CN106700445A - High-temperature resistant polynaphthalene ester microporous diaphragm and preparation method thereof - Google Patents

High-temperature resistant polynaphthalene ester microporous diaphragm and preparation method thereof Download PDF

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CN106700445A
CN106700445A CN201611247496.8A CN201611247496A CN106700445A CN 106700445 A CN106700445 A CN 106700445A CN 201611247496 A CN201611247496 A CN 201611247496A CN 106700445 A CN106700445 A CN 106700445A
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poly
molecular weight
ultra
pore
temperature resistant
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CN106700445B (en
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黄孙息
陈志平
冯羽风
钟立松
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Guilin Electrical Equipment Scientific Research Institute Co Ltd
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Guilin Electrical Equipment Scientific Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/068—Ultra high molecular weight polyethylene
    • 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

Abstract

The invention discloses a high-temperature resistant polynaphthalene ester microporous diaphragm and a preparation method of the diaphragm. The diaphragm is prepared from the following ingredients by weight percentage: 35-64.9% of polyethylene naphthalate, 0-20% of ultra-high molecular weight polyethylene, 35-44.6% of a pore-forming agent and 0.1-0.5% of an antioxidant, wherein the mean molecular weight of polyethylene naphthalate is 2*10[4]-3.5*10[4]; a melting point of polyethylene naphthalate is 250-270 DEG C; a glass transition temperature of polyethylene naphthalate is 110-130 DEG C; and the intrinsic viscosity of polyethylene naphthalate is 0.8-1.2 dL/g; and the mean molecular weight of ultra-high molecular weight polyethylene is 1.5*10[6]-2.5*10[6]. Polyethylene naphthalate resin with specific parameters of the molecular weight, the glass transition temperature and the intrinsic viscosity, ultra-high molecular weight polyethylene, the pore-forming agent and the antioxidant are selected for preparation, so that the high temperature resistance and mechanical strength of the prepared polynaphthalene ester microporous diaphragm are obviously improved.

Description

A kind of poly- naphthalene ester micro-pore septum of high temperature resistant and preparation method thereof
Technical field
The present invention relates to a kind of battery diaphragm, and in particular to a kind of poly- naphthalene ester micro-pore septum of high temperature resistant and preparation method thereof.
Background technology
Lithium ion battery separator refers to one layer of diaphragm material between anode and negative pole, is very crucial in battery Part, its Main Function is to isolate positive and negative electrode and prevent electronics in battery from passing freely through, the ion allowed in electrolyte solution Passed freely through between both positive and negative polarity.At present, in the material as lithium ion battery separator, polyethylene or polypropylene are predominantly Position.This kind of material not only wide material sources, cheap, also with chemical inertness, and most polar electrolytes not rising Learn and react and incompatible, but it has the disadvantage poor heat resistance, and percent thermal shrinkage is easily caused more than more than 15% more than 150 DEG C Electrode plates expose and short-circuit.Even the film that the preferable polypropylene of heat resistance is made, its long-term use temperature is usually not more than 120 DEG C are crossed, after the temperature, thin polymer film easily occurs melt and collapses, made so as to cause inside battery both positive and negative polarity to contact Into short circuit, catastrophic result is further may result in.
