CN108258249B - Current collector coating, slurry, preparation method of current collector coating and slurry, battery pole piece and lithium ion battery - Google Patents

Current collector coating, slurry, preparation method of current collector coating and slurry, battery pole piece and lithium ion battery Download PDF

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CN108258249B
CN108258249B CN201711353445.8A CN201711353445A CN108258249B CN 108258249 B CN108258249 B CN 108258249B CN 201711353445 A CN201711353445 A CN 201711353445A CN 108258249 B CN108258249 B CN 108258249B
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current collector
coating
parts
lithium ion
ion battery
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CN108258249A (en
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李科
费伟征
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Shenzhen Yuqiang New Material Co ltd
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Shenzhen Yuqiang New Material Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/654—Means for temperature control structurally associated with the cells located inside the innermost case of the cells, e.g. mandrels, electrodes or electrolytes
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/658—Means for temperature control structurally associated with the cells by thermal insulation or shielding
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/668—Composites of electroconductive material and synthetic resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

In order to overcome the problem of thermal runaway caused by extrusion or thermal abuse of the conventional lithium ion battery, the invention provides a current collector coating which comprises a conductive agent, a conductive and heat-insulating material and a binder. Meanwhile, the invention also discloses coating slurry comprising the current collector coating composition, a preparation method of the coating slurry, a battery pole piece and a lithium ion battery. The lithium ion battery manufactured by the current collector coating provided by the invention not only has high safety, but also has better electrochemical properties, including better rate performance and cycle performance.

Description

Current collector coating, slurry, preparation method of current collector coating and slurry, battery pole piece and lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a current collector coating, slurry, a preparation method of the current collector coating and slurry, a battery pole piece and a lithium ion battery.
Background
At present, with the development of new energy technology, the demand for lithium ion power batteries is increasing. The use requirement of a single battery is converted into the use requirement of a plurality of series-parallel combined batteries. The traditional lithium ion battery is difficult to meet the requirements of high consistency and long service life of a power battery, the surface treatment of the positive electrode and the negative electrode of the battery by using a functional coating material and the formation of the functional coating are breakthrough technical innovation, and the carbon-coated aluminum foil/copper foil is that the dispersed nano conductive graphite and carbon coating particles are uniformly and finely coated on the aluminum foil/copper foil. The conductive material can provide excellent static conductive performance, collect micro-current of active materials, thereby greatly reducing contact resistance between positive/negative active materials and a current collector, improving the adhesion capacity between the positive/negative active materials and the current collector, reducing the usage amount of a binder and further obviously improving the overall performance of the battery.
However, the existing functional coating material is in a nanometer level, and after the slurry is well dispersed, the micro particles are easy to agglomerate to form large particles, which affects the stability and the coating effect of the slurry. Moreover, because people have increasingly requirements on the endurance mileage of the electric vehicle, the overall capacity of the battery pack is continuously increased, and the higher the specific energy of the power battery is, the greater the challenge of the safety of the power battery is, so that the improvement of the safety of the battery module is particularly important, especially the thermal runaway and the anti-extrusion safety of the ternary power battery module.
Disclosure of Invention
The invention provides a current collector coating, slurry, a preparation method of the current collector coating and slurry, a battery pole piece and a lithium ion battery, aiming at the problem of thermal runaway caused by extrusion or thermal abuse of the existing lithium ion battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the present invention provides a current collector coating, the composition of which comprises a conductive agent, a conductive and thermal insulating material, and a binder.
Optionally, the composition comprises the following components in parts by weight: 100 parts of conductive agent, 20-5000 parts of conductive heat insulation material and 10-500 parts of binder.
Optionally, the conductive and heat-insulating material is nanoparticles, and the average particle size is 50-500 nm.
Optionally, the conductive and insulating material comprises a metal oxide of one or more of tin, antimony, titanium, vanadium, niobium, tantalum, tungsten and ruthenium.
Optionally, the conductive agent includes one or more of graphene, carbon nanotubes, carbon fibers, activated carbon, graphite flakes, graphite particles, conductive carbon black, ketjen black, acetylene black, and mesocarbon microbeads.
Optionally, the binder includes one or more of polyvinylidene fluoride, polyacrylate, sodium carboxymethyl cellulose, styrene-butadiene rubber, epoxy resin, organic silicon resin, polyimide resin, phenolic resin, polyurethane, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and acrylonitrile multipolymer.
Optionally, the current collector coating further includes, in parts by weight, based on 100 parts of the conductive agent: 1-15 parts of a chelating agent; the chelating agent comprises one or more of calcium hydroxide, ammonia water, potassium hydroxide and sodium hydroxide.
Optionally, the current collector coating further includes, in parts by weight, based on 100 parts of the conductive agent: 1-15 parts of a dispersing agent; the dispersing agent comprises one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyethylene oxide ether, polyacrylamide and polyethylene glycol octyl phenyl ether.
Optionally, the current collector coating further includes, in parts by weight, based on 100 parts of the conductive agent: 1-15 parts of a defoaming agent; the antifoaming agent comprises one or more of ethanol and n-butanol.
