CN109065804A - A kind of aqueous ceramic/PVDF mixing coating slurry and its preparation method and application - Google Patents
A kind of aqueous ceramic/PVDF mixing coating slurry and its preparation method and application Download PDFInfo
- Publication number
- CN109065804A CN109065804A CN201810795492.6A CN201810795492A CN109065804A CN 109065804 A CN109065804 A CN 109065804A CN 201810795492 A CN201810795492 A CN 201810795492A CN 109065804 A CN109065804 A CN 109065804A
- Authority
- CN
- China
- Prior art keywords
- pvdf
- aqueous
- ceramic
- mixing
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic 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
- H01M50/431—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of aqueous ceramic/PVDF mixing coating slurry and its preparation method and application, its by by high purity water, perfluoroalkyl class dispersing agent, tert-butyl hydroperoxide and acetone after mixing, it is continually fed into vinylidene and hexafluoropropene gas, obtains aqueous PVDF lotion;It disperses ceramic material and the first dispersing agent in deionized water, adds thickener and bonding agent, aqueous PVDF lotion and wetting agent, obtain slurry after mixing.Aqueous ceramic prepared by the present invention/PVDF is mixed into coating slurry and is coated in polyethylene diagrams, obtains wet film;It is dried to obtain aqueous ceramic/PVDF mixing coating diaphragm.The dispersing uniformity that slurry is blended the present invention is directed to significantly improve ceramics/PVDF improves ceramics/PVDF mixing coating diaphragm coating uniformity and is obviously improved the comprehensive performance of lithium ion battery separator in conjunction with the characteristic of ceramic material and PVDF material.
Description
Technical field
The present invention relates to battery diaphragm material technical fields, it particularly relates to a kind of aqueous ceramic/PVDF mixing coating
Slurry and its preparation method and application.
Background technique
Lithium ion battery separator is broadly divided into single layer microporous film, composite membrane, blend film and non-woven membrane.Coating diaphragm belongs to
One of composite membrane.Ternary battery is matched with wet coating diaphragm currently on the market, with ternary Battery Market accounting
Lasting to be promoted, wet coating diaphragm demand also can sustainable growth.Coating diaphragm is broadly divided into inorganic ceramic coating and polymer applies
It covers, coating layer and property can generate very big variation according to the difference of raw material and technique, and then influence the performance of battery.
Battery performance includes chemical property, such as inoxidizability, cementability, electrolyte wetability, is by the property of coating material itself
It determines;Coating structure, such as cell morphology, porosity, consistency are determined by coating processes process;Thermal stability, water
Point, electrolyte conservation rate etc., these properties were not only related with raw material, but also related with coating processes process.According to different electricity
The requirement in pond can pass through the product of change raw material and technical process flexible design different performance.
Ceramic particle coats diaphragm using PE or PP film as matrix, and surface coats one layer of Al2O3、SiO2、Mg(OH)2Or other
The inorganic matter ceramic particle of excellent heat resistance.The main technique of ceramic coated are as follows: by deionized water, ceramic material, dispersing agent, glue
Connect agent, slurry regulator (thickener, surfactant etc.) stirs evenly, obtain the slurry of coating.Be coated on coating machine,
Coating diaphragm is obtained after drying.The factors such as coating method, workshop condition temperature and humidity and oven temperature have a fixing to properties of product
It rings.The advantages of ceramic coating membrane, is as follows: 1, diaphragm thermal stability is improved, the contraction of ceramic coating membrane at high temperature is smaller,
It can avoid film contraction and cause internal short-circuit, be obviously improved battery safety;2, diaphragm is followed by improved to the profit of electrolyte
It is moist, be conducive to internal resistance of cell reduction, discharge power is promoted;3, then there is that can prevent or reduce Membrane Oxygenation, be conducive to cooperate
The cycle life of high-voltage anode used and extend battery.
PVDF, that is, Kynoar, is a kind of white powder semicrystalline polymeric, 170 DEG C of fusing point, thermal decomposition temperature
316 DEG C or more, there is excellent chemical corrosion resistance, oxidative resistance, flexibility and very high anti-rise intensity and impact resistance
Intensity.PVDF coating diaphragm has the characteristics that low internal resistance, mechanical property are good, chemical good with electrochemical stability.PVDF is being electrolysed
Be capable of providing after being swollen in liquid it is certain lead it is ionic.PVDF can connect positive and negative pole material due to the connectivity of itself
It is connected together, greatly shortens transmission range of the lithium ion between positive and negative pole material, exactly this adhesive property disassembles battery
Afterwards, just as one piece of brick, the assembly efficiency that is greatly improved in our cell assembling processes.If without this connection
Layer, occur to need after certain diaphragm dislocation in cell assembling processes it is subsequent adjust again, but the diaphragm of PVDF coating is then reduced
The work of this respect.Since it shortens the transmission range of positive and negative anodes ion, make battery that there are a series of excellent performances, such as
Cycle performance also gives the certain safety of battery simultaneously as being tightly bonded with positive and negative anodes.Currently, more and more electricity
Core producer selects PVDF coating film, especially high-end energy-storage battery, automobile power cell during its battery design.
