CN108565381B - Battery coating film slurry, battery diaphragm, secondary battery and preparation method thereof - Google Patents

Battery coating film slurry, battery diaphragm, secondary battery and preparation method thereof Download PDF

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CN108565381B
CN108565381B CN201810289099.XA CN201810289099A CN108565381B CN 108565381 B CN108565381 B CN 108565381B CN 201810289099 A CN201810289099 A CN 201810289099A CN 108565381 B CN108565381 B CN 108565381B
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slurry
battery
copolymer
solvent
coating film
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CN108565381A (en
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程跃
王连杰
陈永乐
王治学
黄灿灿
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Shanghai Energy New Materials Technology Co Ltd
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Shanghai Energy New Materials Technology Co Ltd
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Priority to PCT/CN2019/081007 priority patent/WO2019192475A1/en
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4056—(I) or (II) containing sulfur
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a battery coating film slurry, a battery diaphragm, a secondary battery and respective preparation methods, wherein the preparation of the battery coating film slurry comprises the following steps: providing a first copolymer comprising tetrafluoroethylene; providing a second copolymer; copolymerizing the first copolymer with the second copolymer to obtain a slurry copolymer; and preparing the battery coating film slurry based on the slurry copolymer. Through the technical scheme, the battery coating film slurry is designed, and a non-aqueous system is adopted, so that the diaphragm and the pole piece can be bonded together, the hardness of the battery is improved, and the prepared polymer has higher crystallinity, smaller swelling ratio and more excellent bonding property; the prepared battery has smaller internal resistance and more excellent cycle performance.

Description

Battery coating film slurry, battery diaphragm, secondary battery and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to battery coating film slurry, a battery diaphragm, a secondary battery and a preparation method thereof.
Background
The lithium ion battery generally mainly comprises a positive electrode, a negative electrode, a diaphragm, an electrolyte and a battery shell. In the structure of the lithium ion battery, a diaphragm is one of key inner layer components. The diaphragm is mainly used for separating the positive electrode from the negative electrode of the battery, preventing the short circuit caused by the direct contact of the positive electrode and the negative electrode, enabling electrolyte ions to smoothly pass through the diaphragm in the charging and discharging process of the battery to form current, closing a migration channel of the electrolyte ions when the working temperature of the battery is abnormally increased, and cutting off the current to ensure the safety of the battery. Therefore, the performance of the diaphragm determines the interface structure, internal resistance and the like of the battery, the characteristics of the battery such as capacity, cycle and safety performance are directly influenced, and the diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery.
With the development of electric automobile industry, the improvement of battery performance is more and more important, the existing PVDF (polyvinylidene fluoride) -coated copolymer diaphragm has adhesive property, so that the diaphragm and a pole piece can be bonded together, and the hardness of the battery is improved, so that the PVDF copolymer is very important, at present, the PVDF applied to the coating of the diaphragm in the market has crystallinity (generally between 20% and 30%), swelling ratio (30% to 150%) and adhesive property which are not completely suitable for the current battery system, and the search for PVDF with stronger performance is particularly important. In addition, the existing PVDF has two main synthesis methods, one is a homopolymer generally applied to a positive electrode and a negative electrode, the other is a copolymer generally applied to a lithium ion battery separator, where the PVDF mainly used for coating the lithium ion battery separator is daily used, and the PVDF generally used in daily life is prepared by copolymerizing vinylidene fluoride (VDF) and Hexafluoropropylene (HFP), however, the PVDF obtained by copolymerization has a relatively low crystallinity, and a relatively high swelling coefficient in an electrolyte, and the prepared separator has a relatively low adhesive property, so that the problems of relatively high internal resistance and relatively poor cycle performance of the battery are caused, and the performance of the battery is affected.
Therefore, how to provide a battery coating film slurry, a battery diaphragm, a secondary battery and respective preparation methods thereof are necessary to solve the problems that the existing polyvinylidene fluoride (PVDF) copolymer is low in crystallinity and relatively large in swelling, and the obtained diaphragm is relatively small in bonding performance, so that the internal resistance of the battery is relatively large and the cycle performance is relatively poor.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a battery coating film slurry, a battery separator, a secondary battery and their respective preparations, which are used to solve the problems of the prior art, such as low crystallinity and relatively high swelling ratio of polyvinylidene fluoride (PVDF) copolymer, and relatively low adhesion of the obtained separator, resulting in relatively high internal resistance and relatively poor cycle performance of the battery.
