CN106486632A - A kind of battery isolating film and preparation method thereof - Google Patents
A kind of battery isolating film and preparation method thereof Download PDFInfo
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- CN106486632A CN106486632A CN201611052346.1A CN201611052346A CN106486632A CN 106486632 A CN106486632 A CN 106486632A CN 201611052346 A CN201611052346 A CN 201611052346A CN 106486632 A CN106486632 A CN 106486632A
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of battery isolating film and preparation method thereof.By the raw material extrusion of mixing, cooling shaping, extraction, stretching and thermal finalization are obtained battery isolating film, it is 1.0 × 10 that described raw material includes molecular weight to methods described6‑10.0×106Ultra-high molecular weight polyethylene, density be 0.940 0.976g/cm3In the range of high density polyethylene (HDPE), antioxidant and pore former, methods described includes crosslinking.
Description
Technical field
The present invention relates to electrochemical field, more particularly, to a kind of preparation method of battery isolating film.
Background technology
Generally mainly by positive pole, negative pole, barrier film, electrolyte, battery case forms lithium ion battery.Lithium ion battery structure
In, barrier film is one of crucial interior layer assembly.The Main Function of barrier film is to separate the positive and negative electrode of battery, prevents positive and negative
Pole directly contact and short-circuit, electrolyte ion also to be made can pass through in battery charge and discharge process simultaneously, formed electric current,
When battery operating temperature occurs abnormal rising, close the migrating channels of electrolyte ion, cut-out electric current ensures cell safety.By
This is visible, and the performance of barrier film determines the interfacial structure of battery, internal resistance etc., directly affects capacity, circulation and the safety of battery
The characteristics such as performance, the barrier film of excellent performance has important effect to the combination property improving battery.Presently commercially available lithium ion
Battery diaphragm typically adopts 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 barrier film
Thickness requirement is thin as far as possible.Although battery diaphragm itself is non-conductive, conductive ion needs to be migrated by barrier film, this
Require that barrier film needs to there is a number of hole in itself, i.e. porosity, but porosity is too high certainly will to lead to barrier film intensity to drop
Low, affect battery global reliability.In addition, wellability on barrier film for the electrolyte directly affects the resistance of ion migration,
Wellability is better, and the resistance that ion is migrated by barrier film is less, and the internal resistance of cell is also less.Generally, 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
Barrier film is drawn, also needs to after finishing assembly ensure that barrier film will not be pierced through by electrode material, therefore barrier film not only needs
Enough tensile strengths also need to certain puncture intensity.Polymeric barrier films can occur heat receipts under certain heating condition
Contracting, for avoiding the both positive and negative polarity directly contact that thermal contraction brings and the internal short-circuit causing, also has one to the percent thermal shrinkage of isolating membrane
Fixed requirement.Lithium ion battery in exception conditions, when such as outside line is short-circuited, because electric current is excessive, inside battery temperature
Degree drastically raises, and this is accomplished by the migrating channels that barrier film can close conductive ion in time.Therefore, by the micropore of battery isolating film
The temperature that melting closure occurs is referred to as closed pore temperature.When temperature continues to raise, there is isolating membrane fusing rupture, will be broken for this fusing
Split temperature and be referred to as broken film temperature.To consider, the closed pore temperature of barrier film and broken film temperature are necessary from the security standpoint of lithium ion battery
There is certain temperature difference, even if to ensure that after diaphragm closed pore cut-out electric current, temperature continues to rise, and also has sufficient temp buffering interval
There are not membrane ruptures.
In order to improve the safety in utilization of lithium ion battery isolating membrane, modal method is that polyolefin porous membrane is carried out
Ceramic size coating process although coating process can significantly improve the broken film temperature of polyolefin porous membrane, but but cannot be with
When reduce diaphragm closed pore temperature, and coating process technique requires very high, overall raw material and process costs for ceramic size
Of a relatively high.
Therefore, this area is in the urgent need to providing one kind to significantly improve broken film temperature and closed pore temperature difference and thermal contraction
Rate, has the good intensity of conventional polymer isolating membrane, average pore size and pore-size distribution concurrently simultaneously, thus excellent cell performance in guarantee
On the basis of energy, improve the reliability of battery and the battery isolating film of safety.
Content of the invention
The present invention is intended to provide a kind of more excellent battery isolating film of performance.
In a first aspect of the present invention, there is provided a kind of preparation method of battery isolating film, methods described is passed through to mix
Raw material extrusion, cooling shaping, extraction, stretching and thermal finalization obtain battery isolating film, methods described includes crosslinking；Described crosslinking
For cross-linking radiation or chemical crosslinking；Assistant crosslinking agent is contained in described raw material.
In another preference, described assistant crosslinking agent is selected from one or more following mixing：Sulfydryl benzo thiophene
Azoles, benzothiazole disulfide, N- cyclohexylbenzothiazole sulfenamide, divinyl oxide base benzothiazole sulfenamide, a sulfuration
Tetra methylthiuram, tetramethylthiuram disulfide, PZ, diethyldithiocar bamic acid
Zinc, diphenylguanidine, di-o-tolylguanidine, ethylene thiourea, N, N '-diethyl thiourea, hexamethylenetetramine, zinc isopropyl xanthate,
Trimethylol-propane trimethacrylate, trimethylolpropane trimethacrylate, cyanuric acid tripropylene and triallyl
Isocyanuric acid ester；More preferably Triallyl isocyanurate.
