CN108192116A - A kind of photo-initiated crosslinking polymerization object isolation film and preparation method thereof - Google Patents
A kind of photo-initiated crosslinking polymerization object isolation film and preparation method thereof Download PDFInfo
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- CN108192116A CN108192116A CN201711474230.1A CN201711474230A CN108192116A CN 108192116 A CN108192116 A CN 108192116A CN 201711474230 A CN201711474230 A CN 201711474230A CN 108192116 A CN108192116 A CN 108192116A
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- H—ELECTRICITY
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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Abstract
The present invention provides a kind of photo-initiated crosslinking polymerization object isolation film and preparation method thereof, the isolation film includes High molecular weight polyethylene, antioxidant, assistant crosslinking agent and the photoinitiator of cross-linked polymeric, and the average molecular weight of the High molecular weight polyethylene is between 10.0 × 104~1000 × 104Between and density between 0.940~0.976g/cm3Between；Weight by the High molecular weight polyethylene is based on 100 parts, the weight of the antioxidant is between 0.1~10 part, and the weight of the assistant crosslinking agent is between 0.1~10 part, and the weight of the photoinitiator is between 0.1~10 part；Wherein, the photo-initiated crosslinking polymerization object isolation film is made up of photo-initiated crosslinking mode.Isolation film thickness produced by the present invention is 5~30 μm, and micropore size is 0.01~0.1 μm, and porosity is 30~60%, and closed pore temperature is 30~60 DEG C with broken film temperature difference, and percent thermal shrinkage is most down to 0.5%.Therefore, the broken film temperature of photo-initiated crosslinking polymerization object isolation film of the present invention with closed pore temperature difference and percent thermal shrinkage has and significantly improves compared with the prior art, and with good intensity, average pore size and pore-size distribution.
Description
Technical field
The present invention relates to battery isolating film field, more particularly to a kind of photo-initiated crosslinking polymerization object isolation film and its preparation
Method.
Background technology
Lithium ion battery is usually mainly by anode, cathode, diaphragm, electrolyte, battery case composition.Lithium ion battery structure
In, diaphragm is one of crucial interior layer assembly.The main function of diaphragm is to separate the positive and negative electrode of battery, is prevented positive and negative
Pole is in direct contact and short-circuit, while electrolyte ion also to be enable to be passed through in battery charge and discharge process, forms electric current,
When battery operating temperature is abnormal raising, the migrating channels of electrolyte ion are closed, cut-out electric current ensures cell safety.By
This directly affects capacity, cycle and the safety of battery as it can be seen that the performance of diaphragm determines the interfacial structure of battery, internal resistance etc.
The characteristics such as performance, the diaphragm haveing excellent performance play an important role the comprehensive performance for improving battery.Presently commercially available lithium ion
Battery diaphragm generally uses polyolefin porous membrane.
The Specifeca tion speeification of battery isolating film includes thickness, porosity, pore size, pore-size distribution, intensity, thermal contraction
Rate, closed pore temperature and broken film temperature etc..In order to reduce the internal resistance of cell, electrode area must be as big as possible, so for diaphragm
Thickness requirement is thin as far as possible.Although battery diaphragm is non-conductive in itself, conductive ion needs to be migrated by diaphragm, this
Diaphragm is required to be needed in itself there are a certain number of holes, i.e. porosity, but porosity is excessively high certainly will to cause diaphragm intensity to drop
It is low, influence battery global reliability.In addition to this, wellability of the electrolyte on diaphragm directly affects the resistance of Ion transfer,
Wellability is better, and ion is smaller by the resistance that diaphragm is migrated, and the internal resistance of cell is also just smaller.In general, in aperture not right and wrong
In the case of often big, pore-size distribution is more uniform, and the wellability of electrolyte is better.Battery component needs during its production and assembly
Diaphragm is drawn, also needs to ensure that diaphragm will not be pierced through, therefore diaphragm is not only needed by electrode material after finishing assembly
Enough tensile strengths also need to certain puncture intensity.Hot receipts can occur under certain heating condition for polymeric barrier films
Contracting, for avoid being heat-shrinked the positive and negative anodes that bring be in direct contact and caused by internal short-circuit, also have one to the percent thermal shrinkage of isolation film
Fixed requirement.Lithium ion battery in exception conditions, as outside line occur short circuit when, since electric current is excessive, inside battery temperature
Degree drastically increases, this just needs diaphragm that can close the migrating channels of conductive ion in time.Therefore, by the micropore of battery isolating film
The temperature that melting is closed occurs and is known as closed pore temperature.When temperature continues raising, isolation film fusing rupture occurs, this fusing is broken
It splits temperature and is known as broken film temperature.Consider from the security standpoint of lithium ion battery, the closed pore temperature and broken film temperature of diaphragm are necessary
There is certain temperature difference, even if to ensure that temperature continues to rise after diaphragm closed pore cut-out electric current, also has sufficient temp to buffer section
Membrane ruptures do not occur.
In order to improve the safety in utilization of lithium ion battery isolation film, most common method is that polyolefin porous membrane is carried out
Ceramic slurry coating process, although coating process can significantly improve the broken film temperature of polyolefin porous membrane, but can not be same
When reduce diaphragm closed pore temperature, and coating process technique requires ceramic slurry very high, whole raw material and process costs
It is relatively high.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of photo-initiated crosslinking polymerization object every
From film and preparation method thereof, for solve the broken film temperature of battery isolating film in the prior art it is small with closed pore temperature difference and every
The problems such as higher from film coating process cost.
In order to achieve the above objects and other related objects, the present invention provides a kind of photo-initiated crosslinking polymerization object isolation film, institute
State High molecular weight polyethylene, antioxidant, assistant crosslinking agent and light that photo-initiated crosslinking polymerization object isolation film includes cross-linked polymeric
Initiator, the average molecular weight of the High molecular weight polyethylene is between 10.0 × 104~1000 × 104Between and density between
0.940~0.976g/cm3Between；
Weight by the High molecular weight polyethylene for based on 100 parts, the weight of the antioxidant between 0.1~10 part it
Between, the weight of the assistant crosslinking agent is between 0.1~10 part, and the weight of the photoinitiator is between 0.1~10 part.