With lithium ion battery industrial expansion, battery volume is less and less, energy and power density more and more higher, and this is just It is required that the membrane for polymer material of composition battery has more preferable heat resistance.Compared with polyolefin based materials, polyester material is same With excellent electrical insulating property, electrolyte resistance corrosivity and electrochemical stability, additionally with mechanical property and heat higher Stability.In the prior art, using polyester as lithium battery diaphragm material relevant report, such as Publication No. The patent of invention of CN102969470A, discloses a kind of polyester lithium ion battery diaphragm and preparation method thereof, and it is first by nothing Machine particle filled composite is prepared into polyester masterbatch with polyester (including PEN (PEN))；Again by gained masterbatch with it is many The raw material of permeability polyester film is mixed by metering part, and polyester base film is made by stretch processes；Processed with organic solvent again The polyester base film of gained, makes the inorganic fill particle that the precipitation basement membrane that is separated to occur, to obtain described polyester Li-like ions Battery diaphragm.Using polyester material as matrix, polyester material has mechanical property and dimensional stability higher for the invention；With SiO2、CaCO3Deng as particle filled composite, by adjusting size, shape and its weight percentage of inorganic fill particle, with reality Now to the regulation of the shape and porosity of membranes pores, although gained porous polyester film has tensile strength higher and endurable From the point of view of thorn intensity, but the data be given from its specification, its mechanical performance etc. is preferable not enough；On the other hand, the invention is adopted The method of inorganic filler pore-forming is added to prepare polyester micro-pore septum in polyester resin, and the addition of inorganic filler causes this Just big melt viscosity becomes much larger body viscosity, and this can increase difficulty of processing, causes mixing uneven, and causes gained barrier film product Matter heterogeneity and thus caused pin hole are formed.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of low shrinkage factor, tensile strength and molten broken temperature resistance to height higher Poly- naphthalene ester micro-pore septum of temperature and preparation method thereof.
The poly- naphthalene ester micro-pore septum of high temperature resistant of the present invention, it is made up of following components in percentage by weight：
PEN 35~64.9%, ultra-high molecular weight polyethylene 0~20%, pore former 35~ 44.5%th, antioxidant 0.1~0.5%；Wherein：
The mean molecule quantity of the PEN is 2 × 104~3.5 × 104, fusing point is 250~270 DEG C, Glass transition temperature is 110~130 DEG C, and inherent viscosity is 0.8~1.2dL/g；
The mean molecule quantity of the ultra-high molecular weight polyethylene is 1.5 × 106~2.5 × 106。
The present invention is by choosing the poly- naphthalenedicarboxylic acid with specified molecular weight, glass transition temperature and inherent viscosity parameter Glycol ester resin is assembled with ultra-high molecular weight polyethylene, pore former and antioxidant, make obtained poly- naphthalene ester micropore every The resistance to elevated temperatures and mechanical strength of film are significantly improved, its molten broken temperature >=220 DEG C, and longitudinal percent thermal shrinkage at 150 DEG C≤ 2.0%, longitudinal tensile strength >=170MPa, can at 160~180 DEG C long-term use.
It is 2.5 × 10 preferably from mean molecule quantity in above-mentioned technical proposal4~3.0 × 104, fusing point is 255~265 DEG C, glass transition temperature is 115~125 DEG C, and inherent viscosity is the PEN of 0.85~1.10dL/g, with Further improve the resistance to elevated temperatures of gained barrier film.
In above-mentioned technical proposal, the percentage by weight of each component is preferably：
PEN 40.1~54.8%, ultra-high molecular weight polyethylene 10~15%, pore former 35~ 44.5%th, antioxidant 0.2~0.4%.
In above-mentioned technical proposal, the selection of the pore former is same as the prior art, can be specifically selected from n-hexane, liquid One or more combination in body paraffin, phthalic acid ester and methyl alcohol, preferably atoleine.When the choosing of pore former During the combination being selected as more than above two, the proportioning between them is any proportioning.
In above-mentioned technical proposal, the selection of the antioxidant is same as the prior art, can be specifically selected from three (2,4- bis- Tert-butyl-phenyl) phosphite ester, triphenyl phosphite, the β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid One or more combination in [four β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.When anti- When the selection of oxygen agent is combination more than above two, the proportioning between them is any proportioning.
The present invention also provides the preparation method of the poly- naphthalene ester micro-pore septum of above-mentioned high temperature resistant, comprises the following steps：
1) each component is weighed by formula, it is standby；
2) it is well mixed with antioxidant after taking PEN and ultra-high molecular weight polyethylene drying, is obtained Mixture；
3) gained mixture mixes with pore former, through melting extrusion, slab, biaxial tension, thermal finalization, refrigerating work procedure, system Obtain poly- naphthalene ester oil film；
4) the poly- naphthalene ester oil film extractant of gained processes 10~35s under the conditions of 25~40 DEG C, is dried after taking-up, that is, obtain The poly- naphthalene ester micro-pore septum of described high temperature resistant.