Mixed painting is the new coating processes developed in recent years, which is mainly configured to PVDF and ceramic material uniformly
It is coated again after slurry.The advantages of capable of being coated in conjunction with ceramic coated and PVDF using mixed painting technique, can significantly improve every
The comprehensive performance of film.However, PVDF belongs to hydrophobic high molecular material, ceramics are hydrophilic material, and the two is difficult in same individual
Disperse in system.Routine techniques allows to disperse coating material, it is also difficult to is uniformly dispersed, lead to the mixed coating for applying diaphragm
Particle dispersion is uneven, and non-uniform coating will lead to battery and generate non-uniform local current densities in charge and discharge process,
The structure of electrode material is set to be easier to destroy in cyclic process, to substantially reduce the cycle life of lithium ion battery.
Summary of the invention
For above-mentioned technical problem in the related technology, the present invention provides a kind of aqueous ceramic/PVDF mixing coating materials
Material and preparation method thereof, and the coating diaphragm and preparation method thereof using the slurry, it is intended to significantly improve ceramics/PVDF and slurry is blended
The dispersing uniformity of material improves the uniformity of ceramics/PVDF mixing coating diaphragm coating, in conjunction with ceramic material and PVDF material
Characteristic is obviously improved the comprehensive performance of lithium ion battery separator.
To realize the above-mentioned technical purpose, the technical scheme of the present invention is realized as follows:
On the one hand, the present invention provides a kind of preparation method of aqueous ceramic/PVDF mixing coating slurry, and detailed process is such as
Under:
1) high purity water, perfluoroalkyl class dispersing agent, tert-butyl hydroperoxide and acetone are stirred in nitrogen atmosphere
After uniformly, it is continually fed into vinylidene fluoride monomers and hexafluoropropene monomer gas under heating, controls reaction pressure, after the reaction was completed mistake
Filter, washing adjust solid content and obtain aqueous PVDF lotion;
2) it disperses ceramic material and the first dispersing agent in deionized water, after adding thickener and bonding agent dispersion,
Aqueous PVDF lotion and wetting agent obtained by step 1) are added while stirring, obtains aqueous ceramic/PVDF mixing after mixing and applies
Cover slurry.
Further, in step 1), the high purity water, perfluoroalkyl class dispersing agent, tert-butyl hydroperoxide, acetone, partially
The proportion of fluoride monomers and hexafluoropropene monomer, according to the mass fraction, be 150~200: 0.5~1: 0.3~0.9: 0.8~
1.7∶60∶40。
Further, in step 1), the revolving speed being uniformly mixed is 70rpm/min, and mixing time is 1~5h.
Further, in step 1), the heating temperature is 60~100 DEG C.
Further, in step 1), control reaction pressure is realized by adjusting gas flow, control pressure 1.5~
4.0Mpa, the reaction time is in 8~15h.
Further, in step 1), the washing, which is adopted, to be washed with deionized, and number is 3~5 times.
Further, in step 1), the solid content that adjusts refers to that using deionized water preparation mass fraction be 20%
Aqueous PVDF polymer emulsion.
Further, in step 2), the ceramic material, the first dispersing agent, deionized water, thickener, bonding agent, step
1) proportion of gained aqueous PVDF lotion and wetting agent is according to the mass fraction 10~30: 0.01~2: 45: 0.1~0.5:
7~15: 10~40: 0.05~0.5.
Further, ceramic material described in step 2) and the first dispersing agent are scattered in mixing time in deionized water and are
0.5~8h.
Further, thickener described in step 2) and the mixing time of bonding agent dispersion are 2~10h.
Further, aqueous PVDF lotion obtained by step 1) described in step 2) and the mixing time after wetting agent addition are
3~9h.
Further, the perfluoroalkyl class dispersing agent includes perfluor alkyl ethyl acrylate, perfluorooctanoic acid, perfluor
One of enanthic acid, perfluorododecyl sodium sulfonate are a variety of.
Further, the ceramic material include aluminium oxide, boehmite, silica, magnesium hydroxide, in titanium dioxide
It is one or more.
Further, first dispersing agent includes maleic anhydride-vinylacetate, phenylethylene-maleic anhydride, poly- second two
One of alcohol, Sodium Polyacrylate, polyacrylic acid potassium are a variety of.
