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CN111341974B - PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof, PVDF coated layer and lithium battery - Google Patents

PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof, PVDF coated layer and lithium battery Download PDF

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CN111341974B
CN111341974B CN202010174922.XA CN202010174922A CN111341974B CN 111341974 B CN111341974 B CN 111341974B CN 202010174922 A CN202010174922 A CN 202010174922A CN 111341974 B CN111341974 B CN 111341974B
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pvdf
slurry
cross
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glued
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CN111341974A (en
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王成豪
李正林
贡晶晶
张立斌
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Jiangsu Housheng New Energy Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403Manufacturing processes of separators, membranes or diaphragms
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

本发明属于锂电池技术领域,具体涉及一种PVDF涂胶隔膜及其制备方法、PVDF涂胶层、锂电池。本PVDF涂胶隔膜包括:基膜、位于基膜表面的PVDF涂胶层;其中所述PVDF涂胶层包括以下原料:PVDF浆料、交联剂、含有亲油基团的高分子材料;以及在催化作用下,所述高分子材料通过交联剂与PVDF浆料发生交联反应,以将亲油基团接枝在PVDF浆料上。

Figure 202010174922

The invention belongs to the technical field of lithium batteries, and in particular relates to a PVDF glue-coated separator and a preparation method thereof, a PVDF glue-coated layer and a lithium battery. The PVDF glue-coated diaphragm includes: a base film and a PVDF glue-coated layer on the surface of the base film; wherein the PVDF glue-coated layer includes the following raw materials: PVDF slurry, cross-linking agent, and polymer material containing lipophilic groups; and Under the action of catalysis, the polymer material undergoes a cross-linking reaction with the PVDF slurry through a cross-linking agent, so as to graft lipophilic groups on the PVDF slurry.