In another preference, described cross-linking radiation be selected from energetic gamma rays cross-linking radiation, high-energy electron beam irradiation crosslinked,
Or photo-initiated crosslinking；Described irradiation dose scope is 5-1000kGy；It is preferably 10-500kGy；More preferably 50-400kGy；?
It is preferably 100-300kGy；Described energetic gamma rays derive from artificial or natural radioisotope, selected from cobalt (60Co) element,
Caesium (137Cs) element, zinc (65Zn) element, hydrargyrum (203Hg) element, cerium (141Ce) element, antimony (124Sb) element, or iridium
(192Ir) element；Described high-power electron beam is energy range 0.1-10MeV, the electron beam of line scope 1-100mA；More preferably
Energy range 1-10MeV, the electron beam of line scope 1-30mA；Most preferably energy range 2-5MeV, line scope 3-15mA
Electron beam；During described photo-initiated crosslinking, raw material includes light trigger；Described initiation light source is wave-length coverage in 250-420nm
Ultraviolet light or 400-800nm visible ray, light application time 5-60min；Preferred illumination time 5-50min；More preferably illumination
Time 10-40min；Most preferably light application time 20-30min.
In another preference, described light trigger is selected from one or more following mixing：Benzoinum, rest in peace
Fragrant double methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenylethan, α, alpha, alpha-dimethyl epoxide-α-phenyl benzene
Ethyl ketone, α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine oxide, double Benzoylbenzene
Base phosphine oxide, benzophenone, 2,4 dihydroxyl benzophenone, Michler's keton, thio propoxyl group thioxanthone, isopropyl thioxanthone anthracene
Ketone, diaryl group iodized salt, triaryl iodine salt, alkyl iodine salt and isopropylbenzene cyclopentadienyl ferrum hexafluorophosphate.
In another preference, during described chemical crosslinking, described raw material includes peroxide cross-linking agent and/or crosslinked with silicane
Agent.
In another preference, described peroxide cross-linking agent is selected from cumyl peroxide, dual-tert-butyl peroxidating two
The double tert-butyl peroxy base -3,3,5- trimethyl-cyclohexane of cumene, 1,1- or tert butyl isopropyl benzene peroxide；Described silane
Cross-linking agent is selected from methyl triacetoxysilane, MTMS or methyl tributanoximo silane.
In another preference, it is 1.0 × 10 that described raw material includes molecular weight6-10.0×106Superhigh molecular weight polyethylene
Alkene, density are 0.940-0.976g/cm3In the range of high density polyethylene (HDPE), antioxidant, pore former and assistant crosslinking agent；Described former
In material, the weight of ultra-high molecular weight polyethylene and high density polyethylene (HDPE) is than for 1:1-20；More preferably 1:2-10；Most preferably 1:
5-10；
By described ultra-high molecular weight polyethylene and the mixture of high density polyethylene (HDPE) weight be 100 parts based on, containing 500-
The pore former of 2000 weight portions；More preferably 700-1800 weight portion；Most preferably 800-1600 weight portion；
By described ultra-high molecular weight polyethylene and the mixture of high density polyethylene (HDPE) weight be 100 parts based on, containing 0.5-
20 parts of antioxidants；More preferably 1.5-16 weight portion；Most preferably 2-12 weight portion；
By described ultra-high molecular weight polyethylene and the mixture of high density polyethylene (HDPE) weight be 100 parts based on, containing 0.1-
10 parts of assistant crosslinking agents；More preferably 0.5-5 weight portion；Most preferably 0.5-3 weight portion.
In another preference, the weight by described ultra-high molecular weight polyethylene and the mixture of high density polyethylene (HDPE) is
100 parts of meters, containing 0.1-10 part light trigger；More preferably 0.5-5 weight portion；Most preferably 0.5-3 weight portion.
In another preference, the weight by described ultra-high molecular weight polyethylene and the mixture of high density polyethylene (HDPE) is
100 parts of meters, containing 0.1-10 part peroxide cross-linking agent and/or silane crosslinker；More preferably 0.5-5 weight portion；Most preferably
0.5-3 weight portion.
In another preference, the molecular weight of described ultra-high molecular weight polyethylene is 2.0 × 106-8.0×106；More preferably
For 3.5 × 106-5.0×106；The density of described high density polyethylene (HDPE) is 0.940-0.960g/cm3；More preferably 0.950-
0.960g/cm3.
In another preference, described pore former is selected from one or more following mixing：Crude mineral oils,
C6-15Alkane, C8-15Aliphatic carboxylic acid, C8-15Aliphatic carboxylic acid C1-4Alkyl ester and C2-6Halogenated alkane.
In another preference, described antioxidant is selected from one or more following mixing：4,4- thiobiss
(6- tert-butyl-m-cresol), dibenzylatiooluene, phosphite ester, tert-butylhydroquinone, β-(3,5- di-t-butyl -4- hydroxyl
Base phenyl) positive ten caprylates of propanoic acid, 1,1,3- tri- (2- methyl -4 hydroxyl -5- 2-methyl-2-phenylpropane base) butane, 2- tertiary butyl -6- methyl
Phenol, N, the double lauryl of N '-two-betanaphthyl p-phenylenediamine, thio-2 acid, phosphorous acid three (nonyl phenyl) ester and phosphorous acid three
Phenyl ester.
