CN105552284A - Composite coating lithium-ion battery separator and preparation method thereof - Google Patents
Composite coating lithium-ion battery separator and preparation method thereof Download PDFInfo
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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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- 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
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Abstract
The invention relates to a composite coating lithium-ion battery separator. The composite coating lithium-ion battery separator is composed of a base film, an aramid fiber coating coated on one side of the base film and a PVDF coating coated on the other side of the base film; the aramid fiber coating is obtained by an aramid fiber sizing agent after coating, soaking and drying, and the thickness of the coating is 0.5-4 microns; the PVDF coating is obtained by a water-based PVDF sizing agent after coating and drying, and the thickness of the coating is 0.1-2 microns. The invention also provides a preparation method of the separator. According to the composite coating lithium-ion battery separator and the preparation method thereof, the separator has the characteristics that the aramid fiber coating is good in thermal performance and mechanical performance and the PVDF coating has good wettability and liquid retention property for electrolytes, can effectively adhere batteries and pole pieces and is little in environmental pollution, and is beneficial for preparing lithium-ion batteries with longer cycle life and higher safety. Tests indicate that the separator has good air permeability, liquid absorption rate, thermal contraction and tensile strength, so that the cycle life of the batteries can be obviously prolonged by using the lithium-ion batteries prepared by the separator.
Description
Technical field
The present invention relates to a kind of lithium ion battery technology, particularly a kind of aramid fiber and PVDF composite coating lithium ion battery separator and preparation method thereof, belong to cell art.
Background technology
The formation of lithium ion battery comprises positive pole, negative pole, barrier film and electrolyte, barrier film as one of large material of lithium ion battery four, although do not participate in the electrochemical reaction in battery, but interior layer assembly crucial in lithium battery.Capacity, the key performance such as cycle performance and charging and discharging currents density of battery all have direct relation with barrier film, the fail safe of barrier film affects the key factor of lithium ion battery security especially.The lithium ion battery separator of extensive commercialization makes material and is mainly polyolefin at present, along with requiring more and more higher to performance of lithium ion battery, the barrier film thermal safety of simple polyolefin material and keep the ability of electrolyte to be difficult to meet the demands, the most important direction that other materials and polyolefinic high-performance composite diaphragm become current diagram modification is prepared in research.
Aramid fiber coating barrier film has the advantages such as resistance to elevated temperatures is good, energy density is high, wettability is excellent, long service life, obtains industry personage extensive concern.There is bibliographical information by organic solvent dissolution aramid fiber and carry out barrier film coating, adopting pure water to prepare the method for aramid fiber coating barrier film as coagulating bath, this method reduce the drying time of wet film, improve the adhesive property of coating and basement membrane, and environmental friendliness.Existing barrier film coating method mainly contains gravure, narrow slit type coating, the coating of dip-coating formula and jet printing type coating, and wherein except twosided application while that the coating of dip-coating formula can realizing, other modes are the one-sided coating of single.When aramid fiber coating process is the modes such as gravure, narrow slit type coating or jet printing type coating, and preparation process adopt pure water as coagulating bath prepare aramid fiber coating barrier film time, the organic solvent entering into pure water coagulating bath in secondary coating process easily causes the dissolving and the destruction that are coated with aramid fiber coating first, cause the barrier film plug-hole after coating or atresia, therefore when adopting the one-sided coating method of single, and more difficult operation when using coagulating bath method to prepare two-sided coatings aramid fiber barrier film, film forming situation is difficult to control.
PVDF(Kynoar) lithium ion battery separator that applies is on the basis of conventional membrane, through special process treatment surface coating PVDF material.Compared with common diaphragm, PVDF applies barrier film to be had good wetability to electrolyte and protects fluidity, can effective bonding barrier film and pole piece, increases the cycle performance of battery, significantly improves the fail safe of battery.The coating technology of existing lithium ion battery PVDF barrier film, generally adopt oiliness coating processes, oiliness coating processes many employings acetone makees solvent, and acetone is inflammable, explosive, and has very major injury to human body, has unsafe factor in process of production; Acetone is the raw material manufacturing methamphetamine simultaneously, and it uses the control being subject to relevant department strict.In addition, adopt the coating that the oil-based solvents such as acetone make, after barrier film carries out surface-coated, because oil slurry and barrier film material compatibility are better, slurry can penetrate in the micropore of basement membrane, causes ventilative loss very large, easily cause barrier film plug-hole, affect battery performance, what reduce positive and negative pole material in battery effectively utilizes space, and battery capacity and performance are restricted.
Summary of the invention
The present invention is intended to the defect overcoming prior art, provide a kind of have good hot property and mechanical performance, service life cycle long, electrolyte had to good wettability and protects fluidity, fail safe is high, environmental pollution is little composite coating lithium ion battery separator.
In addition, present invention also offers the preparation method of described composite coating lithium ion battery separator.