The step of above-mentioned preparation method 2) in, the drying parameter of PEN and ultra-high molecular weight polyethylene It is same as the prior art, 2~6h is dried typically at 120~150 DEG C.In the step, can be using conventional in the prior art Technological means realize that dried PEN and ultra-high molecular weight polyethylene are uniform mixed with antioxidant Close, in the application, preferably they are placed in high speed dispersor disperse to realize their uniform mixing at a high speed, more excellent Choosing is to disperse 0.5~2h at a high speed under the rotating speed of 1000~3000rpm to realize their uniform mixing.
The step of above-mentioned preparation method 3) in, the temperature of the melting extrusion is usually 270~320 DEG C, and slab temperature is led to It is often 35~65 DEG C.Described biaxial tension can be synchro-draw, and draft temperature is 120~140 DEG C, the stretching in each direction Multiplying power is 3~5 times；Can also be step drawing, wherein longitudinal stretching multiplying power is 3~5 times, draft temperature is 120~140 DEG C, Cross directional stretch multiplying power is 2~4 times, and draft temperature is 125~135 DEG C.The temperature of the thermal finalization is 165~195 DEG C, and the time is 8~15s；Cold wind temperature is 10~40 DEG C in the refrigerating work procedure, and the time is 5~10s；
The step of above-mentioned preparation method 4) in, the selection of the extractant is identical with existing technology, can be specifically selected from two One or more combination in chloromethanes, ethanol, dichloroethanes, hexane, preferably dichloromethane.When the choosing of extractant During the combination being selected as more than above two, the proportioning between them is any proportioning.
Compared with prior art, the method have the characteristics that：
1st, by choosing the poly- naphthalenedicarboxylic acid second two with specified molecular weight, glass transition temperature and inherent viscosity parameter Alcohol ester resin is assembled with ultra-high molecular weight polyethylene, pore former and antioxidant, makes obtained poly- naphthalene ester micro-pore septum Resistance to elevated temperatures and mechanical strength are significantly improved, its molten broken temperature >=220 DEG C, longitudinal percent thermal shrinkage≤2.0% at 150 DEG C, Longitudinal tensile strength >=170MPa, can at 160~180 DEG C long-term use.
2nd, preparation method is simple to operation, causes that the mixing of material is more easy to uniformly using liquid pore former, it is to avoid inorganic grain Son is as pore former because mixing inequality causes gained barrier film streaking one and thus caused pin hole to form problem.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, to more fully understand present disclosure, but The present invention is not limited to following examples.
Embodiment 1
1) by PEN, (mean molecule quantity is 2.0 × 104, fusing point is 250 DEG C, glass transition temperature It is 110 DEG C to spend, and inherent viscosity is 0.8dL/g), ultra-high molecular weight polyethylene (mean molecule quantity be 1.5 × 106) at 120 DEG C 6h is dried, it is standby；
2) weigh through step 1) dried PEN 35kg, ultra-high molecular weight polyethylene 20kg with it is anti- Oxidant (triphenyl phosphite) 0.5kg disperses at a high speed 2h in high speed dispersor under 1000rpm, obtain mixture；
3) by step 2) in gained mixture and pore former (atoleine) 44.5kg by double screw extruder at 270 DEG C Lower melting extrusion, slab at 35 DEG C, 3 times of synchro-draw at 120 DEG C, thermal finalization 8S at 165 DEG C is cooled down at 10 DEG C of cold wind temperature 5S, is obtained poly- naphthalene ester oil film；
4) with dichloromethane process step 3 at 25 DEG C) the poly- naphthalene ester oil film 35S of gained, takes out, in 120 DEG C of dryings 30min, prepared thickness is 40 μm of high temperature resistant.
Comparative example 1
Embodiment 1 is repeated, unlike：
Step 2) in, with polyethylene terephthalate (PET), (mean molecule quantity is 2.0 × 104, fusing point is 250 DEG C, glass transition temperature is 70 DEG C, and inherent viscosity is 0.62dL/g) replace the poly- naphthalene ester micro-pore septum dioctyl phthalate ethylene glycol of poly- naphthalene Ester.