Optionally, the current collector coating further includes, in parts by weight, based on 100 parts of the conductive agent: 1-10 parts of a preservative; the antiseptic comprises one or more of phenol, cresol, chlorocresol, thymol, hydroxybenzene esters, benzoic acid and its salts, sorbic acid and its salts, boric acid and its salts, propionic acid, dehydroacetic acid, formaldehyde and glutaraldehyde.
According to the current collector coating provided by the invention, the conductive agent and the conductive and heat-insulating material with good conductivity are added, and the conductive agent and the conductive and heat-insulating material can be attached to the current collector through the binder, so that the contact resistance between the active layer and the current collector can be reduced, and the adhesive force of the active layer can be improved.
In another aspect, the present invention provides a coating slurry comprising a solvent and the composition of the current collector coating as described above.
The coating slurry has good stability after dispersion and uniform thickness after coating.
Optionally, the coating slurry comprises the following components in parts by weight: 100 parts of conductive agent, 20-5000 parts of conductive heat insulation material, 10-500 parts of binder and 20-8000 parts of solvent.
Optionally, the solvent includes an organic solvent and/or an inorganic solvent, wherein the organic solvent includes one or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and the inorganic solvent includes one or more of deionized water, distilled water and purified water.
In another aspect, the present invention provides a method for preparing the coating slurry as described above, comprising the steps of:
mixing the conductive agent, the conductive and heat-insulating material, the binder and the solvent, and grinding to obtain the coating slurry.
Optionally, the step of mixing the conductive agent, the conductive and heat-insulating material, the binder and the solvent, and grinding to obtain the coating slurry comprises:
adding 1-15 parts by weight of chelating agent into 10-500 parts by weight of binder and 200-8000 parts by weight of solvent, stirring for chelation reaction, adding 100 parts by weight of conductive agent and 20-5000 parts by weight of conductive and heat-insulating material, adding 1-15 parts by weight of dispersing agent, 1-15 parts by weight of defoaming agent and 1-10 parts by weight of preservative, continuously stirring, and grinding until the dispersing is uniform to obtain coating slurry.
Optionally, the linear speed of stirring is 10-30 m/s, the stirring time is 1-24 h, the ball mill is adopted for grinding, the particle size of zirconium beads used by the ball mill is 0.3-1.2 mm, the high-speed dispersion machine is adopted for dispersion, and the slurry temperature is kept below 50 ℃ in the dispersion.
In another aspect, the invention provides a battery pole piece comprising a current collector, an active layer and a current collector coating as described above, the current collector coating being located between the current collector and the active layer.
In another aspect, the invention provides a lithium ion battery, which includes the battery pole piece as described above.
The lithium ion battery manufactured by the current collector coating provided by the invention not only has high safety, but also has better electrochemical properties, including better rate performance and cycle performance.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following 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.
An embodiment of the present invention provides a current collector coating, which comprises a conductive agent, a conductive and heat insulating material, and a binder.
The current collector coating is applied to the surface of a current collector of a lithium ion battery, the conductive agent and the conductive and heat-insulating material are attached to the current collector through the binder, excellent static conductive performance can be provided, micro-current of the active material is collected, the reduction of contact resistance between the active layer and the current collector is facilitated, the current collector coating and the active layer have good affinity, the adhesive force of the active layer on the current collector is improved, the using amount of the binder can be reduced, and the overall performance of the battery is remarkably improved. The conductive and heat-insulating material also has a good heat-insulating effect, and can avoid the influence on the conductivity of the current collector coating, so that when the battery is abused and extruded by heat, the good heat-insulating property can effectively reduce the generation and the transmission of heat, prevent the battery from generating thermal runaway, and improve the safety performance of the battery.
In some embodiments of the present invention, the composition of the current collector coating comprises, in parts by weight: 100 parts of conductive agent, 20-5000 parts of conductive heat insulation material and 10-500 parts of binder.
More preferably, the composition of the current collector coating comprises, in parts by weight: 100 parts of conductive agent, 80-150 parts of conductive heat insulation material and 60-100 parts of binder.
In some embodiments of the present invention, the conductive and thermal insulation material is nanoparticles, and the average particle size is 50-500 nm, and if the particle size of the conductive and thermal insulation material is too large, the coating effect of the coating is affected; if the particle size of the heat and electricity conductive material is too small, the conductive material cannot be coated, which affects the conductivity.
In some embodiments of the invention, the electrically conductive and thermally insulating material comprises a metal oxide of one or more of tin, antimony, titanium, vanadium, niobium, tantalum, tungsten and ruthenium.
Preferably, the conductive and heat-insulating material is one or more of tin oxide and antimony oxide.
More preferably, the conductive and heat-insulating material is a mixture of tin oxide and antimony oxide, and the average particle size of the mixture is 100-500 nm.
The metal oxide of one or more of tin, antimony, titanium, vanadium, niobium, tantalum, tungsten and ruthenium is used as the conductive and heat-insulating material, so that the conductive coating has better conductive performance, and the heat conduction efficiency of the current collector coating can be reduced to a certain extent.
According to the conductive agent provided by the invention, the carbon material is adopted, and the effect of the carbon material is that the contact resistance between the electrode active layer and the current collector is reduced, so that the internal resistance of the battery is reduced, and the electron transmission speed is improved.
