CN105552284B - A kind of composite coating lithium ion battery separator and preparation method thereof - Google Patents
A kind of composite coating lithium ion battery separator and preparation method thereof Download PDFInfo
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- CN105552284B CN105552284B CN201510967229.7A CN201510967229A CN105552284B CN 105552284 B CN105552284 B CN 105552284B CN 201510967229 A CN201510967229 A CN 201510967229A CN 105552284 B CN105552284 B CN 105552284B
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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
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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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
A kind of composite coating lithium ion battery separator is made of basement membrane and the aramid fiber coating for being coated on basement membrane side with the PVDF coatings for being coated on the basement membrane other side, and the aramid fiber coating is coated by aramid fiber slurry, soaks, is obtained after drying, and coating layer thickness is 0.5-4 μm；The PVDF coatings are coated by aqueous PVDF slurries, are obtained after drying, and coating layer thickness is 0.1-2 μm.The present invention also provides the preparation methods of the diaphragm.Diaphragm of the present invention is while having the good hot property of aramid fiber coating and mechanical performance, there is good wettability to electrolyte but also with PVDF coatings and protect fluidity, can effectively be bonded battery and pole piece, environmental pollution are small, is conducive to prepare that cycle life is longer, the higher lithium ion battery of safety.Experiments have shown that the diaphragm has good gas permeability, imbibition rate, thermal contraction, tensile strength, battery cycle life can be significantly improved with lithium ion battery prepared by this described diaphragm.
Description
Technical field
The present invention relates to a kind of lithium ion battery technology, especially a kind of aramid fiber and PVDF composite coatings lithium ion battery every
Film and preparation method thereof belongs to battery technology field.
Background technology
The composition of lithium ion battery includes anode, cathode, diaphragm and electrolyte, and diaphragm is as four big material of lithium ion battery
One of, although being not involved in the electrochemical reaction in battery, but interior layer assembly crucial in lithium battery.The capacity of battery follows
It is even more to influence lithium that the key performances such as ring performance and charging and discharging currents density all have direct relationship, the safety of diaphragm with diaphragm
An important factor for ion battery safety.It is mainly polyene that the lithium ion battery separator of extensive commercialization, which makes material, at present
Hydrocarbon, the diaphragm thermal safety and holding electrolyte of simple polyolefin material higher and higher with requiring performance of lithium ion battery
Ability be difficult to meet the requirements, the high-performance composite diaphragm that research prepares other materials and polyolefin becomes current diagram modification
Most important direction.
Aramid fiber, which coats diaphragm, has the advantages such as high temperature resistance is good, energy density is high, wellability is excellent, service life length,
Obtain industry personage's extensive concern.There is document report to dissolve aramid fiber by organic solvent and carry out diaphragm coating, adopts
Pure water is used to prepare the method that aramid fiber coats diaphragm as coagulating bath, this method reduce the drying times of wet film, improve coating
It is and environmental-friendly with the adhesive property of basement membrane.Existing diaphragm coating method mainly has gravure, narrow slit type coating, dip-coating
Formula is coated with and jet printing type coating, wherein in addition to twosided application simultaneously can be achieved in the coating of dip-coating formula, other modes are single unilateral side
Coating.When aramid fiber coating process is the modes such as gravure, narrow slit type coating or jet printing type coating, and preparation process is using pure
When water prepares aramid fiber coating diaphragm as coagulating bath, the organic solvent entered in pure water coagulating bath in secondary coating process is easily led
The dissolving and destruction that are coated with aramid fiber coating for the first time are caused, the diaphragm plug-hole or non-porous after coating is caused, therefore is applied when using single unilateral side
Mode for cloth, and solidification bath method is used to prepare more difficult operation when two-sided coatings aramid fiber diaphragm, film forming situation is difficult to control.
PVDF（Kynoar）The lithium ion battery separator of coating is on the basis of conventional membrane, by special process
It handles surface and coats PVDF materials.Compared with common diaphragm, PVDF coating diaphragms have good wetability and guarantor to electrolyte
Fluidity can effectively be bonded diaphragm and pole piece, increase the cycle performance of battery, significantly improve the safety of battery.Existing lithium ion
The coating technology of battery PVDF diaphragms generally uses oiliness coating processes, oiliness coating processes to mostly use acetone and do solvent, acetone
It is inflammable, explosive, and have very major injury to human body, there is insecurity in process of production；Acetone is manufacture methamphetamine simultaneously
Raw material, using stringent by the control of relevant department.In addition, the coating made of oil-based solvents such as acetone, diaphragm carries out
After the coating of surface, since oil slurry and diaphragm material compatibility are preferable, slurry can penetrate into the micropore of basement membrane, cause to breathe freely
Loss is very big, be easy to cause diaphragm plug-hole, influences battery performance, and reduce positive and negative pole material in battery efficiently uses space,
Battery capacity and performance is set to be restricted.
Invention content
The present invention is directed to overcome the deficiencies of existing technologies, providing one kind, there is good hot property and mechanical performance, cycle to make
With long lifespan, there is good wettability to electrolyte and protect fluidity, the composite coating lithium ion battery that safe, environmental pollution is small
Diaphragm.
In addition, the present invention also provides the preparation methods of the composite coating lithium ion battery separator.
