CN106252565B - A kind of lithium ion battery separator and preparation method thereof of composite coated processing - Google Patents
A kind of lithium ion battery separator and preparation method thereof of composite coated processing Download PDFInfo
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- CN106252565B CN106252565B CN201610847515.4A CN201610847515A CN106252565B CN 106252565 B CN106252565 B CN 106252565B CN 201610847515 A CN201610847515 A CN 201610847515A CN 106252565 B CN106252565 B CN 106252565B
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
- C09D177/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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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
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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
- H01M50/431—Inorganic material
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of lithium ion battery separator and preparation method thereof of composite coated processing, which includes that basement membrane and the polymer coating coated on basement membrane side and the inorganic particulate coating coated on the basement membrane other side are constituted；For polymer coating by being coated in epilamellar aramid fiber coating and constituting coated in the polyvinylidene fluoride coating on aramid fiber coating, polymer coating thickness is 0.3-5 μm；Inorganic particulate coating is made of the inorganic particulate of different-grain diameter and binder, and inorganic particulate coating layer thickness is 0.5-5 μm.Lithium ion battery separator of the invention has the characteristics that mechanical property and heat resistance are outstanding, have good wetability to electrolyte and liquid retention, cycle performance are outstanding and security performance is high.
Description
Technical field
The present invention relates to technical field of lithium ion, compound more specifically to a kind of polymer and inorganic particulate
Coating enhancing security performance and the lithium ion battery separator of cycle performance and preparation method thereof.
Background technique
Diaphragm is one of indispensable four big critical material in lithium ion battery, it, which is primarily served, prevents positive and negative anodes direct
Contact and short circuit occurs, while allowing the ion in electrolyte is freely through to act on.The performance of diaphragm determines battery
Internal resistance and cell interface structure etc., directly affect chemical property and the safety of battery.The diaphragm haveing excellent performance is to raising
The comprehensive performance of lithium ion battery has great influence.
The commercialization diaphragm of current main-stream is MIcroporous polyolefin film, since the fusing point of these MIcroporous polyolefin films is lower, because
, when battery temperature increases, this polyalkene diaphragm, which can be shunk, even to be melted for this, is occurred so as to lead to battery short circuit
Fire even explodes.In addition, this kind of polyalkene diaphragm is not good enough to the wetability of electrolyte, this causes diaphragm that cannot absorb and keep
A large amount of electrolyte, to influence the charge-discharge performance of battery.
With the development of electric vehicle and portable dam etc., increasingly to the performance requirement of power battery currently
It is high.The High-performance diaphragm for being used for power battery field it is therefore desirable to develop a new generation.
To polyalkene diaphragm carry out inorganic particulate or (and) polymer-coated processing can improve diaphragm to a certain extent
Heat-resistant stability and electrolyte wetability, but due to inorganic particulate or (and) bonding of polymer and MIcroporous polyolefin film
Property is poor, the problem of being easy to fall off there is easy inorganic particulate and polymer coating.Simultaneously as inorganic particulate and polymer
Coating falls off, so that contact of the diaphragm with battery pole piece is deteriorated, to influence the charge-discharge performance and cycle life of battery.It is single
Purely to polyalkene diaphragm carry out polymer-coated, although the electrolyte wetability of diaphragm can be improved, diaphragm it is heat-resisting
Performance improves unobvious；And inorganic particulate coating individually is carried out to polyalkene diaphragm, although the heat-resisting of diaphragm can be significantly improved
Property, but inorganic particulate is easy to fall off, and inorganic particulate density is big, is unfavorable for improving the energy per mass density of battery.
Summary of the invention
The technical problem to be solved in the present invention is that in view of the above drawbacks of the prior art, providing a kind of novel polymerization
Object and the composite diaphragm for lithium ion battery of inorganic particulate coating processing and preparation method thereof.The method preparation announced with the present invention
Diaphragm have good electrolyte affinity, outstanding heat-resistant stability and mechanical strength, with electrode slice bonding it is even closer,
Inorganic particulate and polymer coating are not easy the advantages that falling, and have greater security energy using lithium ion battery prepared by the diaphragm
More preferably cycle performance, while the preparation method has the characteristics that simple to operation and cost is relatively low.
The technical solution adopted by the present invention to solve the technical problems is: providing a kind of lithium-ion electric of composite coated processing
Pond diaphragm, the polymer coating including basement membrane and coated on basement membrane side and the inorganic particulate coating coated on the basement membrane other side
It constitutes；The polymer coating is by being coated in epilamellar aramid fiber coating and coated in the polyvinylidene fluoride coating on aramid fiber coating
It constitutes, polymer coating thickness is 0.3-5 μm；The inorganic particulate coating by different-grain diameter inorganic particulate and binder structure
At inorganic particulate coating layer thickness is 0.5-5 μm.