The carbon material may be a carbon crystal having a high degree of crystallization and/or an amorphous carbon having a low degree of crystallization.
In some embodiments of the invention, the conductive agent comprises one or more of graphene, carbon nanotubes, carbon fibers, activated carbon, graphite flakes, graphite particles, conductive carbon black, ketjen black, acetylene black, and mesocarbon microbeads.
More preferably, the conductive agent adopts conductive carbon black with the average particle size of 30-50 nm.
In some embodiments of the invention, the binder comprises one or more of polyvinylidene fluoride, polyacrylate, sodium carboxymethyl cellulose, styrene butadiene rubber, epoxy resin, silicone resin, polyimide resin, phenolic resin, polyurethane, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, acrylonitrile multipolymer.
Preferably, the binder is a polyacrylate.
In some embodiments of the invention, a chelating agent is added to the adhesive to perform a chelating reaction in order to improve the bond strength between the binder and the current collector.
Based on 100 parts of the conductive agent, the current collector coating further comprises, by weight: 1-15 parts of a chelating agent.
The chelating agent comprises one or more of calcium hydroxide, ammonia water, potassium hydroxide and sodium hydroxide.
In the present invention, the current collector coating may further include other functional aids according to the actual production needs, for example, one or more of a dispersant, an antifoaming agent, and an antiseptic may be added, but is not limited thereto.
Specifically, in some embodiments, the composition of the current collector coating further includes a dispersant, and the current collector coating further includes, based on 100 parts by weight of the conductive agent: 1-15 parts of a dispersing agent; the dispersing agent comprises one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyethylene oxide ether, polyacrylamide and polyethylene glycol octyl phenyl ether.
The dispersing agent is a surfactant with two opposite properties of lipophilicity and hydrophilcity, and is beneficial to uniformly dispersing solid particles such as a conductive agent, a conductive heat-insulating material and the like in a solvent in the stage of preparing slurry, and can prevent the particles from settling.
In some embodiments, the composition of the current collector coating further comprises an antifoaming agent, and the current collector coating further comprises, based on 100 parts by weight of the conductive agent: 1-15 parts of a defoaming agent; the antifoaming agent comprises one or more of ethanol and n-butanol.
The defoamer acts to reduce bubbles that may form in the slurry due to agitation or other causes during the stage of slurry deployment.
In some embodiments, the composition of the current collector coating further comprises a preservative, and the current collector coating further comprises, based on 100 parts by weight of the conductive agent: 1-10 parts of a preservative; the antiseptic comprises one or more of phenol, cresol, chlorocresol, thymol, hydroxybenzene esters, benzoic acid and its salts, sorbic acid and its salts, boric acid and its salts, propionic acid, dehydroacetic acid, formaldehyde and glutaraldehyde.
The preservative is used for preventing bacteria from breeding.
Another embodiment of the invention discloses a coating slurry comprising a solvent and the composition of the current collector coating as described above.
The above-described characteristic definitions for the components of the current collector coating are also applicable to the components of the coating slurry described in this embodiment.
The coating slurry is used for forming the current collector coating, the coating slurry is good in stability after being dispersed, and the thickness is uniform after coating.
The coating slurry comprises the following components in parts by weight: 100 parts of conductive agent, 20-5000 parts of conductive heat insulation material, 10-500 parts of binder and 20-8000 parts of solvent.
The conductive agent, the conductive and heat insulating material and the binder are used for forming the current collector coating, and the functions of the current collector coating are as described above and are not described in detail.
Preferably, the solid content of the binder is 20-30% of polyacrylate emulsion.
The solvent is used for dispersing and mixing the conductive agent, the conductive and heat-insulating material and the binder to form a slurry form, so that the coating on the current collector is convenient, and after the current collector coating is formed, the solvent can be removed by heating and drying.
In some embodiments of the present invention, the solvent comprises an organic solvent and/or an inorganic solvent, wherein the organic solvent comprises one or more of N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide, and the inorganic solvent comprises one or more of deionized water, distilled water, and purified water.
The coating slurry also comprises one or more of a dispersing agent, a defoaming agent and a preservative, and the effects of the dispersing agent, the defoaming agent and the preservative are as described above and are not repeated.
Another embodiment of the present invention provides a method for preparing the coating slurry as described above, comprising the steps of:
mixing the conductive agent, the conductive and heat-insulating material, the binder and the solvent, and grinding to obtain the coating slurry.
The method for preparing the coating slurry by mixing the conductive agent, the conductive and heat-insulating material, the binder and the solvent and grinding comprises the following steps:
adding 1-15 parts by weight of chelating agent into 10-500 parts by weight of binder and 200-8000 parts by weight of solvent, stirring for chelation reaction, adding 100 parts by weight of conductive agent and 20-5000 parts by weight of conductive and heat-insulating material, adding 1-15 parts by weight of dispersing agent, 1-15 parts by weight of defoaming agent and 1-10 parts by weight of preservative, continuously stirring, and grinding until the dispersing is uniform to obtain coating slurry.