In order to achieve the above objectives, the technical solution adopted by the present invention is such：
A kind of composite coating lithium ion battery separator by basement membrane and is coated on the aramid fiber coating of basement membrane side and is coated on base
The PVDF coatings of the film other side are constituted, and the aramid fiber coating is coated by aramid fiber slurry, soaks, is obtained after drying, coating layer thickness
It is 0.5-4 μm；The PVDF coatings are coated by aqueous PVDF slurries, are obtained after drying, and coating layer thickness is 0.1-2 μm.
Above-mentioned composite coating lithium ion battery separator, the aqueous PVDF slurries contain 1-10% in percentage by weight
Base-material, surplus is deionized water, the base-material by following mass parts material composition, it is 65-85 parts of PVDF toners, aqueous
3-10 parts of adhesive, 1.5-5 parts of surfactant, 8-20 parts of triethyl phosphate dispersant.
Above-mentioned composite coating lithium ion battery separator, the PVDF toners are vinylidene fluoride homopolymer or vinylidene
With one kind in hexafluoropropylene copolymer, grain size 100-150nm；The aqueous binder is butadiene-styrene latex, styrene-acrylic latex, pure
Atrolactamide, polymethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethene-vinyl acetate
The mixture of one or more of copolymer, polyvinyl acetate or polyurethane；The surfactant is fluoro-alkyl first
One or more of oxygroup ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, polyoxyethylene alkylamide, fatty alcohol polyoxyethylene ether
Mixture.
Above-mentioned composite coating lithium ion battery separator, the aramid fiber slurry by following mass parts material composition：Aramid fiber is fine
3-8 parts of dimension, the first 60-80 parts of solvent, the second 8-25 parts of solvent, 3-5 parts of cosolvent, 0.5-1 parts of polyethylene glycol oxide dispersant, breast
0.5-2.5 parts of agent, 1-2 parts of polymer adhesive.
Above-mentioned composite coating lithium ion battery separator, the cosolvent are in calcium chloride, potassium hydroxide, lithium chloride, pyridine
One or more combination；The polyethylene glycol oxide dispersant is 200 mesh powder of grain size, and molecular weight is 10-100 ten thousand；It is described
First solvent is one kind in NMP, DMSO, DMF or DMAC；Second solvent be ethyl acetate, isopropanol, dichloromethane or
One or more of triethyl phosphate combines；The emulsifier is in polyvinyl alcohol, Sodium Polyacrylate or polyacrylamide
One or more combination；The polymer adhesive is vinyl pyrrolidone and vinyl acetate copolymer；The aramid fiber is fine
Dimension is one or more combinations in meta-aramid fibers, para-aramid fiber, meta-aramid pulp, para-aramid pulp, virtue
Synthetic fibre fiber molecule amount is 0.5-10 ten thousand.
Above-mentioned composite coating lithium ion battery separator, the basement membrane are polyethylene diagrams, polypropylene diaphragm, polypropylene/poly-
Ethylene/polypropylene composite diaphragm, polyimide diaphragm, Kynoar diaphragm, polyethylene non-woven cloth diaphragm, polypropylene non-woven fabric
One kind in diaphragm, polyimide nonwoven fabric diaphragm, basement membrane thickness are 5-40 μm, porosity 30-60%.
A method of composite coating lithium ion battery separator is prepared, is included the following steps：
A, aramid fiber slurry is prepared：Each substance that composition aramid fiber slurry is weighed according to proportioning, by the first solvent of proportional quantity and
After cosolvent stirring and dissolving, it is slowly homogeneously added into proportional quantity polyethylene glycol oxide dispersant, stirs while adding, waits for polyoxyethylene
Aramid fiber is added in alkene dispersant after being completely dissolved, boiling water bath heating is stirred to being completely dissolved, and dissolving aramid fiber liquid is made；
Second solvent of proportional quantity, emulsifier are mixed, are uniformly dispersed, aramid fiber is added in the polymer adhesive with proportional quantity together
In lysate, be uniformly dispersed obtained aramid fiber slurry；
B, aqueous PVDF slurries are prepared：Each substance for forming aqueous PVDF slurries is weighed according to proportioning, takes point of proportional quantity
The PVDF resin-oatmeals of proportional quantity are added after stirring 10-30 minutes in powder, deionized water, the two mixing, 50 DEG C of -70 DEG C of heating
End, grinding obtain PVDF dispersion liquids in 1-2 hours；The aqueous binder of proportional quantity is added into above-mentioned PVDF dispersion liquids, surface is lived
Property agent, after stirring evenly, with 400 mesh stainless steel mesh filter be made aqueous PVDF slurries；
C, the coating of aramid fiber slurry：Aramid fiber slurry made from step a is coated on to the side of basement membrane, soak 3-15s, drying
It obtains unilateral aramid fiber and coats diaphragm；
D. the coating of aqueous PVDF slurries：Aqueous PVDF slurries made from step b are coated on above-mentioned unilateral aramid fiber coating
Composite coating lithium ion battery separator is made after dry in the uncoated side of diaphragm.
The preparation method of above-mentioned PVDF coatings lithium ion battery separator, coating method is gravure, narrow slit type is coated with,
One kind in the coating of dip-coating formula or jet printing type coating.
Compared with prior art, the present invention having following major advantage：
1, aramid fiber and PVDF composite coating lithium ion battery separator of the present invention, compared with traditional two-sided coatings aramid fiber diaphragm,
With PVDF coatings instead of the aramid fiber coating of side, avoid using gravure, narrow slit type coating or jet printing type coating etc.