The lithium ion battery separator of composite coated processing of the present invention, wherein the aramid fiber in the polymer coating
Coating is coated by aramid fiber coating solution, immersion, obtains after drying, aramid fiber coating with a thickness of 0.2-3 μm；The polymer coating
In polyvinylidene fluoride coating obtained after being coated with, drying by polyvinylidene fluoride coating liquid, polyvinylidene fluoride coating with a thickness of
0.1-2μm；The inorganic particulate coating is obtained after being coated with, drying by inorganic particulate coating solution.
The lithium ion battery separator of composite coated processing of the present invention, wherein the aramid fiber coating solution is by following matter
The material composition of amount part: 3-10 parts of aramid fiber, 60-87 parts of solvent, 3-5 parts of cosolvent, 0.5-1 parts of dispersing agent, emulsifier
0.5-2 parts, 1-2 parts of polymeric binder.
The lithium ion battery separator of composite coated processing of the present invention, wherein the aramid fiber is meta-aramid
The combination of one or more of fiber, para-aramid fiber, meta-aramid pulp, para-aramid pulp, the molecular weight of aramid fiber
For 1-10 ten thousand；The solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl Asia
One of sulfone；The cosolvent is one or more of sodium benzoate, lithium chloride, calcium chloride, sodium hydroxide, acetamide
Combination；The dispersing agent be one of polyethylene glycol oxide, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer or
Person's multiple combinations；The emulsifier be hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, Sodium Polyacrylate,
Polyacrylic acid potassium, polyacrylamide, dodecyl trimethyl ammonium chloride, ethylene oxide-butylene oxide copolymer, ethylene oxide-
The combination of one or more of propylene oxide-epoxy butane copolymer；The polymeric binder be polyvinylpyrrolidone,
The combination of one or more of vinylpyridine network alkanone, vinyl acetate copolymer.
The lithium ion battery separator of composite coated of the present invention processing, wherein the polyvinylidene fluoride coating liquid by
Polyvinylidene fluoride resin, organic solvent and pore-foaming agent composition；Wherein in polyvinylidene fluoride coating liquid polyvinylidene fluoride resin matter
Amount score is 1%-20%, and the mass fraction of pore-foaming agent is 0.2%-20%, and surplus is organic solvent.
The lithium ion battery separator of composite coated processing of the present invention, wherein the polyvinylidene fluoride resin is poly-
Vinylidene fluoride homopolymer or one of vinylidene and hexafluoropropylene copolymer；The organic solvent is N, N- dimethyl methyl
The combination of one or more of amide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, acetone；It is described
Pore-foaming agent is one of methanol, ethyl alcohol, propyl alcohol, butanol and deionized water.
The lithium ion battery separator of composite coated processing of the present invention, wherein the inorganic particulate coating solution is by pressing
The base-material of the 5%-40% calculated according to weight percent and the solvent composition of 60%-95%, the weight percent of said components it
Be 100%；The base-material is by the inorganic particulate of 60%-95% count by weight percentage and the polymer group of 5%-40%
At the sum of weight percent of said components is 100%.
The lithium ion battery separator of composite coated of the present invention processing, wherein the inorganic particulate is aluminium oxide, vigorous
Nurse stone, aluminium hydroxide, aluminium nitride, magnesia, magnesium hydroxide, boron nitride, bayerite, silica, titanium oxide, zirconium oxide,
The combination of one or more of nickel oxide, zeolite particles；The particle diameter distribution of all inorganic particulates is and inorganic at 0.03-1 μm
Particle diameter is distributed as 0.03-0.3 μm and accounts for 60%-80% mass share, and 0.3-0.6 μm accounts for 10%-20% mass share, 0.6-
1 μm accounts for 10%-20% mass share；The polymer is by Kynoar, vinylidene -- hexafluoropropylene copolymer, inclined fluorine second
Alkene -- chlorotrifluoroethylcopolymer copolymer, vinylidene -- trifluoro-ethylene copolymer, polymethyl methacrylate, polymethylacrylic acid fourth
The combination of one or more of ester, polyacrylonitrile, poly(aryl ether ketone), polyimides；The solvent be N,N-dimethylformamide,
DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, ethyl alcohol, acetone, butanone, methylene chloride, petroleum ether, four
Any one of hydrogen furans or multiple combinations.
The lithium ion battery separator of composite coated of the present invention processing, wherein the basement membrane be polyethene microporous membrane,
Microporous polypropylene membrane, polyethylene/polypropylene microporous barrier, polypropylene/polypropylene microporous barrier, polypropylene, polyethylene/polypropylene composite materials
One of microporous barrier, basement membrane thickness are 5~40 μm, and porosity is 35~65%；The basement membrane passes through corona or plasma
One of body processing or two methods are pre-processed.
