so that the grinding can be completed at one time, and the grinding efficiency is improved.
The embodiment of the invention provides a preparation method of conductive paste, as shown in fig. 1, the preparation method of the conductive paste comprises the following steps:
step S100: a carbonaceous conductive material is provided, the carbonaceous conductive material including at least carbon nanotubes. The size of the carbon nanotubes can be adjusted according to actual conditions. For example: in order to improve the performance of the battery, the purity of carbon of the carbon nano tube is more than 98.5 percent, the tube diameter of the carbon nano tube ranges from 5nm to 15nm, and the specific surface area of the carbon nano tube is more than 260m2(ii) in terms of/g. At the moment, the carbon nano tube has small tube diameter and high purity and specific surface area, and when the conductive slurry prepared by using the carbon conductive material containing the carbon nano tube is used for a battery, the energy density, the rate capability, the cycle life and other properties of the battery can be fully improved.
Step S200: and forming defects on the tube wall of the carbon nano tube included in the carbon conductive material to obtain the minimally invasive carbon conductive material. The carbonaceous conductive material can contain other conductive carbon powder with the property of difficult grinding besides the carbon nano tube. For example: the organic combination of one or more combinations of graphene, conductive carbon black and carbon fibers and carbon structures with various sizes can provide more abundant conductive networks, and the obtained conductive slurry has higher conductive efficiency.
Step S300: the conductive slurry is prepared by taking minimally invasive carbonaceous conductive materials as conductive agents. It is understood that a grinding process must be performed during the preparation of the conductive paste.
As can be seen from the above preparation method of the conductive paste, in the preparation method of the conductive paste provided by the present invention, before the conductive paste is prepared using the carbonaceous conductive material including the carbon nanotubes, the tube walls of the carbon nanotubes contained in the carbonaceous conductive material are damaged, so that the tube walls of the carbon nanotubes form local defects, thereby obtaining the minimally invasive carbonaceous conductive material. Therefore, the tube wall of the carbon nano tube contained in the minimally invasive carbonaceous conductive material forms local defects, and the local defects are presented in the form of wall holes on the tube wall of the carbon nano tube. When the wall of the carbon nanotube has the wall hole, the liquid entering the carbon nanotube can flow out from the wall hole of the side wall, so that the liquid absorption of the carbon nanotube is reduced, and therefore, compared with the viscosity of the conductive paste prepared from the carbon nanotube paste with larger specific surface area and higher purity, the viscosity of the conductive paste prepared from the minimally invasive carbonaceous conductive material containing the carbon nanotube with the wall hole as the conductive agent is lower. In addition, since the specific surface area of the carbon nanotubes having wall holes is reduced and the van der waals force between the carbon nanotubes having wall holes is low as compared with the carbon nanotubes having no wall holes, the viscosity of the conductive paste prepared using the minimally invasive carbonaceous conductive material containing the carbon nanotubes having wall holes as a conductive agent is low as compared with the viscosity of the conductive paste prepared using the carbon nanotube paste having a large specific surface area and a high purity.
Therefore, in the preparation method of the conductive paste provided by the embodiment of the invention, the liquid absorption property of the carbon nanotubes contained in the minimally invasive carbonaceous conductive material is lower, the van der waals force between the carbon nanotubes contained in the minimally invasive carbonaceous conductive material is lower, and the problem of viscosity increase of the conductive paste caused by adding the carbon nanotubes with larger specific surface area and higher purity can be effectively relieved.
In addition, in the preparation method of the conductive paste provided by the invention, the liquid absorption of the carbon nanotubes contained in the minimally invasive carbonaceous conductive material is low, and the van der waals force between the carbon nanotubes is low, so that in the process of preparing the conductive paste by using the minimally invasive carbonaceous conductive material as a conductive agent, the components of the conductive paste can be added at one time in the grinding process, the viscosity of the conductive paste can be kept stable in the grinding process, and the phenomenon that the viscosity obviously rises along with the deepening of the grinding degree can not occur in the grinding process, therefore, all the materials to be ground can be added and ground at one time, more than half of grinding time can be saved compared with the existing grinding method, and the grinding efficiency is high.