In another preference, described assistant crosslinking agent is selected from one or more following mixing：Sulfydryl benzo thiophene
Azoles, benzothiazole disulfide, N- cyclohexylbenzothiazole sulfenamide, divinyl oxide base benzothiazole sulfenamide, a sulfuration
Tetra methylthiuram, tetramethylthiuram disulfide, PZ, diethyldithiocar bamic acid
Zinc, diphenylguanidine, di-o-tolylguanidine, ethylene thiourea, N, N '-diethyl thiourea, hexamethylenetetramine, zinc isopropyl xanthate,
Trimethylol-propane trimethacrylate, trimethylolpropane trimethacrylate, cyanuric acid tripropylene and triallyl
Isocyanuric acid ester；More preferably Triallyl isocyanurate.
In another preference, described light trigger is selected from one or more following mixing：Benzoinum, rest in peace
Fragrant double methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenylethan, α, alpha, alpha-dimethyl epoxide-α-phenyl benzene
Ethyl ketone, α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine oxide, double Benzoylbenzene
Base phosphine oxide, benzophenone, 2,4 dihydroxyl benzophenone, Michler's keton, thio propoxyl group thioxanthone, isopropyl thioxanthone anthracene
Ketone, diaryl group iodized salt, triaryl iodine salt, alkyl iodine salt and isopropylbenzene cyclopentadienyl ferrum hexafluorophosphate.
In another preference, described peroxide cross-linking agent is selected from cumyl peroxide, dual-tert-butyl peroxidating two
The double tert-butyl peroxy base -3,3,5- trimethyl-cyclohexane of cumene, 1,1- or tert butyl isopropyl benzene peroxide；Described silane
Cross-linking agent is selected from methyl triacetoxysilane, MTMS or methyl tributanoximo silane.
In a second aspect of the present invention, there is provided a kind of preparation method being provided by the present invention as above is obtained
Battery isolating film；The thickness of described isolating membrane is 9-35 μm, and micropore size is 0.3-0.65 μm, and porosity is 40-50%, closed pore
Temperature is 65-90 DEG C with broken film temperature difference, percent thermal shrinkage the most as little as 0.7%.
In a third aspect of the present invention, there is provided a kind of application of the battery diaphragm that present invention as above provides.
Accordingly, the invention provides one kind significantly improves broken film temperature and closed pore temperature difference and percent thermal shrinkage, with
When have the good intensity of conventional polymer isolating membrane, average pore size and pore-size distribution concurrently, thus ensureing excellent battery performance
On the basis of, improve the reliability of battery and the battery isolating film of safety.
Specific embodiment
, through extensively in-depth study discovery, preparing battery isolating film according to crosslinked method can be effective for inventor
Solve the problems, such as that the broken film temperature that current isolating membrane exists is undesirable with closed pore temperature difference difference and percent thermal shrinkage.Further,
Inventor finds that the effect using cross-linking radiation is preferable, in the case of especially employing assistant crosslinking agent in the feed, has imaginary
Less than excellent effect occur.On this basis, complete the present invention.
Preparation method
The preparation method of this area battery isolating film has some conventional steps, such as but not limited to, including raw material mixing, mixes
Compound extruded by double screw extruder after by slot die be expressed into curtain coating chill roll make to become band thing, ribbon extracted
Take, clean acquisition thin film, but the method preparing battery isolating film of the present invention also includes crosslinking unlike the prior art
Step, and in raw material, contain assistant crosslinking agent.Described crosslinking can be cross-linking radiation or chemical crosslinking, preferably spoke
According to crosslinking.Described assistant crosslinking agent can be mercaptobenzothiazoler, benzothiazole disulfide, N- cyclohexylbenzothiazole time sulphonyl
Amine, divinyl oxide base benzothiazole sulfenamide, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, dimethyl two
Zinc thiocarbamate, (DDC)2Zn, diphenylguanidine, di-o-tolylguanidine, ethylene thiourea, N, N '-diethyl
Base thiourea, hexamethylenetetramine, zinc isopropyl xanthate, trimethylol-propane trimethacrylate, trimethylolpropane tris
One or more of acrylate, cyanuric acid tripropylene, and Triallyl isocyanurate compositionss；Preferably three allyls
Base isocyanuric acid ester.
If carrying out cross-linking radiation, being that the thin film of acquisition is carried out thermal finalization, winding by the conventional method of this area, obtaining
Uncrosslinked battery isolating film, then carries out radiation treatment to the uncrosslinked battery isolating film of this acquisition, thus obtaining this
The battery isolating film containing cross linked polymer of bright offer.
Described radiation treatment is selected from energetic gamma rays cross-linking radiation, high-energy electron beam irradiation crosslinking or photo-initiated crosslinking；High
The irradiation dose scope that energy gamma-ray irradiation is crosslinked or high-energy electron beam irradiation is crosslinked is 5-1000kGy；It is preferably 10-
500kGy；More preferably 50-400kGy；Most preferably 100-300kGy.
Described energetic gamma rays derive from artificial or natural radioisotope, selected from cobalt (60Co) element, caesium (137Cs)
Element, zinc (65Zn) element, hydrargyrum (203Hg) element, cerium (141Ce) element, antimony (124Sb) element, or iridium (192Ir) element.
Described high-power electron beam is energy range 0.1-10MeV, the electron beam of line scope 1-100mA；Preferred energy model
Enclose 1-10MeV, the electron beam of line scope 1-30mA；Most preferably energy range 2-5MeV, the electron beam of line scope 3-15mA.