For achieving the above object, the technical solution used in the present invention is such:
A kind of composite coating lithium ion battery separator, is made up of with the PVDF coating coating basement membrane opposite side basement membrane and the aramid fiber coating coating basement membrane side, and described aramid fiber coating is by the acquisition after being coated with, soaking, drying of aramid fiber slurry, and coating layer thickness is 0.5-4 μm; Described PVDF coating is obtained after coating, oven dry by water-based PVDF slurry, and coating layer thickness is 0.1-2 μm.
Above-mentioned composite coating lithium ion battery separator, described water-based PVDF slurry contains the base-material of 1-10% according to weight percent meter, surplus is deionized water, described base-material is made up of the material of following mass parts, PVDF toner 65-85 part, aqueous binder 3-10 part, surfactant 1.5-5 part, triethyl phosphate dispersant 8-20 part.
Above-mentioned composite coating lithium ion battery separator, described PVDF toner is the one in vinylidene fluoride homopolymer or vinylidene and hexafluoropropylene copolymer, and particle diameter is 100-150nm; Described aqueous binder is the mixture of one or more in butadiene-styrene latex, styrene-acrylic latex, purified petroleum benzin latex, polymethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate or polyurethane; Described surfactant is the mixture of one or more in fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, polyoxyethylene alkylamide, AEO.
Above-mentioned composite coating lithium ion battery separator, described aramid fiber slurry is made up of the material of following mass parts: aramid fiber 3-8 part, first solvent 60-80 part, second solvent 8-25 part, cosolvent 3-5 part, polyethylene glycol oxide dispersant 0.5-1 part, emulsifying agent 0.5-2.5 part, polymer adhesive 1-2 part.
Above-mentioned composite coating lithium ion battery separator, described cosolvent is the one or more combination in calcium chloride, potassium hydroxide, lithium chloride, pyridine; Described polyethylene glycol oxide dispersant is particle diameter 200 object powder, and molecular weight is 10-100 ten thousand; Described first solvent is the one in NMP, DMSO, DMF or DMAC; Described second solvent is the one or more combination in ethyl acetate, isopropyl alcohol, carrene or triethyl phosphate; Described emulsifying agent is the one or more combination in polyvinyl alcohol, Sodium Polyacrylate or polyacrylamide; Described polymer adhesive is vinyl pyrrolidone and vinyl acetate copolymer; Described aramid fiber is one or more combinations in meta-aramid fibers, para-aramid fiber, meta-aramid pulp, PPTA-pulp, and aramid fiber molecular weight is 0.5-10 ten thousand.
Above-mentioned composite coating lithium ion battery separator, described basement membrane is the one in polyethylene diagrams, polypropylene diaphragm, polypropylene, polyethylene/polypropylene composite materials barrier film, polyimide diaphragm, Kynoar barrier film, polyethylene non-woven cloth diaphragm, polypropylene non-woven cloth diaphragm, polyimide nonwoven fabric barrier film, basement membrane thickness is 5-40 μm, and porosity is 30-60%.
Prepare a method for composite coating lithium ion battery separator, comprise the steps:
A, prepare aramid fiber slurry: each material taking composition aramid fiber slurry according to proportioning, after the first solvent of proportional quantity and cosolvent stirring and dissolving, slowly add proportional quantity polyethylene glycol oxide dispersant equably, stir while adding, aramid fiber is added after polyethylene glycol oxide dispersant dissolves completely, boiling water bath heats, is stirred to and dissolves completely, obtained dissolving aramid fiber liquid; By the second solvent of proportional quantity, emulsifying agent mixing, be uniformly dispersed, the polymer adhesive with proportional quantity adds in dissolving aramid fiber liquid together, and be uniformly dispersed obtained aramid fiber slurry;
B, preparation water-based PVDF slurry: each material taking composition water-based PVDF slurry according to proportioning, get the dispersant of proportional quantity, deionized water, both mixing, 50 DEG C-70 DEG C heating, stir after 10-30 minute, add the PVDF toner of proportional quantity, grind and obtain PVDF dispersion liquid in 1-2 hour; In above-mentioned PVDF dispersion liquid, add aqueous binder, the surfactant of proportional quantity, after stirring, obtain water-based PVDF slurry with 400 order stainless steel sift net filtrations;
The coating of c, aramid fiber slurry: the aramid fiber slurry obtained by step a is coated on the side of basement membrane, immersion 3-15s, dries to obtain one-sided aramid fiber coating barrier film;
D. the coating of water-based PVDF slurry: the uncoated side of above-mentioned one-sided aramid fiber coating barrier film coated by the water-based PVDF slurry obtained by step b, obtained composite coating lithium ion battery separator after dry.
Above-mentioned PVDF applies the preparation method of lithium ion battery separator, and coating method is the one in gravure, narrow slit type coating, the coating of dip-coating formula or jet printing type coating.