The stirring linear speed is 10-30 m/s, the stirring time is 1-24 h, the grinding operation adopts a ball mill, the particle size of zirconium beads used by the ball mill is 0.3-1.2 mm, the dispersion operation adopts a high-speed dispersion machine, and the temperature of slurry is kept below 50 ℃ in the dispersion operation.
Another embodiment of the present invention provides a method for preparing a current collector coating as described above, comprising the steps of:
and providing the coating slurry prepared by the preparation method of the coating slurry, coating the coating slurry on a current collector, and drying to obtain the current collector coating.
Another embodiment of the present invention provides a battery pole piece comprising a current collector, an active layer, and a current collector coating as described above, the current collector coating being located between the current collector and the active layer.
In some embodiments, the battery pole piece is a positive pole piece. As a current collector for the positive electrode, the current collector may be an aluminum foil or a stainless steel foil, and may be in the shape of a mesh or a foil; the coating slurry prepared by the preparation method of the coating slurry is provided, the coating slurry is coated on a current collector, the current collector coating is obtained after drying, the positive electrode slurry obtained by mixing a positive electrode active material, a positive electrode binder, a positive electrode dispersing agent and a positive electrode solvent is coated on the current collector coating, and the active layer is obtained after drying and tabletting. The positive electrode active material may be one or more of a lithium cobalt composite oxide and a modified material thereof, a lithium manganese composite oxide and a modified material thereof, a lithium nickel composite oxide and a modified material thereof, a lithium iron phosphate composite oxide and a modified material thereof, a lithium manganese phosphate composite oxide and a modified material thereof, a lithium vanadium phosphate composite oxide and a modified material thereof, a multi-transition metal lithium oxide and a modified material thereof, and a lithium-rich manganese-based multi-transition metal lithium oxide and a modified material thereof, but is not limited thereto. The positive electrode binder may employ one or more of fluorine-containing resin, polyether resin, cellulose-type binder, rubber-type binder, polyacrylate-type binder, and polyimide, but is not limited thereto. The cathode solvent can adopt various organic solvents used for preparing cathode slurry, and the cathode dispersant can adopt various dispersants used for preparing cathode slurry. In some embodiments, a positive electrode conductive agent may be further added, and the positive electrode conductive agent is made of a carbon material with high conductivity.
In some embodiments, the battery pole piece is a negative pole piece, and as a current collector for a negative pole, the current collector can be a copper foil, a stainless steel foil or a nickel foil, and the shape of the current collector can be a mesh shape or a foil shape; and coating the coating slurry on a current collector, drying to obtain the current collector coating, coating the anode slurry on the current collector coating, drying and tabletting to obtain the active layer, wherein the anode slurry can be obtained by mixing an anode active material, an anode binder, an anode dispersant and an anode solvent. The negative active material may be one or more of graphite, petroleum coke, hard carbon, soft carbon, organic cracked carbon, mesocarbon microbeads, carbon fibers, tin alloy, and silicon alloy, but is not limited thereto. The negative electrode binder may employ one or more of fluorine-containing resin, polyether resin, cellulose-type binder, rubber-type binder, polyacrylate-type binder, and polyimide, but is not limited thereto. The cathode solvent can adopt various organic solvents used for preparing cathode slurry, and the cathode dispersant can adopt various dispersants used for preparing cathode slurry. In some embodiments, a negative electrode conductive agent may be further added, and the negative electrode conductive agent is made of a carbon material with high conductivity.
An embodiment of the present invention provides a lithium ion battery, including the battery pole piece as described above.
Specifically, the lithium ion battery comprises a battery shell, a pole core sealed in the battery shell and a non-aqueous electrolyte; the pole core comprises a diaphragm, the positive pole piece in the embodiment and the negative pole piece in the embodiment.
In some embodiments, the separator is a nonwoven fabric or a synthetic resin microporous membrane; preferably, the separator is a synthetic resin microporous membrane; more preferably, the diaphragm is selected from one or more of a polyethylene microporous membrane, a polypropylene microporous membrane, a polyethylene polypropylene composite microporous membrane and a polyolefin microporous membrane; more preferably, the separator is a polyolefin microporous membrane.
In some embodiments, the electrolyte is a non-aqueous electrolyte. The electrolyte comprises electrolyte and electrolyte solvent, and the electrolyte can adopt electrolyte salt used by the existing non-aqueous electrolyte, such as LiPF6、LiBF4、LiAsF6、LiClO4、LiSbF6、LiCl、LiBr、LiCF2SO3Lithium salt, more preferably, the electrolyte is selected from LiPF from the viewpoint of oxidation stability6、LiClO4、LiBF4、LiAsF6One or more of them. The electrolyte solvent is an organic solvent.
The key point of the invention is that a layer of coating slurry is coated on the current collector of the positive plate and/or the negative plate, the current collector coating is formed after drying, and then the positive slurry or the negative slurry is coated to form an active layer; through the mass flow body coating can provide splendid static electric conductive property, collects the micro-current of active layer to can reduce the contact resistance between active layer and the mass flow body by a wide margin, and can improve the adhesive force between the two, the use amount of reducible binder, and then make the wholeness ability of battery produce apparent promotion. Meanwhile, when the battery is abused or extruded, the conductive and heat-insulating material in the current collector coating has good heat-insulating property, so that the generation and the transmission of heat can be effectively reduced, the thermal runaway of the battery is prevented, and the safety performance of the lithium ion battery is improved.