Single unilateral side coating method, and use film forming situation disadvantage rambunctious when solidification bath method preparation two-sided coatings aramid fiber diaphragm.
The composite diaphragm has electrolyte but also with PVDF coatings while having the good hot property of aramid fiber coating and mechanical performance
It good wettability and protects fluidity, can effectively be bonded battery and the small feature of pole piece, environmental pollution, be conducive to prepare cycle life
Longer, the higher lithium ion battery of safety.
2, PVDF coatings of the present invention are coated by aqueous PVDF slurries, are obtained after drying, have abandoned existing PVDF and have applied
The traditional handicraft that lithium ion battery separator makees solvent with oily matters such as acetone is covered, using water as solvent, production process environment
It is friendly, safe；In addition production cost can be greatly reduced with water as solvent, is conducive to industrialized production.Have for PVDF resins
There is extremely strong hydrophobicity, reunite in water-based system serious, selects triethyl phosphate as dispersant.Triethyl phosphate is made
It is added for the intermediate medium of water and PVDF, when triethyl phosphate, which hydrolyzes, generates diethyl phosphate and ethyl alcohol, in PVDF molecule weeks
It encloses and generates a large amount of hydroxyl, so that PVDF is preferably dispersed in water, effectively improve the caking property of PVDF, while improving coating and existing
In drying course caused by moisture evaporation is too fast crack phenomenon.In addition, triethyl phosphate is cheap, and it is easy to operate, it reduces
Production cost is conducive to industrialized production.
Experiments have shown that diaphragm of the present invention has good gas permeability, imbibition rate, thermal contraction, tensile strength, with this hair
The bright diaphragm, which prepares lithium ion battery, can significantly improve battery cycle life.
Description of the drawings
Fig. 1 is the diagrammatic cross-section of composite coating lithium ion battery separator of the present invention；
Fig. 2 is the lithium ion battery prepared with composite coating lithium ion battery separator of the present invention and two-sided coatings aramid fiber diaphragm
The constant-current discharge loop test datagram of the lithium ion battery of preparation.
Attached figure label is as follows：1, PVDF coatings, 2, basement membrane, 3, aramid fiber coating.
Specific implementation mode
Referring to Fig. 1, composite coating lithium ion battery separator of the present invention, by basement membrane 2 and the virtue for being coated on basement membrane side
Synthetic fibre coating 3 and the PVDF coatings 1 of the other side are constituted.The aramid fiber coating is coated by aramid fiber slurry, soaks, is obtained after drying,
Coating layer thickness is 0.5-4 μm；The PVDF coatings are coated by aqueous PVDF coating slurries, are obtained after drying, and coating layer thickness is
0.1-2μm.The formation of above-mentioned aramid fiber coating is to form basement membrane porous through mass transport process by soaking after being coated with aramid fiber slurry
Aramid fiber coating；The formation of above-mentioned PVDF coatings, is dispersed in water by PVDF resin particles and slurry is made, and being heated after coating makes
Moisture evaporation, remaining solid particle are packed together layered arrangement, and the gap pore-forming between particle and particle is formed final
PVDF coatings.
The aqueous PVDF coating slurries are that common oil-based solvent is substituted using water as decentralized medium.In structure due to
Fluorine atom is symmetrical on PVDF strands, results in that the material surface energy is low, hydrophobicity is strong, difficult dispersion in water, simultaneously
PVDF does not have hydrophilic radical again, to have permanent stability, it is necessary to which introducing hydroxyl, carboxyl, amino etc. on its surface has parent
Aqueous polar group.The present invention is using triethyl phosphate as dispersant, when it is hydrolyzed, produce diethyl phosphate and
Contain hydrophilic hydroxyl, and the ester group containing oleophylic and alkyl in ethyl alcohol, diethyl phosphate and ethanol molecule structure.Ester group and
Alkyl is adsorbed on PVDF particle surfaces, reduces the interfacial tension between PVDF and water, and PVDF particle surfaces is made to be easy to moisten.Together
When, when PVDF particles are close, due to adsorption diethyl phosphate and ethyl alcohol generate space steric effect, PVDF particles it
Between can mutually slide and be staggered, it is difficult to reunite again, keep PVDF well dispersed, active area increases, and cementability is promoted.In addition,
The volatilization temperature of water is relatively low, when using water as solvent, diaphragm coating drying course in can because moisture evaporation too soon caused by coating be cracked,
It can slow down drying process after appropriate triethyl phosphate is added, coating crack phenomenon is made to disappear.Tradition point is substituted with triethyl phosphate
Powder, easy to operate, dispersion effect is good, reduces cost, is conducive to industrialized production.
Base-material containing 1-10% in aqueous PVDF slurries of the present invention, surplus is deionized water.The base-material by with
The material composition of lower mass parts：65-85 parts of PVDF toners, 3-10 parts of aqueous binder, 1.5-5 parts of surfactant, phosphorus
8-20 parts of triethylenetetraminehexaacetic acid ester dispersant.The PVDF toners are that vinylidene fluoride homopolymer or vinylidene are copolymerized with hexafluoropropene
One kind in object, grain size 100-150nm；The aqueous binder is butadiene-styrene latex, styrene-acrylic latex, purified petroleum benzin latex, poly- methyl
Methyl acrylate, polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, poly-vinegar acid
The mixture of one or more of vinyl acetate or polyurethane；The surfactant is fluoro-alkyl methoxyl group ether alcohol, fluoro
The mixture of one or more of alkyl ethoxy ether alcohol, polyoxyethylene alkylamide, fatty alcohol polyoxyethylene ether.