It is polyester micro-pore septum that thickness is 40 μm obtained in this comparative example.
Comparative example 2
Embodiment 1 is repeated, unlike：
Step 2) in, with polypropylene (PP), (mean molecule quantity is 8.0 × 104, fusing point is 165 DEG C, glass transition temperature It is -20 DEG C, inherent viscosity is 2.2dL/g) replace PEN；
Step 3) in, the temperature of melting extrusion is changed to 230 DEG C, biaxial tension be changed to 150 DEG C at 3 times of synchro-draw.
It is polypropylene micropore diaphragm that thickness is 40 μm obtained in this comparative example.
Comparative example 3
Embodiment 1 is repeated, unlike：
Step 2) in, with high density polyethylene (HDPE) (HDPE), (mean molecule quantity is 2.5 × 105, fusing point is 135 DEG C, vitrifying Transition temperature is -60 DEG C, and inherent viscosity is 0.55dL/g) replace PEN；
Step 3) in, the temperature of melting extrusion is changed to 200 DEG C, biaxial tension be changed to 110 DEG C at 3 times of synchro-draw, Heat setting process be changed to 165 DEG C at thermal finalization 8s.
It is polyethylene micropore barrier film that thickness is 40 μm obtained in this comparative example.
Comparative example 4
Embodiment 1 is repeated, unlike：
Step 2) in, it is 4.0 × 10 with mean molecule quantity4, fusing point is 275 DEG C, and glass transition temperature is 132 DEG C, special Property viscosity for 1.3dL/g PEN replace embodiment 1 in PEN.
It is poly- naphthalene ester micro-pore septum that thickness is 40 μm obtained in this comparative example.
Comparative example 5
Embodiment 1 is repeated, unlike：
Step 2) in, it is 4.5 × 10 with mean molecule quantity4, fusing point is 278 DEG C, and glass transition temperature is 135 DEG C, special Property viscosity for 1.5dL/g PEN replace embodiment 1 in PEN；Use average mark Son amount is 3.0 × 106Ultra-high molecular weight polyethylene replace embodiment 1 in ultra-high molecular weight polyethylene.
It is poly- naphthalene ester micro-pore septum that thickness is 40 μm obtained in this comparative example.
Comparative example 6
Embodiment 1 is repeated, unlike：
Step 2) in, it is 1.8 × 10 with mean molecule quantity4, fusing point is 245 DEG C, and glass transition temperature is 102 DEG C, special Property viscosity for 0.6dL/g PEN replace embodiment 1 in PEN；Use average mark Son amount is 1.2 × 106Ultra-high molecular weight polyethylene replace embodiment 1 in ultra-high molecular weight polyethylene.
It is poly- naphthalene ester micro-pore septum that thickness is 40 μm obtained in this comparative example.
Embodiment 2
1) by PEN, (mean molecule quantity is 2.3 × 104, fusing point is 255 DEG C, glass transition temperature It is 115 DEG C to spend, and inherent viscosity is 0.85dL/g), ultra-high molecular weight polyethylene (mean molecule quantity be 1.7 × 106) at 125 DEG C 5h is dried, it is standby；
2) will be through step 1) dried PEN 40kg, ultra-high molecular weight polyethylene 16kg and antioxygen Agent (triphenyl phosphite) 0.4kg disperses at a high speed 0.5h in high speed dispersor under 1400rpm, obtain mixture；
3) by step 2) in gained mixture and pore former (atoleine) 43.6kg by double screw extruder at 275 DEG C Lower melting extrusion, slab at 40 DEG C, 4 times of synchro-draw at 125 DEG C, thermal finalization 9s at 170 DEG C is cooled down at 15 DEG C of cold wind temperature 6s, is obtained poly- naphthalene ester oil film；
4) with dichloroethanes process step 3 at 30 DEG C) the poly- naphthalene ester oil film 30s of gained, 25min is dried through 125 DEG C, it is obtained Thickness is 45 μm of the poly- naphthalene ester micro-pore septum of high temperature resistant.