Carry out photo-initiated crosslinking and carry out radiation treatment, in raw material, also contain light trigger；Described light trigger can be
Benzoinum, benzoin dimethylether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenylethan, α, alpha, alpha-dimethyl oxygen
Base-α-phenyl acetophenone, α, α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, aroyl phosphine oxide,
Bis(benzoylphenyl) phosphine oxide, benzophenone, 2,4-DihydroxyBenzophenone, Michler's keton, thio propoxyl group thioxanthone, different
Propyl group thioxanthone, diaryl group iodized salt, triaryl iodine salt, alkyl iodine salt, in isopropylbenzene cyclopentadienyl ferrum hexafluorophosphate
Plant or numerous compositions.Light source is wave-length coverage that what described photo-initiated crosslinking used cause in the ultraviolet light of 250-420nm or
The visible ray of 400-800nm, light application time is 5-60min；The preferred illumination time is 5-50min；More preferably light application time is 10-
40min；Most preferably light application time is 20-30min.
If being chemically crosslinked, in raw material, also contain peroxide cross-linking agent and/or silane crosslinker, conventional by some
Step, such as but not limited to, it is cold that raw material mixing, mixture are expressed into curtain coating by slot die after being extruded by double screw extruder
But roller make to become band thing, ribbon is carried out extract, cleans acquisition thin film, the thin film of acquisition is carried out thermal finalization, winding, obtain
The battery isolating film containing cross linked polymer that the present invention provides.Cross-linking agent used by described peroxide crosslinking can be peroxide
Change diisopropylbenzene (DIPB), dual-tert-butyl dicumyl peroxide, 1,1- double tert-butyl peroxy base -3,3,5- trimethyl-cyclohexanes, tertiary fourth
One of base cumyl peroxide.Cross-linking agent used by described crosslinked with silicane can be methyl triacetoxysilane,
MTMS, one of methyl tributanoximo silane.
Except above-mentioned assistant crosslinking agent for the distinctive cross-linking step of the present invention, light trigger, peroxide cross-linking agent, silicon
Alkane cross-linking agent, the present invention also needs to the raw material of the routine of some formation battery isolating films, such as but not limited to, supra polymer certainly
The mixture of weight northylen and high density polyethylene (HDPE), pore former and antioxidant.
In the preferred embodiment of the present invention, described ultra-high molecular weight polyethylene, its molecular weight is 1.0 × 106-
10.0×106, more preferably 2.0 × 106-8.0×106, most preferably 3.5 × 106-5.0×106.
In the preferred embodiment of the present invention, the density of described high density polyethylene (HDPE) is 0.940-0.976g/
cm3, more preferably 0.940-0.960g/cm3, most preferably 0.950-0.960g/cm3.
In the preferred embodiment of the present invention, the weight of described ultra-high molecular weight polyethylene and high density polyethylene (HDPE)
Than for 1:1-20, more preferably 1:2-10, most preferably 1:5-10.
In the preferred embodiment of the present invention, described pore former can be crude mineral oils, C6-15Alkane, C8-15
Aliphatic carboxylic acid, C8-15Aliphatic carboxylic acid C1-4Alkyl ester and C2-6One or more of halogenated alkane mixture.Gather by super high molecular weight
The weight of the mixture of ethylene and high density polyethylene (HDPE) is 100 parts of meters, and porogen content is 500-2000 weight portion, more preferably
700-1800 weight portion, most preferably 800-1600 weight portion.
In the preferred embodiment of the present invention, described antioxidant can be 4,4- thiobiss (between the 6- tert-butyl group
Cresol), dibenzylatiooluene, phosphite ester, tert-butylhydroquinone, β-(3,5- di-tert-butyl-hydroxy phenyl) propanoic acid
Positive ten caprylates, 1,1,3- tri- (2- methyl -4 hydroxyl -5- 2-methyl-2-phenylpropane base) butane, 2- tertiary butyl -6- methylphenol, N, N ' -
Two-betanaphthyl p-phenylenediamine, the double lauryl of thio-2 acid, phosphorous acid three (nonyl phenyl) ester, in triphenyl phosphite
Plant or numerous compositions.By ultra-high molecular weight polyethylene and the mixture of high density polyethylene (HDPE) weight be 100 parts based on, antioxidant
Content is 0.5-20 weight portion, more preferably 1.5-16 weight portion, most preferably 2-12 weight portion.
In the preferred embodiment of the present invention, by the mixture of ultra-high molecular weight polyethylene and high density polyethylene (HDPE)
Weight be 100 parts meter, assistant crosslinking agent content be 0.1-10 weight portion, more preferably 0.5-5 weight portion, most preferably 0.5-3
Weight portion.
In the preferred embodiment of the present invention, by the mixture of ultra-high molecular weight polyethylene and high density polyethylene (HDPE)
Weight be 100 parts meter, initiator content be 0.1-10 weight portion, more preferably 0.5-5 weight portion, most preferably 0.5-3 weight
Amount part.
In the preferred embodiment of the present invention, by the mixture of ultra-high molecular weight polyethylene and high density polyethylene (HDPE)
Weight be 100 parts of meters, peroxide cross-linking agent and/or crosslinked with silicane agent content are 0.1-10 weight portion, more preferably 0.5-5
Weight portion, most preferably 0.5-3 weight portion.