Aramid fiber slurry of the present invention by following mass parts material composition：3-8 parts of aramid fiber, the first solvent 60-80
Part, the second 8-25 parts of solvent, 3-5 parts of cosolvent, 0.5-1 parts of polyethylene glycol oxide dispersant, 0.5-2.5 parts of emulsifier, polymer
1-2 parts of adhesive.The cosolvent is one or more of calcium chloride, potassium hydroxide, lithium chloride, pyridine；The dispersant
For the polyethylene glycol oxide powder of 200 mesh of grain size, molecular weight is 10-100 ten thousand；First solvent is NMP, DMSO, DMF or DMAC
In one kind；Second solvent is one or more of ethyl acetate, isopropanol, dichloromethane or triethyl phosphate；Institute
It is one or more of polyvinyl alcohol, Sodium Polyacrylate or polyacrylamide to state emulsifier；The polymer adhesive is second
Vinyl pyrrolidone and vinyl acetate copolymer；The aramid fiber is meta-aramid fibers, para-aramid fiber, meta position virtue
One or more combinations in synthetic fibre pulp, para-aramid pulp, aramid fiber molecular weight are 0.5-10 ten thousand.
Basement membrane of the present invention is polyethylene diagrams, polypropylene diaphragm, polypropylene, polyethylene/polypropylene composite materials diaphragm, gathers
Acid imide diaphragm, Kynoar diaphragm, polyethylene non-woven cloth diaphragm, polypropylene non-woven cloth diaphragm, polyimide nonwoven fabric every
One kind in film, basement membrane thickness are 5-40 μm, porosity 30-60%.
The preparation method of composite coating lithium ion battery separator of the present invention is as follows：
A, aramid fiber slurry is prepared：Each substance that composition aramid fiber slurry is weighed according to proportioning, by the first solvent of proportional quantity and
After cosolvent stirring and dissolving, it is slowly homogeneously added into proportional quantity polyethylene glycol oxide dispersant, stirs while adding, waits for polyoxyethylene
Aramid fiber is added in alkene dispersant after being completely dissolved, boiling water bath heating is stirred to being completely dissolved, and dissolving aramid fiber liquid is made；
Second solvent of proportional quantity, emulsifier are mixed, are uniformly dispersed, aramid fiber is added in the polymer adhesive with proportional quantity together
In lysate, be uniformly dispersed obtained aramid fiber slurry；
B, aqueous PVDF slurries are prepared：Each substance for forming aqueous PVDF slurries is weighed according to proportioning, takes the phosphorus of proportional quantity
Proportional quantity is added after stirring 10-30 minutes in triethylenetetraminehexaacetic acid ester dispersant, deionized water, the two mixing, 50 DEG C of -70 DEG C of heating
PVDF toners, grinding obtain PVDF dispersion liquids in 1-2 hours；The aqueous binder of proportional quantity is added into above-mentioned PVDF dispersion liquids
Agent, surfactant after stirring evenly, are filtered with 400 mesh stainless steel mesh and aqueous PVDF slurries are made；
C, the coating of aramid fiber slurry：Aramid fiber slurry made from step a is coated on to the side of basement membrane, soak 3-15s, drying
It obtains unilateral aramid fiber and coats diaphragm；
D, the coating of aqueous PVDF slurries：Aqueous PVDF slurries made from step b are coated on above-mentioned unilateral aramid fiber coating
Composite coating lithium ion battery separator is made after dry in the uncoated side of diaphragm.
Coating method is one kind in gravure, narrow slit type coating, the coating of dip-coating formula or jet printing type coating.
Several specific embodiments of the present invention presented below：
Embodiment 1：
A, aramid fiber slurry is prepared：Weigh meta-aramid fibers 0.7kg, the first solvent DMAC that molecular weight is 8-10 ten thousand
The polyethylene glycol oxide dispersant of 6kg, the second methylene chloride 2.5kg, cosolvent lithium chloride 0.4kg, molecular weight 40-50 ten thousand
0.05kg, emulsifier pva powder 0.25kg, polymer adhesive vinyl pyrrolidone and vinyl acetate copolymer
0.1 kg.Cosolvent lithium chloride is added in the first solvent DMAC and is stirred to being completely dissolved, it is slow and uniform while stirring
Polyethylene glycol oxide dispersant is added, stirring at low speed to polyethylene glycol oxide is completely dissolved, and meta-aramid fibers, boiling water bath heating is added
And stir to being completely dissolved, obtain meta-aramid fibers lysate.The second methylene chloride is taken, emulsifier polyvinyl alcohol is added
Powder is added to above-mentioned aramid fiber lysate after disperseing 40min with polymer adhesive vinyl pyrrolidone and vinyl acetate
In, be uniformly dispersed obtained aramid fiber slurry.
