CN117501480A - Method for manufacturing positive electrode current collector coated with adhesion-enhancing layer, positive electrode current collector coated with adhesion-enhancing layer manufactured thereby, method for manufacturing positive electrode for lithium secondary battery, positive electrode for lithium secondary battery manufactured thereby, and lithium secondary battery comprising same - Google Patents
Method for manufacturing positive electrode current collector coated with adhesion-enhancing layer, positive electrode current collector coated with adhesion-enhancing layer manufactured thereby, method for manufacturing positive electrode for lithium secondary battery, positive electrode for lithium secondary battery manufactured thereby, and lithium secondary battery comprising same Download PDFInfo
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- CN117501480A CN117501480A CN202280041868.9A CN202280041868A CN117501480A CN 117501480 A CN117501480 A CN 117501480A CN 202280041868 A CN202280041868 A CN 202280041868A CN 117501480 A CN117501480 A CN 117501480A
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- Prior art keywords
- positive electrode
- current collector
- enhancing layer
- adhesion
- secondary battery
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- H—ELECTRICITY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention discloses a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, the method comprising the steps of: preparing an aqueous slurry at 0.5:1 to 8:1, comprising a first binder polymer and a first conductive material, the first binder polymer comprising polyvinylidene fluoride-based polymer particles having a melting point of 50 ℃ to 150 ℃; and coating an aqueous slurry on at least one surface of the metal current collector and drying by heat treatment at a temperature higher than the melting point of the polyvinylidene fluoride-based polymer particles to form an adhesion enhancing layer.
Description
Technical Field
The present invention relates to a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, a positive electrode current collector coated with an adhesion enhancing layer manufactured thereby, a method of manufacturing a positive electrode for a lithium secondary battery, a positive electrode for a lithium secondary battery manufactured thereby, and a lithium secondary battery including the positive electrode.
The present application claims priority from korean patent application No. 10-2021-0150118, filed on 3 of 11 in 2021, and korean patent application No. 10-2021-0150119, filed on 3 of 11 in 2021, the disclosures of which are incorporated herein by reference.
Background
In recent years, with the rapid widespread use of electronic devices using batteries, such as mobile phones, notebook computers, and electric vehicles, the demand for secondary batteries having small size, light weight, and relatively high capacity has also rapidly increased. In particular, lithium secondary batteries are attracting attention as power sources for driving mobile devices due to their advantages of light weight and high energy density. Accordingly, many research and development efforts have been made to improve the performance of lithium secondary batteries.
The lithium secondary battery includes a positive electrode and a negative electrode made of an active material capable of intercalating and deintercalating lithium ions, and an organic electrolyte or a polymer electrolyte filled between the positive electrode and the negative electrode, and generates electric energy through oxidation and reduction reactions during intercalation/deintercalation of lithium ions at the positive electrode and the negative electrode.
In general, a positive electrode of a lithium secondary battery is manufactured by: a positive electrode active material slurry containing a positive electrode active material, a conductive material, a binder polymer, and a solvent is coated on a positive electrode current collector made of a metal such as aluminum and dried to form a positive electrode active material layer. Specifically, the positive electrode is manufactured by the steps of: the constituent materials of the positive electrode active material slurry are weighed and mixed, and the positive electrode active material slurry is coated on a positive electrode current collector and dried, and then compressed.
The manufactured positive electrode is assembled into a lithium secondary battery through post-treatment, and because the adhesion strength of the positive electrode active material layer and the current collector is low, there is a possibility that the positive electrode active material may be detached. This problem becomes more serious when the positive electrode active material is a lithium iron phosphate type positive electrode active material or the size of the active material is small.
In order to solve this problem, it has been proposed to form an adhesion enhancing layer containing a binder polymer on a current collector before forming a positive electrode active material layer on the current collector, but it is necessary to develop an adhesion enhancing layer in which the adhesion strength of the positive electrode active material layer to the current collector is high and the interfacial resistance is low.
Further, it is necessary to manufacture a lithium secondary battery: the energy required for drying the slurry forming the coated adhesion-enhancing layer is reduced, and the adhesion strength to the electrode is improved when applied to a lithium secondary battery including an electrolyte.
Disclosure of Invention
Technical problem
An aspect of the present invention is directed to providing a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer having a low interfacial resistance for improving adhesion strength between a positive electrode active material layer and a current collector, a positive electrode current collector coated with an adhesion enhancing layer manufactured thereby, a method of manufacturing a positive electrode for a lithium secondary battery, a positive electrode for a lithium secondary battery manufactured thereby, and a lithium secondary battery including the positive electrode.
Another aspect of the present invention is directed to providing a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer for reducing energy required for drying an aqueous slurry for forming the coated adhesion enhancing layer and maintaining adhesive strength with an electrode when applied to a lithium secondary battery including an electrolyte, a positive electrode current collector coated with an adhesion enhancing layer manufactured thereby, a method of manufacturing a positive electrode for a lithium secondary battery, a positive electrode for a lithium secondary battery manufactured thereby, and a lithium secondary battery including the positive electrode.
Technical proposal
In one aspect of the present invention, there is provided a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer according to the following embodiment.
The first embodiment relates to a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, the method comprising the steps of:
preparing an aqueous slurry at 0.5:1 to 8:1, comprising a first binder polymer and a first conductive material, the first binder polymer comprising polyvinylidene fluoride-based polymer particles having a melting point of 50 ℃ to 150 ℃; and
the aqueous slurry is coated on at least one surface of a metal current collector and dried by heat treatment at a temperature higher than the melting point of the polyvinylidene fluoride-based polymer particles to form an adhesion enhancing layer.
In the first embodiment, the second embodiment relates to a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, wherein the polyvinylidene fluoride-based polymer has a melting point of 70 to 150 ℃, more specifically 90 to 150 ℃.
In the first or second embodiment, the third embodiment relates to a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, wherein the polyvinylidene fluoride-based polymer is a vinylidene fluoride-hexafluoropropylene copolymer.
In any of the first to third embodiments, the fourth embodiment is directed to a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, wherein the polyvinylidene fluoride-based polymer has a weight average molecular weight of 700,000 to 1,300,000, more specifically 800,000 to 1,100,000.
In any one of the first to fourth embodiments, the fifth embodiment relates to a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, wherein the polyvinylidene fluoride-based polymer particles have an average particle size of 10nm to 3 μm.
In any one of the first to fifth embodiments, the sixth embodiment is directed to a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, wherein the polyvinylidene fluoride-based polymer particles have an average particle size of 100nm to 1,000nm, and the first conductive material has an average particle size of 10nm to 1,000nm.