Further, the thickener include hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose,
One of polyacrylamide, sodium alginate are a variety of.
Further, the bonding agent includes butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethene-vinyl acetate copolymerization
One of object, polyurethane are a variety of.
Further, the wetting agent is fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, alkyl phenol polyoxy
One of vinethene, fatty alcohol polyoxyethylene ether, aliphatic acid polyethenoxy ether are a variety of.
On the other hand, the present invention provides a kind of preparation method of aqueous ceramic/PVDF mixing coating diaphragm, and detailed process is such as
Under:
A aqueous ceramic prepared by the present invention/PVDF) is mixed into coating slurry and is coated in polyethylene diagrams, obtains wet film;
B gained wet film) is dried to obtain aqueous ceramic/PVDF and mixes coating diaphragm.
Further, the step A) in wet film with a thickness of 3~50 μm.
Further, the step B) in dry condition it is as follows: temperature is 30~50 DEG C, relative humidity is 0.1~
10%, drying time is 10~30min.
On the other hand, the present invention provides a kind of aqueous ceramic/PVDF mixing coating slurry, through the invention the side
Method is prepared.
On the other hand, the present invention provides a kind of aqueous ceramic/PVDF mixing coating diaphragm, through the invention the side
Method is prepared.
On the other hand, the present invention provides a kind of lithium ion battery, including positive electrode and negative electrode material, in positive electrode and
There is above-mentioned aqueous ceramic/PVDF mixing coating diaphragm between negative electrode material.
Beneficial effects of the present invention:
The present invention provides a kind of aqueous ceramic/PVDF mixing coating slurry and its preparation method and application, has following excellent
Gesture:
When the aqueous ceramic of preparation/PVDF mixing coating slurry, advantage is as follows:
1) using perfluoroalkyl class dispersing agent as emulsifier, during the emulsion polymerization of PVDF, in emulsifier
Hydrophobic segment (such as: perfluoroalkyl) can be embedded in PVDF emulsion particle, PVDF particle surface hydrophilic segment (such as: third
Olefin(e) acid segment, sad amine section, amine carboxylic acid section, sodium sulfonate section) with water there is good compatibility, significantly improve PVDF particle
Hydrophily, while significantly reducing the crystallinity of PVDF particle.Compared with the PVDF particle of conventional method preparation, present invention process system
Standby PVDF lotion evenly dispersed can not occur to reunite in aqueous solution and settle, and hydrophilic segment is conducive to subsequent and electrolysis
Wetability between liquid, the PVDF of low-crystallinity are more advantageous to the imbibition rate and ionic conductivity for improving diaphragm.
2) ceramic material and the first dispersing agent is evenly dispersed in water, ceramics can be broken up and be prevented to dispersing agent therein
Material it is agglomerating, avoid the occurrence of the agglomeration of ceramic material;It is further to add the more thickener of hydrophilic radical, bonding agent
It is uniformly dispersed;PVDF lotion prepared by the present invention and wetting agent progress is evenly dispersed, and wetting agent therein can increase ceramics
The interfacial tension of material, improves its hydrophily and the wetability between PVDF, bonding agent therein can guarantee coating with
The cementability of barrier film base material;
3) ceramic particle in aqueous ceramic/PVDF mixing coating slurry prepared by is can be uniformly dispersed with PVDF particle
In the slurry, there is good dispersion stabilization, the uniformity of slurry is good.
Aqueous ceramic prepared by the present invention/PVDF mixing coating diaphragm advantage is as follows:
The slurry uniformity of preparation is good, and after being coated in barrier film base material film surface, film surface is smooth, and particle is uniformly dispersed, soilless sticking
Phenomenon, uniform coating is conducive to improve the uniformity of the local current in lithium ion battery charge and discharge process, to significantly mention
The high cycle life of battery.
Coating diaphragm is dried using the condition of low temperature and low humidity, avoids low melting point PVDF particle prepared by the present invention
Melt plug-hole in coating diaphragm drying course, it is possible to increase coat the gas permeability of diaphragm, gained membrane surface is fine and close, thickness is equal
Even, heat resistance is high;Binding force between the coating and diaphragm of preparation is strong, especially thermal contraction performance, can effectively inhibit diaphragm
Dusting problems;
Preparation method simple process of the invention, no pollution to the environment are suitable for industrialized production.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without creative efforts, can also obtain according to these attached drawings
Obtain other attached drawings.
Fig. 1 is the SEM figure of the aqueous PVDF lotion of preferred embodiment of the present invention preparation.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained, shall fall within the protection scope of the present invention.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Except there is a special instruction, the various reagents used in the present invention, raw material be can commodity commercially or
Person can the product as made from well known method.