B, aqueous PVDF slurries are prepared：Weigh 6.5 kg of vinylidene fluoride homopolymer, triethyl phosphate 0.8kg, deionized water
792kg, polyvinyl alcohol 0.55kg, polyoxyethylene alkylamide 0.15kg.Both triethyl phosphate and deionized water are mixed equal
After even, stirred 10 minutes using magnetic force heating stirrer, be heated to 50 DEG C and mixture one is made；Vinylidene fluoride homopolymer is taken to be added
In mixture one, grinding obtains mixture two in 1 hour；Polyvinyl alcohol and polyoxyethylene alkylamide are added into mixture two,
After stirring evenly aqueous PVDF slurries are obtained with the filtering of 400 mesh stainless steel mesh.
C, the coating of aramid fiber slurry：The polypropylene diaphragm that thickness is 12 μm is chosen, porosity 40% is applied using intaglio plate formula
The aramid fiber slurry prepared in a steps is coated on the unilateral side of diaphragm by mode for cloth, and application rate 8m/min, soak 10s；Use three
Grade baking oven is dried, and oven temperatures at different levels are respectively 50 DEG C, 60 DEG C, 65 DEG C, and unilateral aramid fiber is made after dry and coats diaphragm.
D, the coating of aqueous PVDF slurries：The aqueous PVDF slurries prepared in b steps are applied using gravure mode
It is distributed in the side of the above-mentioned unilateral aramid fiber coating uncoated aramid fiber coating of diaphragm, application rate 25m/min；Using three-level baking oven into
Row drying, oven temperatures at different levels are respectively 40 DEG C, 50 DEG C, 45 DEG C, and PVDF composite coating lithium ion battery separators are made after dry.
The thickness of above-mentioned composite coating lithium ion battery separator is 15.1 μm, and aramid fiber coating layer thickness is 3 μm, and PVDF applies thickness
Degree is 0.1 μm.
Embodiment 2：
A, aramid fiber slurry is prepared：Weigh para-aramid fiber 0.3kg, the first solvent NMP that molecular weight is 0.5-2 ten thousand
8kg, the second solvent isopropanol 1.5kg, cosolvent pyridine 0.5kg, molecular weight 10-30 ten thousand polyethylene glycol oxide dispersant 0.1kg,
Emulsifier Sodium Polyacrylate powder 0.2kg, 0.1 kg of polymer adhesive vinyl pyrrolidone and vinyl acetate copolymer.
Cosolvent pyridine is added in the first solvent NMP and is stirred to being completely dissolved, polyoxygenated is uniformly slowly added while stirring
Ethylene dispersant, stirring at low speed to polyethylene glycol oxide are completely dissolved, and para-aramid fiber is added, and boiling water bath is heated and stirred to complete
Fully dissolved obtains para-aramid fiber lysate.The second solvent isopropanol is taken, emulsifier Sodium Polyacrylate powder, dispersion is added
It after 30min, is added in above-mentioned aramid fiber lysate with polymer adhesive vinyl pyrrolidone and vinyl acetate, dispersion is equal
Even obtained aramid fiber slurry.
B, aqueous PVDF slurries are prepared：Weigh vinylidene and 8.5 kg of hexafluoropropylene copolymer, triethyl phosphate
1.8kg, deionized water 105.3kg, butadiene-styrene latex 1kg, fluoro-alkyl methoxyl group ether alcohol 0.4kg.By triethyl phosphate and go from
Both sub- water after mixing, is stirred 30 minutes using magnetic force heating stirrer, is heated to 60 DEG C and mixture one is made；Take inclined fluorine
Ethylene is added with hexafluoropropylene copolymer in mixture one, and grinding obtains mixture two in 2 hours；Butylbenzene is added into mixture two
Latex and fluoro-alkyl methoxyl group ether alcohol obtain aqueous PVDF slurries after stirring evenly with the filtering of 400 mesh stainless steel mesh.
C, the coating of aramid fiber slurry：The polyethylene diagrams that thickness is 20 μm are chosen, porosity 38% is applied using narrow slit type
The aramid fiber slurry prepared in a steps is coated on the unilateral side of diaphragm by mode for cloth, and application rate 15m/min, soak 3s；Use three
Grade baking oven is dried, and oven temperatures at different levels are respectively 55 DEG C, 60 DEG C, 50 DEG C, and unilateral aramid fiber is made after dry and coats diaphragm.
D, the coating of aqueous PVDF slurries：The aqueous PVDF slurries prepared in b steps are applied using gravure mode
It is distributed in the side of the above-mentioned unilateral aramid fiber coating uncoated aramid fiber coating of diaphragm, application rate 20m/min；Using three-level baking oven into
Row drying, oven temperatures at different levels are respectively 60 DEG C, 70 DEG C, 65 DEG C, and PVDF composite coating lithium ion battery separators are made after dry.
The thickness of above-mentioned composite coating lithium ion battery separator is 22.5 μm, and aramid fiber coating layer thickness is 0.5 μm, PVDF coatings
Thickness is 2 μm.
Embodiment 3：
A, aramid fiber slurry is prepared：It is the meta-aramid fibers 0.8kg of 5-8 ten thousand, the first solvent DMF to weigh molecular weight
The polyethylene glycol oxide point of 6.8kg, the second methylene chloride 1.5kg, 0.47 kg of cosolvent potassium hydroxide, molecular weight 60-70 ten thousand
Powder 0.08kg, emulsifier pva powder 0.15kg, polymer adhesive vinyl pyrrolidone and vinyl acetate are total
Polymers 0.2kg.Cosolvent potassium hydroxide is added in the first solvent DMF and is stirred to being completely dissolved, it is slow and equal while stirring
Even addition polyethylene glycol oxide dispersant, stirring at low speed to polyethylene glycol oxide are completely dissolved, and meta-aramid fibers, boiling water bath is added
It heats and stirs to being completely dissolved, obtain meta-aramid fibers lysate.The second methylene chloride is taken, the poly- second of emulsifier is added
It is molten to be added to above-mentioned aramid fiber after disperseing 30min with polymer adhesive vinyl pyrrolidone and vinyl acetate for enol powder
It solves in liquid, be uniformly dispersed obtained aramid fiber slurry.
