CN106129313A - A kind of electrochemical appliance isolating membrane and its production and use - Google Patents
A kind of electrochemical appliance isolating membrane and its production and use Download PDFInfo
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- CN106129313A CN106129313A CN201610605699.3A CN201610605699A CN106129313A CN 106129313 A CN106129313 A CN 106129313A CN 201610605699 A CN201610605699 A CN 201610605699A CN 106129313 A CN106129313 A CN 106129313A
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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
- H01M50/409—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
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/429—Natural polymers
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/443—Particulate material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of electrochemical appliance isolating membrane and its production and use.Described isolating membrane coating contains viscous polymer granule and additive and is distributed in intergranular micropore.
Description
Technical field
The present invention relates to technical field of electrochemistry, particularly relate to a kind of electrochemical appliance isolating membrane with superperformance and
Its preparation method.
Background technology
Traditional electrochemical appliance (such as lithium rechargeable battery) is most using polyolefin porous base material as isolating membrane, but
This isolating membrane has bigger contraction when being heated, be therefore easily caused both positive and negative polarity short circuit and cause security incident.In order to solve
This problem, people in the industry attempts utilizing binding agent to be made on porous substrate by coating inorganic particles and comprises inorganic matter coating
Organic/inorganic composite porous isolating membrane, it is desirable to reduced the thermal contraction of isolating membrane by the heat stability of inorganic particle, and have
It is bonding that machine material increases between barrier film with both positive and negative polarity interface, thus reaches prevent the short circuit of electrochemical appliance generation both positive and negative polarity and carry
The purpose of high battery core hardness.But, still there is defect in various degree in these isolating membrane newly developed.
Such as, someone discloses and a kind of includes porous substrate, inorganic matter coating and the polymer Li-ion of Organic substance coating
Battery isolating film, described Organic substance coating is coated on porous substrate and/or inorganic matter coating surface, and in island and/or wire
Distribution.But, this isolating membrane needs when coating coats to use the Organic substance such as NMP, ethanol repeatedly to coat as solvent,
Endanger environment and complex process, it is often more important that its cementability is the strongest, it is impossible to meet the battery requirement to hardness.
Somebody discloses a kind of oiliness coating isolating membrane with porous active coating layer, and it is by the mixing of oil-based polymer
Thing coating forms porous active coating layer on porous substrate, and this coating uses dipping process, and coating speed is slow, production efficiency
Low.In addition, the use meeting serious environment pollution of a large amount of organic solvents, also make manufacturing cost increase considerably.
Therefore, this area is in the urgent need to providing the electrochemical appliance that a kind of preparation technology is simple and interfacial adhesion is good
Isolating membrane.
Summary of the invention
It is desirable to provide the electrochemical appliance isolating membrane that a kind of interfacial adhesion is good.
In a first aspect of the present invention, it is provided that a kind of isolating membrane coating that can be used for electrochemical appliance, described coating contains
There are viscous polymer granule and additive and are distributed in intergranular micropore.
In another preference, described coating is also possible to containing binding agent.
In another preference, a diameter of 0.01-10 μm of described viscous polymer granule.
In another preference, described viscous polymer is selected from following one or more: polyacrylic acid, poly-first
Base acrylic acid, polymethyl acrylate, polyethyl acrylate, pure-acrylic emulsion, polyacrylic acid-styrol copolymer, polyvinyl pyrrole
Alkanone, butadiene-styrene rubber, epoxy resin, neopentylglycol diacrylate, sodium polyacrylate series, politef, polyimides,
Polyamide-based, polyester, cellulose derivative, polysulfones, polyacrylonitrile.
In another preference, described additive is selected from following one or more: polyvinyl alcohol, Polyethylene Glycol,
1,4-butanediol, polyethers, methanol, ethanol, stearic acid, dodecylbenzene sodium sulfonate, quaternary ammonium compound lecithin, amino acid pattern, sweet
Dish alkaline fatty glyceride, fatty acid Pyrusussuriensis smooth (span), Polysorbate (tween).