In order to achieve the above and other related objects, the present invention provides a method for preparing a battery coating film slurry, comprising the steps of:
1) providing a first copolymer comprising tetrafluoroethylene;
2) providing a second copolymer;
3) copolymerizing the first copolymer with the second copolymer to obtain a slurry copolymer; and
4) and preparing the battery coating film slurry based on the slurry copolymer.
In a preferred embodiment of the present invention, the second copolymer includes at least one of vinylidene fluoride, acrylic acid, methacrylic acid, methyl acrylate, and ethyl acrylate.
In a preferred embodiment of the present invention, the second copolymer is vinylidene fluoride.
In a preferred embodiment of the present invention, the weight percentage of the tetrafluoroethylene in the syrup copolymer is between 0.1% and 20%.
As a preferable embodiment of the present invention, the specific step of obtaining the battery coating film slurry in step 4) includes: and dissolving the slurry copolymer in a first solvent to obtain a first mixed solution, wherein the first mixed solution forms the battery coating film slurry.
As a preferable embodiment of the present invention, the specific step of obtaining the battery coating film slurry in step 4) includes:
4-1) dissolving the slurry copolymer in a first solvent to obtain a first mixed solution;
4-2) providing a filler, and dissolving the filler in a second solvent to obtain a second mixed solution; and
4-3) mixing the second mixed solution with the first mixed solution to obtain the battery coating film slurry.
In a preferred embodiment of the present invention, the first solvent includes at least one of DMAC, DMF, NMP, and acetone.
In a preferred embodiment of the present invention, in the step 4-2), the filler includes at least one of aluminum trioxide, silicon dioxide, titanium dioxide, cerium dioxide, calcium carbonate, calcium oxide, zinc oxide, magnesium oxide, cerium titanate, calcium titanate, barium titanate, lithium phosphate, lithium titanium phosphate, lithium aluminum titanium phosphate, lithium nitride, and lithium lanthanum titanate.
In a preferred embodiment of the present invention, in the step 4-2), the second solvent includes at least one of DMAC, DMF, NMP, and acetone.
In a preferred embodiment of the present invention, the second solvent is the same as the first solvent.
In a preferable embodiment of the present invention, in the step 4-2), the filler is less than 4 parts by weight and the second solvent is 8 to 50 parts by weight in the second mixed solution.
In a preferable embodiment of the present invention, in the step 4-3), the weight percentage of the first mixed solution in the battery coating film slurry is between 50% and 90%.
The invention also provides a preparation method of the battery diaphragm, which comprises the following steps: providing a base film; preparing battery coating film slurry according to the preparation method of any one of the above schemes; and coating the battery coating film slurry on at least one surface of the base film to obtain the battery diaphragm.
The invention also provides a preparation method of the secondary battery, which comprises the step of preparing the battery diaphragm by adopting the preparation method of the battery diaphragm according to any scheme.
The invention also provides battery coating film slurry, and the preparation raw material of the battery coating film slurry comprises a slurry copolymer, wherein the slurry copolymer is obtained by copolymerizing a first copolymer and a second copolymer, and the first copolymer comprises tetrafluoroethylene.
In a preferred embodiment of the present invention, the second copolymer includes at least one of vinylidene fluoride, acrylic acid, methacrylic acid, methyl acrylate, and ethyl acrylate.
In a preferred embodiment of the present invention, the weight percentage of the tetrafluoroethylene in the syrup copolymer is between 0.1% and 20%.
In a preferred embodiment of the present invention, the second copolymer is vinylidene fluoride.
In a preferred embodiment of the present invention, the raw material for preparing the battery coating film slurry further includes a first solvent, wherein the slurry copolymer is dissolved in the first solvent to form a first mixed solution, and the first mixed solution forms the battery coating slurry.
In a preferred embodiment of the present invention, the first solvent includes at least one of DMAC, DMF, NMP, and acetone.
In a preferred embodiment of the present invention, the raw material for preparing the battery coating film slurry further includes a first solvent, a filler, and a second solvent, wherein the slurry copolymer is dissolved in the first solvent to form a first mixed solution, the filler is dissolved in the second solvent to form a second mixed solution, the first mixed solution and the second mixed solution are mixed to form the battery coating slurry, and the weight percentage of the first mixed solution in the battery coating film slurry is 50% to 90%, wherein the filler in the second mixed solution is less than 4 parts, and the second solvent in the second mixed solution is 8 to 50 parts.