Figure 202010174922

Description

PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof, PVDF coated layer and lithium battery
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a PVDF (polyvinylidene fluoride) glue-coated diaphragm and a preparation method thereof, a PVDF glue-coated layer and a lithium battery.
Background
The gel coating in the traditional gel coating diaphragm is not easy to be soaked by electrolyte in the battery due to poor oleophylic capability, so that the aging time of the lithium battery is long, and the production efficiency of the battery is reduced. In order to improve the oleophylic ability of PVDF, the invention grafts an oleophylic group on PVDF through a cross-linking agent, and the wetting ability of PVDF to electrolyte is increased through the oleophylic group.
Disclosure of Invention
The invention provides a PVDF (polyvinylidene fluoride) gluing membrane and a preparation method thereof, a PVDF gluing layer and a lithium battery.
In order to solve the technical problem, the invention provides a PVDF gummed membrane, which is characterized by comprising: the PVDF glue coating layer is positioned on the surface of the base film; wherein the PVDF rubber coating layer comprises the following raw materials: PVDF sizing agent, cross-linking agent, macromolecular material containing oleophylic group; and under the catalytic action, the polymer material and the PVDF slurry generate a crosslinking reaction through a crosslinking agent so as to graft the oleophilic group on the PVDF slurry.
In a second aspect, the invention also provides a preparation method of the PVDF gummed membrane, which comprises the following steps: preparing PVDF slurry; coating PVDF slurry on a base film; spraying a cross-linking agent; spraying a high polymer material containing lipophilic groups; and (3) catalyzing to enable the high polymer material and the PVDF slurry to generate a crosslinking reaction, namely grafting the oleophylic group on the PVDF slurry.
In a third aspect, the invention also provides a PVDF glue coating layer, which comprises the following raw materials: PVDF sizing agent, cross-linking agent, macromolecular material containing oleophylic group; and the polymer material is suitable for carrying out a crosslinking reaction with the PVDF sizing agent under the catalytic action so as to graft the oleophilic group on the PVDF sizing agent.
In a fourth aspect, the present invention also provides a lithium battery, including: a diaphragm; the membrane was a PVDF rubberized membrane as described previously.
The PVDF gluing diaphragm and the preparation method thereof, the PVDF gluing layer and the lithium battery have the beneficial effects that oleophylic groups are grafted to the PVDF through a cross-linking agent, and the wetting capacity of the PVDF to electrolyte is improved by using the oleophylic groups.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow diagram of a process for preparing a PVDF rubberized membrane of the invention;
figure 2 is a graph comparing the wetting times of PVDF rubberized membranes to conventional rubberized membranes.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A first part:
the gel coating in the traditional gel coating diaphragm is not easy to be soaked by electrolyte in the battery due to poor oleophylic capability, so that the aging time of the lithium battery is long, and the production efficiency of the battery is reduced. In order to improve the oleophilic capacity of PVDF (polyvinylidene fluoride), the invention provides a PVDF gluing membrane, which comprises: the PVDF glue coating layer is positioned on the surface of the base film; wherein the PVDF rubber coating layer comprises the following raw materials: PVDF sizing agent, cross-linking agent, macromolecular material containing oleophylic group; and under the catalytic action, the polymer material and the PVDF slurry generate a crosslinking reaction through a crosslinking agent so as to graft the oleophilic group on the PVDF slurry.
Optionally, the base film includes, but is not limited to, high polymer films such as PP film, PE film, PI film, PET film, and the like, and composite films thereof. And the catalysis comprises illumination at a wavelength of 350 nm.
Specifically, the reaction formula of the crosslinking reaction of the PVDF slurry, the crosslinking agent and the polymer material containing the oleophylic group is as follows:
Figure BDA0002410479680000031
wherein the structural formula of the high polymer material is
Figure BDA0002410479680000032
R is a hydrocarbon chain;
the structural formula of the oleophilic group is as follows:
Figure BDA0002410479680000033
the structural formula of the cross-linking agent is as follows:
Figure BDA0002410479680000041
and
the structural formula of PVDF is:
Figure BDA0002410479680000042
the structural formula of the finally generated PVDF gummed layer is shown as
Figure BDA0002410479680000043