B, aqueous PVDF slurries are prepared：Weigh 7 kg of vinylidene fluoride homopolymer, triethyl phosphate 1.5kg, deionized water
216kg, polyvinyl acetate 0.3kg, fatty alcohol polyoxyethylene ether 0.2kg.Both triethyl phosphate and deionized water are mixed
After uniformly, is stirred 20 minutes using magnetic force heating stirrer, be heated to 70 DEG C and mixture one is made；Vinylidene fluoride homopolymer is taken to add
Enter in mixture one, grinding obtains mixture two in 1.5 hours；Polyvinyl acetate and fatty alcohol polyoxy are added into mixture two
Vinethene obtains aqueous PVDF slurries after stirring evenly with the filtering of 400 mesh stainless steel mesh.
C, the coating of aramid fiber slurry：The polypropylene diaphragm that thickness is 40 μm is chosen, porosity 60% is applied using jet printing type
The aramid fiber slurry prepared in a steps is coated on the unilateral side of diaphragm by mode for cloth, and application rate 5m/min, soak 15s；Use three
Grade baking oven is dried, and oven temperatures at different levels are respectively 55 DEG C, 65 DEG C, 60 DEG C, and unilateral aramid fiber is made after dry and coats diaphragm.
D, the coating of aqueous PVDF slurries：The aqueous PVDF slurries prepared in b steps are applied using narrow slit type coating method
It is distributed in the side of the above-mentioned unilateral aramid fiber coating uncoated aramid fiber coating of diaphragm, application rate 20m/min；Using three-level baking oven into
Row drying, oven temperatures at different levels are respectively 45 DEG C, 55 DEG C, 50 DEG C, and PVDF composite coating lithium ion battery separators are made after dry.
The thickness of above-mentioned composite coating lithium ion battery separator is 44.5 μm, and aramid fiber coating layer thickness is 4 μm, and PVDF applies thickness
Degree is 0.5 μm.
Embodiment 4：
A, aramid fiber slurry is prepared：Weigh meta-aramid pulp 0.55kg, the first solvent DMSO that molecular weight is 6-8 ten thousand
The polyethylene glycol oxide point of 6.75kg, the second solvent ethyl acetate 2.03kg, cosolvent calcium chloride 0.35kg, molecular weight 50-60 ten thousand
Powder 0.07kg, emulsifier Polyacrylamide Powder 0.05kg, polymer adhesive vinyl pyrrolidone and vinyl acetate
0.15 kg of copolymer.Cosolvent calcium chloride is added in the first solvent DMSO and is stirred to being completely dissolved, while stirring slowly and
Uniform that polyethylene glycol oxide dispersant is added, stirring at low speed to polyethylene glycol oxide is completely dissolved, and meta-aramid pulp, boiling water is added
Bath is heated and is stirred to being completely dissolved, and meta-aramid pulp lysate is obtained.The second solvent ethyl acetate is taken, it is poly- that emulsifier is added
Acrylamide powder is added to above-mentioned virtue after disperseing 30min with polymer adhesive vinyl pyrrolidone and vinyl acetate
In synthetic fibre lysate, be uniformly dispersed obtained aramid fiber slurry.
B, aqueous PVDF slurries are prepared：Weigh vinylidene and 7.5 kg of hexafluoropropylene copolymer, triethyl phosphate
1.3kg, deionized water 178.6kg, polyethyl acrylate 0.4kg, polyoxyethylene alkylamide 0.2kg.By triethyl phosphate and
Both deionized waters after mixing, are stirred 18 minutes using magnetic force heating stirrer, are heated to 55 DEG C and mixture one is made；It takes
Vinylidene is added with hexafluoropropylene copolymer in mixture one, and grinding obtains mixture two in 2 hours；It is added into mixture two
Polyethyl acrylate and polyoxyethylene alkylamide obtain aqueous PVDF after stirring evenly with the filtering of 400 mesh stainless steel mesh
Slurry.
C, the coating of aramid fiber slurry：Choose the polyethylene diagrams that thickness is 5 μm, porosity 30%, using gravure
The aramid fiber slurry prepared in a steps is coated on the unilateral side of diaphragm by mode, and application rate 12m/min, soak 5s；Use three-level
Baking oven is dried, and oven temperatures at different levels are respectively 50 DEG C, 65 DEG C, 60 DEG C, and unilateral aramid fiber is made after dry and coats diaphragm.
D, the coating of aqueous PVDF slurries：The aqueous PVDF slurries prepared in b steps are applied using jet printing type coating method
It is distributed in the side of the above-mentioned unilateral aramid fiber coating uncoated aramid fiber coating of diaphragm, application rate 25m/min；Using three-level baking oven into
Row drying, oven temperatures at different levels are respectively 55 DEG C, 65 DEG C, 60 DEG C, and PVDF composite coating lithium ion battery separators are made after dry.