In another preference, described binding agent is selected from following one or more: polyacrylic acid, polymethyl
Acid, polymethyl acrylate, polyethyl acrylate, pure-acrylic emulsion, polyacrylic acid-styrol copolymer, polyvinylpyrrolidone, fourth
Benzene rubber, epoxy resin, neopentylglycol diacrylate, sodium polyacrylate series, politef.
In a second aspect of the present invention, it is provided that a kind of electrochemical appliance isolating membrane, described isolating membrane is coated with as above
The coating that the described present invention provides.
In a third aspect of the present invention, it is provided that the electrochemical appliance isolating membrane that a kind of present invention as above provides
Preparation method, described method includes step: be coated with on porous substrate by the slurry containing viscous polymer granule, obtain as
The battery isolating film that the upper described present invention provides.
In another preference, the described slurry containing viscous polymer granule by by viscous polymer granule,
Additive and water mix；Or by viscous polymer granule, binding agent, additive and water are mixed.
In a fourth aspect of the present invention, it is provided that a kind of electrochemical appliance, described electrochemical appliance contains as above
The electrochemical appliance isolating membrane that the present invention provides.
Accordingly, the invention provides the electrochemical appliance isolation that a kind of preparation technology is simple and interfacial adhesion is good
Film.
Accompanying drawing explanation
Fig. 1 is the isolating membrane schematic diagram that the present invention provides.
Detailed description of the invention
Inventor, through extensively in-depth study, finds that some polymer can increase electricity as battery isolating film coating
The hardness in pond.On this basis, the present invention is completed.
Isolating membrane/viscous polymer coating
The invention provides a kind of electrochemical appliance isolating membrane, it includes porous substrate and is coated on porous substrate at least
Viscous polymer coating on individual face.
As used in the present invention, " viscous polymer coating " and " isolating membrane coating " can exchange use, all include high viscous
Property polymer beads, additive and be evenly distributed on the micropore between viscous polymer granule.In terms of the gross area of base material,
Described viscous polymer coating area coverage ratio on base material is 5%-90%.
The viscous polymer coating of electrochemical appliance isolating membrane of the present invention has the highest viscosity, and has between particles
Substantial amounts of micropore (sees Fig. 1), therefore, it can that isolating membrane is effectively ensured and has excellent breathability and ionic conductivity；Meanwhile,
Owing to the granule of viscous polymer is the least, therefore can be effectively reduced the thickness of viscous polymer coating, reduce simultaneously every
From the risk of membrane coat uneven thickness, and ensure that isolating membrane has the interfacial adhesion of excellence, mechanical performance, heat stability
And oxidation resistance, make isolating membrane in the later stage battery core course of processing and between pole piece, form the interface that caking property is the strongest, and therefore
Improve security performance and the hardness of battery core.
A diameter of 0.01 μm-10 μm of described viscous polymer granule, preferably 0.1 μm-2 μm.
The thickness of described viscous polymer coating is 0.1 μm-10 μm, preferably 0.5 μm-5 μm
It is preferred that described viscous polymer grain structure is nucleocapsid structure, spherical structure or similar structures.Described height glues
The property nuclear material of polymer beads, shell material or integral material be polyacrylic acid, polymethylacrylic acid, polymethyl acrylate,
Polyethyl acrylate, pure-acrylic emulsion, polyacrylic acid-styrol copolymer, polyvinylpyrrolidone, butadiene-styrene rubber, epoxy resin,
Neopentylglycol diacrylate, sodium polyacrylate series, politef, polyimides, polyamide-based, polyester, cellulose spread out
At least one in biology, polysulfones, polyacrylonitrile；Optimization polypropylene acid methyl ester, polyethyl acrylate, neopentyl glycol two propylene
At least one in acid esters, polyester.