From the above reaction formula, under the catalysis of illumination, the polymer material and the PVDF slurry undergo a cross-linking reaction through the cross-linking agent, the oleophilic group is grafted on the PVDF slurry, and then the wettability of the PVDF to the electrolyte is increased through the oleophilic group.
As an alternative embodiment to PVDF slurries.
The PVDF sizing agent comprises the following raw materials: PVDF colloidal particles, a dispersing agent, a wetting agent, a binder, a defoaming agent, an anti-settling agent and water; and the mass ratio of each component is 1: (0.04-0.11): (0.004-0.010): (0.12-0.53): (0.052-0.34): (0.011-0.32): (3-16).
Optionally, PVDF colloidal particles, a dispersing agent, a wetting agent, a binder, a defoaming agent, an anti-settling agent and water; and the mass ratio of each component is 1: 0.8: 0.006: 0.3: 0.1: 0.2: 10.
optionally, PVDF colloidal particles, a dispersing agent, a wetting agent, a binder, a defoaming agent, an anti-settling agent and water; and the mass ratio of each component is 1: 0.2: 0.008: 0.45: 0.2: 0.08: 6.
wherein:
the dispersing agent comprises silicate (such as water glass), alkali metal phosphate (such as sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and the like), and organic dispersing agent; the organic dispersant includes: at least one of triethylhexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivative, polyacrylamide, Gule gum and fatty acid polyglycol ester.
The wetting agent includes, but is not limited to, at least one of anionic and nonionic surfactants and the like.
The binder includes, but is not limited to, an acrylic-type binder.
The defoaming agent comprises but is not limited to emulsified silicone oil, high alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane and the like, or a combination of a plurality of materials.
The anti-settling agent comprises at least one of but not limited to solvent-based rheological additive, solvent-free rheological additive, novel rheological additive (German Bick BYK410) and the like.
As described above, referring to fig. 1, the present invention also provides a method for preparing a PVDF rubberized membrane, comprising: preparing PVDF slurry; coating PVDF slurry on a base film; spraying a cross-linking agent; spraying a high polymer material containing lipophilic groups; and (3) catalyzing to enable the high polymer material and the PVDF slurry to generate a crosslinking reaction, namely grafting the oleophylic group on the PVDF slurry.
As mentioned above, the invention also provides a PVDF glue coating layer, which comprises the following raw materials: PVDF sizing agent, cross-linking agent, macromolecular material containing oleophylic group; the polymer material is suitable for carrying out a crosslinking reaction with PVDF slurry under the catalysis action so as to graft lipophilic groups on the PVDF slurry to form a PVDF glue coating layer, and the molecular structural formula of the PVDF glue coating layer is as follows:
Figure BDA0002410479680000061
wherein R is a hydrocarbon chain.
As described above, the present invention also provides a lithium battery including: a diaphragm; the membrane was a PVDF rubberized membrane as described previously.
A second part:
example 1
Firstly, adding 5.1kg of dispersing agent into 310kg of water, and stirring and dispersing for 30 min; then 0.65kg of wetting agent is added, and stirring and dispersion are carried out for 30 min; then adding 12kg of defoaming agent and 3.6kg of anti-settling agent, and stirring and dispersing for 30 min; dissolving 100kg of PVDF in the stirred solution, and performing sand grinding or mechanical dispersion until the dispersion is uniform; adding 45kg of binder into the uniformly dispersed solution, and stirring and dispersing for 60min to prepare PVDF slurry;
selecting a PE film with the thickness of 12 micrometers as a base film, and coating a diaphragm by micro gravure coating, wherein the thickness of the coating is 2 micrometers;
then spraying a layer of cross-linking agent with the thickness of 0.2 mu m;
then spraying a layer of 0.1 mu m thick polymer material containing oleophilic groups;
after spraying, illumination with the wavelength of 350nm is used, and crosslinking reaction is carried out on the PVDF and the macromolecule containing oleophylic groups;
and after the reaction is completed, carrying out rolling operation to obtain the PVDF gluing diaphragm.
Example 2
Firstly, adding 11kg of triethyl hexyl phosphoric acid into 1600kg of water, and stirring and dispersing for 30 min; then 0.4kg of nonionic surfactant is added, and stirring and dispersing are carried out for 30 min; then adding 5.2kg of emulsified silicone oil and 1.1kg of solvent type rheological additive, and stirring and dispersing for 30 min; dissolving 100kg of PVDF in the stirred solution, and performing sand grinding or mechanical dispersion until the dispersion is uniform; adding 53kg of acrylic acid type binder into the uniformly dispersed solution, and stirring and dispersing for 60min to prepare PVDF slurry;