The thickness of above-mentioned composite coating lithium ion battery separator is 7 μm, and aramid fiber coating layer thickness is 1 μm, PVDF coating layer thicknesses
It is 1 μm.
Embodiment 5：
A, aramid fiber slurry is prepared：Weigh para-aramid pulp 0.5kg, the first solvent DMAC that molecular weight is 3-5 ten thousand
The polyethylene glycol oxide dispersant of 6.9kg, the second solvent triethyl phosphate 2kg, cosolvent lithium chloride 0.3kg, molecular weight 30-40 ten thousand
0.09kg, emulsifier pva powder 0.1kg, polymer adhesive vinyl pyrrolidone and vinyl acetate copolymer
0.11 kg.Cosolvent lithium chloride is added in the first solvent DMAC and is stirred to being completely dissolved, it is slow and uniform while stirring
Polyethylene glycol oxide dispersant is added, stirring at low speed to polyethylene glycol oxide is completely dissolved, and para-aramid pulp, boiling water bath heating is added
And stir to being completely dissolved, obtain para-aramid pulp lysate.The second solvent triethyl phosphate is taken, emulsifier polyethylene is added
After disperseing 30min, above-mentioned aramid fiber dissolving is added to polymer adhesive vinyl pyrrolidone and vinyl acetate for alcohol powder
In liquid, be uniformly dispersed obtained aramid fiber slurry.
B, aqueous PVDF slurries are prepared：Weigh vinylidene and 7.5 kg of hexafluoropropylene copolymer, triethyl phosphate 2kg,
Deionized water 130kg, polyurethane 0.8kg, fluoro-alkyl methoxyl group ether alcohol 0.5kg.By both triethyl phosphate and deionized water
After mixing, it is stirred 15 minutes using magnetic force heating stirrer, is heated to 65 DEG C and mixture one is made；Take vinylidene and six
Fluoropropene copolymer is added in mixture one, and grinding obtains mixture two in 1 hour；Polyurethane and fluoro are added into mixture two
Alkyl methoxyl group ether alcohol obtains aqueous PVDF slurries after stirring evenly with the filtering of 400 mesh stainless steel mesh.
C, the coating of aramid fiber slurry：The polyethylene diagrams that thickness is 16 μm are chosen, porosity 38% is applied using intaglio plate formula
The aramid fiber slurry prepared in a steps is coated on the unilateral side of diaphragm by mode for cloth, and application rate 10m/min, soak 8s；Use three
Grade baking oven is dried, and oven temperatures at different levels are respectively 50 DEG C, 55 DEG C, 60 DEG C, and unilateral aramid fiber is made after dry and coats diaphragm.
D, the coating of aqueous PVDF slurries：The aqueous PVDF slurries prepared in b steps are applied using gravure mode
It is distributed in the side of the above-mentioned unilateral aramid fiber coating uncoated aramid fiber coating of diaphragm, application rate 25m/min；Using three-level baking oven into
Row drying, oven temperatures at different levels are respectively 55 DEG C, 65 DEG C, 60 DEG C, and PVDF composite coating lithium ion battery separators are made after dry.
The thickness of above-mentioned composite coating lithium ion battery separator is 19.5 μm, and aramid fiber coating layer thickness is 2 μm, and PVDF applies thickness
Degree is 1.5 μm.
Comparative example：
According in embodiment 5 aramid fiber slurry proportional quantity prepare aramid fiber slurry, choose thickness be 16 μm, porosity 38%
Polypropylene screen, the aramid fiber slurry prepared is coated on to the bilateral of diaphragm using gravure mode, application rate is
15m/min, soak 10s, is dried using three-level baking oven, and oven temperatures at different levels are respectively 50 DEG C, 55 DEG C, 60 DEG C, after dry
Obtain two-sided coatings aramid fiber lithium ion battery separator.The bilateral aramid fiber coating lithium ion battery separator thickness is 20 μm, each side
Coating layer thickness is 2 μm.
The two-sided coatings aramid fiber lithium-ion electric that composite coating lithium ion battery separator prepared by embodiment 5 is prepared with comparative example
Pond membrane properties test data is referring to table 1：
Table 1
By table 1 as it can be seen that the composite coating lithium ion battery separator for preparing of the embodiment of the present invention 5 is in gas permeability, imbibition rate, warm
Contraction, longitudinal tensile strength etc. are significantly better than comparative example.When using identical basement membrane, good permeability illustrates coating to diaphragm
Micropore influences small；Imbibition rate height illustrates that the imbibition water retainability of diaphragm is better；It is heat-shrinked under high temperature and smaller illustrates coated adhesive
Property is good；Tensile strength height illustrates that remaining dimensionally-stable property of diaphragm is good, excellent in mechanical performance.
Example 5 prepare diaphragm and comparative example prepare diaphragm, be respectively adopted same process be made flexible-packaged lithium from
Sub- battery chip carries out loop test using 0.5C constant-current constant-voltage chargings/1.0C constant-current discharges.From Figure 2 it can be seen that with the present invention every
The cycle performance of lithium ion battery of film preparation is obviously due to the lithium ion battery of comparative example diaphragm preparation.