In a sixth embodiment, the seventh embodiment is directed to a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, wherein the average particle size of the polyvinylidene fluoride-based polymer particles is 3 to 20 times the average particle size of the first conductive material.
In any one of the first to seventh embodiments, the eighth embodiment is directed to a method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, wherein the drying is performed at a temperature 10 to 80 ℃ higher than the melting point of the polyvinylidene fluoride-based polymer particles.
Another aspect of the present invention provides a positive electrode current collector coated with an adhesion enhancing layer according to the following embodiment.
A ninth embodiment relates to a positive electrode current collector coated with an adhesion-enhancing layer, the positive electrode current collector comprising:
a metal current collector; and
an adhesion enhancing layer on at least one surface of the metal current collector, the adhesion enhancing layer being at 0.5:1 to 8:1 comprises a first binder polymer and a first conductive material,
wherein the first binder polymer comprises a polyvinylidene fluoride based polymer,
the first binder polymer is distributed in an island-like array over the surface of the metal current collector, and
The melting point of the polyvinylidene fluoride polymer is 50 ℃ to 150 ℃.
In a ninth embodiment, the tenth embodiment relates to a positive electrode current collector coated with an adhesion enhancing layer, wherein the polyvinylidene fluoride-based polymer has a melting point of 70 ℃ to 150 ℃, more specifically 90 ℃ to 150 ℃.
In a ninth or tenth embodiment, the eleventh embodiment is directed to a positive electrode current collector coated with an adhesion enhancing layer, wherein the polyvinylidene fluoride-based polymer is a vinylidene fluoride-hexafluoropropylene copolymer.
In any of the ninth to eleventh embodiments, the twelfth embodiment is directed to a positive electrode current collector coated with an adhesion enhancing layer, wherein the polyvinylidene fluoride-based polymer has a weight average molecular weight of 700,000 to 1,300,000, more specifically 800,000 to 1,100,000.
Another aspect of the present invention provides a method of manufacturing a positive electrode for a lithium secondary battery according to the following embodiment.
A thirteenth embodiment relates to a method of manufacturing a positive electrode for a lithium secondary battery, the method comprising the steps of:
manufacturing the positive electrode current collector coated with the adhesion enhancing layer according to any one of the first to eighth embodiments; and
a positive electrode active material layer including a positive electrode active material, a second conductive material, and a second binder polymer is stacked on and attached to the adhesion enhancing layer.
In a thirteenth embodiment, the fourteenth embodiment relates to a method of manufacturing a positive electrode for a lithium secondary battery, wherein,
the metal current collector is made of aluminum, and
the positive electrode active material is represented by the following chemical formula 1:
< chemical formula 1>
Li 1+a Fe 1-x M x (PO 4-b )X b ，
Wherein,
m is at least one selected from Al, mg, ni, co, mn, ti, ga, cu, V, nb, zr, ce, in, zn and Y, and
x is at least one selected from F, S and N,
-0.5≤a≤+0.5，0≤x≤0.5，0≤b≤0.1。
in a thirteenth or fourteenth embodiment, the fifteenth embodiment relates to the method for manufacturing a positive electrode for a lithium secondary battery, wherein the second binder polymer is at least one selected from the group consisting of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), and poly (vinylidene fluoride-chlorotrifluoroethylene).
In any one of the thirteenth to fifteenth embodiments, the sixteenth embodiment is directed to a method for manufacturing a positive electrode for a lithium secondary battery, wherein the adhesion enhancing layer on one surface of the metal current collector has a thickness of 50nm to 5,000nm, and the positive electrode active material layer on one surface of the adhesion enhancing layer has a thickness of 40 μm to 200 μm.
Another aspect of the present invention provides a positive electrode for a lithium secondary battery according to the following embodiment.
A seventeenth embodiment relates to a positive electrode for a lithium secondary battery, the positive electrode comprising:
the positive electrode current collector coated with the adhesion enhancing layer according to any one of the ninth to twelfth embodiments; and
a positive electrode active material layer attached to the adhesion enhancing layer, and the positive electrode active material layer includes a positive electrode active material, a second conductive material, and a second binder polymer.
In a seventeenth embodiment, the eighteenth embodiment relates to a positive electrode for a lithium secondary battery, wherein,
the metal current collector is made of aluminum, and
the positive electrode active material is represented by the following chemical formula 1:
< chemical formula 1>
Li 1+a Fe 1-x M x (PO 4-b )X b ，
Wherein,
(M is at least one selected from Al, mg, ni, co, mn, ti, ga, cu, V, nb, zr, ce, in, zn and Y, and
x is at least one selected from F, S and N,
-0.5≤a≤+0.5，0≤x≤0.5，0≤b≤0.1)。
in a seventeenth or eighteenth embodiment, the nineteenth embodiment relates to the positive electrode for a lithium secondary battery, wherein the second binder polymer is at least one selected from the group consisting of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), and poly (vinylidene fluoride-chlorotrifluoroethylene).
In any one of the seventeenth to nineteenth embodiments, the twentieth embodiment relates to a positive electrode for a lithium secondary battery, wherein the adhesion-enhancing layer on one surface of the metal current collector has a thickness of 50nm to 5,000nm, and the positive electrode active material layer on one surface of the adhesion-enhancing layer has a thickness of 40 μm to 200 μm.
A twenty-first embodiment provides a lithium secondary battery comprising the positive electrode according to any one of the seventeenth to twentieth embodiments.
Advantageous effects
According to one embodiment of the present invention, an aqueous slurry forming an adhesion enhancing layer, which contains polyvinylidene fluoride polymer particles having a predetermined melting point range and a first conductive material in a predetermined amount ratio range, is coated on a metal current collector and dried at a temperature higher than the melting point, and when solidified after melting, the polyvinylidene fluoride polymer of the adhesion enhancing layer is distributed in an island-like array over the surface of the current collector. That is, the polyvinylidene fluoride-based polymer distributed in an island-like array does not cover the entire surface of the current collector. Therefore, the adhesion enhancing layer improves the adhesion strength between the positive electrode active material layer and the current collector, and the interfacial resistance is low.
Further, with the polyvinylidene fluoride polymer having a predetermined melting point range, even when the aqueous slurry is dried at a relatively low temperature to reduce energy, the polyvinylidene fluoride polymer particles can exhibit good adhesion performance as an adhesion enhancing layer after melting and solidification, and have resistance to dissolution in an electrolyte when applied to a lithium secondary battery including the electrolyte, thereby maintaining adhesion strength with a positive electrode.