As a preferred embodiment of the present invention, the first solvent includes at least one of DMAC, DMF, NMP, and acetone; the second solvent comprises at least one of DMAC, DMF, NMP, and acetone.
In a preferred embodiment of the present invention, the second solvent is the same as the first solvent.
The invention also provides a battery separator, comprising a base film; and a coating layer on at least one surface of the base film, and the coating layer is prepared by using the battery coating film slurry according to any one of the above aspects.
The present invention also provides a secondary battery including the battery separator according to any one of the above aspects.
As described above, the battery coating film slurry, the battery separator, the secondary battery and the respective manufacturing methods according to the present invention have the following advantageous effects:
the battery coating film slurry is designed, and a non-aqueous system is adopted, so that the diaphragm and the pole piece can be bonded together, the hardness of the battery is improved, and the prepared polymer has higher crystallinity, smaller swelling ratio and more excellent bonding property; the prepared battery has smaller internal resistance and more excellent cycle performance.
Drawings
Fig. 1 shows a flow chart of a method for preparing a battery coating film slurry according to the present invention.
Fig. 2 is a schematic structural view of a battery separator provided in the present invention.
Fig. 3 shows an electron micrograph of a battery separator coating layer according to the present invention.
Description of the element reference numerals
11 base film
21,22 coating layer
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 3. It should be noted that the drawings provided in the present embodiment are only schematic and illustrate the basic idea of the present invention, and although the drawings only show the components related to the present invention and are not drawn according to the number, shape and size of the components in actual implementation, the form, quantity and proportion of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
As shown in fig. 1, the present invention provides a method for preparing a battery coating film slurry, comprising the steps of:
1) providing a first copolymer comprising tetrafluoroethylene;
2) providing a second copolymer;
3) copolymerizing the first copolymer with the second copolymer to obtain a slurry copolymer; and
4) and preparing the battery coating film slurry based on the slurry copolymer.
By way of example, the second copolymer includes at least one of vinylidene fluoride, acrylic acid, methacrylic acid, methyl acrylate, and ethyl acrylate.
Specifically, the invention provides a preparation method of a nonaqueous system battery coating film slurry, which can be used for preparing a battery diaphragm of a secondary battery, wherein the first copolymer and the second copolymer refer to materials copolymerized in the subsequent step, in addition, the second copolymer can be one of the materials or the combination of any two or more of the materials, the first copolymer and the second copolymer are copolymerized to obtain a slurry copolymer (PVDF copolymer) for preparing the battery coating film slurry in the subsequent step, preferably, the second copolymer comprises at least two of vinylidene fluoride, acrylic acid, methacrylic acid, methyl acrylate and ethyl acrylate, one of the two is vinylidene fluoride, and the second copolymer is vinylidene fluoride, so that the process is simplified, and the good performance is achieved, Compared with the coating film slurry in the prior art, the slurry copolymer has high crystallinity which is generally between 30 and 70 percent, small swelling ratio which is between 5 and 30 and more excellent bonding property, thereby being beneficial to obtaining secondary batteries with excellent performance in the follow-up process.
As an example, the specific step of obtaining the battery coating film slurry in step 4) comprises: and dissolving the slurry copolymer in a first solvent to obtain a first mixed solution, wherein the first mixed solution forms the battery coating film slurry.
Illustratively, the weight percentage of the tetrafluoroethylene in the slurry copolymer is between 0.1% and 20%.
Illustratively, the first solvent comprises at least one of DMAC, DMF, NMP, and acetone.
In this example, the first mixed solution prepared by dissolving the prepared slurry copolymer in the first solvent can be used as the slurry for the battery coating film as it is, and further, the weight percentage of the tetrafluoroethylene in the slurry copolymer is preferably 3 to 15% to obtain the coating film slurry having excellent performance, and the first solvent is selected, and may be any one of NMP (N-methylpyrrolidone), DMAC (dimethylacetamide), acetone, and DMF (dimethylformamide), or may be a combination of any two or more of the above solvents, and is not particularly limited.
As an example, the specific step of obtaining the battery coating film slurry in step 4) comprises:
4-1) dissolving the slurry copolymer in a first solvent to obtain a first mixed solution;
4-2) providing a filler, and dissolving the filler in a second solvent to obtain a second mixed solution; and
4-3) mixing the second mixed solution with the first mixed solution to obtain the battery coating film slurry.