Embodiment 1
170g high purity water, 0.5g perfluoroalkyl acrylate, 0.5g perfluor are added in the autoclave full of nitrogen
Alkyl carboxylic acid amine, 0.5g tert-butyl hydroperoxide and 1g acetone continue in mixed solution under the conditions of 60 DEG C after mixing
60g vinylidene fluoride monomers and 40g hexafluoropropene monomer gas are passed through, controlling reaction pressure by adjusting gas flow is
4.0Mpa, after reacting 8h, filtering with pure water water washing 5 times, obtains dense PVDF polymer emulsion, in dense PVDF polymer emulsion
Middle addition deionized water adjusts solid content, is configured to the aqueous PVDF polymer emulsion that mass fraction is 20%.
20g magnesium hydroxide, 0.1g phenylethylene-maleic anhydride and 0.4g Sodium Polyacrylate are added in 45g deionized water, stirs
After mixing 3 hours, 0.2g hydroxyethyl cellulose and 15g polyurethane is added, continues stirring 6 hours, finally polymerize the aqueous PVDF of 20g
Object lotion and 0.21g fatty alcohol polyoxyethylene ether are added and stir 9 hours simultaneously, obtain aqueous ceramic/PVDF mixing coating materials
Material.
Aqueous ceramic/PVDF is mixed coating slurry to be coated on polyethylene diagrams, obtains the wet film with a thickness of 10 μm.?
40 DEG C, under 1% damp condition, by the dry 10min of wet film after coating, obtain aqueous ceramic/PVDF mixing coating diaphragm.
The diaphragm decomposition voltage be 4.9V, under the conditions of 150 DEG C toast 1h after be heat-shrinked be respectively 1.8% (direction MD),
0.9% (direction TD), puncture strength 5.1N, tensile strength are 210Mpa (direction MD), 180Mpa (direction TD), and imbibition rate is
170%, broken film temperature is 170 DEG C, and lithium ion conductivity is 1.58 × 10-3S/cm, lithium ion transference number 0.73.By cobalt acid
Lithium, lithium piece, electrolyte and aqueous ceramic/PVDF mixing coating diaphragm are assembled into button cell and test its performance, in filling for 3C
Capacity retention ratio is 81.7% after 300 circle of circulation under discharge-rate.
Embodiment 2
150g high purity water, 0.5g perfluoro alkyl sulfonic acid sodium, 0.9g tert-butyl are added in the autoclave full of nitrogen
Hydrogen peroxide and 0.8g acetone are continually fed into 60g vinylidene fluoride monomers under the conditions of 80 DEG C after mixing in mixed solution
With 40g hexafluoropropene monomer gas, controlling reaction pressure by adjusting gas flow is that 2.0Mpa will be prepared into after reacting 10h
The PVDF lotion filtering arrived, with pure water water washing 3 times, obtains dense PVDF polymer emulsion, adds in dense PVDF polymer emulsion
Enter deionized water and adjust solid content, is configured to the aqueous PVDF polymer emulsion that mass fraction is 20%.
10g aluminium oxide and 0.01g Sodium Polyacrylate are added in 45g deionized water, 0.25g carboxylic is added after stirring 8 hours
Sodium carboxymethylcellulose pyce, 0.25 sodium alginate and 7.5g butadiene-styrene latex continue stirring 10 hours, finally polymerize the aqueous PVDF of 40g
Object lotion, 0.21g aliphatic acid polyethenoxy ether and 0.29g fluoro-alkyl methoxyl group ether alcohol are added and stir 3 hours simultaneously, obtain
Aqueous ceramic/PVDF mixes coating slurry.
Aqueous ceramic/PVDF is mixed coating slurry to be coated on polyethylene diagrams, obtains the wet film with a thickness of 30 μm.?
50 DEG C, under 10% damp condition, by the dry 15min of wet film after coating, obtain aqueous ceramic/PVDF mixing coating diaphragm.
The diaphragm decomposition voltage be 4.7V, under the conditions of 150 DEG C toast 1h after be heat-shrinked be respectively 1.5% (direction MD),
0.7% (direction TD), puncture strength 5.3N, tensile strength are 250Mpa (direction MD), 192Mpa (direction TD), and imbibition rate is
283%, broken film temperature is 180 DEG C, and lithium ion conductivity is 1.73 × 10-3S/cm, lithium ion transference number 0.69.By cobalt acid
Lithium, lithium piece, electrolyte and aqueous ceramic/PVDF mixing coating diaphragm are assembled into button cell and test its performance, in filling for 3C
Capacity retention ratio is 83.5% after 300 circle of circulation under discharge-rate.