Battery isolating film
The battery isolating film being obtained by the preparation method that the invention described above provides is that one kind contains crosslinked polymer component
Battery isolating film, thickness be 9-35 μm, micropore size be 0.3-0.65 μm, porosity be 40-50%, closed pore temperature and rupture of membranes
Temperature difference is 65-90 DEG C, percent thermal shrinkage the most as little as 0.7%.
The battery isolating film that the present invention provides can be used for lithium ion battery, especially power lithium-ion battery.
The features described above that the present invention mentions, or the feature that embodiment is mentioned can be in any combination.Disclosed in this case description
All features can be used in combination with any combinations thing form, each feature disclosed in description, can any provide identical,
The alternative characteristics of impartial or similar purpose replace.Therefore removing has special instruction, and disclosed feature is only impartial or similar spy
The general example levied.
Main advantages of the present invention are：
1st, the crosslinked method of first passage of the present invention obtains a kind of battery isolating film, especially lithium ion battery isolating membrane.
2nd, the battery diaphragm that the present invention provides has excellent combination property, such as has relatively low average pore size, uniformly
Pore-size distribution, good porosity and film-strength, the broken film temperature of especially lower closed pore temperature and Geng Gao, lower heat is received
Shrinkage.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip
Part or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise all of percent, ratio, ratio or number are pressed
Weight meter.The unit in percent weight in volume in the present invention is well-known to those skilled in the art, for example, refer to 100
The weight of solute in the solution of milliliter.Unless otherwise defined, all specialties used in literary composition are ripe with this area with scientific words
Practice same meaning familiar to personnel institute.Additionally, any method similar or impartial to described content and material all can be applicable to
In the inventive method.Preferable implementation described in literary composition is only presented a demonstration with material and is used.
Used in following embodiments, raw material is as follows：
Antioxidant is：β-positive ten caprylates of (3,5- di-tert-butyl-hydroxy phenyl) propanoic acid,
Assistant crosslinking agent is：Triallyl isocyanurate,
Light trigger：Benzophenone,
Peroxide cross-linking agent：Cumyl peroxide
Silane crosslinker：Methyl triacetoxysilane
Mineral oil：Crude mineral oils (CAS8020-83-5, purchased from Lanzhou Petrochemical Company)
Embodiment 1
220 grams of density are 0.956g/cm3High density polyethylene (HDPE), 100 gram-molecular weights be 5.0 × 106Supra polymer
Weight northylen, 6.4 grams of antioxidant, 3.2 grams of assistant crosslinking agents, 2200 grams of mineral oil add in continuous batching coppers, with 50 revs/min
Speed stirring, by raw material mix homogeneously.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, described ultra-high molecular weight polyethylene, highly dense
Degree polyethylene, antioxidant and assistant crosslinking agent in double screw extruder continuous-dissolution in mineral oil, then by double screw extruder
Continuously extruded with 200 revs/min of speed, mixture continuously enters in slot die, and mixture is expressed into by slot die
Curtain coating chill roll, is cast into ribbon under the conditions of 80 DEG C.
The ribbon obtaining is inserted in the extraction tank containing dichloromethane and is extracted, in order to remove the ore deposit in ribbon
Thing oil.Under the conditions of 120 DEG C, the ribbon through extraction is continuously introduced into biaxial orientation stretching machine afterwards and is drawn into thin film, then with two
Chloromethanes carry out reextraction to gained thin-film material, and deionized water cleans gained thin film.Thermal finalization 15 under the conditions of 120 DEG C
Minute, thin film is wound with 20 ms/min of speed, obtains uncrosslinked battery isolating film.Select using cobalt (60Co) element as γ
Radiographic source, irradiation dose is respectively 50kGy, 100kGy, 200kGy, 300kGy, carries out radiation treatment to uncrosslinked isolating membrane,
Obtain a kind of isolating membrane containing cross linked polymer eventually, its specific performance parameter is as shown in the table through test：
Embodiment 2
220 grams of density are 0.956g/cm3High density polyethylene (HDPE), 100 gram-molecular weights be 5.0 × 106Supra polymer
Weight northylen, 6.4 grams of antioxidant, 3.2 grams of assistant crosslinking agents, 2200 grams of mineral oil add in continuous batching coppers, with 50 revs/min
Speed stirring, by raw material mix homogeneously.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, described ultra-high molecular weight polyethylene, highly dense
Degree polyethylene, antioxidant and assistant crosslinking agent in double screw extruder continuous-dissolution in mineral oil, then by double screw extruder
Continuously extruded with 200 revs/min of speed, mixture continuously enters in slot die, and mixture is expressed into by slot die
Curtain coating chill roll, is cast into ribbon under the conditions of 80 DEG C.