In some embodiments, if the amount of the minimally invasive carbonaceous conductive material added is too small, the minimally invasive carbonaceous conductive material contained in the obtained conductive paste is less, and when a battery is prepared by using the conductive paste, the conductive paste provides fewer electronic conductive channels, which is not beneficial to large-current charging and discharging, so that the high-rate discharge performance of the battery is reduced. Based on the above, the mass of the minimally invasive carbonaceous conductive material accounts for 4-10% of the mass of the conductive paste. At the moment, the conductive paste obtained by the minimally invasive carbonaceous conductive material has better fluidity and is convenient to disperse uniformly, and when the conductive paste is used for preparing the battery, sufficient electronic conductive channels can be provided, the battery meeting the expected requirements can be obtained, and the cost is lower.
Wherein, the above-mentioned defect is formed on the tube wall of the carbon nanotube included in the carbonaceous conductive material, and the way of obtaining the minimally invasive carbonaceous conductive material is various, for example: the above-mentioned defect is formed on the tube wall of the carbon nanotube included in the carbonaceous conductive material, and the obtaining of the minimally invasive carbonaceous conductive material includes: performing minimally invasive pretreatment on the carbonaceous conductive material by adopting at least one of high-pressure airflow crushing, chemical agent corrosion, supercritical treatment and mechanical crushing to form wall holes on the tube wall of the carbon nano tube contained in the carbonaceous conductive material, thereby obtaining the minimally invasive carbonaceous conductive material.
The following will explain the process of forming defects on the wall of the carbon nanotube included in the carbonaceous conductive material by way of example of mechanical crushing. The following description is for explanation only, and not for limitation.
The minimally invasive carbonaceous conductive material obtained by forming defects on the wall of the carbon nanotube included in the carbonaceous conductive material, with reference to fig. 2, includes:
step S220: performing first ball milling on the carbonaceous conductive material at the rotating speed of 200 r/min-1000 r/min to obtain the minimally invasive carbonaceous conductive material. The carbonaceous conductive material is subjected to minimally invasive pretreatment by adopting a mechanical crushing mode, so that the implementation is easy and the cost is low. The carbon nano tube is subjected to minimally invasive pretreatment by a pot-type ball mill, so that the tube wall of the carbon nano tube can be damaged by using a grinding body in the ball mill, and wall holes are formed on the tube wall of the carbon nano tube locally; and the ultra-long carbon nano tubes can be broken, so that the entangled state of the long-fiber carbon nano tubes is destroyed, and the carbon nano tubes are conveniently and uniformly dispersed.
The first ball milling time is 5 min-30 min. In this case, local defects are formed on the tube wall of most of the carbon nanotubes contained in the carbonaceous conductive material by the impact action of the grinding bodies and the grinding action of the grinding bodies and the inner wall of the ball mill, and these local defects are present in the form of wall pores on the tube wall of the carbon nanotubes. Meanwhile, the carbon nanotubes with ultra-long length contained in the carbonaceous conductive material can be broken to form the carbon nanotubes with shorter tube length, so that the phenomenon that the long fibrous carbon nanotubes are easy to be entangled and agglomerated is avoided. The temperature of the first ball milling is less than or equal to 70 ℃, so that the solvent evaporation caused by high temperature is avoided, the equipment is protected, and the service life of the equipment is prolonged. Specifically, in the first ball milling process, cooling circulating water is introduced into the ball mill to control the temperature of the first ball milling to be less than or equal to 70 ℃.
It is understood that the inside of the above ball mill is provided with a grinding body, the diameter of which is preferably 1mm to 5mm, the contact area of the grinding body is large, and the grinding ability is high. In addition, the grinding body is usually selected from zirconium balls, and has the characteristics of high strength, good toughness, high wear resistance and high temperature resistance. Of course, other abrasive bodies can be selected according to actual needs.