Embodiment 3
200g high purity water, 0.8g perfluoroalkyl acrylate, the tertiary fourth of 0.3g are added in the autoclave full of nitrogen
Base hydrogen peroxide and 1.7g acetone are continually fed into 60g vinylidene under the conditions of 100 DEG C after mixing in mixed solution
Monomer and 40g hexafluoropropene monomer gas, controlling reaction pressure by adjusting gas flow is that 1.5Mpa will make after reacting 15h
Standby obtained PVDF lotion filtering, with pure water water washing 4 times, obtains dense PVDF polymer emulsion, in dense PVDF polymer emulsion
Middle addition deionized water adjusts solid content, is configured to the aqueous PVDF polymer emulsion that mass fraction is 20%.
10g titanium dioxide, 20g boehmite and 2.0g polyethylene glycol are added in 45g deionized water to add after stirring 3 hours
Enter 0.5g methyl hydroxyethylcellulose, 5.0g styrene-acrylic latex and 6.0g polyacrylate dispersion, continue stirring 6 hours, finally will
The aqueous PVDF polymer emulsion of 10g and 0.05g fluoro-alkyl ethyoxyl ether alcohol are added and stir 9 hours simultaneously, obtain PVDF/ oxygen
Change aluminium and slurry is blended.
Aqueous ceramic/PVDF is mixed coating slurry to be coated on polyethylene diagrams, obtains the wet film with a thickness of 50 μm.?
30 DEG C, under 0.1% damp condition, by the dry 30min of wet film after coating, obtain aqueous ceramic/PVDF mixing coating diaphragm.
The diaphragm decomposition voltage be 5.1V, under the conditions of 150 DEG C toast 1h after be heat-shrinked be respectively 1.2% (direction MD),
0.6% (direction TD), puncture strength 5.6N, tensile strength are 351Mpa (direction MD), 215Mpa (direction TD), and imbibition rate is
337%, broken film temperature is 210 DEG C, and lithium ion conductivity is 2.75 × 10-3S/cm, lithium ion transference number 0.77.By cobalt acid
Lithium, lithium piece, electrolyte and aqueous ceramic/PVDF mixing coating diaphragm are assembled into button cell and test its performance, in filling for 3C
Capacity retention ratio is 86.9% after 300 circle of circulation under discharge-rate.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of aqueous ceramic/PVDF mixing coating slurry preparation method, which is characterized in that detailed process is as follows:
1) high purity water, perfluoroalkyl class dispersing agent, tert-butyl hydroperoxide and acetone are uniformly mixed in nitrogen atmosphere
Afterwards, it is continually fed into vinylidene fluoride monomers and hexafluoropropene monomer gas under heating, controls reaction pressure, filter after the reaction was completed,
Washing adjusts solid content and obtains aqueous PVDF lotion;
2) it disperses ceramic material and the first dispersing agent in deionized water, after adding thickener and bonding agent dispersion, while stirring
It mixes side and aqueous PVDF lotion and wetting agent obtained by step 1) is added, obtain aqueous ceramic/PVDF mixing coating materials after mixing
Material.
2. aqueous ceramic according to claim 1/PVDF mixing coating slurry preparation method, which is characterized in that step
1) in, the high purity water, perfluoroalkyl class dispersing agent, tert-butyl hydroperoxide, acetone, vinylidene fluoride monomers and hexafluoropropene list
The proportion of body is according to the mass fraction 150 ~ 200:0.5 ~ 1:0.3 ~ 0.9:0.8 ~ 1.7:60:40;
The revolving speed being uniformly mixed is 70rpm/min, and mixing time is 1 ~ 5h;
The heating temperature is 60 ~ 100 DEG C;
The control reaction pressure realized by adjusting gas flow, control pressure in 1.5 ~ 4.0Mpa, the reaction time 8 ~
15h;
The washing, which is adopted, to be washed with deionized, and number is 3 ~ 5 times;
It is described to adjust solid content to refer to the aqueous PVDF polymer emulsion for the use of deionized water preparation mass fraction being 20%.
3. aqueous ceramic according to claim 1/PVDF mixing coating slurry preparation method, which is characterized in that step
2) in, the ceramic material, the first dispersing agent, deionized water, thickener, bonding agent, aqueous PVDF lotion obtained by step 1) and
The proportion of wetting agent is according to the mass fraction 10 ~ 30:0.01 ~ 2:45:0.1 ~ 0.5:7 ~ 15:10 ~ 40:0.05 ~ 0.5;
It is 0.5 ~ 8h that the ceramic material and the first dispersing agent, which are scattered in mixing time in deionized water,;
The thickener and the mixing time of bonding agent dispersion are 2 ~ 10h;
Mixing time after aqueous PVDF lotion and wetting agent obtained by the step 1) are added is 3 ~ 9h.