The present invention compared with prior art, has following major advantage:
1, aramid fiber of the present invention and PVDF composite coating lithium ion battery separator, compared with traditional two-sided coatings aramid fiber barrier film, the aramid fiber coating of side is instead of with PVDF coating, avoid and adopt the coating of gravure, narrow slit type or the one-sided coating method of single such as jet printing type coating, and film forming situation shortcoming rambunctious when using coagulating bath method to prepare two-sided coatings aramid fiber barrier film.This composite diaphragm is while possessing the good hot property of aramid fiber coating and mechanical performance, possessed again PVDF coating have good wettability to electrolyte and protect fluidity, can effective bonding battery and pole piece, feature that environmental pollution is little, be conducive to preparing the lithium ion battery that cycle life is longer, fail safe is higher.
2, PVDF coating of the present invention is obtained after coating, oven dry by water-based PVDF slurry, abandon existing PVDF and apply lithium ion battery separator makes solvent traditional handicraft with oily matters such as acetone, adopt water as solvent, production process environmental friendliness, fail safe are high; Use water as solvent in addition and greatly can reduce production cost, be beneficial to suitability for industrialized production.For PVDF resin, there is extremely strong hydrophobicity, serious feature of reuniting in water-based system, select triethyl phosphate as dispersant.Triethyl phosphate adds as the intermediate medium of water and PVDF, when triethyl phosphate hydrolysis generates diethyl phosphate and ethanol, a large amount of hydroxyls is generated at PVDF surrounding molecules, PVDF is dispersed in water preferably, the caking property of effective raising PVDF, improves coating in drying course because of crack performance that moisture evaporation causes too soon simultaneously.In addition, triethyl phosphate is cheap, simple to operate, reduces production cost, is beneficial to suitability for industrialized production.
Test shows, barrier film of the present invention has good gas permeability, pick up, thermal contraction, hot strength, and preparing lithium ion battery with barrier film of the present invention can significantly improve battery cycle life.
Accompanying drawing explanation
Fig. 1 is the generalized section of composite coating lithium ion battery separator of the present invention;
Fig. 2 is the constant-current discharge loop test datagram of lithium ion battery prepared by the lithium ion battery prepared with composite coating lithium ion battery separator of the present invention and two-sided coatings aramid fiber barrier film.
Attached number in the figure is as follows: 1, PVDF coating, and 2, basement membrane, 3, aramid fiber coating.
Embodiment
Referring to Fig. 1, composite coating lithium ion battery separator of the present invention, is made up of the PVDF coating 1 of basement membrane 2 with the aramid fiber coating 3 and opposite side of coating basement membrane side.Described aramid fiber coating is obtained after coating, immersion, oven dry by aramid fiber slurry, and coating layer thickness is 0.5-4 μm; Described PVDF coating applies slurry by water-based PVDF and obtains after coating, oven dry, and coating layer thickness is 0.1-2 μm.The formation of above-mentioned aramid fiber coating is by basement membrane by soaking after coating aramid fiber slurry, through mass transport process formation porous aramid fiber coating; The formation of above-mentioned PVDF coating, is dispersed in water by PVDF resin particle and makes slurry, and after coating, heating makes moisture evaporation, and remaining solid particle is deposited in layered arrangement together, and the gap pore-forming between particle and particle, forms final PVDF coating.
It is substitute conventional oil-based solvent using water as decentralized medium that described water-based PVDF applies slurry.Symmetrical structurally due to fluorine atom on PVDF strand, result in that this material surface energy is low, hydrophobicity be strong, difficult dispersion in water, PVDF does not possess hydrophilic radical again simultaneously, possess permanent stability, hydroxyl, carboxyl, amino etc. must be introduced on its surface and there is hydrophilic polar group.Triethyl phosphate as dispersant, when hydrolysis occurs for it, can be generated diethyl phosphate and ethanol by the present invention, all containing hydrophilic hydroxyl in diethyl phosphate and ethanol molecule structure, contains again ester group and the alkyl of oleophylic.Ester group and alkyl are adsorbed on PVDF particle surface, reduce the interfacial tension between PVDF and water, make PVDF particle surface be easy to moistening.Meanwhile, when PVDF particle close to time, because the diethyl phosphate of adsorption and ethanol produce space steric effect, mutually can slide between PVDF particle and stagger, be difficult to reunite again, make PVDF good dispersion, active area increases, and cementability promotes.In addition, the volatilization temperature of water is lower, and when taking water as solvent, coating can be caused too soon to chap because of moisture evaporation in barrier film coating drying course, can slow down after adding appropriate triethyl phosphate dry run, and coating crack performance is disappeared.Substitute traditional dispersant with triethyl phosphate, simple to operate, dispersion effect is good, reduces cost, is beneficial to suitability for industrialized production.