In addition, the present example provides another mode of obtaining the battery coating film slurry, in which the first mixed solution of the slurry copolymer is first obtained, then the filler is dissolved in another second solvent to obtain a second mixed solution, and then the prepared first mixed solution and the prepared second mixed solution are mixed, and preferably, the second mixed solution is added to the first mixed solution to obtain the battery coating film slurry, wherein the filler can further reduce the air permeability of the battery separator to be prepared later.
Illustratively, the first solvent comprises at least one of DMAC, DMF, NMP, and acetone.
As an example, in the step 4-2), the filler includes at least one of aluminum trioxide, silicon dioxide, titanium dioxide, cerium dioxide, calcium carbonate, calcium oxide, zinc oxide, magnesium oxide, cerium titanate, calcium titanate, barium titanate, lithium phosphate, lithium titanium phosphate, lithium aluminum titanium phosphate, lithium nitride, and lithium lanthanum titanate.
Illustratively, in step 4-2), the second solvent includes at least one of DMAC, DMF, NMP, and acetone.
As an example, the second solvent is the same as the first solvent.
Specifically, in this example, the first solvent may be any one of NMP (N-methylpyrrolidone), DMAC (dimethylacetamide), acetone, DMF (dimethylformamide), or a combination of any two or more of the above solvents; the second solvent may be any one of NMP (N-methylpyrrolidone), DMAC (dimethylacetamide), acetone, DMF (dimethylformamide), or a combination of any two or more of the above solvents. Preferably, the first solvent and the second solvent are the same in type, so that uniformity and stability of the battery separator slurry prepared subsequently can be guaranteed. The filler may be any one of the above materials, or may be a combination of any two or more of the above materials, and is not particularly limited herein.
Illustratively, the weight percentage of the tetrafluoroethylene in the slurry copolymer is between 0.1% and 20%.
As an example, in the step 4-2), the filler is less than 4 parts by weight and the second solvent is 8 to 50 parts by weight in the second mixed solution.
As an example, in step 4-3), the weight percentage of the first mixed solution in the battery coating film slurry is between 50% and 90%.
Specifically, in order to obtain a battery coating film with good performance, in this example, the weight percentage of the tetrafluoroethylene in the slurry copolymer is between 0.1% and 20%, preferably between 3% and 15%, and in addition, in parts by weight, the filler is preferably between 2 and 3 parts, and the second solvent is preferably between 20 and 30 parts, and after the second mixed solution is uniformly dispersed, the second mixed solution is added to 50 to 90 parts of the first mixed solution, and further, the first mixed solution is preferably between 60 and 80 parts, so as to obtain a battery coating film with good performance.
As an example, the particle size of the resulting syrup copolymer is between 0.1 μm and 20 μm.
Specifically, the size of the slurry copolymer prepared by the method can be preferably between 2 μm and 10 μm, so that the proper particle size can ensure good copolymer performance, and a diaphragm and a battery with excellent performance can be obtained.
The invention also provides a battery coating film slurry, wherein the battery coating film slurry is preferably prepared by the battery coating film slurry preparation method, the raw material for preparing the battery coating film slurry comprises a slurry copolymer, the slurry copolymer is obtained by copolymerizing a first copolymer and a second copolymer, and the first copolymer comprises tetrafluoroethylene.
By way of example, the second copolymer includes at least one of vinylidene fluoride, acrylic acid, methacrylic acid, methyl acrylate, and ethyl acrylate.
Specifically, the invention provides a preparation method of a nonaqueous system battery coating film slurry, which can be used for preparing a battery diaphragm of a secondary battery, wherein the first copolymer and the second copolymer refer to substances copolymerized in the subsequent step, in addition, the second copolymer can be one of the substances or the combination of any two or more of the substances, the first copolymer and the second copolymer are copolymerized to obtain the slurry copolymer for preparing the battery coating film slurry, preferably, the second copolymer comprises at least two of vinylidene fluoride, acrylic acid, methacrylic acid, methyl acrylate and ethyl acrylate, one of the two is vinylidene fluoride, and further preferably, the second copolymer is vinylidene fluoride, so that the process is simplified, and the good performance is achieved, Compared with the coating film slurry in the prior art, the slurry copolymer has high crystallinity which is generally between 30 and 70 percent, small swelling ratio which is between 5 and 30 and more excellent bonding property, thereby being beneficial to obtaining secondary batteries with excellent performance in the follow-up process.
Illustratively, the weight percentage of the tetrafluoroethylene in the slurry copolymer is between 0.1% and 20%.