The manufacturing method of the lithium ion battery is a conventional manufacturing method of the lithium ion battery, and the lithium ion battery is manufactured by forming a pole core by adopting a winding type or a laminating type through the manufactured anode, the manufactured cathode and the diaphragm, then putting the pole core into a battery shell, welding a cap, injecting liquid, sealing and forming. The difference is that when the anode and the cathode are manufactured, the multifunctional slurry is coated on the current collector, and the current collector coating is formed after drying.
Compared with the existing lithium ion battery, the lithium ion battery provided by the invention has better electrochemical performance, and specifically has low internal resistance, high multiplying power, long service life, good high-temperature performance and high safety. The lithium ion battery coating slurry has good stability after dispersion, uniform thickness after coating and good appearance; therefore, the lithium ion battery manufactured by the current collector coating of the lithium ion battery not only has high safety, but also has better electrochemical properties including better rate performance and cycle performance.
The present invention will be further described with reference to specific examples.
Example 1
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 3kg of polyacrylate emulsion with the solid content of 25% and 7kg of deionized water, stirring for 24 hours to carry out chelation reaction, then sequentially adding 1kg of conductive carbon black, 0.9kg of tin oxide and 0.1kg of antimony oxide (wherein the particle size of the tin antimony oxide is 100-500 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear speed is 20m/s), then adding 0.05kg of polyvinylpyrrolidone, 0.05kg of ethanol and 0.05kg of propionic acid, and grinding by a ball mill until the mixture is uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured by adopting the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 mu m is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 1 is obtained.
Example 2
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 2.4kg of polyacrylate emulsion with the solid content of 25% and 7kg of deionized water, stirring for 24 hours for chelation reaction, then sequentially adding 1kg of conductive carbon black, 0.7kg of tin oxide and 0.1kg of antimony oxide (wherein the particle size of the tin antimony oxide is 100-500 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear speed is 20m/s), then adding 0.05kg of polyvinylpyrrolidone, 0.05kg of ethanol and 0.05kg of propionic acid, and grinding by a ball mill until the mixture is uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured by adopting the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 mu m is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 2 is obtained.
Example 3
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 4kg of polyacrylate emulsion with the solid content of 25% and 7kg of deionized water, stirring for 24 hours to carry out chelation reaction, then sequentially adding 1kg of conductive carbon black, 1.35kg of tin oxide and 0.15kg of antimony oxide (wherein the particle size of the tin antimony oxide is 100-500 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear speed is 20m/s), then adding 0.05kg of polyvinylpyrrolidone, 0.05kg of ethanol and 0.05kg of propionic acid, and grinding by a ball mill until the mixture is uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 mu m is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 3 is obtained.
Example 4
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.01kg of calcium hydroxide into 0.4kg of polyacrylate emulsion with the solid content of 25% and 2kg of deionized water, stirring for 24 hours for chelation reaction, then sequentially adding 1kg of conductive carbon black, 0.1kg of tin oxide and 0.1kg of antimony oxide (wherein the particle size of the tin antimony oxide is 100-500 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear speed is 20m/s), then adding 0.01kg of polyvinylpyrrolidone, 0.01kg of ethanol and 0.01kg of propionic acid, and grinding by a ball mill until the mixture is uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 mu m is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 4 is obtained.
Example 5
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.15kg of calcium hydroxide into 20kg of polyacrylate emulsion with the solid content of 25% and 80kg of deionized water, stirring for 24 hours to carry out chelation reaction, then sequentially adding 1kg of conductive carbon black, 45kg of tin oxide and 5kg of antimony oxide (wherein the particle size of the tin antimony oxide is 100-500 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear speed is 20m/s), then adding 0.15kg of polyvinylpyrrolidone, 0.15kg of ethanol and 0.10kg of propionic acid, and grinding by a ball mill until the materials are uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 mu m is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 5 is obtained.
Example 6
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 3kg of polyacrylate emulsion with the solid content of 25% and 7kg of deionized water, stirring for 24 hours to carry out chelation reaction, then sequentially adding 1kg of conductive carbon black, 1.8kg of tin oxide and 0.2kg of antimony oxide (wherein the particle size of the tin antimony oxide is 100-500 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear speed is 20m/s), then adding 0.01kg of polyvinylpyrrolidone, 0.01kg of ethanol and 0.01kg of propionic acid, and grinding by a ball mill until the mixture is uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that the positive electrode of the lithium ion battery is coated with a current collector coating with the thickness of 0.5-2 mu m, and the negative electrode current collector is not coated with the current collector coating, so that the lithium ion battery of the embodiment 6 is obtained.
Example 7
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 3kg of polyacrylate emulsion with the solid content of 25% and 7kg of deionized water, stirring for 24 hours for chelation reaction, then sequentially adding 1kg of conductive carbon black, 1.8kg of tin oxide and 0.2kg of antimony oxide (wherein the particle size of the tin antimony oxide is 100-500 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear speed is 20m/s), then adding 0.15kg of polyvinylpyrrolidone, 0.15kg of ethanol and 0.10kg of propionic acid, and grinding by a ball mill until the mixture is uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that current collector coatings with the thickness of 0.5-2 mu m are adopted for the negative electrodes of the lithium ion battery, and the current collector coating is not coated on the positive current collector, so that the lithium ion battery of the embodiment 7 is obtained.