Specifically, referring to fig. 2, before the carbonaceous conductive material is ball-milled for the first time at a rotation speed of 200r/min to 1000r/min, the forming of defects on the tube wall of the carbon nanotubes included in the carbonaceous conductive material, and the obtaining of the minimally invasive carbonaceous conductive material further includes:
step S210: the milling bodies used for ball milling are wetted with a solvent. Under the condition, certain buffering exists between the grinding bodies and between the grinding bodies and the inner wall of the ball mill, so that the grinding bodies and the ball mill are protected to a certain extent; meanwhile, the grinding body can adsorb more carbonaceous conductive materials, so that the carbonaceous conductive materials are ground more fully.
In some possible implementations, the preparing of the conductive paste with the minimally invasive carbonaceous conductive material as the conductive agent, as shown in fig. 3, specifically includes:
step 320: and uniformly mixing the minimally invasive carbonaceous conductive material, the dispersing agent and the solvent to obtain the conductive slurry.
The choice of the above solvents is manifold. For example: the solvent is one or more of water, N-alkyl pyrrolidone and ethanol, but is not limited thereto. Illustratively, the water may be deionized water, and the N-alkylpyrrolidone includes one or more combinations of N-cyclohexaneprodone and N-methylpyrrolidone.
Likewise, the above dispersants may be selected from a wide variety of dispersants, for example: the dispersant is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and carboxymethyl cellulose.
In some embodiments, if the amount of the dispersant is too small, the prepared conductive paste has poor fluidity and is difficult to disperse uniformly when the minimally invasive carbonaceous conductive material, the dispersant and the solvent are mixed uniformly; if the amount of the dispersant added is too large, the dispersant is precipitated in the solvent, which causes waste and high cost. Based on the above, the mass of the dispersant accounts for 1 to 5 percent of the mass of the conductive paste; therefore, the conductive paste with better fluidity can be obtained under the condition of using less dispersing agent, so that the conductive paste is uniformly dispersed under the condition of using less bonding regulator, and the minimally invasive carbonaceous conductive material is uniformly dispersed in the solvent to obtain the conductive paste meeting the requirements.
In some embodiments, if the amount of the solvent is too small, the viscosity of the conductive paste formed by the minimally invasive carbonaceous conductive material, the dispersant and the solvent is high during the process of mixing the minimally invasive carbonaceous conductive material, the dispersant and the solvent, and the conductive paste is difficult to disperse uniformly. If the addition amount of the solvent is too large, in the process of mixing the minimally invasive carbonaceous conductive material, the dispersing agent and the solvent, the viscosity of the conductive slurry formed by the minimally invasive carbonaceous conductive material, the dispersing agent and the solvent is low, particles of the minimally invasive carbonaceous conductive material are prone to sedimentation and agglomeration, and the conductive slurry with stable properties is difficult to obtain. Drying is difficult and inefficient during subsequent cell fabrication. Based on this, the mass of the solvent accounts for 85 to 95 percent of the mass of the conductive paste. Under the condition, in the process of mixing the minimally invasive carbonaceous conductive material, the dispersing agent and the solvent, the viscosity of the conductive slurry formed by the minimally invasive carbonaceous conductive material, the dispersing agent and the solvent is moderate, the uniform dispersion is facilitated, and the drying efficiency is higher when the battery is manufactured.
In order to obtain a more uniform conductive paste, referring to fig. 3, before uniformly mixing the minimally invasive carbonaceous conductive material, the dispersant and the solvent, the preparing of the conductive paste using the minimally invasive carbonaceous conductive material as the conductive agent further includes:
step S310: adding surfactant into the minimally invasive carbonaceous conductive material, wherein the addition amount of the surfactant is 1000-3000 PPM. The surface active agent has important influence on the dispersion of particle agglomeration in the preparation process of the conductive slurry, and is one or more of sodium dodecyl sulfate, cetyl trimethyl ammonium bromide and sodium naphthalene sulfonate.