As an example, the raw material for preparing the battery coating film slurry further comprises a first solvent, wherein the slurry copolymer is dissolved in the first solvent to form a first mixed solution, and the first mixed solution forms the battery coating slurry.
Specifically, the present example provides a battery coating film slurry prepared based on the slurry copolymer, the slurry copolymer is dissolved in the first solvent, and the first mixed solution thus prepared can be directly used as the slurry of the battery coating film, further, the weight percentage of the tetrafluoroethylene in the slurry copolymer is preferably between 3% and 15%, so that a coating film slurry with excellent performance can be obtained, and the first solvent is selected, and may be any one of NMP (N-methylpyrrolidone), DMAC (dimethylacetamide), acetone, and DMF (dimethylformamide), or a combination of any two or more of the above solvents, which is not particularly limited herein.
In an example, the raw material for preparing the battery coating film slurry further includes a first solvent, a filler and a second solvent, wherein the slurry copolymer is dissolved in the first solvent to form a first mixed solution, the filler is dissolved in the second solvent to form a second mixed solution, the first mixed solution and the second mixed solution are mixed to form the battery coating slurry, and in parts by weight, the filler in the second mixed solution is less than 4 parts, the second solvent is 8-50 parts, and the weight percentage of the first mixed solution in the obtained battery coating film slurry is between 50% and 90%.
Illustratively, the first solvent comprises at least one of DMAC, DMF, NMP, and acetone; the second solvent comprises at least one of DMAC, DMF, NMP, and acetone.
As an example, the second solvent is the same as the first solvent.
Specifically, the present example provides another battery coating film slurry prepared based on the slurry copolymer, in which the first mixed solution of the slurry copolymer is first obtained, the filler is then dissolved in another second solvent to obtain a second mixed solution, the prepared first mixed solution and the prepared second mixed solution are then mixed, and the second mixed solution is preferably added to the first mixed solution to obtain the battery coating film slurry, wherein the filler can further reduce the air permeability of a subsequently prepared battery separator.
Wherein, in order to obtain a battery coating film with good performance, the weight percentage of the tetrafluoroethylene in the slurry copolymer in the first mixed solution is between 0.1 and 20 percent, preferably between 3 and 15 percent, in addition, the filler in the second mixed solution is preferably between 2 and 3 parts by weight, the second solvent is preferably between 20 and 30 parts by weight, and after the second mixed solution is uniformly dispersed, the second mixed solution is added into 50 to 90 parts by weight of the first mixed solution, and further, the first mixed solution is preferably between 60 and 80 parts by weight, so as to obtain the battery coating film with good performance.
As shown in fig. 2, the present invention also provides a method for preparing a battery separator, comprising: providing a base film 11; preparing the battery coating film slurry according to the preparation method of any one of the above schemes; and coating the battery coating film slurry on at least one surface of the base film to obtain the battery diaphragm.
The invention also provides a battery diaphragm, wherein the battery diaphragm is preferably prepared by the battery diaphragm preparation method provided by the invention, the battery diaphragm comprises a base film 11 and coating layers 21 and 22 positioned on at least one surface of the base film, and the coating layers are prepared by the battery coating film slurry according to any scheme.
The battery coating film slurry may be coated on a surface of a base film on one side, or may be coated on two opposite surfaces of the base film, wherein the base film 11 may be a PE material or a PP material, but not limited thereto, and is preferably coated by a gravure roll method, and the specific method is: and (2) pumping the slurry onto the gravure roller through a pump, rotating the gravure roller, carrying the material onto the gravure roller, contacting the material with the base film, and coating the slurry onto the base film. The battery diaphragm obtained by the battery coating film slurry provided by the invention has better bonding performance.
The invention also provides a preparation method of the secondary battery, which comprises the step of preparing the battery diaphragm by adopting the preparation method of the battery diaphragm according to any scheme.
The invention also provides a secondary battery, wherein the secondary battery is preferably prepared by adopting the preparation method of the secondary battery provided by the invention, and the secondary battery comprises the battery diaphragm according to any one scheme.
The secondary battery obtained by the battery coating film slurry provided by the invention has smaller internal resistance and better cycle performance.
The invention further describes battery diaphragm slurry, a battery diaphragm, a lithium ion battery and respective preparation methods thereof by combining specific embodiments.