selecting a PET film with the thickness of 12 microns as a base film, and coating a diaphragm by micro gravure coating, wherein the thickness of the coating is 2 microns;
then spraying a layer of cross-linking agent with the thickness of 0.2 mu m;
then spraying a layer of 0.1 mu m thick polymer material containing oleophilic groups;
after spraying, illumination with the wavelength of 350nm is used, and crosslinking reaction is carried out on the PVDF and the macromolecule containing oleophylic groups;
and after the reaction is completed, carrying out rolling operation to obtain the PVDF gluing diaphragm.
Example 3
Firstly, adding 4kg of Guerban into 300kg of water, and stirring and dispersing for 30 min; then 1kg of anionic surfactant is added, and stirring and dispersing are carried out for 30 min; then 34kg of polydimethylsiloxane and 32kg of solvent-free rheological additive are added, and stirring and dispersing are carried out for 30 min; dissolving 100kg of PVDF in the stirred solution, and performing sand grinding or mechanical dispersion until the dispersion is uniform; adding 12kg of acrylic acid type binder into the uniformly dispersed solution, and stirring and dispersing for 60min to prepare PVDF slurry;
selecting a PI film with the thickness of 12 microns as a base film, and coating a diaphragm by micro gravure coating, wherein the thickness of the coating is 2 microns;
then spraying a layer of cross-linking agent with the thickness of 0.2 mu m;
then spraying a layer of 0.1 mu m thick polymer material containing oleophilic groups;
after spraying, illumination with the wavelength of 350nm is used, and crosslinking reaction is carried out on the PVDF and the macromolecule containing oleophylic groups;
and after the reaction is completed, carrying out rolling operation to obtain the PVDF gluing diaphragm.
Example 4
Firstly, adding 8kg of Guerban into 1000kg of water, and stirring and dispersing for 30 min; then 0.8kg of anionic surfactant is added, and stirring and dispersing are carried out for 30 min; then adding 15kg of polyoxypropylene glycerol ether and 20kg of solvent-free rheological additive, and stirring and dispersing for 30 min; dissolving 100kg of PVDF in the stirred solution, and performing sand grinding or mechanical dispersion until the dispersion is uniform; adding 35kg of acrylic acid type binder into the uniformly dispersed solution, and stirring and dispersing for 60min to prepare PVDF slurry;
selecting a PP film with the thickness of 12 micrometers as a base film, and coating a diaphragm by micro-gravure coating, wherein the thickness of the coating is 2 micrometers;
then spraying a layer of cross-linking agent with the thickness of 0.2 mu m;
then spraying a layer of 0.1 mu m thick polymer material containing oleophilic groups;
after spraying, illumination with the wavelength of 350nm is used, and crosslinking reaction is carried out on the PVDF and the macromolecule containing oleophylic groups;
and after the reaction is completed, carrying out rolling operation to obtain the PVDF gluing diaphragm.
Example 5
Referring to fig. 2, this example 5 performed a wet time test on the PVDF rubberized membrane (corresponding to the new model in fig. 2) prepared in example 1 and a conventional rubberized membrane (corresponding to the conventional one in fig. 2). It can be seen that the wetting time of the PVDF gummed membrane of the invention is 20 seconds, while the wetting time of the traditional membrane is 300 seconds, the wetting time of the PVDF gummed membrane is greatly shortened, which indicates that the wetting ability of the PVDF gummed membrane to the electrolyte is greatly improved, namely the oleophylic ability of the PVDF is improved. Of course, the wetting ability of the PVDF gumming membrane to the electrolyte is greatly improved, mainly because the oleophilic groups on the PVDF gumming membrane are grafted to the PVDF by the cross-linking agent, and then the wetting ability of the PVDF to the electrolyte is increased by using the oleophilic groups. Meanwhile, through the combination of chemical reaction and chemical bonds, the stability and the overall consistency of the PVDF gluing membrane are superior to those of the traditional gluing membrane.
In summary, according to the PVDF gumming diaphragm and the preparation method thereof, the PVDF gumming layer and the lithium battery, the lipophilic groups are grafted to the PVDF through the cross-linking agent, the wetting capacity of the PVDF to the electrolyte is improved by utilizing the lipophilic groups, and the stability and the overall consistency of the PVDF gumming diaphragm are superior to those of the traditional gumming diaphragm through the combination of chemical reaction and chemical bonds, so that the PVDF gumming diaphragm is more suitable for being applied to the lithium battery.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (8)