Base-material containing 1-10% in water-based PVDF slurry of the present invention, surplus is deionized water.Described base-material is made up of the material of following mass parts: PVDF toner 65-85 part, aqueous binder 3-10 part, surfactant 1.5-5 part, triethyl phosphate dispersant 8-20 part.Described PVDF toner is the one in vinylidene fluoride homopolymer or vinylidene and hexafluoropropylene copolymer, and particle diameter is 100-150nm; Described aqueous binder is the mixture of one or more in butadiene-styrene latex, styrene-acrylic latex, purified petroleum benzin latex, polymethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate or polyurethane; Described surfactant is the mixture of one or more in fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, polyoxyethylene alkylamide, AEO.
Aramid fiber slurry of the present invention is made up of the material of following mass parts: aramid fiber 3-8 part, first solvent 60-80 part, second solvent 8-25 part, cosolvent 3-5 part, polyethylene glycol oxide dispersant 0.5-1 part, emulsifying agent 0.5-2.5 part, polymer adhesive 1-2 part.Described cosolvent is one or more in calcium chloride, potassium hydroxide, lithium chloride, pyridine; Described dispersant is particle diameter 200 object polyethylene glycol oxide powder, and molecular weight is 10-100 ten thousand; Described first solvent is the one in NMP, DMSO, DMF or DMAC; Described second solvent is one or more in ethyl acetate, isopropyl alcohol, carrene or triethyl phosphate; Described emulsifying agent is one or more in polyvinyl alcohol, Sodium Polyacrylate or polyacrylamide; Described polymer adhesive is vinyl pyrrolidone and vinyl acetate copolymer; Described aramid fiber is one or more combinations in meta-aramid fibers, para-aramid fiber, meta-aramid pulp, PPTA-pulp, and aramid fiber molecular weight is 0.5-10 ten thousand.
Basement membrane of the present invention is the one in polyethylene diagrams, polypropylene diaphragm, polypropylene, polyethylene/polypropylene composite materials barrier film, polyimide diaphragm, Kynoar barrier film, polyethylene non-woven cloth diaphragm, polypropylene non-woven cloth diaphragm, polyimide nonwoven fabric barrier film, basement membrane thickness is 5-40 μm, and porosity is 30-60%.
The preparation method of composite coating lithium ion battery separator of the present invention is as follows:
A, prepare aramid fiber slurry: each material taking composition aramid fiber slurry according to proportioning, after the first solvent of proportional quantity and cosolvent stirring and dissolving, slowly add proportional quantity polyethylene glycol oxide dispersant equably, stir while adding, aramid fiber is added after polyethylene glycol oxide dispersant dissolves completely, boiling water bath heats, is stirred to and dissolves completely, obtained dissolving aramid fiber liquid; By the second solvent of proportional quantity, emulsifying agent mixing, be uniformly dispersed, the polymer adhesive with proportional quantity adds in dissolving aramid fiber liquid together, and be uniformly dispersed obtained aramid fiber slurry;
B, preparation water-based PVDF slurry: each material taking composition water-based PVDF slurry according to proportioning, get triethyl phosphate dispersant, the deionized water of proportional quantity, both mixing, 50 DEG C-70 DEG C heating, stir after 10-30 minute, add the PVDF toner of proportional quantity, grind and obtain PVDF dispersion liquid in 1-2 hour; In above-mentioned PVDF dispersion liquid, add aqueous binder, the surfactant of proportional quantity, after stirring, obtain water-based PVDF slurry with 400 order stainless steel sift net filtrations;
The coating of c, aramid fiber slurry: the aramid fiber slurry obtained by step a is coated on the side of basement membrane, immersion 3-15s, dries to obtain one-sided aramid fiber coating barrier film;
The coating of d, water-based PVDF slurry: the uncoated side of above-mentioned one-sided aramid fiber coating barrier film coated by the water-based PVDF slurry obtained by step b, obtained composite coating lithium ion battery separator after dry.
Coating method is the one in gravure, narrow slit type coating, the coating of dip-coating formula or jet printing type coating.
Several specific embodiments of the invention are below provided:
Embodiment 1:
A, prepare aramid fiber slurry: take meta-aramid fibers 0.7kg that molecular weight is 8-10 ten thousand, the first solvent DMAC6kg, the second methylene chloride 2.5kg, cosolvent lithium chloride 0.4kg, polyethylene glycol oxide dispersant 0.05kg, the emulsifying agent pva powder 0.25kg of molecular weight 40-50 ten thousand, polymer adhesive vinyl pyrrolidone and vinyl acetate copolymer 0.1kg.Cosolvent lithium chloride is joined in the first solvent DMAC to be stirred to and dissolve completely, slowly and uniformly add polyethylene glycol oxide dispersant while stirring, stirring at low speed is dissolved completely to polyethylene glycol oxide, add meta-aramid fibers, boiling water bath heats and is stirred to and dissolves completely, obtains meta-aramid fibers lysate.Get the second methylene chloride, add emulsifying agent pva powder, after dispersion 40min, join in above-mentioned aramid fiber lysate with polymer adhesive vinyl pyrrolidone and vinyl acetate, be uniformly dispersed obtained aramid fiber slurry.