A kind of scheme of optimization as photo-initiated crosslinking polymerization object isolation film of the present invention, the photo-initiated crosslinking polymerization object
The thickness of isolation film between 5~30 μm, micropore size between 0.01~0.1 μm, porosity between 30~60% it
Between.
A kind of scheme of optimization as photo-initiated crosslinking polymerization object isolation film of the present invention, the photo-initiated crosslinking polymerization object
For the closed pore temperature and broken film temperature difference of isolation film between 30~60 DEG C, percent thermal shrinkage is more than or equal to 0.5%.
A kind of scheme of optimization as photo-initiated crosslinking polymerization object isolation film of the present invention, the antioxidant are selected from 4,4-
Thiobis (6- tert-butyl-m-cresols), dibutyl hydroxy toluene, phosphite ester, tert-butylhydroquinone, β-(bis- tertiary fourths of 3,5-
Base -4- hydroxy phenyls) positive ten caprylate of propionic acid, 1,1,3- tri- (- 4 hydroxyl -5- 2-methyl-2-phenylpropanes base of 2- methyl) butane, 2- spy's fourth
The double lauryl of base -6- methylphenols, N, N '-two-betanaphthyl p-phenylenediamine, thio-2 acid, phosphorous acid three (nonyl phenyl) ester,
One or more compositions in triphenyl phosphite.
A kind of scheme of optimization as photo-initiated crosslinking polymerization object isolation film of the present invention, the assistant crosslinking agent are selected from sulfydryl
Benzothiazole, benzothiazole disulfide, N- cyclohexylbenzothiazoles sulfenamide, divinyl oxide base benzothiazole sulfenamide,
Tetramethylthiuram monosulfide, tetramethylthiuram disulfide, zinc dimethyl dithiocarbamate, diethyl-dithio amino
Zinc formate, diphenylguanidine, di-o-tolylguanidine, ethylene thiourea, N, N '-diethyl thiourea, hexa, isopropyl xanthan acid
Zinc, trimethylol-propane trimethacrylate, trimethylolpropane trimethacrylate, cyanuric acid tripropylene, three allyls
One or more compositions in base isocyanuric acid ester.
A kind of scheme of optimization as photo-initiated crosslinking polymerization object isolation film of the present invention, the photoinitiator, which is selected from, rests in peace
Perfume, benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenylethan, α, alpha, alpha-dimethyl oxygroup-α-
Phenyl acetophenone, α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine oxide, double benzene first
Aminosulfonylphenyl phosphine oxide, benzophenone, 2,4 dihydroxyl benzophenone, Michler's keton, thio propoxyl group thioxanthone, isopropyl sulphur
One kind or more in miscellaneous anthrone, diaryl iodonium salt, triaryl salt compounded of iodine, alkyl salt compounded of iodine, isopropylbenzene cyclopentadienyl iron hexafluorophosphate
The composition of kind.
The present invention also provides a kind of preparation method of photo-initiated crosslinking polymerization object isolation film, the preparation method is at least wrapped
It includes：
1) High molecular weight polyethylene, pore former, antioxidant, assistant crosslinking agent and photoinitiator are mixed, and stirred equal
Even formation mixture, wherein, the average molecular weight of the High molecular weight polyethylene is between 10.0 × 104~1000 × 104Between and
Density is between 0.940~0.976g/cm3Between；
2) using twin screw extrusion process, at a certain temperature, make the High molecular weight polyethylene, antioxidant helps friendship
Connection agent and photoinitiator are dissolved in the pore former, are then squeezed out；
3) mixture for squeezing out the step 2) is cast the object that becomes band；
4) extraction removes the pore former in the ribbon, then the ribbon is stretched to form film, and to institute
It states film and carries out reextraction, then cleaned；
5) thermal finalization and winding step are carried out, obtains uncrosslinked isolation film；
6) photo-irradiation treatment is carried out to the uncrosslinked isolation film, obtains photo-initiated crosslinking polymerization object isolation film.
A kind of scheme of optimization of preparation method as photo-initiated crosslinking polymerization object isolation film of the present invention, the step 1)
In, at least one High molecular weight polyethylene, pore former, antioxidant, assistant crosslinking agent and photoinitiator are added in into continuous batching
It is mixed in coppers, and stirs evenly to form mixture with 45~55 revs/min of speed.
A kind of scheme of optimization of preparation method as photo-initiated crosslinking polymerization object isolation film of the present invention, the step 1)
In, the weight by the High molecular weight polyethylene is based on 100 parts, the weight of the pore former is between 100~500 parts.
A kind of scheme of optimization of preparation method as photo-initiated crosslinking polymerization object isolation film of the present invention, the pore former
Selected from crude mineral oils, C6-15Alkane, C8-15Aliphatic carboxylic acid, C8-15Aliphatic carboxylic acid C1-4Alkyl ester, C2-6Halogenated alkane, O-phthalic
Acid esters, trimellitate, adipate ester, sebacate, maleate, benzoic ether, epoxidized vegetable oil, benzsulfamide, phosphoric acid
Three esters, one kind or more in glycol ether, acetylated monoglyceride, citrate, hexamethylene -1,2- dicarboxylic acids dinonyl
The mixture of kind.
A kind of scheme of optimization of preparation method as photo-initiated crosslinking polymerization object isolation film of the present invention, the pore former
40 DEG C of kinematic viscosity between 10~100mm2Between/s, the initial boiling point of the pore former is more than or equal to 110 DEG C.
A kind of scheme of optimization of preparation method as photo-initiated crosslinking polymerization object isolation film of the present invention, the step 2)
In, at a temperature of 170~230 DEG C, make the High molecular weight polyethylene, antioxidant, assistant crosslinking agent and photoinitiator are molten
In pore former described in Xie Yu, then continuously squeezed out with 150~250 revs/min of speed.