The present invention also provides a kind of preparation methods of the lithium ion battery separator of composite coated processing as described above, including
Following steps:
(1) aramid fiber coating first is carried out to the side of basement membrane after treatment, completes the coating of aramid fiber coating；
(2) Kynoar coating is then carried out on the aramid fiber coating of the same side of basement membrane, is completed Kynoar and is applied
The coating of layer；
(3) coating processing that inorganic particulate is finally carried out to the other side of basement membrane, completes the coating of inorganic particulate coating.
The lithium ion battery separator and preparation method thereof for implementing composite coated processing of the invention, has below beneficial to effect
Fruit:
1. the diaphragm of Inventive polymers and the processing of inorganic particulate composite coated, compared with traditional polymer coats diaphragm,
Because the presence of aramid fiber coating increases roughness, so that between aramid fiber coating and polyvinylidene fluoride coating and polymerizeing
The bonding of object coating and basement membrane is even closer, not easily to fall off, and due to the presence of Kynoar, diaphragm can be with electrode slice
Bond it is even closer, reduce gap, promote the volume energy density of battery.
2. compared with traditional ceramic coating membrane, the inorganic particulate of different-grain diameter arrange between each other it is even closer, with
Basement membrane bonding is closer, inorganic particulate coating is not easily to fall off, it is closer to bond with electrode slice.The composite diaphragm has aramid fiber coating
Outside good heat resistance and mechanical property, but with polyvinylidene fluoride coating good electrolyte wellability and liquid retention,
The characteristics of battery pole piece can effectively be bonded, furthermore the inorganic particulate of different-grain diameter can form even closer bonding, not allow
Easy to fall off, the surface covering that inorganic particulate is formed absorbs more electrolyte using capillarity and is stored in diaphragm, favorably
In the high rate performance for improving stability and battery of the diaphragm in high power charging-discharging when, simultaneously because inorganic particulate coating heat resistance
Can be quite outstanding, and there is certain hardness, perforation destruction when hindering lithium dendrite growth to diaphragm can be played.
3. polymer coating of the present invention and inorganic particulate coating, which can cooperate with, plays enhancing diaphragm heat resistance, and
And since polymeric layer and pole piece bonding are even closer, and inorganic particulate coating is also not easily to fall off, improves the security performance of battery；
It can also cooperate with simultaneously and play the tensile strength for improving diaphragm and puncture strength, electrolyte wellability, battery high rate performance and follow
Ring service life etc..
Experiments have shown that diaphragm of the present invention has good gas permeability, imbibition rate, mechanical stretch intensity, heat-resisting size
Stability is obviously obtained with security performance, high rate performance and the cycle performance of the lithium ion battery of diaphragm of the present invention preparation
Improve.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples, in attached drawing:
Fig. 1 is the diagrammatic cross-section of the diaphragm of present pre-ferred embodiments composite coated processing；
Wherein, 1, polyvinylidene fluoride coating；2, aramid fiber coating；3, basement membrane；4, inorganic particulate coating.
Specific embodiment
In the following, being described further in conjunction with attached drawing and specific embodiment to the present invention:
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc.
It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field
Rule method.
As shown in Figure 1, the diaphragm for lithium ion battery of a kind of polymer and the processing of inorganic particulate composite coated, including basement membrane
3 and the polymer coating coated on basement membrane side and the inorganic particulate coating 4 coated on the basement membrane other side constitute；The polymerization
Object coating is by being coated in epilamellar aramid fiber coating 2 and constituting coated in the polyvinylidene fluoride coating 1 on aramid fiber coating, polymer
The overall thickness of coating is 0.3-5 μm；Aramid fiber coating is coated by aramid fiber coating solution, soaks, obtains after drying, and coating layer thickness is
0.2-3μm；Polyvinylidene fluoride coating is obtained after being coated with, drying by polyvinylidene fluoride coating liquid, and coating layer thickness is 0.1-2 μ
m.The formation of the aramid fiber coating is to form basement membrane with porous through mass transport process by soaking after coating aramid fiber coating solution
The aramid fiber coating of structure.The formation of above-mentioned polyvinylidene fluoride coating is passed through by polyvinylidene fluoride coating liquid by coating, drying
The effect of pore-foaming agent forms the polyvinylidene fluoride coating of porous structure.The inorganic particulate coating by different-grain diameter inorganic particulate
It is constituted with binder, inorganic particulate coating layer thickness is 0.5-5 μm.