Example 1:
firstly, copolymerizing 5% of tetrafluoroethylene and 95% of vinylidene fluoride to prepare a vinylidene fluoride-tetrafluoroethylene copolymer, dissolving 1.44Kg of the copolymer in 16.56Kg of DMAC (dimethylacetamide) to obtain 8% of solid content, firstly dispersing 0.16Kg of alumina powder in 1.84Kg of DMAC, uniformly dispersing, and then adding 18Kg of prepared polymer solution into the dispersed alumina dispersion to prepare the experimental slurry.
Taking a PE base film with the thickness of 12 microns, adopting a gravure roll coating mode (the concrete method for coating by adopting the gravure roll mode is that slurry is pumped onto a gravure roll through a pump, then the gravure roll rotates, the material is carried onto the gravure roll, and then the slurry is contacted with the base film, so that the slurry can be coated on the base film), coating the polymer slurry on one side of the base film, wherein the coating speed is 15m/min, drying is carried out by adopting three stages of drying ovens after water is passed, the temperatures of the drying ovens at all stages are respectively 50 ℃, 60 ℃ and 55 ℃, and the lithium ion battery diaphragm coated by the oily polymer can be obtained after drying, wherein the thickness of the coated lithium ion battery diaphragm is 14 microns, and the thickness of the coating is 2 microns.
Example 2:
firstly, 8 percent of tetrafluoroethylene and 92 percent of vinylidene fluoride are copolymerized to prepare a copolymer, 1.2Kg of polymer is dissolved in 13.8Kg of DMAC, the solid content is 8 percent, 0.4Kg of alumina powder is firstly dispersed in 4.6Kg of DMAC, after uniform dispersion, 15Kg of prepared PVDF solution is added into the dispersed alumina dispersion liquid, and the experimental slurry can be prepared.
Taking a PE base film with the thickness of 12 microns, adopting a gravure roll coating mode (the concrete method for coating by adopting the gravure roll mode is that slurry is pumped onto a gravure roll through a pump, then the gravure roll rotates, the material is carried onto the gravure roll, and then the slurry is contacted with the base film, so that the slurry can be coated on the base film), coating the polymer slurry on one side of the base film, wherein the coating speed is 15m/min, drying is carried out by adopting three stages of drying ovens after water is passed, the temperatures of the drying ovens at all stages are respectively 50 ℃, 60 ℃ and 55 ℃, and the lithium ion battery diaphragm coated by the oily polymer can be obtained after drying, wherein the thickness of the coated lithium ion battery diaphragm is 14 microns, and the thickness of the coating is 2 microns.
Example 3:
firstly, copolymerizing 15% of tetrafluoroethylene and 85% of vinylidene fluoride to prepare a copolymer, dissolving 0.8Kg of polymer in 9.2Kg of DMAC (dimethylacetamide) with the solid content of 10%, firstly dispersing 0.8Kg of alumina powder in 9.2Kg of DMAC, uniformly dispersing, and then adding 10Kg of the prepared polymer solution into the dispersed alumina dispersion to prepare the experimental slurry.
Taking a PE base film with the thickness of 12 microns, adopting a gravure roll coating mode (the concrete method for coating by adopting the gravure roll mode is that slurry is pumped onto a gravure roll through a pump, then the gravure roll rotates, the material is carried onto the gravure roll, and then the slurry is contacted with the base film, so that the slurry can be coated on the base film), coating the polymer slurry on one side of the base film, wherein the coating speed is 15m/min, drying is carried out by adopting three stages of drying ovens after water is passed, the temperatures of the drying ovens at all stages are respectively 50 ℃, 60 ℃ and 55 ℃, and the lithium ion battery diaphragm coated by the oily polymer can be obtained after drying, wherein the thickness of the coated lithium ion battery diaphragm is 14 microns, and the thickness of the coating is 2 microns.
Example 4:
first, 8% tetrafluoroethylene and 92% acrylic acid were copolymerized to prepare a polymer, 1.6Kg of the polymer was dissolved in 18.4Kg of DMAC to obtain 8% solids, and no inorganic substance was added to prepare an experimental slurry.
Taking a PE base film with the thickness of 12 microns, adopting a gravure roll coating mode (the concrete method for coating by adopting the gravure roll mode is that slurry is pumped onto a gravure roll through a pump, then the gravure roll rotates, the material is carried onto the gravure roll, and then the slurry is contacted with the base film, so that the slurry can be coated on the base film), coating the polymer slurry on one side of the base film, wherein the coating speed is 15m/min, drying is carried out by adopting three stages of drying ovens after water is passed, the temperatures of the drying ovens at all stages are respectively 50 ℃, 60 ℃ and 55 ℃, and the lithium ion battery diaphragm coated by the oily polymer can be obtained after drying, wherein the thickness of the coated lithium ion battery diaphragm is 14 microns, and the thickness of the coating is 2 microns.