A kind of scheme of optimization of preparation method as photo-initiated crosslinking polymerization object isolation film of the present invention, the step 3)
In, the mixture of the step 2) extrusion is cast the step of becoming band object and is included：First, the mixing step 2) squeezed out
Object is continuously entered into a slot die, and the mixture of the extrusion then is expressed into curtain coating cooling by the slot die
Roller is cast the object that becomes band under 70~90 DEG C of temperature condition.
A kind of scheme of optimization of preparation method as photo-initiated crosslinking polymerization object isolation film of the present invention, the step 4)
In, the pore former removed in the ribbon is extracted, then at 115 DEG C~125 DEG C as extract liquor using dichloromethane
Temperature condition under, then the ribbon stretched to form film by biaxial orientation stretching machine, and using dichloromethane to described thin
Film carries out reextraction, is then cleaned using deionized water.
A kind of scheme of optimization of preparation method as photo-initiated crosslinking polymerization object isolation film of the present invention, the step 5)
In, the thermal finalization 15~20 minutes under 115 DEG C~125 DEG C of temperature condition, then by the film with 20~50 ms/min of speed
Degree winding, obtains uncrosslinked isolation film.
A kind of scheme of optimization of preparation method as photo-initiated crosslinking polymerization object isolation film of the present invention, the step 6)
In, it is visible between 400~800nm using ultraviolet light of the wave-length coverage between 250~420nm or wave-length coverage
Light carries out photo-irradiation treatment, 5~60min of light application time, so as to obtain photo-initiated crosslinking polymerization object to the uncrosslinked isolation film
Isolation film.
As described above, photo-initiated crosslinking polymerization object isolation film of the present invention and preparation method thereof, the isolation film includes handing over
Join High molecular weight polyethylene, antioxidant, assistant crosslinking agent and the photoinitiator of polymerization, the High molecular weight polyethylene is averaged
Molecular weight is between 10.0 × 104~1000 × 104Between and density between 0.940~0.976g/cm3Between；By the macromolecule
The weight of weight northylen is 100 parts of meters, and the weight of the antioxidant is between 0.1~10 part, the weight of the assistant crosslinking agent
Amount is between 0.1~10 part, and the weight of the photoinitiator is between 0.1~10 part.Wherein, the photo-initiated crosslinking gathers
Object isolation film is closed to be made up of photo-initiated crosslinking mode.Isolation film thickness produced by the present invention is 5~30 μm, and micropore size is
0.01~0.1 μm, porosity is 30~60%, and closed pore temperature and broken film temperature difference are 30~60 DEG C, percent thermal shrinkage most down to
0.5%.The broken film temperature of photo-initiated crosslinking polymerization object isolation film provided by the invention and closed pore temperature difference and percent thermal shrinkage
With significantly improving, while to have both conventional polymer isolation film good strong for the photo-initiated crosslinking polymerization object isolation film of the present invention
Degree, average pore size and pore-size distribution, so as on the basis of excellent battery performance is ensured, improve the reliability and safety of battery
Property.
Description of the drawings
Fig. 1 is the flow diagram of the preparation method of photo-initiated crosslinking polymerization object isolation film of the present invention.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Please refer to attached drawing.It should be noted that the diagram provided in the present embodiment only illustrates the present invention in a schematic way
Basic conception, component count, shape when only display is with related component in the present invention rather than according to actual implementation in schema then
Shape and size are drawn, and kenel, quantity and the ratio of each component can be a kind of random change during actual implementation, and its component cloth
Office's kenel may also be increasingly complex.
The present invention provides a kind of photo-initiated crosslinking polymerization object isolation film, and the isolation film includes the high molecular weight of cross-linked polymeric
Polyethylene, antioxidant, assistant crosslinking agent and photoinitiator, the average molecular weight of the High molecular weight polyethylene between 10.0 ×
104~1000 × 104Between and density between 0.940~0.976g/cm3Between；
Weight by the High molecular weight polyethylene for based on 100 parts, the weight of the antioxidant between 0.1~10 part it
Between, the weight of the assistant crosslinking agent is between 0.1~10 part, and the weight of the photoinitiator is between 0.1~10 part.
Preferably, the average molecular weight of the High molecular weight polyethylene is between 1.0 × 105~5.0 × 106Between, it is more excellent
Ground, between 1.0 × 105~2.0 × 106Between.
Preferably, the density of the High molecular weight polyethylene is between 0.940~0.966g/cm3, between, more preferably, between
0.950~0.966g/cm3Between.
Preferably, by the weight of the High molecular weight polyethylene for based on 100 parts, the weight of the antioxidant is between 0.2
Between~8 parts, the weight of the assistant crosslinking agent between 0.2~8 part, the weight of the photoinitiator between 0.2~5 part it
Between.
More preferably, by the weight of the High molecular weight polyethylene for based on 100 parts, the weight of the antioxidant is between 0.5
Between~5 parts, the weight of the assistant crosslinking agent between 0.5~5 part, the weight of the photoinitiator between 0.5~3 part it
Between.
It should be noted that the High molecular weight polyethylene can be a kind of independent High molecular weight polyethylene or
The mixture of two or more High molecular weight polyethylene.
The thickness of the photo-initiated crosslinking polymerization object isolation film that the present invention is obtained is between 5~30 μm, micropore hole
Diameter is between 0.01~0.1 μm, and porosity is between 30~60%, and closed pore temperature is with broken film temperature difference between 30~60
Between DEG C, percent thermal shrinkage is more than or equal to 0.5% (i.e. minimum can be down to 0.5%).
As an example, the antioxidant is selected from 4,4- thiobis (6- tert-butyl-m-cresols), dibutyl hydroxy toluene, Asia
Phosphate, tert-butylhydroquinone, β-positive ten caprylate of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, tri- (2- of 1,1,3-
- 4 hydroxyl -5- 2-methyl-2-phenylpropanes base of methyl) butane, 2- tertiary butyl -6- methylphenols, N, N '-two-betanaphthyl p-phenylenediamine, thio two
One or more compositions in propionic acid double lauryl, phosphorous acid three (nonyl phenyl) ester, triphenyl phosphites.