In one embodiment of the invention, linear polymer, such as but not limited to polyacrylic acid, polymethyl
Acid, polymethyl acrylate, polyethyl acrylate, pure-acrylic emulsion, polyacrylic acid-styrol copolymer, polyvinylpyrrolidone, new
Diacrylate, sodium polyacrylate series, politef, polyimides, polyamide-based, polyester, cellulose are derivative
The weight average molecular weight of thing, polysulfones, polyacrylonitrile etc. is between 100,000-50 ten thousand；Cross linked polymer, such as but not limited to butylbenzene rubber
It is ether, carboxyl, cyano group, amino ester group etc. that glue, epoxy resin etc. have suitable functional group.
In a preferred embodiment, the material of main part employing of above-mentioned viscous polymer can carry out swelling, as
Swelling ratio is 10-200%, it is preferred that swelling ratio is 30-100%, more preferably, swelling ratio is 50%-80%.Swelling ratio is permissible
Conventional method of the present invention is used to be measured, such as but not limited to, weight method.
In one embodiment of the invention, described viscous polymer coating includes viscous polymer and interpolation
Agent, it is also possible to optionally contain binding agent.In the present invention, the effect of binding agent is primarily to help coating is adhered to electricity
On the isolating membrane base material of chemical devices, and the effect of the so-called viscous polymer in coating is primarily to make electrochemical appliance
Isolating membrane and both positive and negative polarity height effective adhesive.It is said that in general, when described viscous polymer be enough to play above two effect simultaneously
Time, it is not necessary to binding agent will be added in the coating.In terms of the gross weight of described viscous polymer coating, general high viscosity is polymerized
The content of thing is 10-90wt% (preferably 70-90wt%, more preferably 80-90wt%), and the content of described binding agent is then less than
10wt%.
Described binding agent be polyacrylic acid, polymethylacrylic acid, polymethyl acrylate, polyethyl acrylate, pure-acrylic emulsion,
Polyacrylic acid-styrol copolymer, polyvinylpyrrolidone, butadiene-styrene rubber, epoxy resin, neopentylglycol diacrylate, poly-
At least one in sodium acrylate series, politef.
The porous substrate used in the electrochemical appliance isolating membrane that the present invention provides infiltrates mutually with deionized water, and it is selected from
In polyvinyl and copolymer thereof, polyimides, polyamide-based, polyester, cellulose derivative, polysulfones at least one
Kind；Or it is at least one in above-mentioned material and inorganic material alchlor, silicon dioxide, titanium dioxide, ceria, carbon
Acid calcium, calcium oxide, zinc oxide, magnesium oxide, Cerium titanate, calcium titanate, Barium metatitanate., lithium phosphate, titanium phosphate lithium, titanium phosphate aluminum lithium, nitrogen
Change the blend of at least one in lithium, lanthanium titanate lithium；Wherein, described polyvinyl and copolymer thereof can be polyethylene, gather
At least one in propylene, plastic of poly vinyl acetate copolymer, three layers of complex of polypropylene, polyethylene/polypropylene.
In one embodiment of the invention, described porous substrate can be coated with inorganic coating, the inorganic painting of coating
The inorganic material of layer is alchlor, silicon dioxide, titanium dioxide, ceria, calcium carbonate, calcium oxide, zinc oxide, oxidation
In magnesium, Cerium titanate, calcium titanate, Barium metatitanate., lithium phosphate, titanium phosphate lithium, titanium phosphate aluminum lithium, lithium nitride, lanthanium titanate lithium at least one
Kind.What the present invention provided viscous polymer coating can be applied directly on porous substrate, it is also possible to is coated in porous base
On inorganic coating on material.
On described porous substrate, the inorganic coating of coating need to use binding agent just can bond on porous substrate, and binding agent is
Polyacrylic acid, polymethylacrylic acid, polymethyl acrylate, polyethyl acrylate, pure-acrylic emulsion, polyacrylic acid-styrene copolymerized
Thing, polyvinylpyrrolidone, butadiene-styrene rubber, epoxy resin, neopentylglycol diacrylate, sodium polyacrylate series, polytetrafluoro
At least one in ethylene.