Drawings
The accompanying drawings illustrate exemplary embodiments of the invention and, together with the description of the invention, serve to facilitate a further understanding of the technical aspects of the invention, and therefore the invention should not be construed as being limited to the accompanying drawings. On the other hand, the shape, size, scale or proportion of the elements in the drawings may be exaggerated to emphasize a clearer description.
Fig. 1 is a Scanning Electron Microscope (SEM) image of an adhesion enhancing layer according to example 1.
FIG. 2 is a Differential Scanning Calorimeter (DSC) of Polymer A used in example 1.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. Before the description, it should be understood that terms or words used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Thus, the summary of the embodiments described herein is an exemplary embodiment of the invention, but is not intended to fully describe the technical aspects of the invention so that it should be understood that various other equivalents and modifications could be made thereto at the time of filing.
According to a method of manufacturing a positive electrode current collector coated with an adhesion-enhancing layer of one aspect of the present invention, an aqueous slurry is prepared, the aqueous slurry being at 0.5:1 to 8:1, and a first conductive material, the first binder polymer comprising polyvinylidene fluoride-based polymer particles having a melting point of 50 ℃ to 150 ℃.
The slurry forming the adhesion enhancing layer is an aqueous slurry using water as a dispersion medium.
The aqueous slurry may further optionally contain solvents such as isopropyl alcohol, acetone, ethanol, and butanol to reduce surface energy and improve coating properties.
The aqueous slurry contains a first binder polymer to improve the adhesive strength of the metal current collector and the positive electrode active material layer, and for the first binder polymer, the present invention contains particles of a polyvinylidene fluoride-based polymer having a melting point of 50 to 150 ℃, for example. The use of particulate polyvinylidene fluoride-based polymer prevents the increase in resistance of the adhesion enhancing layer.
The average particle size of the polyvinylidene fluoride polymer particles may be, for example, 10nm to 3 μm from the viewpoints of dispersibility and storage safety. In particular, when considering improving the bonding to the positive electrode active material layer, the phase safety in the slurry, and the solvent resistance in the electrolyte, the average particle size of the polyvinylidene fluoride-based polymer particles may be 100nm to 1,000nm. Further, the average particle size of the polyvinylidene fluoride-based polymer particles may be 3 to 20 times the average particle size of the first conductive material.
When the melting point of the polyvinylidene fluoride polymer is lower than 50 ℃, it is highly likely that the polyvinylidene fluoride polymer will dissolve in an electrolyte used in a battery assembly and the adhesive strength with an electrode will be reduced. Further, when the melting point exceeds 150 ℃, the drying temperature of the aqueous slurry as described below increases very much, causing an increase in energy consumption and a decrease in improvement in adhesive strength. In view of this, more specifically, the melting point of the polyvinylidene fluoride-based polymer may be 70 ℃ to 150 ℃, more specifically 90 ℃ to 150 ℃, and most specifically 100 ℃ to 140 ℃. The polyvinylidene fluoride-based polymer may include, for example, vinylidene fluoride-hexafluoropropylene, but is not limited thereto.
The polyvinylidene fluoride-based polymer may have a weight average molecular weight of 700,000 to 1,300,000, more specifically 800,000 to 1,100,000. When the weight average molecular weight is within the above range, the adhesion strength to the positive electrode active material layer is further enhanced.
In addition to the polyvinylidene fluoride-based polymer particles described above, the aqueous slurry may further comprise another binder polymer in the form of microparticles or dissolved in water without departing from the object of the present invention.
On the other hand, the aqueous slurry contains a first conductive material to prevent an increase in resistance of the positive electrode. The amount of the first conductive material may be, for example, 10 to 200 parts by weight based on 100 parts by weight of the first adhesive polymer, but is not limited thereto. When considering dispersibility and conductivity in the slurry, the average particle size of the first conductive material may be 10nm to 1,000nm, but is not limited thereto.
The first conductive material may include, but is not limited to, any type of conductive material that is electrically conductive without causing side reactions with other elements of the battery, such as: graphite such as natural graphite or artificial graphite; carbon black materials such as carbon black (super-p), acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black; conductive fibers such as carbon fibers or metal fibers; carbon nanotubes such as MW-CNT, SW-CNT; a fluorocarbon compound; metal powders such as aluminum and nickel powders; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or conductive materials such as polyphenylene derivatives, and they may be used alone or in combination to reduce interface resistance.
In the aqueous slurry, the weight ratio of the first binder polymer comprising polyvinylidene fluoride polymer particles to the first conductive material is 0.5:1 to 8:1. when the weight ratio is less than 0.5:1, the adhesion strength is poor, when the weight ratio exceeds 8: at 1, the interface resistance increases very much. In view of this, the weight ratio of the polyvinylidene fluoride-based polymer particles to the first conductive material may be 1:1 to 5:1.
The aqueous slurry may further comprise at least one type of thickener to control viscosity. In particular, the thickener may include carboxymethyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, casein, and methyl cellulose, but is not limited thereto.
In addition to the above components, the aqueous slurry may further comprise any other additive such as a dispersant without departing from the object of the present invention.
Subsequently, the prepared aqueous slurry is coated on at least one surface of a metal current collector and dried by heat treatment at a temperature higher than the melting point of the polyvinylidene fluoride-based polymer particles to form an adhesion enhancing layer.
For the positive electrode current collector, a metal current collector such as aluminum is used. In particular, aluminum can be used in the form of foil, and aluminum foil is easily oxidized in air to form a surface layer of aluminum oxide. Thus, an aluminum current collector should be interpreted as a current collector comprising a surface layer having aluminum oxide formed as a result of oxidation of aluminum on the surface. The thickness of the metal current collector may be generally 3 to 500 μm, but is not limited thereto.
Conventional slurry coating methods and apparatuses may be used to coat an aqueous slurry on a metal current collector, and the coating methods may include, for example, a bar coating method such as Meyer bar, a gravure coating method, a 2-roll reverse coating method, a vacuum slot die coating method, and a 2-roll coating method. An adhesion enhancing layer is formed on at least one surface of the metal current collector, i.e., one or both surfaces of the metal current collector, to improve adhesion strength between the metal current collector and a positive electrode active material layer, which will be described later. When considering the adhesion strength improving effect and the increase in the positive electrode resistance, the thickness of the adhesion enhancing layer (the thickness of the adhesion enhancing layer formed on one surface of the metal current collector instead of both surfaces) may be, for example, 50 to 5,000nm, more specifically, may be 100 to 1,000nm, but is not limited thereto.
The metal current collector coated with the aqueous slurry is dried by heat treatment at a temperature higher than the melting point of the polyvinylidene fluoride-based polymer particles to form an adhesion enhancing layer. Specifically, the drying process may be performed at a temperature 10 to 80 ℃ higher than the melting point of the polyvinylidene fluoride polymer particles, but is not limited thereto.