Embodiment 3
1) by PEN, (mean molecule quantity is 2.5 × 104, fusing point is 258 DEG C, glass transition temperature It is 118 DEG C to spend, and inherent viscosity is 0.9dL/g), ultra-high molecular weight polyethylene (mean molecule quantity be 1.9 × 106) at 130 DEG C 4.5h is dried, it is standby；
2) will be through step 1) dried PEN 45kg, ultra-high molecular weight polyethylene 12kg and antioxygen Agent (β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid and [four β-(3,5- di-t-butyl -4- hydroxy benzenes Base) propionic acid] pentaerythritol ester press 6：The combination of 1 mass ratio) 0.35kg disperses at a high speed in high speed dispersor under 1800rpm 1.5h, obtains mixture；
3) by step 2) in gained mixture and pore former (atoleine) 42.65kg by double screw extruder 280 Melting extrusion at DEG C, slab at 45 DEG C, 5 times of longitudinal stretching at 120 DEG C, 4 times of cross directional stretch at 135 DEG C, thermal finalization at 175 DEG C 10s, 7s is cooled down at 20 DEG C of cold wind temperature, and poly- naphthalene ester oil film is obtained；
4) with hexane process step 3 at 35 DEG C) the poly- naphthalene ester oil film 25s of gained, 20min is dried through 130 DEG C, thickness is obtained It is the poly- naphthalene ester micro-pore septum of 30 μm of high temperature resistants.
Embodiment 4
1) by PEN, (mean molecule quantity is 2.75 × 104, fusing point is 260 DEG C, glass transition temperature It is 120 DEG C to spend, and inherent viscosity is 1.0dL/g), ultra-high molecular weight polyethylene (mean molecule quantity be 2.0 × 106) at 135 DEG C 4h is dried, it is standby；
2) will be through step 1) dried PEN 50kg, ultra-high molecular weight polyethylene 10kg and antioxygen Agent (triphenyl phosphite) 0.3kg disperses at a high speed 1h in high speed dispersor under 2000rpm, obtain mixture；
3) by step 2) in gained mixture and pore former (n-hexane) 39.7kg by double screw extruder at 290 DEG C Melting extrusion, slab at 50 DEG C, 5 times of synchro-draw at 130 DEG C, thermal finalization 12s at 180 DEG C cools down 8s at 25 DEG C of cold wind temperature, Poly- naphthalene ester oil film is obtained；
4) ethanol poly- naphthalene ester oil film 20s of process step (3) gained at 40 DEG C is used, 15min is dried through 135 DEG C, thickness is obtained Spend the poly- naphthalene ester micro-pore septum of high temperature resistant for 35 μm.
Embodiment 5
1) by PEN, (mean molecule quantity is 2.8 × 104, fusing point is 262 DEG C, glass transition temperature It is 123 DEG C to spend, and inherent viscosity is 1.05dL/g), ultra-high molecular weight polyethylene (mean molecule quantity be 2.2 × 106) at 140 DEG C 3.5h is dried, it is standby；
2) will be through step 1) dried PEN 55kg, ultra-high molecular weight polyethylene 8kg and antioxygen Agent (β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid) 0.2kg is in high speed dispersor under 2300rpm Dispersion 2h, obtains mixture at a high speed；
3) by step 2) in gained mixture and pore former (phthalic acid ester) 36.8kg existed by double screw extruder Melting extrusion at 300 DEG C, slab at 55 DEG C, 3.5 times of synchro-draw at 135 DEG C, thermal finalization 13s at 185 DEG C, 30 DEG C of cold wind temperature Lower cooling 9s, is obtained poly- naphthalene ester oil film；
4) with dichloromethane and alcohol mixeding liquid, (mass ratio is 1:1) process step 3 at 35 DEG C) the poly- naphthalene ester oil film of gained 15s, 15min is dried through 125 DEG C, and prepared thickness is 25 μm of the poly- naphthalene ester micro-pore septum of high temperature resistant.