The additive used in the present invention mainly increases the slurry wetting action to base material.With viscous polymer coating
Gross weight meter, its content is at 0.01-10wt%；Described additive be polyvinyl alcohol, Polyethylene Glycol, 1,4-butanediol, polyethers,
Methanol, ethanol, stearic acid, dodecylbenzene sodium sulfonate, quaternary ammonium compound lecithin, amino acid pattern, betaine type fatty acid glycerine
At least one in ester, fatty acid Pyrusussuriensis smooth (span), Polysorbate (tween).
Isolating membrane preparation method
The present invention provides the preparation method of a kind of electrochemical appliance isolating membrane, said method comprising the steps of:
The first step, the raw material of viscous polymer coating composition the invention described above provided is made after mixing homogeneously with solvent
Become viscous polymer slurry；
Second step, is coated on viscous polymer slurry porous substrate or to have the above inorganic coating of at least one side many
On at least one face of hole base material；
3rd step, is dried process to the diaphragm after coating, obtains electrochemical appliance isolating membrane.
In the first step of said method, deionized water is used to make viscous polymer slurry as solvent, with make
The gross weight meter of slurry, the consumption of deionized water is 20-99wt%, preferably 60-95wt%.
In the above-mentioned first step, when raw material mixes with solvent, the addition sequence of various material compositions does not limits；Preferred in one
In embodiment, binding agent is joined in viscous polymer and stirs together, make binding agent be dispersed in high viscosity polymerization
In thing；Then additive added and stir, making additive dispersed in the slurry；It is eventually adding appropriate going as solvent
Ionized water, and stir and obtain the viscous polymer slurry of certain denseness；With obtained viscous polymer slurry
Gross weight meter, the content of viscous polymer is 10-90wt%, preferably 70-90wt%, more preferably 80-90wt%.With
Solid content meter in the viscous polymer slurry obtained, mass ratio shared by described binding agent is 0-10wt%, preferably 0-
6wt%.In terms of the solid content in the viscous polymer slurry obtained, mass ratio shared by described additive is 0.01-10wt%,
It is preferably 0.1-10wt%.
The above-mentioned first step can mix in the way of using stirring, it is preferred that described stirring can be kneading, machinery stirs
Mix, at least one in ball milling, ultrasonic disperse.
The porous substrate related in above-mentioned second step is preferably the material infiltrated mutually with deionized water；Use deionized water
It is to reduce cost and ensureing environment good as solvent, uses the porous substrate infiltrated mutually with deionized water then can
Reduce plug-hole risk to a greater degree.
Coating in above-mentioned second step includes but not limited to, the coating of dip coated, intaglio plate, silk screen printing, transfer coated, squeeze
Extrusion cloth, spraying coating and cast coat, the speed of coating is 1-300m/min.
Dried in above-mentioned 3rd step includes but not limited to dry, and baking temperature is 25-130 DEG C；It is preferred that use
Multistage baking oven, the temperature of baking oven sets the temperature temperature less than interlude of head and the tail two sections.
Electrochemical appliance
The present invention provides a kind of electrochemical appliance, including positive pole, negative pole and be interval between adjacent positive and negative pole
The isolating membrane that the present invention provides.
Described electrochemical appliance includes but not limited to, lithium secondary battery, lithium rechargeable battery, ultracapacitor, fuel
Battery and solaode；Described lithium rechargeable battery includes polymer lithium ion secondary battery.
The features described above that the present invention mentions, or the feature that embodiment is mentioned can be in any combination.Disclosed in this case description
All features can be with any composition forms use, each feature disclosed in description, can any provide identical,
The alternative characteristics of impartial or similar purpose replaces.Therefore except having special instruction, disclosed feature to be only impartial or similar spy
The general example levied.
Main advantages of the present invention are:
1, the viscous polymer coating layer thickness that the present invention provides is thin, uniform and distribution is continuous, glues therefore, it is possible to improve height
Property polymer coating and porous substrate/positive/negative plate between cementability, and then improve battery core hardness.
2, the viscous polymer coating that the present invention provides has substantial amounts of micropore between viscous polymer granule,
Ensure that the isolating membrane obtained has preferable breathability and ionic conductivity.