When the polyvinylidene fluoride polymer particles are dried by heat treatment at a temperature higher than the melting point of the polyvinylidene fluoride polymer particles, the polyvinylidene fluoride polymer particles melt and as the temperature decreases, they solidify to form an adhesion enhancing layer bonded to the metal current collector. In this case, the polyvinylidene fluoride-based polymer of the adhesion enhancing layer is distributed in an island-like array over the surface of the current collector. That is, the polyvinylidene fluoride-based polymer distributed in an island-like array does not cover the entire surface of the current collector. Therefore, the adhesion enhancing layer improves the adhesion strength between the positive electrode active material layer and the current collector, and the interfacial resistance is low.
Further, as described above, with the polyvinylidene fluoride-based polymer having a predetermined melting point range, the aqueous slurry can be dried at a relatively low temperature to reduce power consumption, and the adhesion enhancing layer has good adhesion properties. When applied to a lithium secondary battery including an electrolyte, the adhesion enhancing layer resists dissolution in the electrolyte, thereby maintaining adhesion strength with the positive electrode.
The positive electrode current collector coated with the adhesion enhancing layer manufactured by the above-described manufacturing method according to one aspect includes:
a metal current collector; and
an adhesion enhancing layer on at least one surface of the metal current collector, and the adhesion enhancing layer is at 0.5:1 to 8:1 comprises a first binder polymer and a first conductive material,
wherein the first binder polymer comprises a polyvinylidene fluoride based polymer,
the first binder polymer is distributed in an island-like array on the surface of the metal current collector, and
the melting point of the polyvinylidene fluoride polymer is 50 ℃ to 150 ℃.
The types of the metal current collector, the first binder polymer, the first conductive material, and the adhesion enhancing layer, which are made into the positive electrode current collector coated with the adhesion enhancing layer, have been described above, and detailed descriptions thereof are omitted.
After the positive electrode current collector coated with the adhesion enhancing layer is manufactured by the above-described manufacturing method, a positive electrode active material layer including a positive electrode active material, a second conductive material, and a second binder polymer is stacked on and attached to the adhesion enhancing layer to manufacture a positive electrode for a lithium secondary battery.
The positive electrode active material layer includes a positive electrode active material, a second conductive material, and a second binder polymer in the same manner as a conventional positive electrode active material layer for a lithium secondary battery.
The positive electrode active material may include a conventional positive electrode active material used in a lithium secondary battery, for example, a lithium transition metal oxide. Specifically, the positive electrode active material may include a positive electrode active material represented by the following chemical formula 1.
< chemical formula 1>
Li 1+a Fe 1-x M x (PO 4-b )X b
(M is at least one selected from Al, mg, ni, co, mn, ti, ga, cu, V, nb, zr, ce, in, zn and Y, and
x is at least one selected from F, S and N,
-0.5≤a≤+0.5，0≤x≤0.5，0≤b≤0.1)。
the positive electrode active material of the above chemical formula 1 is a lithium iron phosphate compound, and particularly has low bonding strength with an aluminum current collector. Accordingly, when the adhesion enhancing layer according to the present invention is applied, there is an increasing industrial demand for improving the adhesion strength with the current collector.
The second binder polymer for binding the positive electrode active material may generally include a binder polymer applied to the positive electrode material, for example, at least one of the following: polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene Propylene Diene Monomer (EPDM), sulfonated EPDM, styrene Butadiene Rubber (SBR), fluororubber, or various copolymers thereof. More preferably, the second adhesive polymer may comprise a polyvinylidene fluoride-based polymer, and the interaction of the adhesion enhancing layer with the polyvinylidene fluoride-based polymer increases the effect of improving the interlayer adhesion strength. In view of this, more preferably, the second binder polymer may contain at least one selected from the group consisting of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), and poly (vinylidene fluoride-chlorotrifluoroethylene). The content of the binder may be 1 to 30 wt% based on the total weight of the positive electrode active material layer.
As the second conductive material used in the positive electrode active material layer, the first conductive material of the adhesion enhancing layer may be used independently. The content of the second conductive material may generally be 1 to 30 wt% based on the total weight of the positive electrode active material layer.
The method for stacking the positive electrode active material layer and attaching it to the adhesion enhancing layer may include methods commonly used in the art.
For example, a composition for forming a positive electrode active material layer, which contains a positive electrode active material, a second conductive material, and a second binder polymer, may be coated on the adhesion enhancing layer, dried, and pressed.
In this case, the solvent used in the composition for forming the positive electrode active material layer may include solvents commonly used in the art, for example, at least one of the following: dimethyl sulfoxide (DMSO), isopropanol, N-methylpyrrolidone (NMP), acetone or water. From the viewpoints of the coating thickness of the coating solution and the production yield, the solvent may be used in such an amount that the viscosity is sufficient to dissolve the binder polymer, disperse the conductive material and the positive electrode active material, and then achieve good thickness uniformity when the positive electrode is manufactured for coating.
The polyvinylidene fluoride-based polymer contained in the adhesion enhancing layer has fluidity when subjected to heat and pressure. For example, when heat and pressure are subjected to a temperature range from the melting point (Tm) of the polymer to 60 ℃ to the melting point (Tm) +60 ℃ of the binder polymer, more specifically, a temperature range from the melting point (Tm) of the binder polymer to 50 ℃ to the melting point (Tm) +50 ℃ of the binder polymer, more specifically, a temperature range from the melting point (Tm) of the binder polymer to 40 ℃ to the melting point (Tm) +30 ℃ of the binder polymer, at a temperature higher than the glass transition temperature of the polyvinylidene fluoride polymer, the binder polymer of the adhesion enhancing layer becomes flowable by the heat and adheres to the surface layer of the positive electrode active material layer in contact with the adhesion enhancing layer.
In the positive electrode for a lithium secondary battery manufactured by the above-described manufacturing method according to one aspect, the thickness of the positive electrode active material layer (the thickness of the positive electrode active material layer formed on one surface of the adhesion enhancing layer, not on both surfaces of the adhesion enhancing layer, after pressing) may be 40 to 200 μm, but is not limited thereto.
The adhesive strength of the positive electrode active material layer is preferably 30gf/2cm or more, more preferably 40gf/2cm or more. Further, the interfacial resistance of the positive electrode active material layer is preferably 3 Ω cm 2 Hereinafter, it is more preferably 2. OMEGA cm 2 The following is given.