On one hand, the surfactant reduces the difference between the internal acting force of the particle aggregates in the conductive paste and the acting force between the particles and the solvent, and is beneficial to the dispersion of the particle aggregates. On the other hand, the surfactant can effectively prevent the particles after the particle aggregate is dispersed from colliding and combining again under the action of electrostatic force so as to obtain the conductive slurry with the particle size meeting the requirement.
After the minimally invasive carbonaceous conductive material is obtained, the minimally invasive carbonaceous conductive material is required to be uniformly mixed with a dispersant and a solvent and subjected to fine grinding and dispersion. The above-mentioned manner of uniformly mixing the minimally invasive carbonaceous conductive material, the dispersant and the solvent is not exclusive, and in order to reduce the amount of equipment used in the process flow, the components of the conductive slurry are usually pre-dispersed by using the above-mentioned ball mill, and then finely ground by using a sand mill, so that the minimally invasive carbonaceous conductive material, the dispersant and the solvent are uniformly mixed. Specifically, referring to fig. 4, the step of uniformly mixing the minimally invasive carbonaceous conductive material, the dispersant and the solvent to obtain the conductive paste includes:
step 321: performing secondary ball milling on the minimally invasive carbonaceous conductive material, the solvent and the dispersing agent to uniformly disperse the minimally invasive carbonaceous conductive material, the solvent and the dispersing agent to obtain pre-dispersed slurry; wherein, the time of the second ball milling is usually 4 to 10 hours.
Step 322: and sanding the pre-dispersed slurry until the fineness value and the viscosity value of the slurry meet preset indexes to obtain the conductive slurry. Wherein, the fineness value and the viscosity value of the slurry are dynamically detected in the sanding process, and the sanding time is determined according to the dispersion effect of the slurry and the fineness and the viscosity of the slurry, and is usually 2-8 h. The preset indexes comprise that the fineness value of the pre-dispersed slurry is less than 30 mu m and the viscosity value of the pre-dispersed slurry is less than or equal to 6000 mPa. In addition, a blade fineness gauge is generally used to dynamically detect the fineness of the slurry during the sanding process.
In the sanding process, the pre-dispersed slurry may still have an excessive viscosity (i.e. a viscosity greater than 6000mPa · s), and in order to reduce the viscosity of the pre-dispersed slurry, referring to fig. 4, the above-mentioned mixing the minimally invasive carbonaceous conductive material, the dispersant and the solvent uniformly to obtain the conductive slurry further includes:
step S323: in the sanding process of the pre-dispersed slurry, when the viscosity of the pre-dispersed slurry does not meet a preset index, adding a viscosity regulator into the pre-dispersed slurry to reduce the viscosity of the pre-dispersed slurry; wherein the viscosity regulator is one or more of sodium dodecyl sulfate, cetyl trimethyl ammonium bromide, sodium naphthalene sulfonate and sodium lignosulfonate.
The temperature of the second ball milling is less than or equal to 70 ℃, and the temperature of the sand milling is less than or equal to 70 ℃. In this case, irreversible damage to solvents, dispersants and other chemical auxiliaries by high temperatures can be avoided; in addition, the temperature of the second ball milling is less than or equal to 70 ℃, and the temperature of the sand milling is less than or equal to 70 ℃, so that the equipment is protected, and the service life of the equipment is prolonged.
The embodiment of the invention also provides the conductive paste which is prepared by the preparation method of the conductive paste.
Compared with the prior art, the beneficial effects of the conductive paste provided by the embodiment of the invention are the same as those of the preparation method of the conductive paste provided by the technical scheme, and the details are not repeated herein.
The embodiment of the invention also provides application of the conductive paste in a battery.
Compared with the prior art, the beneficial effect of the application of the conductive paste in the battery provided by the embodiment of the invention is the same as that of the preparation method of the conductive paste provided by the technical scheme, and the detailed description is omitted here.