Preferably, the aramid fiber coating solution by following mass parts material composition: 3-10 parts of aramid fiber, solvent 60-87
Part, 3-5 parts of cosolvent, 0.5-1 parts of dispersing agent, 0.5-2 parts of emulsifier, 1-2 parts of polymeric binder.Wherein, the aramid fiber is fine
Dimension is that one or more of meta-aramid fibers, para-aramid fiber, meta-aramid pulp, para-aramid pulp combine,
The molecular weight of aramid fiber is 1-10 ten thousand；The solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- crassitude
One of ketone, dimethyl sulfoxide；The cosolvent is sodium benzoate, in lithium chloride, calcium chloride, sodium hydroxide, acetamide
One or more combination；The dispersing agent is polyethylene glycol oxide, ethylene-acrylic acid copolymer, ethene-vinyl acetate copolymerization
The combination of one or more of object；The emulsifier be hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride,
Sodium Polyacrylate, polyacrylic acid potassium, polyacrylamide, dodecyl trimethyl ammonium chloride, ethylene oxide-butylene oxide copolymerization
The combination of one or more of object, epoxy ethane-epoxy propane-epoxy butane copolymer；The polymeric binder is poly-
The combination of one or more of vinylpyrrolidone, vinylpyridine network alkanone, vinyl acetate copolymer.
Preferably, the polyvinylidene fluoride coating liquid is made of polyvinylidene fluoride resin, organic solvent and pore-foaming agent；Wherein
The mass fraction of polyvinylidene fluoride resin is 1%-20% in polyvinylidene fluoride coating liquid, and the mass fraction of pore-foaming agent is 0.2%-
20%, surplus is organic solvent.The polyvinylidene fluoride resin is polyvinylidene fluoride homopolymer or vinylidene and hexafluoro third
One of alkene copolymer；The organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- crassitude
The combination of one or more of ketone, dimethyl sulfoxide, acetone；The pore-foaming agent be methanol, ethyl alcohol, propyl alcohol, butanol and go from
One of sub- water.
Preferably, the inorganic particulate coating solution is by the base-material and 60%- of the 5%-40% calculated in percentage by weight
95% solvent composition, the sum of weight percent of said components are 100%；The base-material is by count by weight percentage
The inorganic particulate of 60%-95% and the polymer composition of 5%-40%, the sum of weight percent of said components is 100%.Its
In, the inorganic particulate is aluminium oxide, boehmite, aluminium hydroxide, aluminium nitride, magnesia, magnesium hydroxide, boron nitride, three hydroxyl aluminium
The combination of one or more of stone, silica, titanium oxide, zirconium oxide, nickel oxide, zeolite particles；All inorganic particulates
Particle diameter distribution is at 0.03-1 μm, and inorganic particulate particle diameter distribution is 0.03-0.3 μm and accounts for 60%-80% mass share, 0.3-
0.6 μm accounts for 10%-20% mass share, and 0.6-1 μm accounts for 10%-20% mass share；The polymer by Kynoar, partially
-- hexafluoropropylene copolymer, vinylidene -- chlorotrifluoroethylcopolymer copolymer, vinylidene -- trifluoro-ethylene copolymer gathers vinyl fluoride
One or more of methyl methacrylate, polybutyl methacrylate, polyacrylonitrile, poly(aryl ether ketone), polyimides group
It closes；The solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, second
Any one of alcohol, acetone, butanone, methylene chloride, petroleum ether, tetrahydrofuran or multiple combinations.
Preferably, the basement membrane is polyethene microporous membrane, microporous polypropylene membrane, polyethylene/polypropylene microporous barrier, poly- third
One of alkene/microporous polypropylene membrane, polypropylene, polyethylene/polypropylene composite materials microporous barrier etc., basement membrane thickness are 5~40 μm, hole
Gap rate is 35~65%.The basement membrane is located in advance by one of corona or corona treatment or two methods
Reason.
Embodiment 1:
The diaphragm for lithium ion battery of polymer of the invention and the processing of inorganic particulate composite coated, preparation method is such as
Under:
A, it prepares aramid fiber coating solution: weighing meta-aramid fibers 0.5kg, solvent N, the N- dimethyl that molecular weight is 5-7 ten thousand
Formamide is 8.5kg, cosolvent calcium chloride 0.3kg, dispersing agent polyethylene glycol oxide 0.1kg, emulsifier octadecyl trimethyl chlorine
Change ammonium 0.1kg, binder polyvinylpyrrolidone 0.2kg.Cosolvent calcium chloride is added in solvent and is stirred to being completely dissolved,
Dispersing agent polyethylene glycol oxide is added while stirring, stirs at low speed to polyethylene glycol oxide to being completely dissolved, meta-aramid fibers is added,
It is uniformly mixed, obtains meta-aramid coating solution.