Comparative example:
copolymerizing 8% of hexafluoropropylene and 92% of vinylidene fluoride to prepare polyvinylidene fluoride and hexafluoropropylene polymers, dissolving 1.12Kg of the polymers in 12.88Kg of DMAC (dimethylacetamide), wherein the solid content is 8%, firstly dispersing 0.48Kg of alumina powder in 5.52Kg of DMAC, and after uniform dispersion, adding 14Kg of prepared PVDF solution into the dispersed alumina dispersion to prepare the experimental slurry.
Taking a PE base film with the thickness of 12 microns, adopting a gravure roll coating mode (the concrete method for coating by adopting the gravure roll mode is that slurry is pumped onto a gravure roll through a pump, then the gravure roll rotates, the material is carried onto the gravure roll, and then the slurry is contacted with the base film, so that the slurry can be coated on the base film), coating the polymer slurry on one side of the base film, wherein the coating speed is 15m/min, drying is carried out by adopting three stages of drying ovens after water is passed, the temperatures of the drying ovens at all stages are respectively 50 ℃, 60 ℃ and 55 ℃, and the lithium ion battery diaphragm coated by the oily polymer can be obtained after drying, wherein the thickness of the coated lithium ion battery diaphragm is 14 microns, and the thickness of the coating is 2 microns.
The performance of the lithium ion battery separators of the above examples and comparative examples of the present invention was tested, and the data are shown in table 1 below:
TABLE 1
Figure BDA0001616883500000101
Wherein, the polymer crystallinity test: testing by DSC; polymer swell ratio test: dissolving a polymer in DMAC (dimethylacetamide), then carrying out water extraction on a solvent in the DMAC to only leave the polymer, then cutting the polymer into a small membrane, soaking the small membrane in an electrolyte for seven days, and testing the weight of the small membrane before and after soaking, wherein the swelling ratio is (weight after soaking-weight before soaking)/weight before soaking; and (3) testing the interface bonding of the diaphragm: taking a diaphragm with a complete film surface and no abnormal appearance, punching the diaphragm into a sample with the width of 25mm and the length of 100mm, stacking two punched diaphragm samples together, hot-pressing the two punched diaphragm samples on a hot press under the conditions of 1MPa pressure, 100 ℃ and 10 m/min speed, and testing the tension (unit is N) of the two diaphragms bonded together by using a tension machine, wherein the bonding force is equal to the tension/0.025 (unit is N/m); and (3) testing the cycle performance of the lithium ion battery: charging the lithium ion secondary battery at 0.5C multiplying power at room temperature, discharging at 0.5C multiplying power, sequentially performing 500 cycles, and calculating the capacity retention rate by using a formula; capacity retention rate (capacity of battery after 500 cycles/room temperature capacity of battery before cycles) × 100%; testing the internal resistance of the lithium ion battery: the method for measuring the internal resistance of the battery in the alternating current voltage drop is characterized in that the battery is actually equivalent to an active resistor, so that a fixed frequency and a fixed current (currently, a 1KHZ frequency and a small current of 50mA are generally used) are applied to the battery, then the voltage of the battery is sampled, and the internal resistance of the battery is calculated through an operational amplifier circuit after a series of processing such as rectification, filtering and the like.
As can be seen from the data in Table 1, the slurry copolymer obtained by the method has the obvious advantages of high crystallinity and small swelling coefficient, and the bonding property of a coating film prepared by applying the slurry copolymer to the coating of the lithium ion battery diaphragm is higher than that of the original polymer, so that the prepared battery has smaller internal resistance and better cycle performance.