The invention also provides a battery comprising the conductive paste. The battery may be a lithium ion, ion battery, but is not limited thereto.
Compared with the prior art, the beneficial effects of the battery provided by the embodiment of the invention are the same as those of the preparation method of the conductive paste provided by the technical scheme, and are not repeated herein.
In order to prove that the preparation method of the conductive paste provided by the embodiment of the invention can effectively reduce the viscosity of the prepared conductive paste, the following embodiment is combined to describe in detail.
Example one
The preparation method of the conductive paste provided by the embodiment of the invention comprises the following steps:
step S100: providing a carbonaceous conductive material, the carbonaceous conductive material comprising only carbon nanotubes; the purity of the carbon nano tube is 99 percent, the tube diameter is 5nm, and the specific surface area is 270m2/g。
Step S200: forming defects on the tube wall of the carbon nano tube included in the carbon conductive material to obtain the minimally invasive carbon conductive material; the method specifically comprises the following steps:
step S210: the zirconium beads used in the pot ball mill were wetted with deionized water.
Step S220: adding 2kg of zirconium beads into a 2L pot-type ball mill, wherein the diameter of the zirconium beads is between 1mm and 5 mm; and then ball-milling 20g of the carbonaceous conductive material for 5min at the rotating speed of 1000r/min to obtain the minimally invasive carbonaceous conductive material.
Step S300: preparing conductive slurry by using a minimally invasive carbonaceous conductive material as a conductive agent to obtain the conductive agent; the method specifically comprises the following steps:
step S310: adding sodium dodecyl sulfate into the minimally invasive carbonaceous conductive material, wherein the addition amount of the sodium dodecyl sulfate is 1000 PPM.
Step S320: uniformly mixing a minimally invasive carbonaceous conductive material, a dispersing agent and a solvent to obtain conductive slurry; the method specifically comprises the following steps:
step S321: ball-milling minimally invasive carbonaceous conductive materials, polyvinylpyrrolidone and deionized water for 4 hours to obtain pre-dispersed slurry, wherein the mass of the minimally invasive carbonaceous conductive materials accounts for 4% of the mass of the pre-dispersed slurry, the mass of the polyvinylpyrrolidone accounts for 1% of the mass of the pre-dispersed conductive slurry, and the mass of the deionized water accounts for 95% of the mass of the pre-dispersed slurry.
Step S322: and sanding the pre-dispersed slurry for 2 hours, detecting that the fineness value of the slurry is 28 microns, and the viscosity value of the slurry is 5000mPa & s, and meeting the preset index to obtain the conductive slurry.
Example two
The preparation method of the conductive paste provided by the embodiment of the invention comprises the following steps:
step S100: providing a carbonaceous conductive material, wherein the carbonaceous conductive material is carbon nanotubes: the mass ratio of the conductive carbon black is 3: 2; wherein, the purity of the carbon nano tube is 98.8%, the tube diameter is 15nm, and the specific surface area is 285m2/g。
Step S200: forming defects on the tube wall of the carbon nano tube included in the carbon conductive material to obtain the minimally invasive carbon conductive material; the method specifically comprises the following steps:
step S210: the zirconium beads used in the pot ball mill were wetted with N-methylpyrrolidone.
Step S220: adding 2kg of zirconium beads into a 2L pot-type ball mill, wherein the diameter of the zirconium beads is between 1mm and 5 mm; and then ball-milling 300g of the carbonaceous conductive material for 30min at the rotating speed of 300r/min to obtain the minimally invasive carbonaceous conductive material.
Step S300: preparing conductive slurry by using a minimally invasive carbonaceous conductive material as a conductive agent to obtain the conductive agent; the method specifically comprises the following steps:
step S310: cetyl trimethyl ammonium bromide is added into the minimally invasive carbonaceous conductive material, and the addition amount of the cetyl trimethyl ammonium bromide is 3000 PPM.