B, the preparation of polyvinylidene fluoride coating liquid: Kynoar 1kg, solvent are acetone, and pore-foaming agent is ethyl alcohol, wherein third
Ketone 9.5kg, ethyl alcohol 0.5kg.Kynoar, solvent and pore-foaming agent stirring and dissolving are prepared into polyvinylidene fluoride coating liquid.
C, the preparation of inorganic particulate coating solution: weighing the aluminium oxide of different-grain diameter, and wherein partial size is at 0.03-0.3 μm
0.7kg, 0.3-0.6 μm are 0.2kg, and 0.6-1 μm is 0.1kg, Kynoar 0.4kg, solvent N-methyl pyrilidone 8kg.
Kynoar is added to stirring and dissolving in N-Methyl pyrrolidone, is slowly added to three kinds of different sizes while stirring later
Aluminium oxide, while carrying out strength ultrasonic disperse 1h.
D, polymer coating coating preparation: choose by sided corona treatment, with a thickness of 9 μm of polyethylene diagrams, hole
Rate is 40%, and the aramid fiber coating solution prepared in step a is coated on to the unilateral side of diaphragm using gravure mode, and soak 10s,
It is dried using three-level baking oven, the temperature of baking ovens at different levels is 50 DEG C, 55 DEG C, 60 DEG C, aramid fiber is made after dry and coats diaphragm.It adopts
Polyvinylidene fluoride coating liquid prepared by step b is coated on to the same side of above-mentioned aramid fiber coating diaphragm with gravure mode,
60 DEG C of drying, obtain unilateral polymer-coated diaphragm after dry.
E, it the coating preparation of inorganic particulate coating: is applied using the inorganic particulate coating solution that gravure prepares step c
It is distributed in the side of the above-mentioned uncoated polymer coating of polymer-coated diaphragm, is dried using three-level baking oven, baking ovens at different levels
Temperature is respectively 50 DEG C, and 55 DEG C, 60 DEG C, polymer and inorganic particulate composite coated diaphragm is made after dry.
The lithium ion battery separator of above-mentioned composite coated with a thickness of 14.2 μm, aramid fiber coating layer thickness is 2 μm, polyvinylidene fluoride
For ene coatings with a thickness of 1 μm, inorganic particulate coating layer thickness is 2.2 μm.
Embodiment 2:
The diaphragm for lithium ion battery of polymer of the invention and the processing of inorganic particulate composite coated, preparation method is such as
Under:
A, it prepares aramid fiber coating solution: weighing para-aramid fiber 0.3kg, the solvent dimethyl sulfoxide that molecular weight is 1-2 ten thousand
For 7kg, cosolvent sodium hydroxide 0.35kg, dispersing agent ethylene-acrylic acid copolymer 0.1kg, emulsifier trimethyl
Ammonium chloride 0.1kg, binder vinylpyridine network alkanone and vinyl acetate copolymer 0.15kg.Cosolvent calcium chloride is added to
It is stirred in solvent to being completely dissolved, dispersing agent polyethylene glycol oxide is added while stirring, stirred at low speed to polyethylene glycol oxide to complete
Para-aramid fiber is added in dissolution, is uniformly mixed, obtains meta-aramid coating solution.
B, the preparation of polyvinylidene fluoride coating liquid: vinylidene and hexafluoropropylene copolymer 1kg, solvent N, N- dimethyl
Acetamide, pore-foaming agent are propyl alcohol, wherein n,N-dimethylacetamide 9kg, propyl alcohol 0.5kg.Vinylidene and hexafluoropropene are total to
Polymers, solvent and pore-foaming agent stirring and dissolving are prepared into polyvinylidene fluoride coating liquid.
C, the preparation of inorganic particulate coating solution: weighing the magnesia of different-grain diameter, and wherein partial size is at 0.03-0.3 μm
0.6kg, 0.3-0.6 μm are 0.1kg, and 0.6-1 μm is 0.1kg, Kynoar 0.5kg, solvent N-methyl pyrilidone 9kg.
Kynoar is added to stirring and dissolving in N-Methyl pyrrolidone, is slowly added to three kinds of different sizes while stirring later
Magnesia, while carrying out strength ultrasonic disperse 1.5h.
D, polymer coating coating preparation: choose by sided corona treatment, with a thickness of 12 μm of polypropylene diaphragms, hole
Rate is 45%, and the aramid fiber coating solution prepared in step a is coated on to the unilateral side of diaphragm using gravure mode, and soak 12s,
It is dried using three-level baking oven, the temperature of baking ovens at different levels is 55 DEG C, 55 DEG C, 60 DEG C, aramid fiber is made after dry and coats diaphragm.It adopts
Polyvinylidene fluoride coating liquid prepared by step b is coated on to the same side of above-mentioned aramid fiber coating diaphragm with jet printing type coating method,
70 DEG C of drying, obtain unilateral polymer-coated diaphragm after dry.
E, it the coating preparation of inorganic particulate coating: is applied using the inorganic particulate coating solution that gravure prepares step c
It is distributed in the side of the above-mentioned uncoated polymer coating of polymer-coated diaphragm, is dried using baking oven, the temperature of baking oven is 70
DEG C, polymer and inorganic particulate composite coated diaphragm is made after dry.