3, using water system system in the isolating membrane preparation method that the present invention provides, once coating can complete, and has coating
Speed is fast, technique is simple, the feature of mild condition, is especially suitable for volume production.
4, the electrochemical appliance that the present invention provides has good bonding, breathability, ionic conductivity, heat owing to have employed
Stability, the isolating membrane of mechanical strength, therefore chemical property and security performance etc. are greatly improved.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip
Part or according to the condition proposed by manufacturer.Unless otherwise indicated, the most all of percent, ratio, ratio or number are pressed
Weight meter.
The unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as, refer to
The weight of solute in the solution of 100 milliliters.
Unless otherwise defined, the meaning that all specialties used in literary composition are familiar with one skilled in the art with scientific words
Justice is identical.Additionally, any method similar or impartial to described content and material all can be applicable in the inventive method.Wen Zhong
Described preferable implementation only presents a demonstration with material and is used.
Comparative example 1
The preparation of positive plate: cobalt acid lithium, conductive carbon, binding agent Kynoar 96.5:2.0:1.5 in mass ratio are added
In N-methyl ketopyrrolidine (NMP), mix homogeneously makes anode sizing agent, is then coated on aluminium foil, and dries laggard at 85 DEG C
Row is colded pressing, cut into slices, cutting edge, divide bar, tab welding, makes positive plate.
The preparation of negative plate: by graphite, conductive carbon, thickening agent sodium carboxymethyl cellulose, binding agent butadiene-styrene rubber by quality
Add mix homogeneously in deionized water than 97:0.5:1.0:1.5 and make cathode size, be then coated on Copper Foil, and at 85 DEG C
Carry out after lower drying colding pressing, cut into slices, cutting edge, point bar, tab welding, make negative plate.
Isolating membrane: using thickness is that the polyethylene monolayer microporous separators of 12 μm is as isolating membrane.
The preparation of nonaqueous electrolytic solution: by LiPF6It is configured to LiPF with ethylene carbonate (EC) and diethyl carbonate (DEC)6Dense
Degree is the solution (wherein, the mass ratio of EC and DEC is 6:4) of 1.0mol/L, obtains nonaqueous electrolytic solution.
Anode ring forming: above-mentioned positive plate, isolating membrane, negative plate are wound into battery core, is then placed in plastic-aluminum bag by this battery core
In pack, inject the operations such as above-mentioned nonaqueous electrolytic solution, encapsulated, chemical conversion, make battery.
Comparative example 2
The processes such as positive plate, negative plate, nonaqueous electrolytic solution, anode ring forming are identical with comparative example 1, but isolating membrane uses as follows
Prepared by method:
The alumina powder of 16 mass parts and the deionized water of 8 mass parts are joined in double planetary mixer, in room temperature
Lower stirring 60min；Then adding the polyacrylic acid solution of 2 mass parts, mixing 1 hour, obtains ceramic size at normal temperatures；
Using transfer coated mode that polypropylene porous substrate is carried out double spread, coating speed is 25m/min；
Use syllogic oven for drying (every segment length is 3 meters, and each section of temperature is respectively 38 DEG C, 45 DEG C, 42 DEG C), survey after drying
The one side thickness obtaining gained coating is 4 μm.
Comparative example 3
The processes such as positive plate, negative plate, nonaqueous electrolytic solution, anode ring forming are identical with comparative example 1, but isolating membrane uses as follows
Prepared by method:
The deionized water of the alumina powder of 20 mass parts, the Kynoar powder of 10 mass parts and 8 mass parts is added
Enter in double planetary mixer, be stirred at room temperature 30min；Then the polyacrylic acid solution of 5 mass parts is added, at normal temperatures
Mix 2 hours, obtain pottery and Kynoar mixed slurry；
Using plate gravure coating method that polypropylene porous substrate is carried out double spread, coating speed is 15m/min；
Use syllogic oven for drying (every segment length is 3 meters, and each section of temperature is respectively 48 DEG C, 41 DEG C, 38 DEG C), survey after drying
The one side thickness obtaining gained coating is 5 μm.