4. aqueous ceramic according to claim 1/PVDF mixing coating slurry preparation method, which is characterized in that described
Perfluoroalkyl class dispersing agent includes perfluor alkyl ethyl acrylate, perfluorooctanoic acid, perfluoro-heptanoic acid, perfluorododecyl sulfonic acid
One of sodium is a variety of.
5. aqueous ceramic according to claim 1/PVDF mixing coating slurry preparation method, which is characterized in that described
Ceramic material includes one of aluminium oxide, boehmite, silica, magnesium hydroxide, titanium dioxide or a variety of;
First dispersing agent includes maleic anhydride-vinylacetate, phenylethylene-maleic anhydride, polyethylene glycol, polyacrylic acid
One of sodium, polyacrylic acid potassium are a variety of;
The thickener includes hydroxyethyl cellulose, methyl hydroxyethylcellulose, sodium carboxymethylcellulose, polyacrylamide, sea
One of mosanom is a variety of;
The bonding agent includes butadiene-styrene latex, styrene-acrylic latex, polyvinyl alcohol, ethylene-vinyl acetate copolymer, one in polyurethane
Kind is a variety of;
The wetting agent is fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, alkyl phenol polyoxyethylene ether, fatty alcohol
One of polyoxyethylene ether, aliphatic acid polyethenoxy ether are a variety of.
6. a kind of aqueous ceramic/PVDF mixes coating slurry, which is characterized in that pass through any method of claim 1 ~ 5
It is prepared.
7. a kind of aqueous ceramic/PVDF mixing coating diaphragm preparation method, which is characterized in that detailed process is as follows:
A aqueous ceramic/PVDF prepared by any method of claim 1 ~ 5) is mixed into coating slurry and is coated in poly- second
Alkene diaphragm, obtains wet film;
B gained wet film) is dried to obtain aqueous ceramic/PVDF and mixes coating diaphragm.
8. aqueous ceramic according to claim 7/PVDF mixing coating diaphragm preparation method, which is characterized in that described
Step A) in wet film with a thickness of 3 ~ 50 μm;
The step B) in dry condition it is as follows: temperature is 30 ~ 50 DEG C, and relative humidity is 0.1 ~ 10%, drying time is 10 ~
30 min。
9. a kind of aqueous ceramic/PVDF mixing coating diaphragm, which is characterized in that pass through any method of claim 7 ~ 8
It is prepared.
10. a kind of lithium ion battery, which is characterized in that including positive electrode and negative electrode material, in positive electrode and negative electrode material
Between there is aqueous ceramic as claimed in claim 9/PVDF mixing coating diaphragm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810795492.6A CN109065804B (en) | 2018-07-18 | 2018-07-18 | Water-based ceramic/PVDF (polyvinylidene fluoride) mixed coating slurry as well as preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810795492.6A CN109065804B (en) | 2018-07-18 | 2018-07-18 | Water-based ceramic/PVDF (polyvinylidene fluoride) mixed coating slurry as well as preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109065804A true CN109065804A (en) | 2018-12-21 |
CN109065804B CN109065804B (en) | 2021-12-14 |
Family
ID=64817477
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810795492.6A Active CN109065804B (en) | 2018-07-18 | 2018-07-18 | Water-based ceramic/PVDF (polyvinylidene fluoride) mixed coating slurry as well as preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109065804B (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110112348A (en) * | 2019-03-19 | 2019-08-09 | 上海恩捷新材料科技有限公司 | Cell coating film slurry, battery diaphragm, secondary cell and preparation method thereof |
CN110660949A (en) * | 2019-10-08 | 2020-01-07 | 宁波中科达新材料有限公司 | Preparation method of inorganic and organic composite coating diaphragm |
CN110911620A (en) * | 2019-10-19 | 2020-03-24 | 东莞东阳光科研发有限公司 | Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof |
CN111048724A (en) * | 2019-12-27 | 2020-04-21 | 武汉中兴创新材料技术有限公司 | Coating diaphragm and coating slurry |
CN111129405A (en) * | 2019-12-30 | 2020-05-08 | 河北金力新能源科技股份有限公司 | Mixed coating diaphragm slurry and preparation method thereof, mixed coating diaphragm and lithium battery |
CN111883726A (en) * | 2020-08-28 | 2020-11-03 | 芜湖天弋能源科技有限公司 | Lithium ion battery diaphragm slurry and preparation method and application thereof |
CN113363670A (en) * | 2021-04-30 | 2021-09-07 | 万向一二三股份公司 | Diaphragm and lithium ion battery comprising same |