The lithium ion battery separator of above-mentioned composite coated with a thickness of 17 μm, aramid fiber coating layer thickness is 1.5 μm, polyvinylidene fluoride
For ene coatings with a thickness of 1.5 μm, inorganic particulate coating layer thickness is 2 μm.
Embodiment 3:
The diaphragm for lithium ion battery of polymer of the invention and the processing of inorganic particulate composite coated, preparation method is such as
Under:
A, it prepares aramid fiber coating solution: weighing para-aramid pulp 0.32kg, the solvent dimethyl sulfoxide that molecular weight is 3-4 ten thousand
For 7.8kg, cosolvent sodium hydroxide 0.27kg, dispersing agent ethylene-acrylic acid copolymer 0.14kg, emulsifier dodecyl three
Ammonio methacrylate 0.18kg, binder vinylpyridine network alkanone and vinyl acetate copolymer 0.18kg.By cosolvent lithium chloride
It is added in solvent and stirs to being completely dissolved, dispersing agent ethylene-acrylic acid copolymer is added while stirring, stirs at low speed to second
Para-aramid pulp is added to being completely dissolved in alkene-acrylic copolymer, is uniformly mixed, obtains p-aramid fiber coating solution.
B, the preparation of polyvinylidene fluoride coating liquid: Kynoar 1.2kg, solvent are n,N-dimethylacetamide, pore
Agent is propyl alcohol, wherein n,N-dimethylacetamide 8.7kg, methanol 0.45kg.Kynoar, solvent and pore-foaming agent are stirred molten
Solution is prepared into polyvinylidene fluoride coating liquid.
C, the preparation of inorganic particulate coating solution: weighing the boehmite of different-grain diameter, and wherein partial size is at 0.03-0.3 μm
0.7kg, 0.3-0.6 μm are 0.2kg, and 0.6-1 μm is 0.1kg, vinylidene -- trifluoro-ethylene copolymer 0.5kg, solvent acetone
8.5kg.By vinylidene -- trifluoro-ethylene copolymer is added to stirring and dissolving in acetone, is slowly added to three kinds while stirring later
The boehmite of different size, while carrying out strength ultrasonic disperse 1.5h.
D, polymer coating coating preparation: choose by gas ions processing, with a thickness of 20 μm of polypropylene/polypropylenes
The aramid fiber coating solution prepared in step a is coated on diaphragm using gravure mode by microporous barrier diaphragm, porosity 43%
Unilateral side, soak 8s, is dried using baking oven, and temperature is 70 DEG C, and aramid fiber is made after dry and coats diaphragm.It is applied using intaglio plate formula
Polyvinylidene fluoride coating liquid prepared by step b is coated on the same side of above-mentioned aramid fiber coating diaphragm by mode for cloth, and 65 DEG C of drying are done
Unilateral polymer-coated diaphragm is obtained after dry.
E, it the coating preparation of inorganic particulate coating: is applied using the inorganic particulate coating solution that jet printing type coating prepares step c
It is distributed in the side of the above-mentioned uncoated polymer coating of polymer-coated diaphragm, is dried using baking oven, the temperature of baking oven is 80
DEG C, polymer and inorganic particulate composite coated diaphragm is made after dry.
The lithium ion battery separator of above-mentioned composite coated with a thickness of 27 μm, aramid fiber coating layer thickness is 2.5 μm, polyvinylidene fluoride
For ene coatings with a thickness of 2 μm, inorganic particulate coating layer thickness is 2.5 μm.
Comparative example 1:
A kind of diaphragm for lithium ion battery, preparation method are as follows:
Select by sided corona treatment, with a thickness of 9 μm, porosity be 40% polyethylene diagrams, only carry out aramid fiber coating
With the coating processing of polyvinylidene fluoride coating, coating processing without inorganic particulate.Aramid fiber coating and polyvinylidene fluoride coating
Coating formula of liquid, preparation method and coating procedure etc. it is identical with embodiment 1.
Comparative example 2:
A kind of diaphragm for lithium ion battery, preparation method are as follows:
Sided corona treatment is carried out, no with 2 difference of embodiment with a thickness of 12 μm, the polypropylene diaphragm that porosity is 45%
Coat aramid fiber coating, polyvinylidene fluoride coating and inorganic particulate coating.Sided corona treatment condition is identical with embodiment 2.