The ribbon obtaining is inserted in the extraction tank containing dichloromethane and is extracted, in order to remove the ore deposit in ribbon
Thing oil.Under the conditions of 120 DEG C, the ribbon through extraction is continuously introduced into biaxial orientation stretching machine afterwards and is drawn into thin film, then with two
Chloromethanes carry out reextraction to gained thin-film material, and deionized water cleans gained thin film.Thermal finalization 15 under the conditions of 120 DEG C
Minute, thin film is wound with 20 ms/min of speed, obtains uncrosslinked battery isolating film.Select with 5MeV electron accelerator, 8mA
Electric current is respectively 50kGy, 100kGy, 200kGy, 300kGy as irradiation bomb, irradiation dose, carries out spoke to uncrosslinked isolating membrane
According to process, finally give a kind of isolating membrane containing cross linked polymer, its specific performance parameter is as shown in the table through test：
Embodiment 3
220 grams of density are 0.956g/cm3High density polyethylene (HDPE), 100 gram-molecular weights be 5.0 × 106Supra polymer
Weight northylen, 6.4 grams of antioxidant, 3.2 grams of light triggers, 3.2 grams of assistant crosslinking agents, 2200 grams of mineral oil add continuous batching charging
In kettle, with 50 revs/min of speed stirring, by raw material mix homogeneously.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, described ultra-high molecular weight polyethylene, highly dense
Degree polyethylene, antioxidant, light trigger and assistant crosslinking agent in double screw extruder continuous-dissolution in mineral oil, then by double spiral shells
Bar extruder is continuously extruded with 200 revs/min of speed, and mixture continuously enters in slot die, and mixture passes through slit die
Head is expressed into curtain coating chill roll, is cast into ribbon under the conditions of 80 DEG C.
The ribbon obtaining is inserted in the extraction tank containing dichloromethane and is extracted, in order to remove the ore deposit in ribbon
Thing oil.Under the conditions of 120 DEG C, the ribbon through extraction is continuously introduced into biaxial orientation stretching machine afterwards and is drawn into thin film, then with two
Chloromethanes carry out reextraction to gained thin-film material, and deionized water cleans gained thin film.Thermal finalization 15 under the conditions of 120 DEG C
Minute, thin film is wound with 20 ms/min of speed, obtains uncrosslinked battery isolating film.Select with wave-length coverage 250-420nm
Ultraviolet light is irradiated to uncrosslinked isolating membrane processing, and irradiation time is respectively 10min, 15min, 20min, 30min, final
To a kind of isolating membrane containing cross linked polymer, its specific performance parameter is as shown in the table through test：
Embodiment 4
220 grams of density are 0.956g/cm3High density polyethylene (HDPE), 100 gram-molecular weights be 5.0 × 106Supra polymer
Weight northylen, 6.4 grams of antioxidant, 4.8 grams of peroxide cross-linking agents, 3.2 grams of assistant crosslinking agents, 2200 grams of mineral oil add continuously joins
In material coppers, with 50 revs/min of speed stirring, by raw material mix homogeneously.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, described ultra-high molecular weight polyethylene, highly dense
Degree polyethylene, antioxidant, peroxide cross-linking agent and assistant crosslinking agent in double screw extruder continuous-dissolution in mineral oil, then
Continuously extruded with 200 revs/min of speed by double screw extruder, mixture continuously enters in slot die, and mixture passes through
Slot die is expressed into curtain coating chill roll, is cast into ribbon under the conditions of 80 DEG C.
The ribbon obtaining is inserted in the extraction tank containing dichloromethane and is extracted, in order to remove the ore deposit in ribbon
Thing oil.Under the conditions of 120 DEG C, the ribbon through extraction is continuously introduced into biaxial orientation stretching machine afterwards and is drawn into thin film, then with two
Chloromethanes carry out reextraction to gained thin-film material, and deionized water cleans gained thin film.Thermal finalization 30 under the conditions of 120 DEG C
Minute, thin film is wound with 20 ms/min of speed, directly obtains a kind of battery isolating film containing cross linked polymer.It is concrete
Performance parameter is as shown in the table through test：
Embodiment 5
220 grams of density are 0.956g/cm3High density polyethylene (HDPE), 100 gram-molecular weights be 5.0 × 106Supra polymer
Weight northylen, 6.4 grams of antioxidant, 4.8 grams of peroxide cross-linking agents, 4.8 grams of silane crosslinkers, 3.2 grams of assistant crosslinking agents, 2200 grams
Mineral oil adds in continuous batching coppers, with 50 revs/min of speed stirring, by raw material mix homogeneously.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, described ultra-high molecular weight polyethylene, highly dense
Degree polyethylene, antioxidant, peroxide cross-linking agent, silane crosslinker and assistant crosslinking agent in double screw extruder continuous-dissolution in
In mineral oil, more continuously extruded with 200 revs/min of speed by double screw extruder, mixture continuously enters in slot die,
Mixture is expressed into curtain coating chill roll by slot die, is cast into ribbon under the conditions of 80 DEG C.
The ribbon obtaining is inserted in the extraction tank containing dichloromethane and is extracted, in order to remove the ore deposit in ribbon
Thing oil.Under the conditions of 120 DEG C, the ribbon through extraction is continuously introduced into biaxial orientation stretching machine afterwards and is drawn into thin film, then with two
Chloromethanes carry out reextraction to gained thin-film material, gained thin film is placed in 95 DEG C of deionized waters and repeatedly cleans 15min.?
Thermal finalization 15 minutes under the conditions of 120 DEG C, thin film are wound with 20 ms/min of speed, directly obtain one kind and contain cross linked polymer
Battery isolating film.Its specific performance parameter is as shown in the table through test：
Comparative example 1
220 grams of density are 0.956g/cm3High density polyethylene (HDPE), 100 gram-molecular weights be 5.0 × 106Supra polymer
Weight northylen, 6.4 grams of antioxidant, 2200 grams of mineral oil add in continuous batching coppers, with 50 revs/min of speed stirring, will
Raw material mix homogeneously.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, described ultra-high molecular weight polyethylene, highly dense
Degree polyethylene, antioxidant and assistant crosslinking agent in double screw extruder continuous-dissolution in mineral oil, then by double screw extruder
Continuously extruded with 200 revs/min of speed, mixture continuously enters in slot die, and mixture is expressed into by slot die
Curtain coating chill roll, is cast into ribbon under the conditions of 80 DEG C.