As an example, the assistant crosslinking agent is selected from mercaptobenzothiazoler, benzothiazole disulfide, N- cyclohexylbenzothiazoles
Sulfenamide, divinyl oxide base benzothiazole sulfenamide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, two
Zine dimethyldithiocarbamate, zinc diethyl dithiocarbamate, diphenylguanidine, di-o-tolylguanidine, ethylene thiourea, N,
N '-diethyl thiourea, hexa, zinc isopropyl xanthate, trimethylol-propane trimethacrylate, trihydroxy methyl
One or more compositions in propane triacrylate, cyanuric acid tripropylene, Triallyl isocyanurate.
As an example, the photoinitiator be selected from styrax, benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin isobutyl ether, diphenylethan, α, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone, α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzene
Ketone, α-amine alkyl phenones, aroyl phosphine oxide, bis(benzoylphenyl) phosphine oxide, benzophenone, 2,4- dihydroxy hexichol first
Ketone, Michler's keton, thio propoxyl group thioxanthone, isopropyl thioxanthone, diaryl iodonium salt, triaryl salt compounded of iodine, alkyl iodide
One or more compositions in salt, isopropylbenzene cyclopentadienyl iron hexafluorophosphate.
It should be noted that the photo-initiated crosslinking polymerization object isolation film is by the High molecular weight polyethylene, pore former, anti-
Oxidant, assistant crosslinking agent and photoinitiator are made up of photo-initiated crosslinking mode.The photo-initiated crosslinking mode is by drawing
Light emitting source is irradiated so as to cause crosslinked mode.The initiation light source can be wave-length coverage in the ultraviolet light of 250~420nm or
The visible ray of 400~800nm of person, 5~60min of light application time, 5~30min of preferred illumination time, most preferably light application time 10~
30min。
As shown in Figure 1, the present invention also provides a kind of preparation method of photo-initiated crosslinking polymerization object isolation film, the system is utilized
Preparation Method, can prepare above-mentioned isolation film, and the preparation method includes at least：
S1 mixes at least one High molecular weight polyethylene, pore former, antioxidant, assistant crosslinking agent and photoinitiator,
And stir evenly and to form mixture, wherein, the average molecular weight of the High molecular weight polyethylene is between 10.0 × 104~1000 ×
104Between and density between 0.940~0.976g/cm3Between；
S2 using twin screw extrusion process, at a certain temperature, makes the High molecular weight polyethylene, antioxidant helps friendship
Connection agent and photoinitiator are dissolved in the pore former, are then squeezed out；
S3, the mixture that the step S2 is squeezed out are cast the object that becomes band；
S4, extraction removes the pore former in the ribbon, then the ribbon is stretched to form film, and to institute
It states film and carries out reextraction, then cleaned；
S5 carries out thermal finalization and winding step, obtains uncrosslinked isolation film；
S6 carries out photo-irradiation treatment to the uncrosslinked isolation film, obtains photo-initiated crosslinking polymerization object isolation film.
As an example, in the step S1, by least one High molecular weight polyethylene, pore former, antioxidant, crosslinking is helped
Agent and photoinitiator, which are added in continuous batching coppers, to be mixed, and stir evenly to be formed with 45~55 revs/min of speed
Mixture.
It is the pore former based on 100 parts by the weight of the High molecular weight polyethylene as an example, in the step S1
Weight between 100~500 parts.Preferably, the weight of the pore former is between 200~500 parts, more preferably, institute
The weight of pore former is stated between 200~400 parts.
As an example, the pore former is selected from crude mineral oils, C6-15Alkane, C8-15Aliphatic carboxylic acid, C8-15Aliphatic carboxylic acid
C1-4Alkyl ester, C2-6Halogenated alkane, phthalic acid ester, trimellitate, adipate ester, sebacate, maleate, benzoic acid
Ester, epoxidized vegetable oil, benzsulfamide, phosphotriester, glycol ether, acetylated monoglyceride, citrate, hexamethylene -1,
One or more mixtures in 2- dicarboxylic acids dinonyls.
As an example, 40 DEG C of kinematic viscosity of the pore former are between 10~100mm2Between/s, at the beginning of the pore former
It evaporates and is a little more than or equal to 110 DEG C.
Preferably, 40 DEG C of kinematic viscosity of the pore former are between 20~80mm2Between/s.More preferably, the pore former
40 DEG C of kinematic viscosity between 30~70mm2Between/s.
As an example, in the step S2, at a temperature of 170~230 DEG C, make the High molecular weight polyethylene, antioxygen
Agent, assistant crosslinking agent and photoinitiator are dissolved in the pore former, are then continuously squeezed with 150~250 revs/min of speed
Go out.
As an example, in the step S3, the mixture of step S2 extrusions is cast the step of becoming band object and is included：
First, the step S2 mixtures squeezed out are continuously entered into a slot die, then by the slot die by institute
The mixture for stating extrusion is expressed into curtain coating chill roll, and the object that becomes band is cast under 70~90 DEG C of temperature condition.
As an example, in the step S4, removed in the ribbon as extract liquor to extract using dichloromethane
The pore former, then stretch to be formed through biaxial orientation stretching machine under 115 DEG C~125 DEG C of temperature condition, then by the ribbon
Film, and reextraction is carried out to the film using dichloromethane, then cleaned using deionized water.Need what is illustrated
It is that after extraction removes the pore former in the ribbon, hole is formed in ribbon.
As an example, in the step S5, the thermal finalization 15~20 minutes under 115 DEG C~125 DEG C of temperature condition, then
The film with 20~50 ms/min of speed is wound, obtains uncrosslinked isolation film.