Comparative example 4
The processes such as positive plate, negative plate, nonaqueous electrolytic solution, anode ring forming are identical with comparative example 1, but isolating membrane uses as follows
Prepared by method:
The deionized water of the polypropylene powder of 50 mass parts, the pure-acrylic emulsion of 5 mass parts and 20 mass parts is joined double
In planetary mixer, it is stirred at room temperature 30min, obtains polymer paste；
Using plate gravure coating method that polypropylene porous substrate is carried out double spread, coating speed is 20m/min；
Use syllogic oven for drying (every segment length is 3 meters, and each section of temperature is respectively 55 DEG C, 60 DEG C, 60 DEG C), survey after drying
The one side thickness obtaining gained coating is 3 μm.
Embodiment 1
The processes such as positive plate, negative plate, nonaqueous electrolytic solution, anode ring forming are identical with comparative example 1, but isolating membrane uses as follows
Prepared by method:
By the viscous polymer of 40 mass parts, (mass fraction is 30%, and solvent is water, nuclear material: polyacrylic acid, shell material
Material: polymethylacrylic acid), the deionized water of the polyethers of 0.2 mass parts and 30 mass parts join in dimorphism star blender, often
The lower mixing of temperature 0.5 hour, obtains viscous polymer slurry；
Using extrusion coated mode that polypropylene porous substrate is carried out double spread, coating speed is 20m/min；
Use syllogic oven for drying (every segment length is 3 meters, and each section of temperature is respectively 38 DEG C, 40 DEG C, 40 DEG C), survey after drying
The one side thickness obtaining gained coating is 0.5 μm.
Embodiment 2
The processes such as positive plate, negative plate, nonaqueous electrolytic solution, anode ring forming are identical with comparative example 1, but isolating membrane uses as follows
Prepared by method:
By the viscous polymer of 20 mass parts, (mass fraction is 20%, and solvent is water, nuclear material: polyvinylpyrrolidine
Ketone, shell material: butadiene-styrene rubber) and polyacrylic acid join in dimorphism star blender, stir 30min under room temperature, then 5 mass parts
Polyethylene Glycol and the deionized water of 50 mass parts, mixing 1.5 hours, obtain viscous polymer slurry at normal temperatures；
Use plate gravure coating method that three layers of compound porous base material of polypropylene, polyethylene/polypropylene are carried out single spreading, be coated with
Cloth speed is 10m/min；
Use syllogic oven for drying (every segment length is 3 meters, and each section of temperature is respectively 70 DEG C, 65 DEG C, 65 DEG C), survey after drying
The one side thickness obtaining coating is 2 μm.
Embodiment 3
The processes such as positive plate, negative plate, nonaqueous electrolytic solution, anode ring forming are identical with comparative example 1, but isolating membrane uses as follows
Prepared by method:
By the viscous polymer of 25 mass parts, (mass fraction is 10%, and solvent is water, integral material: neopentyl glycol two
Acrylate) and polyvinylpyrrolidone join in dimorphism star blender, stir 60min, then the methanol of 1 mass parts under room temperature
With the deionized water of 40 mass parts, mixing 1.0 hours, obtain viscous polymer slurry at normal temperatures；
Use plate gravure coating method that three layers of compound porous base material of polypropylene, polyethylene/polypropylene are carried out double spread, be coated with
Cloth speed is 60m/min；
Use syllogic oven for drying (every segment length is 3 meters, and each section of temperature is respectively 62 DEG C, 70 DEG C, 64 DEG C), survey after drying
The one side thickness obtaining coating is 1 μm.