The ribbon obtaining is inserted in the extraction tank containing dichloromethane and is extracted, in order to remove the ore deposit in ribbon
Thing oil.Under the conditions of 120 DEG C, the ribbon through extraction is continuously introduced into biaxial orientation stretching machine afterwards and is drawn into thin film, then with two
Chloromethanes carry out reextraction to gained thin-film material, and deionized water cleans gained thin film.Thermal finalization 15 under the conditions of 120 DEG C
Minute, thin film is wound with 20 ms/min of speed, obtains uncrosslinked battery isolating film.Its specific performance parameter is through test such as
Shown in following table：
Comparative example 2
220 grams of density are 0.956g/cm3High density polyethylene (HDPE), 100 gram-molecular weights be 5.0 × 106Supra polymer
Weight northylen, 6.4 grams of antioxidant, 2200 grams of mineral oil add in continuous batching coppers, with 50 revs/min of speed stirring, will
Raw material mix homogeneously.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, described ultra-high molecular weight polyethylene, highly dense
Degree polyethylene, antioxidant and assistant crosslinking agent in double screw extruder continuous-dissolution in mineral oil, then by double screw extruder
Continuously extruded with 200 revs/min of speed, mixture continuously enters in slot die, and mixture is expressed into by slot die
Curtain coating chill roll, is cast into ribbon under the conditions of 80 DEG C.
The ribbon obtaining is inserted in the extraction tank containing dichloromethane and is extracted, in order to remove the ore deposit in ribbon
Thing oil.Under the conditions of 120 DEG C, the ribbon through extraction is continuously introduced into biaxial orientation stretching machine afterwards and is drawn into thin film, then with two
Chloromethanes carry out reextraction to gained thin-film material, and deionized water cleans gained thin film.Thermal finalization 15 under the conditions of 120 DEG C
Minute, thin film is wound with 20 ms/min of speed, obtains uncrosslinked battery isolating film.Select using cobalt (60Co) element as γ
Radiographic source, irradiation dose is respectively 50kGy, 100kGy, 200kGy, 300kGy, carries out radiation treatment to uncrosslinked isolating membrane,
Obtain a kind of isolating membrane containing cross linked polymer eventually, its specific performance parameter is as shown in the table through test：
Comparative example 3
220 grams of density are 0.956g/cm3High density polyethylene (HDPE), 100 gram-molecular weights be 5.0 × 106Supra polymer
Weight northylen, 6.4 grams of antioxidant, 2200 grams of mineral oil add in continuous batching coppers, with 50 revs/min of speed stirring, will
Raw material mix homogeneously.
Mixture is continuously added to double screw extruder, under the conditions of 180 DEG C, described ultra-high molecular weight polyethylene, highly dense
Degree polyethylene, antioxidant and assistant crosslinking agent in double screw extruder continuous-dissolution in mineral oil, then by double screw extruder
Continuously extruded with 200 revs/min of speed, mixture continuously enters in slot die, and mixture is expressed into by slot die
Curtain coating chill roll, is cast into ribbon under the conditions of 80 DEG C.
The ribbon obtaining is inserted in the extraction tank containing dichloromethane and is extracted, in order to remove the ore deposit in ribbon
Thing oil.Under the conditions of 120 DEG C, the ribbon through extraction is continuously introduced into biaxial orientation stretching machine afterwards and is drawn into thin film, then with two
Chloromethanes carry out reextraction to gained thin-film material, and deionized water cleans gained thin film.Thermal finalization 15 under the conditions of 120 DEG C
Minute, thin film is wound with 20 ms/min of speed, obtains uncrosslinked battery isolating film.Select with 5MeV electron accelerator, 8mA
Electric current is respectively 50kGy, 100kGy, 200kGy, 300kGy as irradiation bomb, irradiation dose, carries out spoke to uncrosslinked isolating membrane
According to process, finally give a kind of isolating membrane containing cross linked polymer, its specific performance parameter is as shown in the table through test：
Result shows, no matter taking which kind of crosslinking method, obtained cross linked polymer isolating membrane broken film temperature and closed pore
Temperature difference between temperature by uncrosslinked before when 55 DEG C bring up to 65-90 DEG C, the percent thermal shrinkage after crosslinking also has substantially
Decline, the safety and reliability of isolating membrane significantly lifts.Other performances, such as resistance, transmitance, percent opening and aperture are equal
There is not degradation trend, thus have no effect on the normal use of isolating membrane.Contrast is it is also found that different crosslinking side further
The improvement of the thermostability that formula is obtained is otherwise varied, especially relatively preferable with cross-linking radiation synthesis improvement, and adds
The embodiment having added assistant crosslinking agent has to thermostability and further improves.
The foregoing is only presently preferred embodiments of the present invention, be not limited to the substantial technological content model of the present invention
Enclose, the substantial technological content of the present invention is broadly to be defined in the right of application, any technology that other people complete
Entity or method, if identical with defined in the right of application, also or a kind of equivalent change, all by
It is considered to be covered by among this right.