As an example, in the step S6, using ultraviolet light or wavelength of the wave-length coverage between 250~420nm
Visible ray of the range between 400~800nm carries out the uncrosslinked isolation film photo-irradiation treatment, and light application time 5~
60min, so as to obtain photo-initiated crosslinking polymerization object isolation film.
Battery isolating film provided by the invention can be used for lithium ion battery, especially power lithium-ion battery.
Photo-initiated crosslinking polymerization object isolation film further illustrated the present invention with reference to embodiments and preparation method thereof,
In, the parameter in embodiment table is measured by following method.
1st, thickness
Using Marl, Germany THICKNESS GAUGE FOR THE MEASUREMENT OF THIN FOILS 1216 according to the measure side of GB/T6672-2001 plastic films and sheet thickness
Method measures.
2nd, resistance
It is measured on two points of the isolation film at a distance of 10cm using multimeter, the result used is in different measurement points 10
The average value of secondary measure.
3rd, transmitance
Using Gurley permeating degree testers 4110 according to GB/T1037 plastic films and sheet material water vapor permeability experiment side
Method is measured.
4th, porosity
Water instrument is automatically pressed to measure using PMI AAQ-3K-A-1.
5th, aperture
Water instrument is automatically pressed to measure using PMI AAQ-3K-A-1.
6th, puncture intensity
It is measured using the Shanghai skill QJ210A universal testing machines that incline according to 2679.7 cardboard Punctured Strengths of GB/T.
7th, tensile strength
Inclined stretching standard testing of the skill QJ210A universal testing machines according to ASTM d882-2002 plastic tabs using Shanghai
Method is measured.
8th, shrinking percentage
The distance between the 2 points L on measuring diaphragm under room temperature (23 DEG C) experimental enviroment0, sample is positioned over 120 DEG C ± 1
Stainless steel in DEG C baking oven adds, and is taken out after keeping the temperature 1h, when diaphragm is cooled to cold test environment, on measuring diaphragm 2 points it
Between distance L1, shrinking percentage S calculates as follows：S=(L0-L1)/L0× 100%.
Embodiment 1
It is 0.957g/cm by 100 grams of density3, average molecular weight is 5.0 × 105High molecular weight polyethylene, 0.5 gram of antioxygen
Agent β-positive ten caprylate of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 0.5 gram of photoinitiator benzophenone, 0.5 gram is helped
Crosslinking agent Triallyl isocyanurate, 300 grams of 40 DEG C of kinematic viscosity are 50mm2The mineral oil (i.e. pore former) of/s adds in continuous
In dispensing coppers, stirred with 50 revs/min of speed, raw material is uniformly mixed.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, the High molecular weight polyethylene is anti-oxidant
Continuous-dissolution is in mineral oil in double screw extruder for agent, photoinitiator and assistant crosslinking agent, then by double screw extruder with 200
Rev/min speed continuously squeeze out, mixture is continuously entered in slot die, mixture by slot die be expressed into curtain coating it is cold
But roller is cast into ribbon under the conditions of 80 DEG C.
Obtained ribbon is placed in the extraction tank containing dichloromethane and is extracted, to remove the ore deposit in ribbon
Object oil.Biaxial orientation stretching machine will be continuously introduced under the conditions of 120 DEG C by the ribbon of extraction later and be drawn into film, then with two
Chloromethanes carries out reextraction to gained thin-film material, and gained film is cleaned with deionized water.The thermal finalization 15 under the conditions of 120 DEG C
Minute, film with 20 ms/min of speed is wound, obtains uncrosslinked battery isolating film.Selection is with 250~420nm of wave-length coverage
Ultraviolet light be irradiated processing to uncrosslinked isolation film, irradiation time is respectively 10min, 15min, 20min, 30min, most
A kind of isolation film containing cross-linked polymer is obtained eventually, and specific performance parameter is as shown in table 1 by test：
Table 1
Embodiment 2
It is 0.957g/cm by 100 grams of density3, average molecular weight is 5.0 × 105High molecular weight polyethylene, 0.5 gram of antioxygen
Agent β-positive ten caprylate of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 1.0 grams of photoinitiator benzophenone, 0.5 gram is helped
Crosslinking agent Triallyl isocyanurate, 300 grams of 40 DEG C of kinematic viscosity are 50mm2The mineral oil of/s adds in continuous batching coppers
In, it is stirred with 50 revs/min of speed, raw material is uniformly mixed.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, the High molecular weight polyethylene is anti-oxidant
Continuous-dissolution is in mineral oil in double screw extruder for agent, photoinitiator and assistant crosslinking agent, then by double screw extruder with 200
Rev/min speed continuously squeeze out, mixture is continuously entered in slot die, mixture by slot die be expressed into curtain coating it is cold
But roller is cast into ribbon under the conditions of 80 DEG C.
Obtained ribbon is placed in the extraction tank containing dichloromethane and is extracted, to remove the ore deposit in ribbon
Object oil.Biaxial orientation stretching machine will be continuously introduced under the conditions of 120 DEG C by the ribbon of extraction later and be drawn into film, then with two
Chloromethanes carries out reextraction to gained thin-film material, and gained film is cleaned with deionized water.The thermal finalization 15 under the conditions of 120 DEG C
Minute, film with 20 ms/min of speed is wound, obtains uncrosslinked battery isolating film.Selection is with 250~420nm of wave-length coverage
Ultraviolet light processing is irradiated to uncrosslinked isolation film, irradiation time 30min finally obtains one kind and contains cross-linked polymer
Isolation film, specific performance parameter is as shown in table 2 by test：
Table 2
Embodiment 3
It is 0.957g/cm by 100 grams of density3, average molecular weight is 5.0 × 105High molecular weight polyethylene, 0.5 gram of antioxygen
Agent β-positive ten caprylate of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 0.5 gram of photoinitiator benzophenone, 1.0 grams are helped
Crosslinking agent Triallyl isocyanurate, 300 grams of 40 DEG C of kinematic viscosity are 50mm2The mineral oil of/s adds in continuous batching coppers
In, it is stirred with 50 revs/min of speed, raw material is uniformly mixed.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, the High molecular weight polyethylene is anti-oxidant
Continuous-dissolution is in mineral oil in double screw extruder for agent, photoinitiator and assistant crosslinking agent, then by double screw extruder with 200
Rev/min speed continuously squeeze out, mixture is continuously entered in slot die, mixture by slot die be expressed into curtain coating it is cold
But roller is cast into ribbon under the conditions of 80 DEG C.