Example 8
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 5kg of polyacrylate emulsion with the solid content of 25% and 7kg of deionized water, stirring for 12 hours for chelation reaction, then sequentially adding 1kg of conductive carbon black, 0.9kg of tin oxide and 0.1kg of antimony oxide (wherein the particle size of the tin antimony oxide is 30-100 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear speed is 15m/s), then adding 0.01kg of ethanol and 0.10kg of propionic acid, and grinding by a ball mill until the materials are uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that current collector coatings with the thickness of 0.5-2 mu m are adopted for the negative electrodes of the lithium ion battery, and the current collector coating is not coated on the positive current collector, so that the lithium ion battery of the embodiment 8 is obtained.
Example 9
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 5kg of polyacrylate emulsion with the solid content of 25% and 7kg of deionized water, stirring for 12 hours for chelation reaction, then sequentially adding 1kg of conductive carbon black and 1kg of titanium oxide (wherein the particle size of the titanium oxide is 30-100 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear velocity is 15m/s), then adding 0.05kg of polyvinylpyrrolidone, and grinding by a ball mill until the mixture is uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that current collector coatings with the thickness of 0.5-2 mu m are adopted for the negative electrodes of the lithium ion battery, and the current collector coating is not coated on the positive current collector, so that the lithium ion battery of the embodiment 9 is obtained.
Example 10
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 5kg of polyacrylate emulsion with the solid content of 25% and 7kg of deionized water, stirring for 24 hours to carry out chelation reaction, then sequentially adding 1kg of conductive carbon black and 1kg of tungsten oxide (wherein the particle size of the tungsten oxide is 100-200 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear velocity is 15m/s), and grinding by a ball mill until the materials are uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that current collector coatings with the thickness of 0.5-2 mu m are adopted for the negative electrodes of the lithium ion battery, and the current collector coating is not coated on the positive current collector, so that the lithium ion battery of the embodiment 10 is obtained.
Example 11
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of sodium hydroxide into 5kg of polyacrylate emulsion with the solid content of 25% and 10kg of deionized water, stirring for 12 hours to carry out chelation reaction, then sequentially adding 1kg of Ketjen black and 1kg of tungsten oxide (wherein the particle size of the tungsten oxide is 30-100 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear velocity is 15m/s), and grinding by a ball mill until the materials are uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 μm is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 11 is obtained.
Example 12
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 1kg of polyvinylidene fluoride into 20kg of N-methyl pyrrolidone, stirring for 4 hours to completely dissolve, then sequentially adding 1kg of conductive carbon black, 0.9kg of tin oxide and 0.1kg of antimony oxide (wherein the grain diameter of the tin oxide antimony is 100-500 nm), stirring for 1 hour (wherein the stirring linear velocity is 15m/s), and grinding by a ball mill until the materials are uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 90-100 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 μm is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 12 is obtained.
Example 13
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.1kg of sodium carboxymethyl cellulose into 6.7kg of deionized water, stirring for 4 hours to completely dissolve, then sequentially adding 1kg of conductive carbon black, 0.9kg of tin oxide and 0.1kg of antimony oxide (wherein the grain diameter of the tin antimony oxide is 100-500 nm), stirring for 1 hour (wherein the stirring linear speed is 15m/s), then adding 0.05kg of propionic acid, grinding by a ball mill until the propionic acid is uniformly dispersed, then adding 1.2kg of styrene-butadiene rubber emulsion with the solid content of 48%, and uniformly stirring to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 90-100 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 μm is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 13 is obtained.
Example 14
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 1kg of polyacrylate emulsion with the solid content of 25% and 20kg of deionized water, stirring for 24 hours for chelation reaction, then sequentially adding 1kg of Ketjen black, 0.45kg of tin oxide and 0.05kg of antimony oxide (wherein the particle size of the tin antimony oxide is 100-500 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear velocity is 15m/s), and grinding by a ball mill until the materials are uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 μm is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 14 is obtained.
Example 15
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 1kg of polyacrylate emulsion with the solid content of 25% and 20kg of deionized water, stirring for 24 hours to carry out chelation reaction, then sequentially adding 1kg of carbon nano tube and 0.5kg of titanium oxide (wherein the particle size of the titanium oxide is 30-100 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear velocity is 15m/s), then adding 0.05kg of ethanol, and grinding by a ball mill until the mixture is uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 μm is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 15 is obtained.
Example 16
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 0.20kg of polyacrylate emulsion with the solid content of 25% and 1kg of deionized water, stirring for 24 hours to carry out chelation reaction, then sequentially adding 1kg of conductive carbon black, 0.045kg of tin oxide and 0.005kg of antimony oxide (wherein the particle size of the tin oxide is 100-500 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear velocity is 20m/s), and grinding by a ball mill until the materials are uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 μm is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 16 is obtained.