Comparative example 3:
A kind of diaphragm for lithium ion battery, preparation method are as follows:
Difference from Example 3 is, select it is by corona treatment, with a thickness of 20 μm, porosity 43%
Polypropylene/polypropylene diaphragm, carry out the coating of inorganic particulate coating, and without aramid fiber coating and polyvinylidene fluoride coating
Coating.The coating formula of liquid of inorganic particulate coating, preparation method and coating procedure etc. are identical with embodiment 3.
Comparative example 4:
A kind of diaphragm for lithium ion battery, preparation method are as follows:
Difference from Example 3 is, select it is by corona treatment, with a thickness of 20 μm, porosity 43%
Polypropylene/polypropylene diaphragm, the coating of aramid fiber coating and polyvinylidene fluoride coating is carried out, and without inorganic particulate coating
Coating.Coating formula of liquid, preparation method and coating procedure of aramid fiber coating and polyvinylidene fluoride coating etc. and the complete phase of embodiment 3
Together.
Comparative example 5:
A kind of diaphragm for lithium ion battery, preparation method are as follows:
Difference from Example 3 is, selects with a thickness of 20 μm, the polypropylene/polypropylene diaphragm that porosity is 43%,
Only carry out corona treatment.Plasma process conditions are identical with embodiment 3.
In the following, imbibition rate, contraction to embodiment 1-3 and comparative example the 1-5 diaphragm for lithium ion battery being prepared
800 rate, longitudinal tensile strength, puncture strength, 2C/2C charge and discharge capacity reservations are evaluated, evaluation result such as table 1:
The performance test results for the diaphragm for lithium ion battery that table 1 embodiment 1-3 and comparative example 1-5 is prepared
Find out from upper table experimental result, although individually the correlation of diaphragm can be improved in coated polymer or inorganic particulate
Can, but effect is not particularly evident.The compound of polymer and inorganic particulate is carried out to basement membrane using the method announced of the present invention
Coating can improve the performance of diaphragm more significantly, and polymer and inorganic particulate coating can cooperate with improvement diaphragm to stretch
Intensity and puncture strength, electrolyte absorptivity, heat resistance and cycle performance of battery etc..
Experiments have shown that diaphragm of the present invention has good gas permeability, imbibition rate, mechanical stretch intensity, heat-resisting size
Stability is obviously obtained with security performance, high rate performance and the cycle performance of the lithium ion battery of diaphragm of the present invention preparation
Improve.
It will be apparent to those skilled in the art that can make various other according to the above description of the technical scheme and ideas
Corresponding change and deformation, and all these changes and deformation all should belong to the protection scope of the claims in the present invention
Within.
Claims (9)
1. a kind of lithium ion battery separator of composite coated processing, which is characterized in that including basement membrane and coated on basement membrane side
Polymer coating and inorganic particulate coating coated on the basement membrane other side are constituted；The polymer coating is by being coated on basement membrane
Aramid fiber coating and coated on aramid fiber coating polyvinylidene fluoride coating constitute, polymer coating thickness be 0.3-5 μm；It is described
Inorganic particulate coating is made of the inorganic particulate of different-grain diameter and binder, and inorganic particulate coating layer thickness is 0.5-5 μm；
Aramid fiber coating in the polymer coating is coated by aramid fiber coating solution, immersion, obtains after drying, the thickness of aramid fiber coating
Degree is 0.2-3 μm；Polyvinylidene fluoride coating in the polymer coating is by polyvinylidene fluoride coating liquid after being coated with, drying
It obtains, polyvinylidene fluoride coating is with a thickness of 0.1-2 μm；The inorganic particulate coating is by inorganic particulate coating solution by coating, baking
It is obtained after dry.
2. the lithium ion battery separator of composite coated processing according to claim 1, which is characterized in that the aramid fiber coating
Liquid by following mass parts material composition: 3-10 parts of aramid fiber, 60-87 parts of solvent, 3-5 parts of cosolvent, dispersing agent 0.5-1
Part, 0.5-2 parts of emulsifier, 1-2 parts of polymeric binder.
3. the lithium ion battery separator of composite coated processing according to claim 2, which is characterized in that the aramid fiber
For the combination of one or more of meta-aramid fibers, para-aramid fiber, meta-aramid pulp, para-aramid pulp, virtue
The molecular weight of synthetic fibre is 1-10 ten thousand；The solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- crassitude
One of ketone, dimethyl sulfoxide；The cosolvent is sodium benzoate, in lithium chloride, calcium chloride, sodium hydroxide, acetamide
One or more combination；The dispersing agent is polyethylene glycol oxide, ethylene-acrylic acid copolymer, ethene-vinyl acetate copolymerization
The combination of one or more of object；The emulsifier be hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride,
Sodium Polyacrylate, polyacrylic acid potassium, polyacrylamide, dodecyl trimethyl ammonium chloride, ethylene oxide-butylene oxide copolymerization
The combination of one or more of object, epoxy ethane-epoxy propane-epoxy butane copolymer；The polymeric binder is poly-
The combination of one or more of vinylpyrrolidone, vinylpyridine network alkanone, vinyl acetate copolymer.