Obtained ribbon is placed in the extraction tank containing dichloromethane and is extracted, to remove the ore deposit in ribbon
Object oil.Biaxial orientation stretching machine will be continuously introduced under the conditions of 120 DEG C by the ribbon of extraction later and be drawn into film, then with two
Chloromethanes carries out reextraction to gained thin-film material, and gained film is cleaned with deionized water.The thermal finalization 15 under the conditions of 120 DEG C
Minute, film with 20 ms/min of speed is wound, obtains uncrosslinked battery isolating film.Selection is with 250~420nm of wave-length coverage
Ultraviolet light processing is irradiated to uncrosslinked isolation film, irradiation time 30min finally obtains one kind and contains cross-linked polymer
Isolation film, specific performance parameter is as shown in table 3 by test：
Table 3
Embodiment 4
It is 0.957g/cm by 100 grams of density3, average molecular weight is 5.0 × 105High molecular weight polyethylene, 0.5 gram of antioxygen
Agent β-positive ten caprylate of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 0.5 gram of photoinitiator diphenylethan, 0.5 gram
Assistant crosslinking agent Triallyl isocyanurate, 300 grams of 40 DEG C of kinematic viscosity are 50mm2The mineral oil of/s adds in continuous batching charging
In kettle, stirred with 50 revs/min of speed, raw material is uniformly mixed.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, the High molecular weight polyethylene is anti-oxidant
Continuous-dissolution is in mineral oil in double screw extruder for agent, photoinitiator and assistant crosslinking agent, then by double screw extruder with 200
Rev/min speed continuously squeeze out, mixture is continuously entered in slot die, mixture by slot die be expressed into curtain coating it is cold
But roller is cast into ribbon under the conditions of 80 DEG C.
Obtained ribbon is placed in the extraction tank containing dichloromethane and is extracted, to remove the ore deposit in ribbon
Object oil.Biaxial orientation stretching machine will be continuously introduced under the conditions of 120 DEG C by the ribbon of extraction later and be drawn into film, then with two
Chloromethanes carries out reextraction to gained thin-film material, and gained film is cleaned with deionized water.The thermal finalization 15 under the conditions of 120 DEG C
Minute, film with 20 ms/min of speed is wound, obtains uncrosslinked battery isolating film.Selection is with 250~420nm of wave-length coverage
Ultraviolet light processing is irradiated to uncrosslinked isolation film, irradiation time 30min finally obtains one kind and contains cross-linked polymer
Isolation film, specific performance parameter is as shown in table 4 by test：
Table 4
Embodiment 5
It is 0.957g/cm by 100 grams of density3, average molecular weight is 5.0 × 105High molecular weight polyethylene, 0.5 gram of antioxygen
Agent β-positive ten caprylate of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 0.5 gram of photoinitiator diphenylethan, 0.5 gram
Assistant crosslinking agent cyanuric acid tripropylene, 300 grams of 40 DEG C of kinematic viscosity are 50mm2The mineral oil of/s adds in continuous batching coppers
In, it is stirred with 50 revs/min of speed, raw material is uniformly mixed.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, the High molecular weight polyethylene is anti-oxidant
Continuous-dissolution is in mineral oil in double screw extruder for agent, photoinitiator and assistant crosslinking agent, then by double screw extruder with 200
Rev/min speed continuously squeeze out, mixture is continuously entered in slot die, mixture by slot die be expressed into curtain coating it is cold
But roller is cast into ribbon under the conditions of 80 DEG C.
Obtained ribbon is placed in the extraction tank containing dichloromethane and is extracted, to remove the ore deposit in ribbon
Object oil.Biaxial orientation stretching machine will be continuously introduced under the conditions of 120 DEG C by the ribbon of extraction later and be drawn into film, then with two
Chloromethanes carries out reextraction to gained thin-film material, and gained film is cleaned with deionized water.The thermal finalization 15 under the conditions of 120 DEG C
Minute, film with 20 ms/min of speed is wound, obtains uncrosslinked battery isolating film.Selection is with 250~420nm of wave-length coverage
Ultraviolet light processing is irradiated to uncrosslinked isolation film, irradiation time 30min finally obtains one kind and contains cross-linked polymer
Isolation film, specific performance parameter is as shown in table 5 by test：
Table 5
Comparative example 1
It is 0.957g/cm by 100 grams of density3, average molecular weight is 5.0 × 105High molecular weight polyethylene, 0.5 gram of antioxygen
Agent β-positive ten caprylate of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, 300 grams of 40 DEG C of kinematic viscosity are 50mm2/ s's
Mineral oil is added in continuous batching coppers, is stirred with 50 revs/min of speed, raw material is uniformly mixed.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, the High molecular weight polyethylene is anti-oxidant
Agent, continuous-dissolution is continuously squeezed in mineral oil, then by double screw extruder with 200 revs/min of speed in double screw extruder
Go out, mixture is continuously entered in slot die, and mixture is expressed into curtain coating chill roll by slot die, under the conditions of 80 DEG C
It is cast into ribbon.