Claims (10)
1. a kind of preparation method of battery isolating film, methods described is passed through the raw material extrusion of mixing, cooling shaping, is extracted, draws
Stretch and obtain battery isolating film with thermal finalization it is characterised in that methods described includes crosslinking.
2. preparation method as claimed in claim 1 is it is characterised in that described crosslinking is cross-linking radiation or chemical crosslinking；Described
Assistant crosslinking agent is contained in raw material.
3. preparation method as claimed in claim 2 is it is characterised in that described cross-linking radiation is selected from the friendship of energetic gamma rays irradiation
Connection, high-energy electron beam irradiation crosslinking or photo-initiated crosslinking.
4. preparation method as claimed in claim 3 is it is characterised in that described irradiation dose scope is 5-1000kGy；Preferably
10-500kGy；More preferably 50-400kGy；Most preferably 100-300kGy.
5. the preparation method as described in claim 3 or 4 is it is characterised in that described high-power electron beam is energy range 0.1-
10MeV, the electron beam of line scope 1-100mA；Preferred energy scope 1-10MeV, the electron beam of line scope 1-30mA；Optimum
Select energy range 2-5MeV, the electron beam of line scope 3-15mA.
6. preparation method as claimed in claim 3 it is characterised in that during photo-initiated crosslinking raw material include light trigger；Institute
That states causes the visible ray that light source is the ultraviolet light in 250-420nm for the wave-length coverage or 400-800nm, light application time 5-
60min；Preferred illumination time 5-50min；More preferably light application time 10-40min；Most preferably light application time 20-30min.
7. preparation method as claimed in claim 2 is it is characterised in that during described chemical crosslinking, described raw material includes peroxidating
Thing cross-linking agent and/or silane crosslinker.
8. preparation method as claimed in claim 1 or 2 is it is characterised in that it is 1.0 × 10 that described raw material includes molecular weight6-
10.0×106Ultra-high molecular weight polyethylene, density be 0.940-0.976g/cm3In the range of high density polyethylene (HDPE), antioxidant,
Pore former and assistant crosslinking agent；
In described raw material, the weight of ultra-high molecular weight polyethylene and high density polyethylene (HDPE) is than for 1:1-20；Preferably 1:2-10；More excellent
Select 1:5-10；
By described ultra-high molecular weight polyethylene and the mixture of high density polyethylene (HDPE) weight be 100 parts based on, containing 500-2000
The pore former of weight portion；Preferably 700-1800 weight portion；More preferably 800-1600 weight portion；
By described ultra-high molecular weight polyethylene and the mixture of high density polyethylene (HDPE) weight be 100 parts based on, containing 0.5-20 part
Antioxidant；Preferably 1.5-16 weight portion；More preferably 2-12 weight portion；
By described ultra-high molecular weight polyethylene and the mixture of high density polyethylene (HDPE) weight be 100 parts based on, containing 0.1-10 part
Assistant crosslinking agent；Preferably 0.5-5 weight portion；More preferably 0.5-3 weight portion.
9. a kind of battery isolating film being obtained by the preparation method as described in any one of claim 1-8；Described isolating membrane
Thickness is 9-35 μm, and micropore size is 0.3-0.65 μm, and porosity is 40-50%, and closed pore temperature is 65-90 with broken film temperature difference
DEG C, percent thermal shrinkage the most as little as 0.7%.
10. a kind of application of battery diaphragm as claimed in claim 9.
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| CN201611052346.1A CN106486632A (en) | 2016-11-25 | 2016-11-25 | A kind of battery isolating film and preparation method thereof |
| PCT/CN2017/099371 WO2018095093A1 (en) | 2016-11-25 | 2017-08-29 | Battery separator film and method for fabrication thereof |
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| CN107200901A (en) * | 2017-05-15 | 2017-09-26 | 上海恩捷新材料科技股份有限公司 | Form polymer composition, battery isolating film and the preparation method of battery isolating film |
| CN107987362A (en) * | 2017-12-22 | 2018-05-04 | 江苏美翔体育用品有限公司 | A kind of production method of PE casting films |
| WO2018095094A1 (en) * | 2016-11-25 | 2018-05-31 | 上海恩捷新材料科技股份有限公司 | Method for fabricating battery separator film |
| WO2018095093A1 (en) * | 2016-11-25 | 2018-05-31 | 上海恩捷新材料科技股份有限公司 | Battery separator film and method for fabrication thereof |
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| CN108192116A (en) * | 2017-12-29 | 2018-06-22 | 上海恩捷新材料科技股份有限公司 | A kind of photo-initiated crosslinking polymerization object isolation film and preparation method thereof |
| CN108198986A (en) * | 2017-12-29 | 2018-06-22 | 上海恩捷新材料科技股份有限公司 | A kind of crosslinked with silicane polymeric barrier films and preparation method thereof |
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| CN108550769A (en) * | 2018-05-21 | 2018-09-18 | 珠海光宇电池有限公司 | The preparation method and lithium ion battery of lithium ion battery separator |
| CN108976558A (en) * | 2018-07-10 | 2018-12-11 | 深圳市摩码科技有限公司 | A kind of crosslinked film and preparation method thereof |
| CN115051106A (en) * | 2018-10-11 | 2022-09-13 | 旭化成株式会社 | Lithium ion battery using cross-linked separator |
| CN111040215A (en) * | 2019-12-30 | 2020-04-21 | 江苏厚生新能源科技有限公司 | Method for controlling pore size distribution and size of diaphragm by changing crystal structure of UHMWPE material |
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