The positive electrode for a lithium secondary battery manufactured by the above-described manufacturing method according to one aspect comprises:
a positive electrode current collector coated with an adhesion enhancing layer; and
a positive electrode active material layer attached to the adhesion enhancing layer, and the positive electrode active material layer includes a positive electrode active material, a second conductive material, and a second binder polymer.
The metal current collector, the binder polymer, the conductive material, and the positive electrode active material, which are manufactured into the positive electrode for the lithium secondary battery, have been described above, and detailed descriptions thereof are omitted.
According to another embodiment of the present invention, there is provided a lithium secondary battery including the positive electrode for a lithium secondary battery.
Specifically, the lithium secondary battery includes a positive electrode, a negative electrode opposite to the positive electrode, a separator between the positive electrode and the negative electrode, and an electrolyte, and the positive electrode is the same as described above. Further, optionally, the lithium secondary battery may further include a battery case accommodating the electrode assembly including the positive electrode, the negative electrode, and the separator, and a sealing member sealing the battery case.
In a lithium secondary battery, an anode includes an anode current collector and an anode active material layer on the anode current collector.
The anode current collector is not limited to a specific type, and may contain a current collector having high conductivity without causing any chemical change to the battery, for example: copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel treated with carbon, nickel, titanium or silver on the surface, and aluminum-cadmium alloy, but are not limited thereto. Further, the thickness of the anode current collector may be generally 3 to 500 μm, and in the same manner as the cathode current collector, the anode current collector may have fine irregularities on the surface to improve the bonding strength of the anode active material. For example, the anode current collector may take various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
The anode active material layer optionally contains a binder and a conductive material in addition to the anode active material. For example, the anode active material layer may be formed by: a negative electrode-forming composition comprising a negative electrode active material, and optionally a binder and a conductive material, is coated on a negative electrode current collector and dried, or is formed by the steps of: the negative electrode-forming composition is cast on a support, the film is peeled off from the support, and the film is laminated on a negative electrode current collector.
The anode active material may contain a compound capable of reversibly intercalating and deintercalating lithium. Specific examples may include at least one of the following: carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon; a (semi) metallic material capable of forming an alloy with lithium such as Si, al, sn, pb, zn, bi, in, mg, ga, cd, si alloy, sn alloy or Al alloy; (semi) metal oxides such as SiO which can be doped or undoped with lithium β (0<β<2)、SnO 2 Vanadium oxide, lithium vanadium oxide; or a composite material such as a Si-C composite or a Sn-C composite comprising a (semi) metallic material and a carbonaceous material. In addition, a metallic lithium thin film may be used for the anode active material. Further, the carbon material may include low crystalline carbon and high crystalline carbon. Low crystalline carbon typically includes soft and hard carbon and high crystalline carbon typically includes high temperature sintered carbon such as amorphous, platy, spherical or fibrous natural or artificial graphite, condensed graphite, pyrolytic carbon, mesophase pitch-like carbon fibers, mesophase carbon microspheres, mesophase pitch and petroleum or coal tar pitch derived cokes.
In addition, the binder and the conductive material may be the same as those of the positive electrode described above.
On the other hand, in a lithium secondary battery, a separator separates a negative electrode and a positive electrode and provides a moving channel of lithium ions, and may include, but is not limited to, any separator commonly used in lithium secondary batteries, particularly preferred is a separator having low resistance to movement of electrolyte ions and good wettability with an electrolyte. Specifically, the separator may include, for example, a porous polymer film made of a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer, or a stacked structure of two or more layers of porous polymer films. In addition, the separator may comprise a conventional porous non-woven fabric, such as a non-woven fabric made of high-melting glass fibers and polyethylene terephthalate fibers. In addition, in order to secure heat resistance or mechanical strength, a coated separator including a ceramic-based material or a polymer material may be used, and may be selectively used in a single-layer or multi-layer structure.
In addition, the electrolyte used in the present invention may include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel polymer electrolyte, a solid inorganic electrolyte, and a molten inorganic electrolyte, which may be used to manufacture a lithium secondary battery, but is not limited thereto.
Specifically, the electrolyte may be an electrolyte solution containing an organic solvent and a lithium salt.
The organic solvent may include, but is not limited to, any type of organic solvent that serves as a medium for ion movement that participates in the electrochemical reaction of the cell. Specifically, the organic solvent may include: ester solvents such as methyl acetate, ethyl acetate, gamma-butyrolactone, epsilon-caprolactone; ether solvents such as dibutyl ether or tetrahydrofuran; ketone solvents such as cyclohexanone; aromatic solvents such as benzene and fluorobenzene; carbonate solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), ethylene Carbonate (EC), propylene Carbonate (PC); alcohol solvents such as ethanol, isopropanol; nitriles such as r—cn (R is a C2 to C20 linear, branched or cyclic hydrocarbon group and may contain double bonds, aromatic rings or ether linkages); amides such as dimethylformamide; dioxolanes such as 1, 3-dioxolane; or sulfolane. Among them, a carbonate-based solvent is desirable, and more preferably, a cyclic carbonate (e.g., ethylene carbonate or propylene carbonate) having high ion conductivity and high dielectric constant contributing to the improvement of charge/discharge performance of the battery may be mixed with a linear carbonate-based compound (e.g., ethylene carbonate, dimethyl carbonate or diethyl carbonate) having low viscosity. In this case, the cyclic carbonate and the chain carbonate may be present in an amount of about 1:1 to about 1:9 in a volume ratio to improve the performance of the electrolyte.
The lithium salt may include, but is not limited to, any compound capable of providing lithium ions used in a lithium secondary battery. In particular, the lithium salt may comprise LiPF 6 、LiClO 4 、LiAsF 6 、LiBF 4 、LiSbF 6 、LiAlO 4 、LiAlCl 4 、LiCF 3 SO 3 、LiC 4 F 9 SO 3 、LiN(C 2 F 5 SO 3 ) 2 、LiN(C 2 F 5 SO 2 ) 2 、LiN(CF 3 SO 2 ) 2 LiCl, liI or LiB (C) 2 O 4 ) 2 . The concentration of the lithium salt may be in the range of 0.1 to 2.0M. When the concentration of the lithium salt is included in the above range, the electrolyte has optimal conductivity and viscosity, resulting in good performance of the electrolyte and effective movement of lithium ions.
In order to improve the life characteristics of the battery, prevent the capacity fading of the battery, and improve the discharge capacity of the battery, the electrolyte may further contain, in addition to the above-described constituent substances of the electrolyte, at least one additive such as: halogenated alkylene carbonates such as difluoroethylene carbonate, pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, (formal) glyme, hexamethylphosphoric triamide, nitrobenzene derivatives, sulfur, quinone imine dyes, and N-substitutedOxazolidinone, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salts, pyrrole, 2-methoxyethanol or aluminum trichloride. In this case, the content of the additive may be 0.1 to 5 wt% based on the total weight of the electrolyte.