CN114221088A (en) * | 2021-11-30 | 2022-03-22 | 中材锂膜有限公司 | High-adhesion-strength PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof |
CN115000622A (en) * | 2022-07-21 | 2022-09-02 | 浙江人行道化工有限公司 | PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof |
CN115101894A (en) * | 2022-08-18 | 2022-09-23 | 宁德卓高新材料科技有限公司 | PVDF (polyvinylidene fluoride) coated diaphragm and preparation method and application thereof |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103187549A (en) * | 2011-12-28 | 2013-07-03 | 山东东岳高分子材料有限公司 | Diaphragm for lithium ion battery and preparation method thereof |
CN104143615A (en) * | 2013-08-26 | 2014-11-12 | 河南师范大学 | Lithium ion battery composite diaphragm and preparation method thereof |
US20150024249A1 (en) * | 2013-07-18 | 2015-01-22 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery and method of preparing the same |
CN104332578A (en) * | 2014-11-20 | 2015-02-04 | 深圳市星源材质科技股份有限公司 | Adhesive composite diaphragm and manufacturing method thereof |
CN105061659A (en) * | 2015-07-31 | 2015-11-18 | 深圳诚立胜新材料科技有限公司 | Fluorine-containing material preparation method, and application of fluorine-containing material prepared through using method |
CN105085753A (en) * | 2014-05-07 | 2015-11-25 | 浙江蓝天环保高科技股份有限公司 | Preparation method for polyvinylidene difluoride resin with high thermal stability and copolymer of polyvinylidene difluoride resin |
CN106336476A (en) * | 2016-08-25 | 2017-01-18 | 浙江孚诺林化工新材料有限公司 | Preparation method of vinylidene fluoride copolymer having high breaking elongation |
CN106654123A (en) * | 2017-01-20 | 2017-05-10 | 东莞市卓高电子科技有限公司 | Preparation method of coating membrane containing PVDF and copolymer thereof |
CN106684296A (en) * | 2016-08-26 | 2017-05-17 | 宁德卓高新材料科技有限公司 | PVDF (polyvinylidene fluoride) mixed coating diaphragm with good safety and preparation method thereof |
CN106784534A (en) * | 2016-08-29 | 2017-05-31 | 东莞市卓高电子科技有限公司 | The preparation method of PVDF and its copolymer ceramic coating membrane |
CN107093694A (en) * | 2017-05-17 | 2017-08-25 | 河北金力新能源科技股份有限公司 | A kind of aqueous PVDF coating lithium ions battery diaphragm and preparation method thereof |
-
2018
- 2018-07-18 CN CN201810795492.6A patent/CN109065804B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103187549A (en) * | 2011-12-28 | 2013-07-03 | 山东东岳高分子材料有限公司 | Diaphragm for lithium ion battery and preparation method thereof |
US20150024249A1 (en) * | 2013-07-18 | 2015-01-22 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery and method of preparing the same |
CN104143615A (en) * | 2013-08-26 | 2014-11-12 | 河南师范大学 | Lithium ion battery composite diaphragm and preparation method thereof |
CN105085753A (en) * | 2014-05-07 | 2015-11-25 | 浙江蓝天环保高科技股份有限公司 | Preparation method for polyvinylidene difluoride resin with high thermal stability and copolymer of polyvinylidene difluoride resin |
CN104332578A (en) * | 2014-11-20 | 2015-02-04 | 深圳市星源材质科技股份有限公司 | Adhesive composite diaphragm and manufacturing method thereof |
CN105061659A (en) * | 2015-07-31 | 2015-11-18 | 深圳诚立胜新材料科技有限公司 | Fluorine-containing material preparation method, and application of fluorine-containing material prepared through using method |
CN106336476A (en) * | 2016-08-25 | 2017-01-18 | 浙江孚诺林化工新材料有限公司 | Preparation method of vinylidene fluoride copolymer having high breaking elongation |
CN106684296A (en) * | 2016-08-26 | 2017-05-17 | 宁德卓高新材料科技有限公司 | PVDF (polyvinylidene fluoride) mixed coating diaphragm with good safety and preparation method thereof |
CN106784534A (en) * | 2016-08-29 | 2017-05-31 | 东莞市卓高电子科技有限公司 | The preparation method of PVDF and its copolymer ceramic coating membrane |
CN106654123A (en) * | 2017-01-20 | 2017-05-10 | 东莞市卓高电子科技有限公司 | Preparation method of coating membrane containing PVDF and copolymer thereof |
CN107093694A (en) * | 2017-05-17 | 2017-08-25 | 河北金力新能源科技股份有限公司 | A kind of aqueous PVDF coating lithium ions battery diaphragm and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
中国工程塑料工业协会编: "《工程塑料实用手册[M]》", 30 November 2005 * |
赵亚奇著: "《高分子自由基合成技术研究》", 31 December 2017 * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110112348B (en) * | 2019-03-19 | 2021-09-28 | 上海恩捷新材料科技有限公司 | Battery coating film slurry, battery diaphragm, secondary battery and preparation method thereof |