Embodiment 6
1) by PEN, (mean molecule quantity is 3.0 × 104, fusing point is 265 DEG C, glass transition temperature It is 125 DEG C to spend, and inherent viscosity is 1.1dL/g), ultra-high molecular weight polyethylene (mean molecule quantity be 2.4 × 106) at 145 DEG C 3h is dried, it is standby；
2) will be through step 1) dried PEN 60kg, ultra-high molecular weight polyethylene 5kg and antioxygen Agent (β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid) 0.15kg 2600rpm in high speed dispersor Lower high speed disperses 1.5h, obtains mixture；
3) by step 2) in gained mixture and pore former (phthalic acid ester) 34.85kg existed by double screw extruder Melting extrusion at 310 DEG C, slab at 60 DEG C, 3 times of longitudinal stretching at 140 DEG C, 2 times of cross directional stretch at 125 DEG C, heat is fixed at 190 DEG C Type 14s, 10s is cooled down at 35 DEG C of cold wind temperature, and poly- naphthalene ester oil film is obtained；
4) with dichloroethanes and alcohol mixeding liquid, (mass ratio is 1:1) process step 3 at 30 DEG C) the poly- naphthalene ester oil film of gained 20s, 25min is dried through 135 DEG C, and prepared thickness is 18 μm of the poly- naphthalene ester micro-pore septum of high temperature resistant.
Embodiment 7
1) by PEN, (mean molecule quantity is 3.5 × 104, fusing point is 270 DEG C, glass transition temperature It is 130 DEG C to spend, and inherent viscosity is 1.2dL/g), ultra-high molecular weight polyethylene (mean molecule quantity be 2.5 × 106) at 150 DEG C 2h is dried, it is standby；
2) will be through step 1) dried PEN 64.9kg and antioxidant (three (2,4- bis- tertiary fourths Base phenyl) phosphite ester) 0.1kg disperses at a high speed 1h in high speed dispersor under 3000rpm, obtain mixture；
3) by step 2) (phthalic acid ester and methyl alcohol press 1 to middle gained mixture with pore former：The combination of 1 mass ratio) 35kg is by double screw extruder melting extrusion at 320 DEG C, slab at 65 DEG C, 4.5 times of synchro-draw at 140 DEG C, at 195 DEG C Thermal finalization 15s, 10s is cooled down at 40 DEG C of cold wind temperature, obtains poly- naphthalene ester oil film；
4) with dichloromethane and hexane mixed liquor, (mass ratio is 1:1) process step 3 at 40 DEG C) the poly- naphthalene ester oil film of gained 10s, 10min is dried through 140 DEG C, and prepared thickness is 20 μm of the poly- naphthalene ester micro-pore septum of high temperature resistant.
To the porosity of barrier film, molten broken temperature, percent thermal shrinkage, air penetrability and drawing obtained in the various embodiments described above and comparative example Stretch the parameters such as intensity to be tested, as a result as described in Table 1：
Table 1：
As shown in Table 1, the present invention is by choosing with specified molecular weight, glass transition temperature and inherent viscosity parameter PEN resin is assembled with ultra-high molecular weight polyethylene, pore former and antioxidant, is made obtained poly- The resistance to elevated temperatures and mechanical strength of naphthalene ester micro-pore septum are improved significantly.

Claims (8)

1. the poly- naphthalene ester micro-pore septum of a kind of high temperature resistant, it is characterised in that：The barrier film is made up of following components in percentage by weight：
It is PEN 35~64.9%, ultra-high molecular weight polyethylene 0~20%, pore former 35~44.5%, anti- Oxidant 0.1~0.5%；Wherein：
The mean molecule quantity of the PEN is 2 × 104~3.5 × 104, fusing point is 250~270 DEG C, glass It is 110~130 DEG C to change transition temperature, and inherent viscosity is 0.8~1.2dL/g；
The mean molecule quantity of the ultra-high molecular weight polyethylene is 1.5 × 106~2.5 × 106。
2. the poly- naphthalene ester micro-pore septum of high temperature resistant according to claim 1, it is characterised in that：The poly- naphthalenedicarboxylic acid ethylene glycol The mean molecule quantity of ester is 2.5 × 104~3.0 × 104, fusing point is 255~265 DEG C, and glass transition temperature is 115~125 DEG C, inherent viscosity is 0.85~1.10dL/g.