The lithium secondary battery can be used in the following fields: mobile devices, including mobile phones, laptop computers, and digital cameras; and electric vehicles, including Hybrid Electric Vehicles (HEVs).
Thus, according to another embodiment of the present invention, there are provided a battery module including a lithium secondary battery as a unit cell and a battery pack including the same.
The battery module or the battery pack may be used as a power source for a medium-sized and large-sized device of at least one of the following devices: an electric tool; electric vehicles, including Electric Vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); or an energy storage system.
Hereinafter, embodiments of the present invention will be described in sufficient detail to enable those skilled in the art to which the present invention pertains to easily practice the present invention. This invention may, however, be embodied in many different forms and is not limited to the embodiments disclosed.
Example 1
Polymer A (Solvay, vinylidene fluoride-hexafluoropropylene copolymer, VDF: HFP=3:1 (weight ratio), average particle size: 250nm, melting point: 100 ℃, mw= 1,080,000) as the first binder polymer]And danka carbon black (bet=60 m) 2 /g, dbp=200 ml/100 g) at 2:1 in weight ratio in water and Daicel 2200 as a thickener was supplied in an amount of 1/5 of the weight of the binder polymer to prepare an aqueous slurry containing 10% solids. Subsequently, the aqueous slurry was coated on both surfaces of an aluminum foil having a thickness of 20 μm using a micro gravure coater, and dried at 120 ℃ for 3 minutes to form an adhesion enhancing layer on the aluminum foil. Will be produced by mixing LiFe (PO 4 ) Polyvinylidene fluoride (mw=630,000) and danka carbon black (bet=60 m) as second binder polymers 2 /g, dbp=200 ml/100 g) at 96:2:2, the positive electrode active material slurry prepared by mixing was coated on the adhesion enhancing layer, dried at 140 ℃ for 10 minutes and pressed to prepare a positive electrode.
Lithium metal was used as a negative electrode, and the negative electrode and the positive electrode were stacked with a separator (Celgard) interposed therebetween to manufacture an electrode assembly. Stamping the electrode assembly into a coin shape and injecting 1M LiPF into it 6 Electrolyte dissolved in a mixed solvent (PC: EMC: ec=3:4:3) of Propylene Carbonate (PC), ethylene Methyl Carbonate (EMC) and Ethylene Carbonate (EC) to manufacture a testA lithium secondary battery is used.
Example 2
A lithium secondary battery was fabricated in the same manner as in example 1, except that the changes shown in table 1 below were made.
Example 3
A lithium secondary battery was fabricated in the same manner as in example 1, except that the changes shown in table 1 below were made.
Example 4
A lithium secondary battery was fabricated in the same manner as in example 1, except that polymer B (Solvay, vinylidene fluoride-hexafluoropropylene copolymer, VDF: hfp=97:3 (weight ratio), average particle size: 250nm, melting point: 140 ℃, mw=800,000) ] was used for the first binder polymer, and the changes shown in table 1 below were made.
Example 5
A lithium secondary battery was fabricated in the same manner as in example 1, except that the changes shown in table 1 below were made. Polymer A in example 5: danka carbon black: mw-CNT weight ratio of 2:1:0.1.
comparative example 1
A lithium secondary battery was fabricated in the same manner as in example 1, except that the changes shown in table 1 below were made.
Comparative example 2
A lithium secondary battery was fabricated in the same manner as in example 1, except that polymer C (Solvay, polyvinylidene fluoride, average particle size: 250nm, melting point: 168 ℃, mw=600,000) was used for the first binder polymer, and the changes shown in table 1 below were made.
Comparative example 3
A lithium secondary battery was fabricated in the same manner as in example 1, except that the adhesion enhancing layer was formed as follows.
And (2): polymer D (Solvay, polyvinylidene fluoride, melting point: 168 ℃, mw=630,000) and danard carbon black (product name: li-250) were added as the first binder polymer in a weight ratio of 1 to prepare a 10% organic syrup polymer in which the danard carbon black was dispersed and polymer D was dissolved in NMP. Subsequently, the organic slurry was coated on both surfaces of a 20 μm thick aluminum foil and dried at 120 ℃ for 3 minutes to form an adhesion enhancing layer on the aluminum foil.
Comparative example 4
Except for 2:1 weight ratio of polymer E (Solvay, polyvinylidene fluoride, melting point: 170 ℃, mw=1,000,000) and danka carbon black (bet=60 m) as first binder polymer 2 Per g, dbp=200 ml/100 g) to prepare an organic slurry in which the dan-ca carbon black was dispersed and polymer E was dissolved in NMP, a lithium secondary battery was prepared in the same manner as in comparative example 3.
Example 6
Polymer A (Solvay, vinylidene fluoride-hexafluoropropylene copolymer, VDF: HFP=3:1 (weight ratio), average particle size: 250nm, melting point: 100 ℃, mw= 1,080,000) as the first binder polymer]And DANCAR carbon black (product name: li-250) having an average particle size of 37nm as a first conductive material in an amount of 2:1 in weight ratio in water and Daicel 2200 as a thickener was supplied in an amount of 1/5 of the weight of the binder polymer to prepare an aqueous slurry containing 10% solids. Subsequently, the aqueous slurry was coated on both surfaces of an aluminum foil having a thickness of 20 μm using a micro gravure coater, and dried at 120 ℃ for 3 minutes to form an adhesion enhancing layer on the aluminum foil. Will be produced by mixing LiFe (PO 4 ) Polyvinylidene fluoride (mw=630,000) as a second binder polymer, and danka carbon black (product name: li-250) at 96:2:2, the positive electrode active material slurry prepared by mixing was coated on the adhesion enhancing layer, dried at 140 ℃ for 10 minutes and pressed to prepare a positive electrode.
Lithium metal was used as a negative electrode, and the negative electrode and the positive electrode were stacked with a separator (Celgard) interposed therebetween to manufacture an electrode assembly. Stamping the electrode assembly into a coin shape and injecting 1M LiPF into it 6 An electrolyte dissolved in a mixed solvent (PC: EMC: ec=3:4:3) of Propylene Carbonate (PC), ethylene Methyl Carbonate (EMC) and Ethylene Carbonate (EC) to manufacture a lithium secondary battery for test.
Example 7
Except that the Dancarboblack (product name: li-435) having an average particle size of 23nm was used for the first conductive material, and the ratio of the polymer A to the conductive material was changed to 1: except for 1, a lithium secondary battery was fabricated in the same manner as in example 6.