Step S320: uniformly mixing a minimally invasive carbonaceous conductive material, a dispersing agent and a solvent to obtain conductive slurry; the method specifically comprises the following steps:
step S321: carrying out wet ball milling on the minimally invasive carbonaceous conductive material, polyvinyl alcohol and N-methyl pyrrolidone for 10 hours to obtain pre-dispersed slurry, wherein the mass of the minimally invasive carbonaceous conductive material accounts for 10% of the mass of the pre-dispersed slurry, the mass of the polyvinyl alcohol accounts for 5% of the mass of the pre-dispersed conductive slurry, and the mass of the N-methyl pyrrolidone accounts for 85% of the mass of the pre-dispersed slurry.
Step S322: and sanding the pre-dispersed slurry for 7 hours, and detecting that the fineness value of the slurry is 28 microns, the viscosity value of the slurry is 6800mPa & s, and the viscosity value does not meet the preset index.
Step S323: adding sodium dodecyl sulfate into the slurry, continuously sanding for 1h, detecting that the fineness value of the slurry is 24 mu m, the viscosity value of the slurry is 5800Pa & s, and meeting the preset index to obtain the conductive slurry.
EXAMPLE III
The preparation method of the conductive paste provided by the embodiment of the invention comprises the following steps:
step S100: providing a carbonaceous conductive material, wherein the carbonaceous conductive material is carbon nanotubes: graphene: the mass ratio of the conductive carbon black is 3: 3: 2; wherein, the purity of the carbon nano tube is 98.8 percent, the tube diameter is 8nm, and the specific surface area is 290m2/g。
Step S200: forming defects on the tube wall of the carbon nano tube included in the carbon conductive material to obtain the minimally invasive carbon conductive material; the method specifically comprises the following steps:
step S210: the zirconium beads used in the pot ball mill were wetted with N-cyclohexane pyrrolidone.
Step S220: adding 2kg of zirconium beads into a 2L pot-type ball mill, wherein the diameter of the zirconium beads is between 1mm and 5 mm; and then ball-milling 100g of the carbonaceous conductive material for 20min at the rotating speed of 200r/min to obtain the minimally invasive carbonaceous conductive material.
Step S300: preparing conductive slurry by using a minimally invasive carbonaceous conductive material as a conductive agent to obtain the conductive agent; the method specifically comprises the following steps:
step S310: sodium naphthalenesulfonate is added into the minimally invasive carbonaceous conductive material, and the addition amount of the sodium naphthalenesulfonate is 2000 PPM.
Step S320: uniformly mixing a minimally invasive carbonaceous conductive material, a dispersing agent and a solvent to obtain conductive slurry; the method specifically comprises the following steps:
step S321: ball-milling minimally invasive carbonaceous conductive materials, polyethylene glycol and N-cyclohexane pyrrolidone for 8 hours to obtain pre-dispersed slurry, wherein the mass of the minimally invasive carbonaceous conductive materials accounts for 4% of the mass of the pre-dispersed slurry; the mass of the N-cyclohexane pyrrolidone accounts for 95% of the mass of the pre-dispersed slurry, and the mass of the polyethylene glycol accounts for 1% of the mass of the pre-dispersed conductive slurry.
Step S322: and sanding the pre-dispersed slurry for 2 hours, and detecting that the fineness value of the slurry is 28 microns, the viscosity value of the slurry is 6400mPa & s, and the viscosity value does not meet the preset index.
Step S323: and adding hexadecyl trimethyl ammonium bromide into the slurry, continuously sanding for 1h, detecting that the fineness value of the slurry is 24 mu m, the viscosity value of the slurry is 5800Pa & s, and meeting the preset index to obtain the conductive slurry.