4. the lithium ion battery separator of composite coated processing according to claim 1, which is characterized in that the polyvinylidene fluoride
Ene coatings liquid is made of polyvinylidene fluoride resin, organic solvent and pore-foaming agent；Wherein polyvinylidene fluoride in polyvinylidene fluoride coating liquid
The mass fraction of olefine resin is 1%-20%, and the mass fraction of pore-foaming agent is 0.2%-20%, and surplus is organic solvent.
5. the lithium ion battery separator of composite coated processing according to claim 4, which is characterized in that the polyvinylidene fluoride
Olefine resin is polyvinylidene fluoride homopolymer or one of vinylidene and hexafluoropropylene copolymer；The organic solvent is N,
One of dinethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, acetone are more
Kind combination；The pore-foaming agent is one of methanol, ethyl alcohol, propyl alcohol, butanol and deionized water.
6. the lithium ion battery separator of composite coated processing according to claim 1, which is characterized in that the inorganic particulate
Coating solution is made of the base-material of the 5%-40% calculated in percentage by weight and the solvent of 60%-95%, the weight hundred of said components
The sum of score is 100%；The base-material is by the inorganic particulate of 60%-95% count by weight percentage and the polymer of 5%-40%
Composition, the sum of weight percent of said components are 100%.
7. the lithium ion battery separator of composite coated processing according to claim 6, which is characterized in that the inorganic particulate
It is aluminium oxide, boehmite, aluminium hydroxide, aluminium nitride, magnesia, magnesium hydroxide, boron nitride, bayerite, silica, oxidation
The combination of one or more of titanium, zirconium oxide, nickel oxide, zeolite particles；The particle diameter distribution of all inorganic particulates is in 0.03-1 μ
M, and inorganic particulate particle diameter distribution is 0.03-0.3 μm and accounts for 60%-80% mass share, and 0.3-0.6 μm accounts for 10%-20% mass parts
Volume, 0.6-1 μm accounts for 10%-20% mass share；The polymer is by Kynoar, vinylidene -- hexafluoropropylene copolymer,
Vinylidene -- chlorotrifluoroethylcopolymer copolymer, vinylidene -- trifluoro-ethylene copolymer, polymethyl methacrylate, poly- methyl-prop
The combination of one or more of olefin(e) acid butyl ester, polyacrylonitrile, poly(aryl ether ketone), polyimides；The solvent is N, N- dimethyl
Formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, ethyl alcohol, acetone, butanone, methylene chloride, stone
Any one of oily ether, tetrahydrofuran or multiple combinations.
8. the lithium ion battery separator of composite coated processing according to claim 1, which is characterized in that the basement membrane is poly-
Ethylene microporous barrier, microporous polypropylene membrane, polyethylene/polypropylene microporous barrier, polypropylene/polypropylene microporous barrier, polypropylene/poly- second
One of alkene/polypropylene composite materials microporous barrier, basement membrane thickness are 5~40 μm, and porosity is 35~65%；The basement membrane is by electricity
One of dizzy or corona treatment or two methods are pre-processed.
9. a kind of preparation method of the lithium ion battery separator handled such as the described in any item composite coateds of claim 1-8,
It is characterized in that, includes the following steps:
(1) aramid fiber coating first is carried out to the side of basement membrane after treatment, completes the coating of aramid fiber coating；
(2) Kynoar coating is then carried out on the aramid fiber coating of the same side of basement membrane, completes polyvinylidene fluoride coating
Coating；
(3) coating processing that inorganic particulate is finally carried out to the other side of basement membrane, completes the coating of inorganic particulate coating.
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| CN104681762A (en) * | 2013-10-22 | 2015-06-03 | 万向A一二三系统有限公司 | A preparing method of a lithium ion battery composite separating membrane |
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| CN104157818A (en) * | 2014-09-02 | 2014-11-19 | 深圳市星源材质科技股份有限公司 | Lithium battery diaphragm compounded from aqueous polymer and inorganic nanoparticles and preparation method thereof |
| CN104993089A (en) * | 2015-07-29 | 2015-10-21 | 沧州明珠隔膜科技有限公司 | Aramid coated lithium ion battery diaphragm and preparation method thereof |
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