1.一种PVDF涂胶隔膜,其特征在于,包括:1. a PVDF glued diaphragm, is characterized in that, comprises: 基膜、位于基膜表面的PVDF涂胶层;其中Base film, PVDF coating layer on the surface of base film; wherein 所述PVDF涂胶层包括以下原料:The PVDF coating layer includes the following raw materials: PVDF浆料、交联剂、含有亲油基团的高分子材料;以及PVDF slurries, cross-linking agents, polymer materials containing lipophilic groups; and 在催化作用下,所述高分子材料通过交联剂与PVDF浆料发生交联反应,以将亲油基团接枝在PVDF浆料上;Under the action of catalysis, the polymer material undergoes a cross-linking reaction with the PVDF slurry through a cross-linking agent, so as to graft lipophilic groups on the PVDF slurry; 所述高分子材料的结构式为
Figure FDA0003401223420000011
其中R为碳氢链;
The structural formula of the polymer material is
Figure FDA0003401223420000011
where R is a hydrocarbon chain;
亲油基团的结构式为
Figure FDA0003401223420000012
The structural formula of the lipophilic group is
Figure FDA0003401223420000012
2.根据权利要求1所述的PVDF涂胶隔膜,其特征在于,2. PVDF glued diaphragm according to claim 1, is characterized in that, 所述交联剂的结构式为:
Figure FDA0003401223420000013
The structural formula of the crosslinking agent is:
Figure FDA0003401223420000013
3.根据权利要求1所述的PVDF涂胶隔膜,其特征在于,3. PVDF glued diaphragm according to claim 1, is characterized in that, 所述交联反应的反应式为:The reaction formula of the cross-linking reaction is:
Figure FDA0003401223420000014
Figure FDA0003401223420000014
4.根据权利要求1所述的PVDF涂胶隔膜,其特征在于,4. PVDF glued diaphragm according to claim 1, is characterized in that, 所述催化作用包括波长为350nm的光照。The catalysis involved illumination at a wavelength of 350 nm. 5.根据权利要求1所述的PVDF涂胶隔膜,其特征在于,5. PVDF glued diaphragm according to claim 1, is characterized in that, 所述PVDF浆料包括以下原料:The PVDF slurry includes the following raw materials: PVDF胶粒、分散剂、润湿剂、粘结剂、消泡剂、防沉剂、水;以及PVDF colloidal particles, dispersants, wetting agents, binders, defoamers, anti-settling agents, water; and 各组分的质量比依次为1:(0.04-0.11):(0.004-0.010):(0.12-0.53):(0.052-0.34):(0.011-0.32):(3-16)。The mass ratio of each component is 1:(0.04-0.11):(0.004-0.010):(0.12-0.53):(0.052-0.34):(0.011-0.32):(3-16). 6.一种如权利要求1-5任一项所述的PVDF涂胶隔膜的制备方法,其特征在于,包括:6. a kind of preparation method of PVDF glue-coated diaphragm as described in any one of claim 1-5, is characterized in that, comprises: 制备PVDF浆料;Preparation of PVDF slurry; 将PVDF浆料涂覆到基膜上;Coating the PVDF slurry onto the base film; 喷淋交联剂;spray crosslinking agent; 喷淋含有亲油基团的高分子材料;Spray polymer materials containing lipophilic groups; 催化作用,使高分子材料与PVDF浆料发生交联反应,即亲油基团接枝在PVDF浆料上。Catalysis, the polymer material and PVDF slurry cross-linking reaction, that is, lipophilic groups are grafted on the PVDF slurry. 7.一种如权利要求1-5任一项所述的PVDF涂胶隔膜用PVDF涂胶层,其特征在于,包括以下原料:7. a PVDF glued film for PVDF glued diaphragm as described in any one of claims 1-5, is characterized in that, comprises following raw material: PVDF浆料、交联剂、含有亲油基团的高分子材料;以及PVDF slurries, cross-linking agents, polymer materials containing lipophilic groups; and 所述高分子材料适于在催化作用下与PVDF浆料发生交联反应,以将亲油基团接枝在PVDF浆料上;The polymer material is suitable for cross-linking reaction with PVDF slurry under catalytic action, so as to graft lipophilic groups on PVDF slurry; 所述PVDF涂胶层的分子结构式为:The molecular structural formula of the PVDF coating layer is:
Figure FDA0003401223420000031
其中R为碳氢链。
Figure FDA0003401223420000031
where R is a hydrocarbon chain.
8.一种锂电池,其特征在于,包括:8. A lithium battery, characterized in that, comprising: 隔膜;diaphragm; 所述隔膜采用如权利要求1-5任一项所述的PVDF涂胶隔膜。The diaphragm adopts the PVDF glue-coated diaphragm according to any one of claims 1-5.
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