Example four
The preparation method of the conductive paste provided by the embodiment of the invention comprises the following steps:
step S100: providing a carbonaceous conductive material, wherein the carbonaceous conductive material is carbon nanotubes: graphene: the mass ratio of the carbon fibers is 3: 3: 2; wherein, the purity of the carbon nano tube is 99.3 percent, the tube diameter is 10nm, and the specific surface area is 284m2/g。
Step S200: forming defects on the tube wall of the carbon nano tube included in the carbon conductive material to obtain the minimally invasive carbon conductive material; the method specifically comprises the following steps:
step S210: the zirconium beads used in the pot ball mill were wetted with ethanol.
Step S220: adding 2kg of zirconium beads into a 2L pot-type ball mill, wherein the diameter of the zirconium beads is between 1mm and 5 mm; and then, carrying out ball milling on 150g of the carbonaceous conductive material for 15min at the rotating speed of 500r/min to obtain the minimally invasive carbonaceous conductive material.
Step S300: preparing conductive slurry by using a minimally invasive carbonaceous conductive material as a conductive agent to obtain the conductive agent; the method specifically comprises the following steps:
step S310: adding 2500PPM of sodium dodecyl sulfate into the minimally invasive carbonaceous conductive material.
Step S320: uniformly mixing a minimally invasive carbonaceous conductive material, a dispersing agent and a solvent to obtain conductive slurry; the method specifically comprises the following steps:
step S321: ball-milling minimally invasive carbonaceous conductive materials, carboxymethyl cellulose and ethanol for 6 hours to obtain pre-dispersed slurry, wherein the mass of the minimally invasive carbonaceous conductive materials accounts for 8% of that of the pre-dispersed slurry; the mass of the ethanol accounts for 90% of the mass of the pre-dispersed slurry, and the mass of the carboxymethyl cellulose accounts for 2% of the mass of the pre-dispersed conductive slurry.
Step S322: and sanding the pre-dispersed slurry for 3 hours, and detecting that the fineness value of the slurry is 26 mu m, the viscosity value of the slurry is 7000mPa & s, and the viscosity value does not meet the preset index.
Step S323: and adding sodium naphthalene sulfonate into the slurry, continuously sanding for 2 hours, detecting that the fineness value of the slurry is 20 micrometers, and the viscosity value of the slurry is 5700Pa & s, so as to meet the preset index, and obtaining the conductive slurry.
EXAMPLE five
The preparation method of the conductive paste provided by the embodiment of the invention is different from the fourth embodiment in that:
step S323: and adding sodium lignosulfonate into the slurry, continuously sanding for 2 hours, detecting that the fineness value of the slurry is 22 mu m, and the viscosity value of the slurry is 5650 Pa-s, so as to meet the preset index, and obtaining the conductive slurry.
In the foregoing description of embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (11)

1. A method for preparing conductive paste, comprising:
providing a carbonaceous conductive material, wherein the carbonaceous conductive material at least comprises carbon nanotubes;
forming defects on the tube wall of the carbon nano tube included in the carbonaceous conductive material to obtain a minimally invasive carbonaceous conductive material;
mixing the minimally invasive carbonaceous conductive material serving as a conductive agent with a liquid solvent to prepare conductive slurry;
the defects are presented on the wall of the carbon nano tube in the form of wall holes, and the wall holes enable liquid entering the carbon nano tube to flow out of the wall holes on the side wall.
2. The method for preparing conductive paste according to claim 1, wherein the carbonaceous conductive material further comprises one or more combinations of graphene, conductive carbon black and carbon fiber; and/or the presence of a gas in the gas,
the purity of the carbon nano tube is more than 98.5 percent, the tube diameter of the carbon nano tube ranges from 5nm to 15nm, and the specific surface area of the carbon nano tube is more than 260m2(ii)/g; and/or the presence of a gas in the gas,
the mass of the minimally invasive carbonaceous conductive material accounts for 4-10% of the mass of the conductive paste; and/or the presence of a gas in the gas,
the forming of defects on the tube wall of the carbon nanotube included in the carbonaceous conductive material to obtain the minimally invasive carbonaceous conductive material comprises:
and performing minimally invasive pretreatment on the carbonaceous conductive material by adopting at least one of high-pressure airflow crushing, chemical agent corrosion, supercritical treatment and mechanical crushing to form wall holes on the tube wall of the carbon nano tube contained in the carbonaceous conductive material, thereby obtaining the minimally invasive carbonaceous conductive material.