Embodiment 4
The processes such as positive plate, negative plate, nonaqueous electrolytic solution, anode ring forming are identical with comparative example 1, but isolating membrane uses as follows
Prepared by method:
By the viscous polymer of 20 mass parts (mass fraction is 20%, and solvent is water, nuclear material: polyester, shell material:
Cellulose derivative) and butadiene-styrene rubber join in dimorphism star blender, stir 60min, the more poly-mountain of 10 mass parts under room temperature
Pear ester and the deionized water of 70 mass parts, mixing 2 hours, obtain viscous polymer slurry at normal temperatures；
Use dip coated mode that three layers of compound porous base material of polypropylene, polyethylene/polypropylene are carried out double spread, be coated with
Cloth speed is 20m/min；
Use syllogic oven for drying (every segment length is 3 meters, and each section of temperature is respectively 60 DEG C, 58 DEG C, 58 DEG C), survey after drying
The one side thickness obtaining coating is 0.2 μm.
Embodiment 5
Performance test
Embodiment 1-4 and the isolating membrane of comparative example 1-3 and lithium ion battery are carried out following performance test:
1) the porosity test of isolating membrane: test with mercury injection apparatus；
2) the air permeability test of isolating membrane: test with permeating degree tester；
3) the puncture-resistant strength test of isolating membrane: pierce through isolating membrane with the speed of 50mm/min with the wire nail of diameter 0.5mm；
4) the percent thermal shrinkage test of isolating membrane: isolating membrane cutting die is washed into square piece, isolating membrane is put in the constant temperature of 120 DEG C
In baking oven, take out after drying 2h, the shrinkage factor of isolating membrane before and after mensuration heat treatment；
5) the cycle performance test of lithium ion battery: lithium rechargeable battery at room temperature 0.5C multiplying power is charged, 0.5C
Multiplying power discharging, carries out 500 circulations successively, utilizes formula to calculate its capability retention；Capability retention=(after 500 circulations
The room temperature capacity of battery before the capacity/circulation of battery) × 100%；
6) the high-temperature storage performance test of lithium ion battery: lithium rechargeable battery is carried out under completely filling (4.2V) 80
DEG C, 30 days storage, utilize formula to calculate its thickness swelling；Thickness swelling=(before and after storage before cell thickness change/storage
The thickness of battery core) × 100%；
7) volume test of lithium ion battery: by the lithium rechargeable battery charging of 0.5C multiplying power, 0.5C multiplying power at 35 DEG C
Electric discharge, obtains the capacity of battery core, and then calculates the energy density of battery core.
8) diaphragm interface is bonding: take the N/R barrier film of face integral outer appearance, and being die-cut into width is 15mm, a length of
The sample of 100mm, takes two die-cut good barrier film samples stacked together, with 1MPa pressure on hot press, and temperature 85 degree, speed
The condition hot pressing of 10 meters/min, and test two pulling force (unit is N) being bonded together barrier film, cohesive force=draw with puller system
Power/0.015 (unit is N/m).
9) battery hardness: take the battery after having finished capacity, is placed between two pieces of iron blocks, and the distance between iron block is
30mm, uses the iron prop down piezoelectric battery with round end on puller system, takes pressure required when that past bottom offset being 1mm
Power, unit is kgf@1mm.
Comparative example 1-4 and the isolating membrane of embodiment 1-4 and performance of lithium ion battery test result are as shown in table 1.
Table 1, comparative example and embodiment prepare isolating membrane and battery performance test result
Result shows:
1) embodiment 1-4 and the bonding interface of comparative example 3-4 and battery core hardness all have than comparative example 1-2 and relatively significantly change
Kind, particularly embodiment 1-4, improvement degree is far longer than comparative example 3-4, and therefore, viscous polymer coating isolating membrane is to electricity
Core hardness has greatly improved；
2) compared with comparative example 1-3, the coating layer thickness of embodiment 1-4 is less, and the cycle performance of its battery is more preferable, and thickness is swollen
Swollen rate is less, and battery core energy density is the highest；This is because the polymer beads that viscous polymer coating of the present invention is used
Size is less, and then reduces the thickness of coating, and therefore it can be in the situation ensureing that puncture-resistant intensity, percent thermal shrinkage do not reduce
Under, accomplish the thickness of 0.2 μm, and the coating morphology than comparative example 2-3 be more uniform, simultaneously because viscous polymer have special
Functional group, this makes bonding higher than comparative example 3 of the bonding interface between coating itself and both positive and negative polarity, this guarantees
Battery core is more difficult generation barrier film and both positive and negative polarity ablation in cyclic process, so that battery has more preferable cycle performance
Less thickness swelling；And, the reduction of coating layer thickness also brings the reduction of battery core volume so that battery core energy density
Increase.In addition, compared with comparative example 4, the cycle performance of embodiment 1-4 is significantly superior, just because of the highest
The group that sticky polymers contains is more beneficial for the transmission of battery intermediate ion.