Example 8
A lithium secondary battery was fabricated in the same manner as in example 6, except that the changes shown in table 2 below were made.
Example 9
A lithium secondary battery was fabricated in the same manner as in example 6, except that polymer B (Solvay, vinylidene fluoride-hexafluoropropylene copolymer, VDF: hfp=97:3 (weight ratio), average particle size: 250nm, melting point: 140 ℃, mw=800,000) ] was used for the first binder polymer, and the changes shown in table 2 below were made.
Example 10
Except for using LiNi 0.50 Co 0.20 Mn 0.30 O 2 Instead of LiFe (PO) 4 ) Polyvinylidene fluoride (mw=630,000) was used for the second binder polymer, super-P was used for the second conductive material and their weight ratio was 97.5:1.5: except for 1, a lithium secondary battery was fabricated in the same manner as in example 6.
Comparative examples 5 and 6
A lithium secondary battery was fabricated in the same manner as in example 6, except that the changes shown in table 2 below were made.
Comparative example 7
Except for using LiNi 0.50 Co 0.20 Mn 0.30 O 2 Instead of LiFe (PO) 4 ) Polyvinylidene fluoride (mw=630,000) was used for the second binder polymer, super-P was used for the second conductive material and their weight ratio was 97.5:1.5: except for 1, a lithium secondary battery was fabricated in the same manner as in comparative example 5.
Comparative example 8
A lithium secondary battery was fabricated in the same manner as in example 6, except that an adhesion enhancing layer was formed as described below.
And (2): polymer C (Solvay, polyvinylidene fluoride, melting point: 168 ℃, mw=880,000) and danard carbon black (product name: li-250) as a first binder polymer were added in a weight ratio of 1 to prepare a 10% organic slurry in which the danard carbon black was dispersed and polymer C was dissolved in NMP. Subsequently, the organic slurry was coated on both surfaces of a 20 μm thick aluminum foil and dried at 120 ℃ for 3 minutes to form an adhesion enhancing layer on the aluminum foil.
< measurement of melting Point of adhesive Polymer >
The melting point of the adhesive polymer was measured using Differential Scanning Calorimetry (DSC).
A TA DSC2500 was used to supply 5 to 10mg samples and thermal scans were performed under a nitrogen atmosphere as follows: heating from 50 ℃ to 250 ℃ at a heating rate of 10 ℃/min, cooling at a cooling rate of 10 ℃/min, and heating from 50 ℃ to 250 ℃ at a heating rate of 10 ℃/min.
FIG. 2 is a DSC of Polymer A of example 1. Referring to fig. 2, the melting point can be obtained by an endothermic peak during the second heating, and the melting point is found to be the temperature at the peak top.
< measurement of weight average molecular weight of Polymer >
0.04g of the polymer was taken and dissolved in 10g of tetrahydrofuran to prepare a sample specimen, and the reference specimen (polystyrene) and the sample specimen were filtered through a filter having a pore size of 0.45 μm and injected into a GPC syringe. The number average molecular weight, weight average molecular weight and polydispersity of the acrylic polymer were measured by comparing the dissolution time of the sample specimens with the calibration curve of the reference specimens. The measurement was performed using GPC (information II 1260, agilent) at a flow rate of 1.00 mL/min and column temperature of 35.0deg.C.
< measurement of average particle size of Polymer particles >
The polymer particles were scanned by SEM and the average particle size was measured by averaging the length of the long axis.
< measurement of average particle size of conductive Material >
The average particle size D50 of the conductive material was measured using a laser diffraction method. The conductive material was dispersed in a dispersion medium, and an average particle size D50 at 50% of the particle size distribution was calculated using a laser diffraction particle size measurement apparatus (Microtac MT 3000).
< evaluation of adhesion Strength >
The positive electrodes manufactured according to examples and comparative examples were punched to a size of 2cm (width) ×10cm (length) or more using a punching machine. Glass was used for a substrate (2.5 cm (width) ×7.5cm (length) ×1T (thickness)), a double-sided tape was attached to the glass, and the punched electrodes were attached in parallel. The electrode attached to the tape was 6cm, and the adhesive strength of the electrode was measured while maintaining 90 ° with the substrate using a texture analyzer (LLOYD).
< WET (WET) adhesion Strength evaluation >
Wet adhesion strength evaluation was performed by the following steps: the electrode coated foil was stored at 130 ℃ for 24 hours to remove moisture by a vacuum drying oven, the electrode was received in an aluminum pouch together with the electrolyte, the aluminum pouch was sealed, stored in an oven at 70 ℃ for 2 weeks and the adhesion strength was measured. In this case, to remove the residual electrolyte, the electrodes were washed with DMC washing solution and dried completely, and measurements were made. Since the solubility resistance of the adhesion enhancing layer is deteriorated as compared with before the evaluation of the electrolyte resistance, the adhesion strength of the adhesion enhancing layer to the electrolyte is lowered when applied to a lithium secondary battery.
< evaluation of interfacial resistance >
The positive electrodes manufactured according to examples and comparative examples were punched to a size of 5cm (horizontal) ×5cm (vertical) using a punching machine. The thickness of the punched electrode, the thickness of the aluminum foil and the specific resistance value of the current collector (2.82×10) were inputted using a Mp tester (HIOKI) -6 ) And the punched electrode is placed under the tip of the embedded probe and the measurement is performed by lowering the rod.
TABLE 1
TABLE 2
Referring to the results of tables 1 and 2, it can be seen that, when a specific binder component is used, the adhesive strength of the positive electrodes of examples 1 to 10 having the adhesion enhancing layer comprising the binder polymer and the conductive material according to the present invention is improved and the interfacial resistance is low.
In contrast, it can be seen that comparative example 1, which does not contain a conductive material, has high interfacial resistance, and comparative example 2, which does not contain the binder polymer having a specific melting point of the present invention, has lower adhesive strength than the positive electrode of the example. Further, it can be seen that the interfacial resistances of comparative examples 3, 4 and 8 using the organic slurry in which the binder polymer was dissolved in the solvent were high.
Further, it can be seen that the interfacial resistances of comparative examples 5 and 7, in which the weight ratio of the first conductive material to the first binder polymer is very low, were very high, and the adhesive strength of comparative example 6, in which the weight ratio of the first conductive material to the first binder polymer is very high, was very low.
Claims (21)
1. A method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer, the method comprising the steps of:
preparing an aqueous slurry at 0.5:1 to 8:1, comprising a first binder polymer and a first conductive material, the first binder polymer comprising polyvinylidene fluoride-based polymer particles having a melting point of 50 ℃ to 150 ℃; and
the aqueous slurry is coated on at least one surface of a metal current collector and dried by heat treatment at a temperature higher than the melting point of the polyvinylidene fluoride-based polymer particles to form the adhesion enhancing layer.