Example 17
This embodiment is used to illustrate a lithium ion battery and a method for manufacturing the same disclosed in the present invention, and includes the following steps:
(1) adding 0.05kg of calcium hydroxide into 25kg of polyacrylate emulsion with the solid content of 25% and 85kg of deionized water, stirring for 24 hours to carry out chelation reaction, then sequentially adding 1kg of conductive carbon black, 49.5kg of tin oxide and 5.5kg of antimony oxide (wherein the particle size of the tin oxide is 100-500 nm) into the chelated polyacrylate emulsion, stirring for 1 hour (wherein the stirring linear velocity is 20m/s), and grinding by a ball mill until the materials are uniformly dispersed to obtain the coating slurry of the lithium ion battery.
(2) And uniformly coating the obtained coating slurry on a current collector by using a gravure coater, and baking and drying the coating by using an oven to obtain the current collector coating of the lithium ion battery, wherein the baking temperature is 70-90 ℃, and the thickness of the current collector coating is 0.5-2 mu m.
(3) The ternary system lithium ion battery is manufactured according to the existing lithium ion battery manufacturing method, and the difference is that a current collector coating with the thickness of 0.5-2 μm is coated on a current collector of a positive plate and a negative plate of the lithium ion battery, and an active layer is coated on the current collector coating, so that the lithium ion battery of the embodiment 17 is obtained.
Comparative example 1
This comparative example is used for comparative illustration of the lithium ion battery and the preparation method thereof disclosed by the present invention, and includes most of the operation steps in example 1, except that:
in the lithium ion battery of comparative example 1, the current collectors of the positive plate and the negative plate are not coated with the current collector coating, and the active layer is directly coated on the current collectors of the positive plate and the negative plate.
Comparative example 2
This comparative example is used for comparative illustration of the lithium ion battery and the preparation method thereof disclosed by the present invention, and includes most of the operation steps in example 1, except that:
in the lithium ion battery of comparative example 2, the current collector of the positive electrode sheet was not coated with the current collector coating, and the current collector of the negative electrode sheet was coated with the nano conductive graphite and the carbon-coated particles, which were dispersed as described in the background art.
Comparative example 3
This comparative example is used for comparative illustration of the lithium ion battery and the preparation method thereof disclosed by the present invention, and includes most of the operation steps in example 1, except that:
in the lithium ion battery of comparative example 3, the current collector of the negative electrode sheet was not coated with the current collector coating, and the current collector of the positive electrode sheet was coated with the nano conductive graphite and the carbon-coated particles, which were well dispersed as described in the background art.
Comparative example 4
This comparative example is used for comparative illustration of the lithium ion battery and the preparation method thereof disclosed by the present invention, and includes most of the operation steps in example 1, except that:
in the lithium ion battery of comparative example 4, the current collectors of the positive electrode sheet and the negative electrode sheet were coated with the nano conductive graphite and the carbon-coated particles, which were dispersed as described in the background art.
Performance testing
The lithium ion batteries prepared in examples 1 to 17 of the present invention and comparative examples 1 to 4 were subjected to the following performance tests.
1C rate discharge cycle performance and internal resistance test: after the lithium ion batteries prepared in examples 1 to 17 and comparative examples 1 to 4 were formed and divided in capacity, 20 batteries were each tested for capacity retention rate at 55 ℃ and 1C cycle for 500 times on a Scott BS-9365 secondary battery performance testing device. The method comprises the following steps: standing for 10 min; charging to 4.2V/0.05C at 1C; standing for 10 min; discharging to 3.0V with 1C constant current, namely 1 cycle. And repeating the cycle times for 500 times, recording the capacity retention rate and the internal resistance after 500 times, and averaging each group.
The discharge multiplying power test method comprises the following steps: after the lithium ion batteries prepared in examples 1 to 17 and comparative examples 1 to 4 were formed and subjected to capacity grading, 20 batteries were each used to test the battery capacity at different discharge rates on a new Verr high-precision test system. The method comprises the following steps: standing for 10 min; charging to 4.2V/0.05C at 1C; standing for 10 min; the 1C constant current discharge was made to 3.0V, the capacity values were recorded, the mean value was taken for each group and taken as the initial capacity, and the 1C rate discharge was calculated as 100%. Standing for 10 min; charging to 4.2V/0.05C at 1C; standing for 10 min; and discharging to 3.0V at a constant current of 3C, recording the numerical value of the capacity, taking an average value of each group, and dividing the average value by 1C initial capacity to obtain the 3C discharge multiplying factor. Standing for 10 min; charging to 4.2V/0.05C at 1C; standing for 10 min; and discharging to 3.0V at a constant current of 5C, recording the capacity value, taking an average value of each group, and dividing the average value by 1C initial capacity to obtain the 5C discharge multiplying factor.
And (3) thermal shock test: after the lithium ion batteries prepared in examples 1-17 and comparative examples 1-4 are formed and subjected to capacity grading, 10 batteries are respectively taken, a sample is fully charged at room temperature by 0.5C current, after the battery is kept stand for 1h, the battery is placed in an oven, the initial temperature of the oven is 20 +/-5 ℃, the temperature of the oven is increased to 130 +/-2 ℃ at the speed of 5 +/-2 ℃/min, the heating is stopped after the temperature is maintained for 30min, and the test is carried out after the sample returns to the room temperature. And (4) judging the standard: the battery does not catch fire or explode. The test results are recorded as: number of failed/number tested.