Claims (6)
1. a kind of preparation method of composite coating lithium ion battery separator, which is characterized in that the composite coating lithium ion battery
Diaphragm is made of basement membrane and the aramid fiber coating for being coated on basement membrane side and the PVDF coatings for being coated on the basement membrane other side, the aramid fiber
Coating is coated by aramid fiber slurry, soaks, is obtained after drying, and coating layer thickness is 0.5-4 μm；The PVDF coatings are by aqueous PVDF
Slurry is coated, is obtained after drying, and coating layer thickness is 0.1-2 μm；
The base-material containing 1-10%, surplus are deionized water to the aqueous PVDF slurries in percentage by weight, the base-material
By the material composition of following mass parts, 65-85 parts of PVDF toners, 3-10 parts of aqueous binder, surfactant 1.5-5
Part, 8-20 parts of triethyl phosphate dispersant；
Preparation carries out as follows：
A, aramid fiber slurry is prepared：Each substance that composition aramid fiber slurry is weighed according to proportioning, by the first solvent and hydrotropy of proportional quantity
After agent stirring and dissolving, it is slowly homogeneously added into proportional quantity polyethylene glycol oxide dispersant, is stirred while adding, waits for polyethylene glycol oxide point
Aramid fiber is added in powder after being completely dissolved, boiling water bath heating is stirred to being completely dissolved, and dissolving aramid fiber liquid is made；It will match
Second solvent of proportion, emulsifier mixing, are uniformly dispersed, dissolving aramid fiber is added in the polymer adhesive with proportional quantity together
In liquid, be uniformly dispersed obtained aramid fiber slurry；
B, aqueous PVDF slurries are prepared：Weighed according to proportioning and form each substances of aqueous PVDF slurries, take proportional quantity dispersant,
Deionized water, the two mixing, 50 DEG C of -70 DEG C of heating are added the PVDF toners of proportional quantity after stirring 10-30 minutes, grind
Obtain PVDF dispersion liquids within 1-2 hours；Aqueous binder, the surfactant of proportional quantity are added into above-mentioned PVDF dispersion liquids, stirs
After mixing uniformly, is filtered with 400 mesh stainless steel mesh and aqueous PVDF slurries are made；
C, the coating of aramid fiber slurry：Aramid fiber slurry made from step a is coated on to the side of basement membrane, soak 3-15s, dries single
Side aramid fiber coats diaphragm；
D. the coating of aqueous PVDF slurries：Aqueous PVDF slurries made from step b are coated on above-mentioned unilateral aramid fiber and coat diaphragm
Composite coating lithium ion battery separator is made after dry in uncoated side.
2. preparation method according to claim 1, it is characterised in that：The PVDF toners are vinylidene fluoride homopolymer
Or one kind in vinylidene and hexafluoropropylene copolymer, grain size 100-150nm；The aqueous binder be butadiene-styrene latex,
Styrene-acrylic latex, purified petroleum benzin latex, polymethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, second
The mixture of one or more of alkene-acetate ethylene copolymer, polyvinyl acetate or polyurethane；The surfactant is
One in fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, polyoxyethylene alkylamide, fatty alcohol polyoxyethylene ether
Kind or several mixtures.
3. preparation method according to claim 2, it is characterised in that：The aramid fiber slurry by following mass parts substance group
At：3-8 parts of aramid fiber, the first 60-80 parts of solvent, the second 8-25 parts of solvent, 3-5 parts of cosolvent, polyethylene glycol oxide dispersant
0.5-1 parts, 0.5-2.5 parts of emulsifier, 1-2 parts of polymer adhesive.
4. preparation method according to claim 3, it is characterised in that：The cosolvent is calcium chloride, potassium hydroxide, chlorination
One or more of lithium, pyridine combine；The polyethylene glycol oxide dispersant is 200 mesh powder of grain size, molecular weight 10-
1000000；First solvent is one kind in NMP, DMSO, DMF or DMAC；Second solvent be ethyl acetate, isopropanol,
One or more of dichloromethane or triethyl phosphate combine；The emulsifier is polyvinyl alcohol, Sodium Polyacrylate or poly- third
One or more of acrylamide combines；The polymer adhesive is vinyl pyrrolidone and vinyl acetate copolymer；
The aramid fiber is meta-aramid fibers, para-aramid fiber, meta-aramid pulp, one kind in para-aramid pulp or more
Kind combination, aramid fiber molecular weight are 0.5-10 ten thousand.
5. preparation method according to claim 4, it is characterised in that：The basement membrane be polyethylene diagrams, polypropylene diaphragm,
Polypropylene, polyethylene/polypropylene composite materials diaphragm, Kynoar diaphragm, polyethylene non-woven cloth diaphragm, is gathered polyimide diaphragm
One kind in propylene nonwoven cloth diaphragm, polyimide nonwoven fabric diaphragm, basement membrane thickness are 5-40 μm, porosity 30-60%.
6. preparation method according to claim 1 or 5, it is characterised in that：Coating method is gravure, narrow slit type painting
One kind in cloth, the coating of dip-coating formula or jet printing type coating.
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| CN201510967229.7A CN105552284B (en) | 2015-12-22 | 2015-12-22 | A kind of composite coating lithium ion battery separator and preparation method thereof |
| PCT/CN2016/088411 WO2017107436A1 (en) | 2015-12-22 | 2016-07-04 | Composite lithium-ion battery separator having coating and method for preparing same |
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| CN201510967229.7A CN105552284B (en) | 2015-12-22 | 2015-12-22 | A kind of composite coating lithium ion battery separator and preparation method thereof |
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