The foregoing is only presently preferred embodiments of the present invention, be not limited to the substantial technological content model of the present invention
Enclosing, the substantial technological content of the present invention is broadly to be defined in the right of application, any technology that other people complete
Entity or method, if with the right of application defined in identical, also or the change of a kind of equivalence, all by
It is considered to be covered by among this right.
Claims (10)
1. the isolating membrane coating that can be used for electrochemical appliance, it is characterised in that described coating contains viscous polymer
Grain and additive and be distributed in intergranular micropore.
2. coating as claimed in claim 1, it is characterised in that described coating is also possible to containing binding agent.
3. coating as claimed in claim 1 or 2, it is characterised in that a diameter of 0.01-10 of described viscous polymer granule
μm。
4. coating as claimed in claim 3, it is characterised in that described viscous polymer selected from following one or both with
Upper: polyacrylic acid, polymethylacrylic acid, polymethyl acrylate, polyethyl acrylate, pure-acrylic emulsion, polyacrylic acid-styrene are common
Polymers, polyvinylpyrrolidone, butadiene-styrene rubber, epoxy resin, neopentylglycol diacrylate, sodium polyacrylate serial, poly-four
Fluorothene, polyimides, polyamide-based, polyester, cellulose derivative, polysulfones, polyacrylonitrile.
5. coating as claimed in claim 3, it is characterised in that described additive is selected from following one or more: poly-
Vinyl alcohol, Polyethylene Glycol, 1,4-butanediol, polyethers, methanol, ethanol, stearic acid, dodecylbenzene sodium sulfonate, quaternary ammonium compound ovum
Phospholipid, amino acid pattern, betaine type fatty glyceride, fatty acid Pyrusussuriensis smooth (span), Polysorbate (tween).
6. coating as claimed in claim 2, it is characterised in that described binding agent is selected from following one or more: poly-
Acrylic acid, polymethylacrylic acid, polymethyl acrylate, polyethyl acrylate, pure-acrylic emulsion, polyacrylic acid-styrol copolymer,
Polyvinylpyrrolidone, butadiene-styrene rubber, epoxy resin, neopentylglycol diacrylate, sodium polyacrylate series, polytetrafluoroethyl-ne
Alkene.
7. an electrochemical appliance isolating membrane, it is characterised in that coat on described isolating membrane just like any one of claim 1-6 institute
The coating stated.
8. the preparation method of an electrochemical appliance isolating membrane as claimed in claim 7, it is characterised in that described method includes
Step: by containing viscous polymer granule slurry be coated with on porous substrate, obtain battery as claimed in claim 7 every
From film.
9. preparation method as claimed in claim 8, it is characterised in that the described slurry containing viscous polymer granule passes through
Viscous polymer granule, additive and water are mixed；Or by by viscous polymer granule, binding agent, additive
Mix with water.
10. an electrochemical appliance, it is characterised in that described electrochemical appliance contains electrochemistry as claimed in claim 7 dress
Put isolating membrane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610605699.3A CN106129313A (en) | 2016-07-28 | 2016-07-28 | A kind of electrochemical appliance isolating membrane and its production and use |
| PCT/CN2017/073105 WO2018018870A1 (en) | 2016-07-28 | 2017-02-08 | Separator for electrochemical device and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610605699.3A CN106129313A (en) | 2016-07-28 | 2016-07-28 | A kind of electrochemical appliance isolating membrane and its production and use |
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| WO (1) | WO2018018870A1 (en) |
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