And (3) extrusion testing: after the lithium ion batteries prepared in examples 1 to 17 and comparative examples 1 to 4 were formed and classified, 10 batteries were each subjected to pressing between two planes of the batteries, and the pressing pressure was provided by a hydraulic ram or a similar machine for providing pressure. When both planes were in contact with the cell, the pressing was continued until the pressure was 13kN, and once maximum, the pressure was released immediately. And (4) judging the standard: the battery does not catch fire or explode. The test results are recorded as: number of failed/number tested.
The above test results are shown in Table 1-1:
TABLE 1-1
Figure BDA0001510689770000181
As can be seen from Table 1-1, the lithium ion batteries prepared by the preparation methods of examples 1 to 17 of the present invention have better electrochemical properties and safety properties than the lithium ion batteries prepared by the comparative examples 1 to 4. And it can be seen from the comparison between examples 1 to 17 that the electrochemical performance of the lithium ion battery in the preferred range disclosed in the present invention is better.
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 (15)

1. A current collector coating is characterized by comprising the following components in parts by weight: 100 parts of conductive agent, 70 or 90 parts of tin oxide, 10 parts of antimony oxide and 10-500 parts of binder, wherein the particle size of the tin oxide and the antimony oxide is 100-500 nm.
2. The current collector coating of claim 1, wherein the conductive agent comprises one or more of graphene, carbon nanotubes, carbon fibers, activated carbon, graphite flakes, graphite particles, conductive carbon black, and mesocarbon microbeads.
3. The current collector coating of claim 1, wherein the binder comprises one or more of polyvinylidene fluoride, polyacrylate, sodium carboxymethyl cellulose, styrene butadiene rubber, epoxy, silicone, polyimide, phenolic, polyurethane, ethylene vinyl acetate, ethylene acrylic acid, acrylonitrile multipolymer.
4. The current collector coating of claim 1, further comprising, based on 100 parts by weight of the conductive agent: 1-15 parts of a chelating agent; the chelating agent comprises one or more of calcium hydroxide, ammonia water, potassium hydroxide and sodium hydroxide.
5. The current collector coating of claim 1, further comprising, based on 100 parts by weight of the conductive agent: 1-15 parts of a dispersing agent; the dispersing agent comprises one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyethylene oxide ether, polyacrylamide and polyethylene glycol octyl phenyl ether.
6. The current collector coating of claim 1, further comprising, based on 100 parts by weight of the conductive agent: 1-15 parts of a defoaming agent; the antifoaming agent comprises one or more of ethanol and n-butanol.
7. The current collector coating of claim 1, further comprising, based on 100 parts by weight of the conductive agent: 1-10 parts of a preservative; the antiseptic comprises one or more of phenol, cresol, chlorocresol, thymol, hydroxybenzene esters, benzoic acid and its salts, sorbic acid and its salts, boric acid and its salts, propionic acid, dehydroacetic acid, formaldehyde and glutaraldehyde.
8. A coating slurry comprising a solvent and the composition of the current collector coating according to any one of claims 1 to 7.
9. The coating slip of claim 8, wherein the coating slip comprises, in parts by weight: 100 parts of conductive agent, 70 or 90 parts of tin oxide, 10 parts of antimony oxide, 10-500 parts of binder and 20-8000 parts of solvent.
10. The coating slurry according to claim 8, wherein the solvent comprises an organic solvent and/or an inorganic solvent, wherein the organic solvent comprises one or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide, and the inorganic solvent comprises one or more of deionized water, distilled water and purified water.
11. The method for preparing a coating paste according to any one of claims 8 to 10, comprising the steps of:
mixing a conductive agent, tin oxide, antimony oxide, a binder and a solvent, and grinding to obtain coating slurry.
12. The method for preparing coating slurry according to claim 11, wherein the conductive agent, tin oxide, antimony oxide, binder and solvent are mixed and ground to obtain coating slurry, comprising:
adding 1-15 parts by weight of chelating agent into 10-500 parts by weight of binder and 200-8000 parts by weight of solvent, stirring for chelation reaction, adding 100 parts by weight of conductive agent, 70 or 90 parts by weight of tin oxide and 10 parts by weight of antimony oxide, adding 1-15 parts by weight of dispersing agent, 1-15 parts by weight of defoaming agent and 1-10 parts by weight of preservative, continuously stirring, and grinding until the components are uniformly dispersed to obtain coating slurry.
13. The method for preparing a coating slurry according to claim 12, wherein the stirring is performed at a linear speed of 10 to 30m/s for a stirring time of 1 to 24 hours, the grinding operation uses a ball mill having zirconium beads with a particle diameter of 0.3 to 1.2mm, and the dispersing operation uses a high-speed disperser in which the slurry temperature is maintained at 50 ℃ or lower.
14. A battery pole piece, comprising a current collector, an active layer and a current collector coating according to any one of claims 1 to 7, wherein the current collector coating is located between the current collector and the active layer.
15. A lithium ion battery comprising the battery pole piece of claim 14.
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