2. The method of manufacturing an adhesion-enhancing layer coated positive electrode current collector according to claim 1, wherein the polyvinylidene fluoride-based polymer has a melting point of 70 ℃ to 150 ℃.
3. The method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer according to claim 1, wherein the polyvinylidene fluoride-based polymer is a vinylidene fluoride-hexafluoropropylene copolymer.
4. The method of manufacturing an adhesion-enhancing layer coated positive electrode current collector according to claim 1, wherein the polyvinylidene fluoride-based polymer has a weight average molecular weight of 700,000 to 1,300,000.
5. The method of manufacturing an adhesion-enhancing layer coated positive electrode current collector according to claim 1, wherein the polyvinylidene fluoride-based polymer particles have an average particle size of 10nm to 3 μm.
6. The method for manufacturing a positive electrode current collector coated with an adhesion-enhancing layer according to claim 1, wherein,
the polyvinylidene fluoride polymer particles have an average particle size of 100nm to 1,000nm, and
the first conductive material has an average particle size of 10nm to 1,000nm.
7. The method of manufacturing an adhesion-enhancing layer coated positive electrode current collector according to claim 6, wherein the average particle size of the polyvinylidene fluoride-based polymer particles is 3 to 20 times the average particle size of the first conductive material.
8. The method of manufacturing a positive electrode current collector coated with an adhesion enhancing layer according to claim 1, wherein the drying is performed at a temperature 10 ℃ to 80 ℃ higher than the melting point of the polyvinylidene fluoride-based polymer particles.
9. A positive electrode current collector coated with an adhesion enhancing layer, the positive electrode current collector comprising:
a metal current collector; and
an adhesion enhancing layer on at least one surface of the metal current collector, the adhesion enhancing layer at 0.5:1 to 8:1 comprises a first binder polymer and a first conductive material,
Wherein the first binder polymer comprises a polyvinylidene fluoride based polymer,
wherein the first binder polymer is distributed in an island-like array over the surface of the metal current collector, and
wherein the melting point of the polyvinylidene fluoride polymer is 50-150 ℃.
10. The adhesion-enhancing layer coated positive electrode current collector of claim 9, wherein the polyvinylidene fluoride-based polymer has a melting point of 70 ℃ to 150 ℃.
11. The adhesion-promoting layer coated positive electrode current collector of claim 9, wherein the polyvinylidene fluoride-based polymer is a vinylidene fluoride-hexafluoropropylene copolymer.
12. The adhesion-enhancing layer coated positive electrode current collector of claim 9, wherein the polyvinylidene fluoride-based polymer has a weight average molecular weight of 700,000 to 1,300,000.
13. A method of manufacturing a positive electrode for a lithium secondary battery, the method comprising the steps of:
manufacturing the positive electrode current collector coated with the adhesion-enhancing layer of any one of claims 1 to 8; and
a positive electrode active material layer including a positive electrode active material, a second conductive material, and a second binder polymer is stacked on and attached to the adhesion enhancing layer.
14. The method for manufacturing a positive electrode for a lithium secondary battery according to claim 13, wherein,
the metal current collector is made of aluminum, and
the positive electrode active material is represented by the following chemical formula 1:
< chemical formula 1>
Li 1+a Fe 1-x M x (PO 4-b )X b ，
Wherein,
(M is at least one selected from Al, mg, ni, co, mn, ti, ga, cu, V, nb, zr, ce, in, zn and Y, and
x is at least one selected from F, S and N,
-0.5≤a≤+0.5，0≤x≤0.5，0≤b≤0.1)。
15. the method for manufacturing a positive electrode for a lithium secondary battery according to claim 13, wherein the second binder polymer is at least one selected from the group consisting of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), and poly (vinylidene fluoride-chlorotrifluoroethylene).
16. The method for manufacturing a positive electrode for a lithium secondary battery according to claim 13, wherein,
the adhesion enhancing layer on one surface of the metal current collector has a thickness of 50nm to 5,000nm, and
the thickness of the positive electrode active material layer on one surface of the adhesion enhancing layer is 40 μm to 200 μm.
17. A positive electrode for a lithium secondary battery, the positive electrode comprising:
the positive electrode current collector coated with an adhesion enhancing layer of any one of claims 9 to 12; and
and a positive electrode active material layer attached to the adhesion enhancing layer, the positive electrode active material layer including a positive electrode active material, a second conductive material, and a second binder polymer.
18. The positive electrode for a lithium secondary battery according to claim 17, wherein,
the metal current collector is made of aluminum, and
the positive electrode active material is represented by the following chemical formula 1:
< chemical formula 1>
Li 1+a Fe 1-x M x (PO 4-b )X b ，
(wherein,
m is at least one selected from Al, mg, ni, co, mn, ti, ga, cu, V, nb, zr, ce, in, zn and Y, and
x is at least one selected from F, S and N,
-0.5≤a≤+0.5，0≤x≤0.5，0≤b≤0.1)。
19. the positive electrode for a lithium secondary battery according to claim 17, wherein the second binder polymer is at least one selected from the group consisting of polyvinylidene fluoride, poly (vinylidene fluoride-hexafluoropropylene), and poly (vinylidene fluoride-chlorotrifluoroethylene).
20. The positive electrode for a lithium secondary battery according to claim 17, wherein,
the adhesion enhancing layer on one surface of the metal current collector has a thickness of 50nm to 5,000nm, and
the thickness of the positive electrode active material layer on one surface of the adhesion enhancing layer is 40 μm to 200 μm.
21. A lithium secondary battery comprising the positive electrode of claim 17.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| KR10-2021-0150119 | 2021-11-03 | ||
| KR1020210150119A KR20230064477A (en) | 2021-11-03 | 2021-11-03 | Manufacturing method of positive electrode current collector coated with adhesion enhancement layer, positive electrode current collector coated with adhesion enhancement layer manufactured therefrom, manufacturing method of positive electrode for lithium secondary battery, positive electrode for lithium secondary battery manufactured therefrom and lithium secondary battery comprising same |
| KR10-2021-0150118 | 2021-11-03 | ||
| PCT/KR2022/016295 WO2023080514A1 (en) | 2021-11-03 | 2022-10-24 | Manufacturing method of positive electrode current collector coated with adhesion enhancement layer, positive electrode current collector coated with adhesion enhancement layer manufactured thereby, manufacturing method of positive electrode for lithium secondary battery, positive electrode for lithium secondary battery manufactured thereby, and lithium secondary battery comprising same |
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