Obtained ribbon is placed in the extraction tank containing dichloromethane and is extracted, to remove the ore deposit in ribbon
Object oil.Biaxial orientation stretching machine will be continuously introduced under the conditions of 120 DEG C by the ribbon of extraction later and be drawn into film, then with two
Chloromethanes carries out reextraction to gained thin-film material, and gained film is cleaned with deionized water.The thermal finalization 15 under the conditions of 120 DEG C
Minute, film with 20 ms/min of speed is wound, obtains uncrosslinked battery isolating film.Its specific performance parameter is by testing such as
Shown in table 6：
Table 6
The raw material of the photo-initiated crosslinking polymerization object isolation film of different formulations, obtained it can be seen from more than experimental result
Photo-initiated crosslinking polymerization object isolation film broken film temperature and closed pore temperature between temperature difference by it is uncrosslinked before when 15 DEG C carry
To 30~60 DEG C, the percent thermal shrinkage after being crosslinked using suitable proportioning is also significantly decreased height, it is minimum can be extremely
0.5%, the safety and reliability of isolation film is significantly promoted.Further comparison is it is also found that take different ratios of raw materials
Obtained diaphragm heat resistance is crosslinked to improve significantly.
The present invention technology contents and technical characterstic have revealed that as above, photo-initiated crosslinking polymerization object according to the present invention every
Component from film is not limited to the different materials mentioned by the present invention, does not also limit several formulas mentioned by the present invention,
Other materials and formula with similar characteristics are also covered by the present invention.However those skilled in the art is still potentially based on
The present invention announcement and make various substitutions and modifications without departing substantially from spirit of the present invention.Therefore, protection scope of the present invention should not
It is limited to the revealed content of embodiment, and the various substitutions and modifications without departing substantially from the present invention should be included, and will for appended right
Book is asked to be covered.
Claims (17)
1. a kind of photo-initiated crosslinking polymerization object isolation film, which is characterized in that the isolation film includes the high molecular weight of cross-linked polymeric
Polyethylene, antioxidant, assistant crosslinking agent and photoinitiator, the average molecular weight of the High molecular weight polyethylene between 10.0 ×
104~1000 × 104Between and density between 0.940~0.976g/cm3Between；
Weight by the High molecular weight polyethylene for based on 100 parts, the weight of the antioxidant between 0.1~10 part,
The weight of the assistant crosslinking agent is between 0.1~10 part, and the weight of the photoinitiator is between 0.1~10 part.
2. photo-initiated crosslinking polymerization object isolation film according to claim 1, it is characterised in that：The photo-initiated crosslinking polymerization
The thickness of object isolation film is between 5~30 μm, and micropore size is between 0.01~0.1 μm, and porosity is between 30~60%
Between.
3. photo-initiated crosslinking polymerization object isolation film according to claim 1, it is characterised in that：The photo-initiated crosslinking polymerization
For the closed pore temperature and broken film temperature difference of object isolation film between 30~60 DEG C, percent thermal shrinkage is more than or equal to 0.5%.
4. photo-initiated crosslinking polymerization object isolation film according to claim 1, it is characterised in that：The antioxidant is selected from 4,
4- thiobis (6- tert-butyl-m-cresols), dibutyl hydroxy toluene, phosphite ester, tert-butylhydroquinone, β-(bis- tertiary fourths of 3,5-
Base -4- hydroxy phenyls) positive ten caprylate of propionic acid, 1,1,3- tri- (- 4 hydroxyl -5- 2-methyl-2-phenylpropanes base of 2- methyl) butane, 2- spy's fourth
The double lauryl of base -6- methylphenols, N, N '-two-betanaphthyl p-phenylenediamine, thio-2 acid, phosphorous acid three (nonyl phenyl) ester,
One or more compositions in triphenyl phosphite.
5. photo-initiated crosslinking polymerization object isolation film according to claim 1, it is characterised in that：The assistant crosslinking agent is selected from mercapto
Base benzothiazole, benzothiazole disulfide, N- cyclohexylbenzothiazoles sulfenamide, divinyl oxide base benzothiazole time sulphonyl
Amine, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, zinc dimethyl dithiocarbamate, diethyl-dithio
Carbaminate, diphenylguanidine, di-o-tolylguanidine, ethylene thiourea, N, N '-diethyl thiourea, hexa, isopropyl are yellow
Ortho acid zinc, trimethylol-propane trimethacrylate, trimethylolpropane trimethacrylate, cyanuric acid tripropylene, three
One or more compositions in allyl iso cyanurate.
6. photo-initiated crosslinking polymerization object isolation film according to claim 1, it is characterised in that：The photoinitiator is selected from peace
Breath perfume, benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenylethan, α, alpha, alpha-dimethyl oxygroup-
α-phenyl acetophenone, α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine oxide, double benzene
Fonnylphenyl phosphine oxide, benzophenone, 2,4 dihydroxyl benzophenone, Michler's keton, thio propoxyl group thioxanthone, isopropyl
Thioxanthone, diaryl iodonium salt, triaryl salt compounded of iodine, alkyl salt compounded of iodine, one kind in isopropylbenzene cyclopentadienyl iron hexafluorophosphate or
A variety of compositions.
7. a kind of preparation method of the photo-initiated crosslinking polymerization object isolation film as described in any one of claim 1~6, feature exist
In the preparation method includes at least：
1) High molecular weight polyethylene, pore former, antioxidant, assistant crosslinking agent and photoinitiator are mixed, and stirs evenly shape
Resulting mixture, wherein, the average molecular weight of the High molecular weight polyethylene is between 10.0 × 104~1000 × 104Between and density
Between 0.940~0.976g/cm3Between；
2) using twin screw extrusion process, at a certain temperature, make the High molecular weight polyethylene, antioxidant, assistant crosslinking agent
And photoinitiator is dissolved in the pore former, is then squeezed out；
3) mixture for squeezing out the step 2) is cast the object that becomes band；
4) extraction removes the pore former in the ribbon, then the ribbon is stretched to form film, and to described thin
Film carries out reextraction, is then cleaned；
5) thermal finalization and winding step are carried out, obtains uncrosslinked isolation film；
6) photo-irradiation treatment is carried out to the uncrosslinked isolation film, obtains photo-initiated crosslinking polymerization object isolation film.
8. the preparation method of photo-initiated crosslinking polymerization object isolation film according to claim 7, it is characterised in that：The step
1) in, the addition of at least one High molecular weight polyethylene, pore former, antioxidant, assistant crosslinking agent and photoinitiator is continuously matched
It is mixed, and stir evenly to form mixture with 45~55 revs/min of speed in material coppers.