3. The method for preparing the conductive paste according to claim 1, wherein the forming of the defect on the wall of the carbon nanotube included in the carbonaceous conductive material to obtain the minimally invasive carbonaceous conductive material comprises:
and performing first ball milling on the carbonaceous conductive material at a rotating speed of 200 r/min-1000 r/min to obtain the minimally invasive carbonaceous conductive material, wherein the first ball milling time is 5 min-30 min.
4. The method for preparing conductive paste according to claim 3, wherein before the first ball milling of the carbonaceous conductive material at a rotation speed of 200r/min to 1000r/min, defects are formed on the tube wall of the carbon nanotubes included in the carbonaceous conductive material, and the obtaining of minimally invasive carbonaceous conductive material further comprises: wetting the grinding bodies used for ball milling with a solvent; and/or the presence of a gas in the gas,
the diameter of the grinding body used for ball milling is 1 mm-5 mm.
5. The method for preparing conductive paste according to claim 1, wherein the step of preparing conductive paste by using the minimally invasive carbonaceous conductive material as a conductive agent comprises the steps of:
and uniformly mixing the minimally invasive carbonaceous conductive material, the dispersing agent and the solvent to obtain the conductive slurry.
6. The method for preparing conductive paste according to claim 5, wherein the solvent is one or more of water, N-alkyl pyrrolidone and ethanol; and/or the presence of a gas in the gas,
the dispersing agent is one or a combination of more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and carboxymethyl cellulose; and/or the presence of a gas in the gas,
the mass of the solvent accounts for 85-95% of the mass of the conductive paste, and the mass of the dispersing agent accounts for 1-5% of the mass of the conductive paste; and/or the presence of a gas in the gas,
before the minimally invasive carbonaceous conductive material, the dispersant and the solvent are uniformly mixed, the preparation of the conductive paste by using the minimally invasive carbonaceous conductive material as a conductive agent further comprises:
and adding a surfactant into the minimally invasive carbonaceous conductive material, wherein the addition amount of the surfactant is 1000-3000 PPM.
7. The method for preparing the conductive paste according to claim 5, wherein the step of uniformly mixing the minimally invasive carbonaceous conductive material, the dispersing agent and the solvent to obtain the conductive paste comprises the following steps:
performing secondary ball milling on the minimally invasive carbonaceous conductive material, the solvent and the dispersing agent to uniformly disperse the minimally invasive carbonaceous conductive material, the solvent and the dispersing agent to obtain pre-dispersed slurry;
and sanding the pre-dispersed slurry until the fineness value and the viscosity value of the slurry meet preset indexes to obtain the conductive slurry.
8. The method for preparing conductive paste according to claim 7, wherein the step of uniformly mixing the minimally invasive carbonaceous conductive material, the dispersing agent and the solvent to obtain the conductive paste further comprises the steps of:
in the sanding process of the pre-dispersed slurry, when the viscosity of the pre-dispersed slurry does not meet a preset index, adding a viscosity regulator into the pre-dispersed slurry; and/or the presence of a gas in the gas,
the temperature of the second ball milling and/or the sand milling is less than or equal to 70 ℃; and/or the presence of a gas in the gas,
the preset indexes comprise that the fineness value of the pre-dispersed slurry is less than 30 mu m and the viscosity value of the pre-dispersed slurry is less than or equal to 6000mPa & s.
9. An electroconductive paste, characterized by comprising the electroconductive paste produced by the electroconductive paste production method according to any one of claims 1 to 8.
10. Use of the electroconductive paste according to claim 9 in a battery.
11. A battery comprising the electroconductive paste according to claim 9.
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