In summary, the present invention provides a battery coating film slurry, a battery separator, a secondary battery and respective preparation methods thereof, wherein the preparation of the battery coating film slurry comprises: providing a first copolymer comprising tetrafluoroethylene; providing a second copolymer; copolymerizing the first copolymer with the second copolymer to obtain a slurry copolymer; and preparing the battery coating film slurry based on the slurry copolymer. Through the technical scheme, the battery coating film slurry is designed, and a non-aqueous system is adopted, so that the diaphragm and the pole piece can be bonded together, the hardness of the battery is improved, and the prepared polymer has higher crystallinity, smaller swelling ratio and more excellent bonding property; the prepared battery has smaller internal resistance and more excellent cycle performance. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (11)

1. The preparation method of the battery coating film slurry is characterized by comprising the following steps of:
1) providing a first copolymer comprising tetrafluoroethylene;
2) providing a second copolymer comprising acrylic acid;
3) copolymerizing the first copolymer and the second copolymer to obtain a slurry copolymer, wherein the weight percentage of the tetrafluoroethylene in the slurry copolymer is between 0.1 and 20 percent, and the particle size of the obtained slurry copolymer is between 2 and 10 mu m, so as to improve the crystallinity of the slurry copolymer and reduce the swelling ratio of the slurry copolymer;
4) preparing the battery coating film slurry based on the slurry copolymer, wherein the specific steps of obtaining the battery coating film slurry comprise:
4-1) dissolving the slurry copolymer in a first solvent to obtain a first mixed solution;
4-2) providing a filler, and dissolving the filler in a second solvent to obtain a second mixed solution;
4-3) mixing the second mixed solution with the first mixed solution to obtain the battery coating film slurry;
wherein, in the second mixed solution, the filler is less than 4 parts by weight, the second solvent is 8-50 parts by weight, and the second mixed solution is added into 50-90 parts by weight of the first mixed solution after being uniformly dispersed;
the first solvent is a non-aqueous solvent, and the second solvent is a non-aqueous solvent, so as to obtain coating film slurry of a non-aqueous system; a gravure roll coating mode is adopted when the battery diaphragm is prepared based on the slurry.
2. The method according to claim 1, wherein the first solvent includes at least one of DMAC, DMF, NMP, and acetone.
3. The method for preparing a battery coating film slurry according to claim 1, wherein in step 4-2), the filler comprises at least one of aluminum trioxide, silicon dioxide, titanium dioxide, cerium oxide, calcium carbonate, calcium oxide, zinc oxide, magnesium oxide, cerium titanate, calcium titanate, barium titanate, lithium phosphate, lithium titanium phosphate, lithium aluminum titanium phosphate, lithium nitride, and lithium lanthanum titanate.
4. The method according to claim 1, wherein in step 4-2), the second solvent comprises at least one of DMAC, DMF, NMP, and acetone.
5. A method of making a battery separator, comprising: providing a base film; preparing a battery coating film slurry according to the preparation method of any one of claims 1 to 4; and coating the battery coating film slurry on at least one surface of the base film to obtain the battery diaphragm.
6. A method for manufacturing a secondary battery, comprising a step of manufacturing a battery separator by using the method for manufacturing a battery separator according to claim 5.
7. The battery coating film slurry is characterized in that the raw material for preparing the battery coating film slurry comprises a slurry copolymer, wherein the slurry copolymer is obtained by copolymerizing a first copolymer and a second copolymer, the first copolymer comprises tetrafluoroethylene, and the second copolymer comprises acrylic acid; in the slurry copolymer, the weight percentage of the tetrafluoroethylene is between 0.1 and 20 percent, and the particle size of the obtained slurry copolymer is between 2 and 10 mu m so as to improve the crystallinity of the slurry copolymer and reduce the swelling ratio of the slurry copolymer; the raw materials for preparing the battery coating film slurry further comprise a first solvent, a filler and a second solvent, wherein the slurry copolymer is dissolved in the first solvent to form a first mixed solution, the filler is dissolved in the second solvent to form a second mixed solution, the first mixed solution and the second mixed solution are mixed to form the battery coating slurry, the filler in the second mixed solution is less than 4 parts by weight, the second solvent is 8-50 parts by weight, and the weight percentage of the first mixed solution in the obtained battery coating film slurry is 50-90%; the first solvent is a non-aqueous solvent, and the second solvent is a non-aqueous solvent, so that coating film slurry of a non-aqueous system is obtained.
8. The battery coating film slurry according to claim 7, wherein the raw material for preparing the battery coating film slurry further comprises a first solvent comprising at least one of DMAC, DMF, NMP and acetone, wherein the slurry copolymer is dissolved in the first solvent to form a first mixed solution, and the first mixed solution forms the battery coating slurry.
9. The battery coating film slurry according to claim 7, wherein the first solvent comprises at least one of DMAC, DMF, NMP and acetone; the second solvent comprises at least one of DMAC, DMF, NMP, and acetone.
10. A battery separator comprising a base film; and a coating layer on at least one surface of the base film, the coating layer being a coating layer prepared using the battery coating film slurry according to any one of claims 7 to 9.
11. A secondary battery characterized by comprising the battery separator according to claim 10.
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