B, preparation water-based PVDF slurry: take vinylidene fluoride homopolymer 6.5kg, triethyl phosphate 0.8kg, deionized water 792kg, polyvinyl alcohol 0.55kg, polyoxyethylene alkylamide 0.15kg.After triethyl phosphate and deionized water are mixed, use magnetic force heating stirrer to stir 10 minutes, be heated to 50 DEG C and make mixture one; Getting vinylidene fluoride homopolymer adds in mixture one, grinds and obtains mixture two in 1 hour; Polyvinyl alcohol and polyoxyethylene alkylamide is added, with 400 order stainless steel sift net filtrations i.e. obtained water-based PVDF slurry after stirring in mixture two.
The coating of c, aramid fiber slurry: choose the polypropylene diaphragm that thickness is 12 μm, porosity is 40%, and adopt gravure mode that the aramid fiber slurry prepared in a step is coated the one-sided of barrier film, application rate is 8m/min, immersion 10s; Use three grades of baking ovens to dry, oven temperature at different levels is respectively 50 DEG C, 60 DEG C, 65 DEG C, obtained one-sided aramid fiber coating barrier film after dry.
The coating of d, water-based PVDF slurry: adopt gravure mode the water-based PVDF slurry prepared in b step to be coated the side of the uncoated aramid fiber coating of above-mentioned one-sided aramid fiber coating barrier film, application rate is 25m/min; Use three grades of baking ovens to dry, oven temperature at different levels is respectively 40 DEG C, 50 DEG C, 45 DEG C, obtained PVDF composite coating lithium ion battery separator 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 coating layer thickness is 0.1 μm.
Embodiment 2:
A, prepare aramid fiber slurry: take para-aramid fiber 0.3kg, the first solvent NMP8kg that molecular weight is 0.5-2 ten thousand, the second solvent isopropyl alcohol 1.5kg, cosolvent pyridine 0.5kg, polyethylene glycol oxide dispersant 0.1kg, the emulsifying agent Sodium Polyacrylate powder 0.2kg of molecular weight 10-30 ten thousand, polymer adhesive vinyl pyrrolidone and vinyl acetate copolymer 0.1kg.Cosolvent pyridine is joined in the first solvent NMP to be stirred to and dissolve completely, slowly and uniformly add polyethylene glycol oxide dispersant while stirring, stirring at low speed is dissolved completely to polyethylene glycol oxide, add para-aramid fiber, boiling water bath heats and is stirred to and dissolves completely, obtains para-aramid fiber lysate.Get the second solvent isopropyl alcohol, add emulsifying agent Sodium Polyacrylate powder, after dispersion 30min, join in above-mentioned aramid fiber lysate with polymer adhesive vinyl pyrrolidone and vinyl acetate, be uniformly dispersed obtained aramid fiber slurry.
B, preparation water-based PVDF slurry: take vinylidene and hexafluoropropylene copolymer 8.5kg, triethyl phosphate 1.8kg, deionized water 105.3kg, butadiene-styrene latex 1kg, fluoro-alkyl methoxyl group ether alcohol 0.4kg.After triethyl phosphate and deionized water are mixed, use magnetic force heating stirrer to stir 30 minutes, be heated to 60 DEG C and make mixture one; Get vinylidene and hexafluoropropylene copolymer adds in mixture one, grind and obtain mixture two in 2 hours; Butadiene-styrene latex and fluoro-alkyl methoxyl group ether alcohol is added, with 400 order stainless steel sift net filtrations i.e. obtained water-based PVDF slurry after stirring in mixture two.
The coating of c, aramid fiber slurry: choose the polyethylene diagrams that thickness is 20 μm, porosity is 38%, and adopt narrow slit type coating method that the aramid fiber slurry prepared in a step is coated the one-sided of barrier film, application rate is 15m/min, immersion 3s; Use three grades of baking ovens to dry, oven temperature at different levels is respectively 55 DEG C, 60 DEG C, 50 DEG C, obtained one-sided aramid fiber coating barrier film after dry.
The coating of d, water-based PVDF slurry: adopt gravure mode the water-based PVDF slurry prepared in b step to be coated the side of the uncoated aramid fiber coating of above-mentioned one-sided aramid fiber coating barrier film, application rate is 20m/min; Use three grades of baking ovens to dry, oven temperature at different levels is respectively 60 DEG C, 70 DEG C, 65 DEG C, obtained PVDF composite coating lithium ion battery separator 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, and PVDF coating layer thickness is 2 μm.
Embodiment 3:
A, prepare aramid fiber slurry: take meta-aramid fibers 0.8kg, the first solvent DMF 6.8kg that molecular weight is 5-8 ten thousand, the second methylene chloride 1.5kg, cosolvent potassium hydroxide 0.47kg, polyethylene glycol oxide dispersant 0.08kg, the emulsifying agent pva powder 0.15kg of molecular weight 60-70 ten thousand, polymer adhesive vinyl pyrrolidone and vinyl acetate copolymer 0.2kg.Cosolvent potassium hydroxide is joined in the first solvent DMF to be stirred to and dissolve completely, slowly and uniformly add polyethylene glycol oxide dispersant while stirring, stirring at low speed is dissolved completely to polyethylene glycol oxide, add meta-aramid fibers, boiling water bath heats and is stirred to and dissolves completely, obtains meta-aramid fibers lysate.Get the second methylene chloride, add emulsifying agent pva powder, after dispersion 30min, join in above-mentioned aramid fiber lysate with polymer adhesive vinyl pyrrolidone and vinyl acetate, be uniformly dispersed obtained aramid fiber slurry.
B, preparation water-based PVDF slurry: take vinylidene fluoride homopolymer 7kg, triethyl phosphate 1.5kg, deionized water 216kg, polyvinyl acetate 0.3kg, AEO 0.2kg.After triethyl phosphate and deionized water are mixed, use magnetic force heating stirrer to stir 20 minutes, be heated to 70 DEG C and make mixture one; Getting vinylidene fluoride homopolymer adds in mixture one, grinds and obtains mixture two in 1.5 hours; Polyvinyl acetate and AEO is added, with 400 order stainless steel sift net filtrations i.e. obtained water-based PVDF slurry after stirring in mixture two.
The coating of c, aramid fiber slurry: choose the polypropylene diaphragm that thickness is 40 μm, porosity is 60%, and adopt jet printing type coating method that the aramid fiber slurry prepared in a step is coated the one-sided of barrier film, application rate is 5m/min, immersion 15s; Use three grades of baking ovens to dry, oven temperature at different levels is respectively 55 DEG C, 65 DEG C, 60 DEG C, obtained one-sided aramid fiber coating barrier film after dry.
The coating of d, water-based PVDF slurry: adopt narrow slit type coating method the water-based PVDF slurry prepared in b step to be coated the side of the uncoated aramid fiber coating of above-mentioned one-sided aramid fiber coating barrier film, application rate is 20m/min; Use three grades of baking ovens to dry, oven temperature at different levels is respectively 45 DEG C, 55 DEG C, 50 DEG C, obtained PVDF composite coating lithium ion battery separator 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 coating layer thickness is 0.5 μm.
Embodiment 4:
A, prepare aramid fiber slurry: take meta-aramid pulp 0.55kg that molecular weight is 6-8 ten thousand, the first solvent DMSO6.75kg, the second solvent ethyl acetate 2.03kg, cosolvent calcium chloride 0.35kg, polyethylene glycol oxide dispersant 0.07kg, the emulsifying agent Polyacrylamide Powder 0.05kg of molecular weight 50-60 ten thousand, polymer adhesive vinyl pyrrolidone and vinyl acetate copolymer 0.15kg.Cosolvent calcium chloride is joined in the first solvent DMSO to be stirred to and dissolve completely, slowly and uniformly add polyethylene glycol oxide dispersant while stirring, stirring at low speed is dissolved completely to polyethylene glycol oxide, add meta-aramid pulp, boiling water bath heats and is stirred to and dissolves completely, obtains meta-aramid pulp lysate.Get the second solvent ethyl acetate, add emulsifying agent Polyacrylamide Powder, after dispersion 30min, join in above-mentioned aramid fiber lysate with polymer adhesive vinyl pyrrolidone and vinyl acetate, be uniformly dispersed obtained aramid fiber slurry.
B, preparation water-based PVDF slurry: take vinylidene and hexafluoropropylene copolymer 7.5kg, triethyl phosphate 1.3kg, deionized water 178.6kg, polyethyl acrylate 0.4kg, polyoxyethylene alkylamide 0.2kg.After triethyl phosphate and deionized water are mixed, use magnetic force heating stirrer to stir 18 minutes, be heated to 55 DEG C and make mixture one; Get vinylidene and hexafluoropropylene copolymer adds in mixture one, grind and obtain mixture two in 2 hours; Polyethyl acrylate and polyoxyethylene alkylamide is added, with 400 order stainless steel sift net filtrations i.e. obtained water-based PVDF slurry after stirring in mixture two.
The coating of c, aramid fiber slurry: choose the polyethylene diagrams that thickness is 5 μm, porosity is 30%, and adopt gravure mode that the aramid fiber slurry prepared in a step is coated the one-sided of barrier film, application rate is 12m/min, immersion 5s; Use three grades of baking ovens to dry, oven temperature at different levels is respectively 50 DEG C, 65 DEG C, 60 DEG C, obtained one-sided aramid fiber coating barrier film after dry.
The coating of d, water-based PVDF slurry: adopt jet printing type coating method the water-based PVDF slurry prepared in b step to be coated the side of the uncoated aramid fiber coating of above-mentioned one-sided aramid fiber coating barrier film, application rate is 25m/min; Use three grades of baking ovens to dry, oven temperature at different levels is respectively 55 DEG C, 65 DEG C, 60 DEG C, obtained PVDF composite coating lithium ion battery separator 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, and PVDF coating layer thickness is 1 μm.
Embodiment 5:
A, prepare aramid fiber slurry: take PPTA-pulp 0.5kg, the first solvent DMAC6.9kg that molecular weight is 3-5 ten thousand, the second solvent triethyl phosphate 2kg, cosolvent lithium chloride 0.3kg, polyethylene glycol oxide dispersant 0.09kg, the emulsifying agent pva powder 0.1kg of molecular weight 30-40 ten thousand, polymer adhesive vinyl pyrrolidone and vinyl acetate copolymer 0.11kg.Cosolvent lithium chloride is joined in the first solvent DMAC to be stirred to and dissolve completely, slowly and uniformly add polyethylene glycol oxide dispersant while stirring, stirring at low speed is dissolved completely to polyethylene glycol oxide, add PPTA-pulp, boiling water bath heats and is stirred to and dissolves completely, obtains PPTA-pulp lysate.Get the second solvent triethyl phosphate, add emulsifying agent pva powder, after dispersion 30min, join in above-mentioned aramid fiber lysate with polymer adhesive vinyl pyrrolidone and vinyl acetate, be uniformly dispersed obtained aramid fiber slurry.
B, preparation water-based PVDF slurry: take vinylidene and hexafluoropropylene copolymer 7.5kg, triethyl phosphate 2kg, deionized water 130kg, polyurethane 0.8kg, fluoro-alkyl methoxyl group ether alcohol 0.5kg.After triethyl phosphate and deionized water are mixed, use magnetic force heating stirrer to stir 15 minutes, be heated to 65 DEG C and make mixture one; Get vinylidene and hexafluoropropylene copolymer adds in mixture one, grind and obtain mixture two in 1 hour; Polyurethane and fluoro-alkyl methoxyl group ether alcohol is added, with 400 order stainless steel sift net filtrations i.e. obtained water-based PVDF slurry after stirring in mixture two.
The coating of c, aramid fiber slurry: choose the polyethylene diagrams that thickness is 16 μm, porosity is 38%, and adopt gravure mode that the aramid fiber slurry prepared in a step is coated the one-sided of barrier film, application rate is 10m/min, immersion 8s; Use three grades of baking ovens to dry, oven temperature at different levels is respectively 50 DEG C, 55 DEG C, 60 DEG C, obtained one-sided aramid fiber coating barrier film after dry.
The coating of d, water-based PVDF slurry: adopt gravure mode the water-based PVDF slurry prepared in b step to be coated the side of the uncoated aramid fiber coating of above-mentioned one-sided aramid fiber coating barrier film, application rate is 25m/min; Use three grades of baking ovens to dry, oven temperature at different levels is respectively 55 DEG C, 65 DEG C, 60 DEG C, obtained PVDF composite coating lithium ion battery separator 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 coating layer thickness is 1.5 μm.
Comparative example:
According to the proportional quantity preparation aramid fiber slurry of aramid fiber slurry in embodiment 5, choose that thickness is 16 μm, porosity is the polypropylene screen of 38%, gravure mode is adopted the aramid fiber slurry prepared to be coated the bilateral of barrier film, application rate is 15m/min, immersion 10s, use three grades of baking ovens to dry, oven temperature at different levels is respectively 50 DEG C, 55 DEG C, 60 DEG C, obtains two-sided coatings aramid fiber lithium ion battery separator after drying.Described bilateral aramid fiber coating lithium ion battery separator thickness is 20 μm, and each coating side thickness is 2 μm.
Composite coating lithium ion battery separator prepared by embodiment 5 and two-sided coatings aramid fiber lithium ion battery separator performance test data prepared by comparative example are see table 1:
Table 1
From table 1, composite coating lithium ion battery separator prepared by the embodiment of the present invention 5 is all greatly better than comparative example in gas permeability, pick up, thermal contraction, longitudinal tensile strength etc.When using identical basement membrane, good permeability illustrates that coating is little on diaphragm micro-hole impact; Pick up height illustrates that the imbibition water retainability of barrier film is more excellent; Under high temperature, the less explanation coated adhesive of thermal contraction is good; Hot strength height illustrates that barrier film keeps good stability of the dimension, excellent in mechanical performance.
Barrier film prepared by Example 5 and barrier film prepared by comparative example, adopt same process to make flexible packing lithium ion battery chip respectively, adopt 0.5C constant-current constant-voltage charging/1.0C constant-current discharge to carry out loop test.As seen from Figure 2, the cycle performance of lithium ion battery prepared with barrier film of the present invention is obviously due to lithium ion battery prepared by comparative example barrier film.
Claims (8)
1. a composite coating lithium ion battery separator, it is characterized in that: be made up of with the PVDF coating coating basement membrane opposite side basement membrane and the aramid fiber coating coating basement membrane side, described aramid fiber coating is obtained after coating, immersion, oven dry by aramid fiber slurry, and coating layer thickness is 0.5-4 μm; Described PVDF coating is obtained after coating, oven dry by water-based PVDF slurry, and coating layer thickness is 0.1-2 μm.
2. composite coating lithium ion battery separator according to claim 1, it is characterized in that: described water-based PVDF slurry contains the base-material of 1-10% according to weight percent meter, surplus is deionized water, described base-material is made up of the material of following mass parts, PVDF toner 65-85 part, aqueous binder 3-10 part, surfactant 1.5-5 part, triethyl phosphate dispersant 8-20 part.
3. composite coating lithium ion battery separator according to claim 2, is characterized in that: described PVDF toner is the one in vinylidene fluoride homopolymer or vinylidene and hexafluoropropylene copolymer, and particle diameter is 100-150nm; Described aqueous binder is the mixture of one or more in butadiene-styrene latex, styrene-acrylic latex, purified petroleum benzin latex, polymethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate or polyurethane; Described surfactant is the mixture of one or more in fluoro-alkyl methoxyl group ether alcohol, fluoro-alkyl ethyoxyl ether alcohol, polyoxyethylene alkylamide, AEO.
4. composite coating lithium ion battery separator according to claim 3, it is characterized in that: described aramid fiber slurry is made up of the material of following mass parts: aramid fiber 3-8 part, first solvent 60-80 part, second solvent 8-25 part, cosolvent 3-5 part, polyethylene glycol oxide dispersant 0.5-1 part, emulsifying agent 0.5-2.5 part, polymer adhesive 1-2 part.
5. composite coating lithium ion battery separator according to claim 4, is characterized in that: described cosolvent is the one or more combination in calcium chloride, potassium hydroxide, lithium chloride, pyridine; Described polyethylene glycol oxide dispersant is particle diameter 200 object powder, and molecular weight is 10-100 ten thousand; Described first solvent is the one in NMP, DMSO, DMF or DMAC; Described second solvent is the one or more combination in ethyl acetate, isopropyl alcohol, carrene or triethyl phosphate; Described emulsifying agent is the one or more combination in polyvinyl alcohol, Sodium Polyacrylate or polyacrylamide; Described polymer adhesive is vinyl pyrrolidone and vinyl acetate copolymer; Described aramid fiber is one or more combinations in meta-aramid fibers, para-aramid fiber, meta-aramid pulp, PPTA-pulp, and aramid fiber molecular weight is 0.5-10 ten thousand.
6. composite coating lithium ion battery separator according to claim 5, it is characterized in that: described basement membrane is the one in polyethylene diagrams, polypropylene diaphragm, polypropylene, polyethylene/polypropylene composite materials barrier film, polyimide diaphragm, Kynoar barrier film, polyethylene non-woven cloth diaphragm, polypropylene non-woven cloth diaphragm, polyimide nonwoven fabric barrier film, basement membrane thickness is 5-40 μm, and porosity is 30-60%.
7. prepare a method for composite coating lithium ion battery separator as described in claim 1,2,3,4,5 or 6, it is characterized in that, comprise the steps:
A, prepare aramid fiber slurry: each material taking composition aramid fiber slurry according to proportioning, after the first solvent of proportional quantity and cosolvent stirring and dissolving, slowly add proportional quantity polyethylene glycol oxide dispersant equably, stir while adding, aramid fiber is added after polyethylene glycol oxide dispersant dissolves completely, boiling water bath heats, is stirred to and dissolves completely, obtained dissolving aramid fiber liquid; By the second solvent of proportional quantity, emulsifying agent mixing, be uniformly dispersed, the polymer adhesive with proportional quantity adds in dissolving aramid fiber liquid together, and be uniformly dispersed obtained aramid fiber slurry;
B, preparation water-based PVDF slurry: each material taking composition water-based PVDF slurry according to proportioning, get the dispersant of proportional quantity, deionized water, both mixing, 50 DEG C-70 DEG C heating, stir after 10-30 minute, add the PVDF toner of proportional quantity, grind and obtain PVDF dispersion liquid in 1-2 hour; In above-mentioned PVDF dispersion liquid, add aqueous binder, the surfactant of proportional quantity, after stirring, obtain water-based PVDF slurry with 400 order stainless steel sift net filtrations;
The coating of c, aramid fiber slurry: the aramid fiber slurry obtained by step a is coated on the side of basement membrane, immersion 3-15s, dries to obtain one-sided aramid fiber coating barrier film;
D. the coating of water-based PVDF slurry: the uncoated side of above-mentioned one-sided aramid fiber coating barrier film coated by the water-based PVDF slurry obtained by step b, obtained composite coating lithium ion battery separator after dry.
8. PVDF according to claim 7 applies the preparation method of lithium ion battery separator, it is characterized in that: coating method is the one in gravure, narrow slit type coating, the coating of dip-coating formula or jet printing type coating.
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| CN105552284B (en) | 2018-11-06 |
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