9. the preparation method of photo-initiated crosslinking polymerization object isolation film according to claim 7, it is characterised in that：The step
1) in, the weight by the High molecular weight polyethylene is based on 100 parts, the weight of the pore former is between 100~500 parts.
10. the preparation method of photo-initiated crosslinking polymerization object isolation film according to claim 7, it is characterised in that：It is described into
Hole agent is selected from crude mineral oils, C6-15Alkane, C8-15Aliphatic carboxylic acid, C8-15Aliphatic carboxylic acid C1-4Alkyl ester, C2-6Halogenated alkane, adjacent benzene
Dicarboxylic acid esters, trimellitate, adipate ester, sebacate, maleate, benzoic ether, epoxidized vegetable oil, benzsulfamide,
Phosphotriester, one kind in glycol ether, acetylated monoglyceride, citrate, hexamethylene -1,2- dicarboxylic acids dinonyl
Or a variety of mixture.
11. the preparation method of photo-initiated crosslinking polymerization object isolation film according to claim 7, it is characterised in that：It is described into
40 DEG C of kinematic viscosity of hole agent are between 10~100mm2Between/s, the initial boiling point of the pore former is more than or equal to 110 DEG C.
12. the preparation method of photo-initiated crosslinking polymerization object isolation film according to claim 7, it is characterised in that：The step
It is rapid 2) in, at a temperature of 170~230 DEG C, make the High molecular weight polyethylene, antioxidant, assistant crosslinking agent and light-initiated
Agent is dissolved in the pore former, is then continuously squeezed out with 150~250 revs/min of speed.
13. the preparation method of photo-initiated crosslinking polymerization object isolation film according to claim 7, it is characterised in that：The step
It is rapid 3) in, by the step 2) squeeze out mixture curtain coating become band object the step of include：First, the step 2) is squeezed out
Mixture is continuously entered into a slot die, and the mixture of the extrusion then is expressed into curtain coating by the slot die
Chill roll is cast the object that becomes band under 70~90 DEG C of temperature condition.
14. the preparation method of photo-initiated crosslinking polymerization object isolation film according to claim 7, it is characterised in that：The step
It is rapid 4) in, the pore former removed in the ribbon is extracted as extract liquor using dichloromethane, then 115 DEG C~
Under 125 DEG C of temperature condition, the ribbon is stretched to form film by biaxial orientation stretching machine, and using dichloromethane to described
Film carries out reextraction, is then cleaned using deionized water.
15. the preparation method of photo-initiated crosslinking polymerization object isolation film according to claim 7, it is characterised in that：The step
It is rapid 5) in, the thermal finalization 15~20 minutes under 115 DEG C~125 DEG C of temperature condition, then by the film with 20~50 ms/min
Speed winding, obtain uncrosslinked isolation film.
16. the preparation method of photo-initiated crosslinking polymerization object isolation film according to claim 7, it is characterised in that：The step
It is rapid 6) in, using ultraviolet light of the wave-length coverage between 250~420nm or wave-length coverage between 400~800nm
Visible ray carries out photo-irradiation treatment to the uncrosslinked isolation film, and 5~60min of light application time gathers so as to obtain photo-initiated crosslinking
Close object isolation film.
17. a kind of application of photo-initiated crosslinking polymerization object isolation film in the battery as described in any one of claim 1~6.
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| WO2019129217A1 (en) * | 2017-12-29 | 2019-07-04 | Shanghai Energy New Materials Technology Co., Ltd. | Cross-linked polymer separators for electrochemical devices and preparation methods thereof |
| CN115051106A (en) * | 2018-10-11 | 2022-09-13 | 旭化成株式会社 | Lithium ion battery using cross-linked separator |
| CN109244333A (en) * | 2018-10-16 | 2019-01-18 | 上海恩捷新材料科技有限公司 | A kind of crosslinking lithium ion battery separator and preparation method thereof |
| CN109244333B (en) * | 2018-10-16 | 2021-07-27 | 上海恩捷新材料科技有限公司 | Cross-linked lithium ion battery diaphragm and preparation method thereof |
| JP2020182930A (en) * | 2019-04-26 | 2020-11-12 | ダブリュー−スコープ コリア カンパニー，リミテッド | Crosslinked polyolefin separation membrane and its manufacturing method |
| CN111864159A (en) * | 2019-04-26 | 2020-10-30 | 韩国沃思可福有限公司 | Cross-linked polyolefin isolating membrane and preparation method thereof |
| EP3731305A1 (en) * | 2019-04-26 | 2020-10-28 | W-Scope Korea Co., Ltd. | Crosslinked polyolefin separator and method of manufacturing the same |
| US11557814B2 (en) | 2019-04-26 | 2023-01-17 | W-Scope Korea Co., Ltd. | Crosslinked polyolefin separator and method of manufacturing the same |
| JP7398728B2 (en) | 2019-04-26 | 2023-12-15 | ダブリュー－スコープ コリア カンパニー，リミテッド | Crosslinked polyolefin separation membrane and its manufacturing method |
| CN110305239A (en) * | 2019-05-17 | 2019-10-08 | 华中科技大学 | A kind of photoresist of high strength |
| CN111211275A (en) * | 2020-01-14 | 2020-05-29 | 江苏厚生新能源科技有限公司 | Partially crosslinked composite polyethylene lithium battery diaphragm and preparation method thereof |
| CN114094284A (en) * | 2021-11-16 | 2022-02-25 | 无锡恩捷新材料科技有限公司 | Novel cross-linked diaphragm and preparation method thereof, battery and electronic equipment |
| WO2023087735A1 (en) * | 2021-11-16 | 2023-05-25 | 苏州捷力新能源材料有限公司 | Novel cross-linked separator and preparation method thereof, battery, and electronic device |
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| CN108192116B (en) | 2021-03-23 |
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