3. the poly- naphthalene ester micro-pore septum of high temperature resistant according to claim 1 and 2, it is characterised in that：The weight percent of each component Than for：
PEN 40.1~54.8%, ultra-high molecular weight polyethylene 10~15%, pore former 35~44.5%, Antioxidant 0.2~0.4%.
4. the poly- naphthalene ester micro-pore septum of high temperature resistant according to claim 1 and 2, it is characterised in that：Described pore former is choosing One or more combination from n-hexane, atoleine, phthalic acid ester and methyl alcohol.
5. the poly- naphthalene ester micro-pore septum of high temperature resistant according to claim 1 and 2, it is characterised in that：Described antioxidant is choosing From three (2,4- di-tert-butyl-phenyl) phosphite esters, triphenyl phosphite, β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid is just In octadecanol ester and [four β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester one or more Combination.
6. the preparation method of the poly- naphthalene ester micro-pore septum of high temperature resistant described in claim 1, comprises the following steps：
1) each component is weighed by formula, it is standby；
2) it is well mixed with antioxidant after taking PEN and ultra-high molecular weight polyethylene drying, is mixed Thing；
3) gained mixture mixes with pore former, through melting extrusion, slab, biaxial tension, thermal finalization, refrigerating work procedure, is obtained poly- Naphthalene ester oil film；
4) the poly- naphthalene ester oil film extractant of gained processes 10~35s under the conditions of 25~40 DEG C, is dried after taking-up, that is, obtain described The poly- naphthalene ester micro-pore septum of high temperature resistant.
7. preparation method according to claim 6, it is characterised in that：Step 3) in, described biaxial tension is drawn for synchronous Stretch, draft temperature is 120~140 DEG C, the stretching ratio in each direction is 3~5 times；Or step drawing, wherein longitudinal direction is drawn It is 3~5 times to stretch multiplying power, and draft temperature is 120~140 DEG C, and cross directional stretch multiplying power is 2~4 times, and draft temperature is 125~135 ℃。
8. preparation method according to claim 6, it is characterised in that：Step 4) in, described extractant is selected from dichloro One or more combination in methane, ethanol, dichloroethanes, hexane.
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CN109326761A (en) * 2018-08-10 2019-02-12 泰州衡川新能源材料科技有限公司 For manufacturing the composition of lithium battery diaphragm
CN112490582A (en) * 2020-10-30 2021-03-12 河北金力新能源科技股份有限公司 High-mechanical-strength high-toughness diaphragm and preparation method thereof

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CN101247955A (en) * 2005-08-25 2008-08-20 东燃化学株式会社 Polyethylene multilayer microporous membrane, battery separator using same, and battery
CN202259507U (en) * 2011-08-31 2012-05-30 宁波长阳科技有限公司 Polyester lithium ion battery diaphragm
CN102532645A (en) * 2010-12-17 2012-07-04 合肥杰事杰新材料股份有限公司 Polyethylene-based composite barrier material and preparing method thereof

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CN101247955A (en) * 2005-08-25 2008-08-20 东燃化学株式会社 Polyethylene multilayer microporous membrane, battery separator using same, and battery
CN102532645A (en) * 2010-12-17 2012-07-04 合肥杰事杰新材料股份有限公司 Polyethylene-based composite barrier material and preparing method thereof
CN202259507U (en) * 2011-08-31 2012-05-30 宁波长阳科技有限公司 Polyester lithium ion battery diaphragm

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109326761A (en) * 2018-08-10 2019-02-12 泰州衡川新能源材料科技有限公司 For manufacturing the composition of lithium battery diaphragm
CN112490582A (en) * 2020-10-30 2021-03-12 河北金力新能源科技股份有限公司 High-mechanical-strength high-toughness diaphragm and preparation method thereof

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