CN110112348A (en) * | 2019-03-19 | 2019-08-09 | 上海恩捷新材料科技有限公司 | Cell coating film slurry, battery diaphragm, secondary cell and preparation method thereof |
CN110660949A (en) * | 2019-10-08 | 2020-01-07 | 宁波中科达新材料有限公司 | Preparation method of inorganic and organic composite coating diaphragm |
CN110911620A (en) * | 2019-10-19 | 2020-03-24 | 东莞东阳光科研发有限公司 | Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof |
CN110911620B (en) * | 2019-10-19 | 2022-04-29 | 东莞东阳光科研发有限公司 | Spotted coating diaphragm slurry, composite diaphragm and preparation method thereof |
CN111048724A (en) * | 2019-12-27 | 2020-04-21 | 武汉中兴创新材料技术有限公司 | Coating diaphragm and coating slurry |
CN111129405A (en) * | 2019-12-30 | 2020-05-08 | 河北金力新能源科技股份有限公司 | Mixed coating diaphragm slurry and preparation method thereof, mixed coating diaphragm and lithium battery |
CN111883726A (en) * | 2020-08-28 | 2020-11-03 | 芜湖天弋能源科技有限公司 | Lithium ion battery diaphragm slurry and preparation method and application thereof |
CN113363670A (en) * | 2021-04-30 | 2021-09-07 | 万向一二三股份公司 | Diaphragm and lithium ion battery comprising same |
CN114221088A (en) * | 2021-11-30 | 2022-03-22 | 中材锂膜有限公司 | High-adhesion-strength PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof |
CN115000622A (en) * | 2022-07-21 | 2022-09-02 | 浙江人行道化工有限公司 | PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof |
CN115000622B (en) * | 2022-07-21 | 2024-04-26 | 浙江人行道化工有限公司 | PVDF coated diaphragm and preparation method thereof |
CN115101894A (en) * | 2022-08-18 | 2022-09-23 | 宁德卓高新材料科技有限公司 | PVDF (polyvinylidene fluoride) coated diaphragm and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN109065804B (en) | 2021-12-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109065804A (en) | A kind of aqueous ceramic/PVDF mixing coating slurry and its preparation method and application | |
KR100454773B1 (en) | Lithium-ion battery elements manufactured from a microcomposite powder based on a filler and on a fluoropolymer | |
CN104396048B (en) | Integrated electrode diaphragm component for lithium ion battery | |
CN104183867B (en) | A kind of single ion conductor nano-particle reinforcement lithium battery diaphragm or method for preparing polymer electrolytes and application | |
CN109103397A (en) | A kind of preparation method of lithium ion battery ceramic coating membrane | |
CN109065811B (en) | Water-based PVDF (polyvinylidene fluoride) coated diaphragm and preparation method and application thereof | |
CN113013549B (en) | Coating material for light-weight lithium ion battery diaphragm, preparation method of coating material and light-weight lithium ion battery composite diaphragm | |
CN105428571B (en) | Poly-dopamine modified lithium ceramic particle prepares PVDF HFP based polyalcohols membranes and preparation method | |
KR20170004025A (en) | Aqueous polyvinylidene fluoride composition | |
KR102231591B1 (en) | Core-shell particle and its use and manufacturing method | |
CN105556703A (en) | Solid composite fluoropolymer separator | |
CN105206777B (en) | Lithium battery diaphragm of the porous inorganic oxide containing lithium ion conduction and preparation method thereof | |
CN106816575A (en) | Positive plate and lithium ion battery | |
CN109841785A (en) | A kind of battery diaphragm and preparation method thereof and the lithium ion battery comprising the diaphragm | |
CN109065812A (en) | Diaphragm coating composition, slurry and preparation method thereof, diaphragm and lithium ion battery | |
CN109950461A (en) | A kind of diaphragm and preparation method thereof and battery | |
CN111180641A (en) | Diaphragm with self-crosslinking function and preparation method thereof | |
CN110148777A (en) | A kind of lithium ion battery centre tab core | |
CN107785521A (en) | A kind of battery diaphragm and lithium ion battery and preparation method thereof | |
CN110176568A (en) | A kind of preparation method of high-performance coating diaphragm | |
CN110048058A (en) | A kind of compound lithium ion battery separator and preparation method thereof | |
CN109216635A (en) | Activate film and its preparation method and application | |
CN111584932A (en) | Layered composite solid electrolyte film and preparation method thereof | |
CN113611981A (en) | Low-moisture lithium ion battery diaphragm slurry, preparation method thereof and battery diaphragm | |
CN109817869A (en) | A kind of lithium ion battery separator and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |