CN105206775B - A kind of method that polyethylene surface grafting polyethylene glycol adipate prepares lithium battery diaphragm - Google Patents
A kind of method that polyethylene surface grafting polyethylene glycol adipate prepares lithium battery diaphragm Download PDFInfo
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- CN105206775B CN105206775B CN201510576216.7A CN201510576216A CN105206775B CN 105206775 B CN105206775 B CN 105206775B CN 201510576216 A CN201510576216 A CN 201510576216A CN 105206775 B CN105206775 B CN 105206775B
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- polyethylene
- lithium battery
- glycol adipate
- battery diaphragm
- irradiation
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- -1 polyethylene Polymers 0.000 title claims abstract description 86
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 77
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 77
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 31
- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 31
- 229910052786 argon Inorganic materials 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 13
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000005453 pelletization Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims description 30
- 238000012986 modification Methods 0.000 claims description 24
- 230000004048 modification Effects 0.000 claims description 24
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 238000010348 incorporation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000008301 phosphite esters Chemical class 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 230000005251 gamma ray Effects 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- 125000005487 naphthalate group Chemical group 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 12
- 238000001816 cooling Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 68
- 230000004888 barrier function Effects 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- ZPJGNHUPXGDASP-UHFFFAOYSA-L dilithium;hexanedioate Chemical compound [Li+].[Li+].[O-]C(=O)CCCCC([O-])=O ZPJGNHUPXGDASP-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229920006266 Vinyl film Polymers 0.000 description 2
- 238000001467 acupuncture Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses the method that a kind of polyethylene surface grafting polyethylene glycol adipate prepares lithium battery diaphragm, belong to lithium battery diaphragm preparing technical field.The lithium battery diaphragm of the present invention is to be mixed by choosing polyethylene, polyethylene glycol adipate and composite antioxidant through high-speed stirred, put into extruding pelletization in extruder, pre- modified polyethylene resin particles must be blended, it is added into again in hopper, through cooling, inflation, to be curled into cylinder modified, it is placed under irradiation bottle, vacuum state and is passed through argon gas, is made after grafting polyethylene glycol adipate after cleaning, drying.The beneficial effects of the invention are as follows：The lithium battery diaphragm security performance that this method is prepared is high, and service life extends original 50%, preferable to electrolyte compatibility；More preferable protection can be provided when internal short-circuit, the security of abundance can be provided when overcharging, there is preferable mechanical property and heat endurance.
Description
Technical field
The present invention relates to the method that a kind of polyethylene surface grafting polyethylene glycol adipate prepares lithium battery diaphragm, belong to
Lithium battery diaphragm preparing technical field.
Background technology
Lithium ion battery has the characteristic of high-energy-density, long circulation life, memory-less effect, again have it is safe and reliable and
The advantages of energy fast charging and discharging, lithium ion battery is mainly made up of positive and negative electrode material, electrolyte and barrier film.In lithium ion battery
There are a membrane material, commonly referred to as barrier film between positive pole and negative pole, he is the important component of lithium ion battery.Barrier film it is main
Effect is isolation positive and negative electrode and prevents the electronics in battery from passing freely through, and ion can be allowed to be passed freely through in positive and negative interpolar.Lithium
Battery diaphragm is in the structure of lithium battery, and barrier film is one of crucial interior layer assembly.For lithium battery series, because electrolyte is
Organic solvent system, thus need the diaphragm material of organic solvent-resistant.Because polyethylene, microporous polypropylene membrane have higher hole
Gap rate, relatively low resistance, preferably preferable tearing toughness, antiacid alkali ability, the guarantor of good elastic and aprotic solvent
Performance is held, therefore Study on Li-ion batteries initial stage of development is just adopted and uses it as its diaphragm material.At present, lithium ion battery separator material
Mainly still use polyethylene, microporous polypropylene membrane.But there is poor to electrolyte compatibility lack in polyethylene, polypropylene diaphragm
Point, cause short circuit, overcharge, acupuncture the problems such as, it is therefore desirable to the security feature of battery is improved from material of battery etc., is worked out
It is a kind of to the lithium ion battery separator that electrolyte compatibility is good, security performance is high, application and development to lithium ion have important
Meaning.
The content of the invention
The technical problems to be solved by the invention：Exist for polyethylene, the polypropylene diaphragm used at present to electrolyte
The poor shortcoming of compatibility, cause short circuit, overcharge, acupuncture the problems such as there is provided a kind of polyethylene surface be grafted polyadipate second
The method that diol ester prepares lithium battery diaphragm, the lithium battery diaphragm security performance that this method is prepared is high, affine to electrolyte
Property is preferable.
In order to solve the above technical problems, the present invention is using technical scheme as described below：A kind of polyethylene surface grafting
The preparation method of polyethylene glycol adipate lithium battery diaphragm, its specific preparation process is：
(1) count by weight, choose 75~95 parts polyethylene, 4.5~24.5 parts of polyethylene glycol adipate and
0.5 part of composite antioxidant, with 2000~2500r/min speed mixed at high speed in high-speed mixer, incorporation time is 10
~15min；
(2) material mixed is put into and extruding pelletization is carried out into double screw extruder, obtain blending pre- modified
Polyethylene resin particles, pre- modified polyethylene resin particles are added in hopper, then are come out from die head die orifice, through vane
After cooling, inflation, batched by foam stabilizing frame collapser carry-over pinch rolls, then finished films are rolled into cylinder, obtain polyethylene film；
(3) in the irradiation bottle being placed in the polyethylene film of above-mentioned preparation, after being vacuumized to it, then it is passed through argon gas,
The above-mentioned closed irradiation devices full of argon gas are placed in gamma-ray irradiation source chamber and irradiated, exposure time is 20~30min
Produce the polyethylene film of pre- modification；
(4) after the completion of to be irradiated, then argon gas gas in bottle detached, vacuum pressure is formed for -0.08MPa, in negative pressure
It is 5 by the polyethylene film and polyethylene glycol adipate mass ratio of pre- modification under state:1 ratio, adds polyadipate second
Diol ester, and ensure to submerge the polyethylene film of pre- modification；
(5) plasma radiofrequency frequency is set, radio-frequency power supply is opened, made at the irradiation bottle of the polyethylene film with pre- modification
Centre at radio frequency the two poles of the earth, argon gas in 300~500kw discharge power, processing bottle is added in processing and is formed between outer electrode
Plasma form, processing time is that 1~2min obtains the polyethylene film after the processing of pre-irradiation plasma grafting；
(6) device for opening takes out the polyethylene film after the processing of pre-irradiation plasma grafting, is rinsed with deionized water
Polyethylene film 3~5 times, removes after the homopolymer of surface, 3~5h is dried under vacuum, that is, obtains a kind of polyethylene surface grafting
Polyethylene glycol adipate lithium battery diaphragm.
Described closed irradiation devices radiation dose rate is 6kGy/h, and irradiation dose is 300kGy.
Each area's temperature of described double screw extruder is that an area is 180~185 DEG C, and 2nd area are 185~190 DEG C, and 3rd area are
190~195 DEG C, extruder rotating speed 50r/min.
The each several part parameter of described blown film machine：Screw diameter is Ф 45mm, screw slenderness ratio 28：1, screw speed is
12~100r/min, a diameter of 50~Ф of the Ф 75mm of head film mouthful, diameter of traction-roller is Ф 650mm, traction linear velocity is 8~
50m/min, film folding footpath width is 130~600mm, a diameter of Ф 450mm of vane.
Described composite antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and three
[2,4- di-tert-butyl-phenyls] phosphite ester in mass ratio 1:3 are mixed with and form.
The application process of the present invention：The lithium battery diaphragm prepared is placed between positive pole and negative pole, the use of barrier film
Life it is original 50%, it is to electrolyte compatibility good.
The present invention is compared with other method, and advantageous effects are：
(1) the lithium battery diaphragm security performance that this method is prepared is high, preferable to electrolyte compatibility；
(2) more preferable protection can be provided when internal short-circuit, the security of abundance can be provided when overcharging, had preferably
Mechanical property and heat endurance.
Embodiment
Count by weight first, choose 75~95 parts polyethylene, 4.5~24.5 parts of polyethylene glycol adipate and
0.5 part of composite antioxidant, with 2000~2500r/min speed mixed at high speed in high-speed mixer, incorporation time is 10
~15min；Then the material mixed is put into and extruding pelletization is carried out into double screw extruder, obtain blending pre- modified
Polyethylene resin particles, pre- modified polyethylene resin particles are added in hopper, then are come out from die head die orifice, through vane
After cooling, inflation, batched by foam stabilizing frame collapser carry-over pinch rolls, then finished films are rolled into cylinder, obtain polyethylene film；By above-mentioned system
In the irradiation bottle that standby polyethylene film is placed in, after being vacuumized to it, then argon gas is passed through, will be above-mentioned closed full of argon gas
Irradiation devices are placed in gamma-ray irradiation source chamber and irradiated, and exposure time is thin for the polyethylene that 20~30min produces pre- modification
Film；After the completion of to be irradiated, then argon gas gas in bottle detached, form vacuum pressure for -0.08MPa, under negative pressure state, press
The polyethylene film and polyethylene glycol adipate mass ratio of pre- modification are 5:1 ratio, adds polyethylene glycol adipate, and
Ensure to submerge the polyethylene film of pre- modification；Plasma radiofrequency frequency is set, radio-frequency power supply is opened, made poly- with pre- modification
The irradiation bottle of vinyl film is in the centre at radio frequency the two poles of the earth, adds 300~500kw electric discharge work(between outer electrode in processing
Argon gas formation plasma form in rate, processing bottle, processing time is that 1~2min obtains gathering after the processing of pre-irradiation plasma grafting
Vinyl film；Last device for opening takes out the polyethylene film after the processing of pre-irradiation plasma grafting, is rushed with deionized water
Wash polyethylene film 3~5 times, remove after the homopolymer of surface, 3~5h is dried under vacuum, that is, obtains a kind of polyethylene surface and connects
Branch polyethylene glycol adipate lithium battery diaphragm；Described closed irradiation devices radiation dose rate is 6kGy/h, and irradiation dose is
300kGy；Each area's temperature of described double screw extruder is that an area is 180~185 DEG C, and 2nd area are 185~190 DEG C, and 3rd area are
190~195 DEG C, extruder rotating speed 50r/min；The each several part parameter of described blown film machine：Screw diameter is Ф 45mm, screw rod
Draw ratio 28：1, screw speed is 12~100r/min, a diameter of 50~Ф of the Ф 75mm of head film mouthful, and diameter of traction-roller is Ф
650mm, traction linear velocity is 8~50m/min, and film folding footpath width is 130~600mm, a diameter of Ф 450mm of vane；It is described
Composite antioxidant be four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and three [2,4- di-t-butyls
Phenyl] phosphite ester in mass ratio 1:3 are mixed with and form.
Example 1
Count by weight first, choose 75 parts of polyethylene, 24.5 parts of polyethylene glycol adipate and 0.5 part and answer
Antioxidant is closed, with 2000r/min speed mixed at high speed in high-speed mixer, incorporation time is 10min；Then it will mix
Material put into extruding pelletization carried out into double screw extruder, obtain the pre- modified polyethylene resin particles of blending, will be pre-
Modified polyethylene resin particles are added in hopper, then come out from die head die orifice, are cooled down through vane, after inflation, by foam stabilizing
Frame collapser carry-over pinch rolls are batched, then finished films are rolled into cylinder, obtain polyethylene film；The polyethylene film of above-mentioned preparation is placed in
Irradiation bottle in, after being vacuumized to it, then be passed through argon gas, the above-mentioned closed irradiation devices full of argon gas be placed in gamma-rays
Irradiated in irradiation source chamber, exposure time is the polyethylene film that 20min produces pre- modification；After the completion of to be irradiated, then by bottle
Middle argon gas gas is detached, and forms vacuum pressure for -0.08MPa, under negative pressure state, by the polyethylene film of pre- modification and poly-
Ethylene glycol adipate mass ratio is 5:1 ratio, adds polyethylene glycol adipate, and ensure the polyethylene of pre- modification is thin
Film is submerged；Plasma radiofrequency frequency is set, radio-frequency power supply is opened, the irradiation bottle of the polyethylene film with pre- modification is in and penetrates
The centre at frequency the two poles of the earth, the argon gas formation plasma bodily form in 300kw discharge power, processing bottle is added in processing between outer electrode
State, processing time is that 1min obtains the polyethylene film after the processing of pre-irradiation plasma grafting；Last device for opening takes out pre-irradiation
Polyethylene film after plasma grafting processing, polyethylene film is rinsed with deionized water 3 times, removes surface homopolymer
Afterwards, 3h is dried under vacuum, that is, obtains a kind of polyethylene surface grafting polyethylene glycol adipate lithium battery diaphragm；It is wherein closed
Irradiation devices radiation dose rate is 6kGy/h, and irradiation dose is 300kGy；Each area's temperature of double screw extruder is that an area is 180
DEG C, 2nd area are 185 DEG C, and 3rd area are 190 DEG C, extruder rotating speed 50r/min, each several part parameter of blown film machine：Screw diameter is
Ф 45mm, screw slenderness ratio 28：1, screw speed is 12r/min, a diameter of Ф 50mm of head film mouthful, and diameter of traction-roller is Ф
650mm, traction linear velocity is 8m/min, and film folding footpath width is 130mm, a diameter of Ф 450mm of vane；Composite antioxidant is four
[β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester and three [2,4- di-tert-butyl-phenyls] phosphite esters press matter
Amount compares 1:3 are mixed with and form.
The lithium battery diaphragm prepared is placed between positive pole and negative pole, the service life of barrier film extends original
50%, good to electrolyte compatibility, security performance is high.
Example 2
Count by weight first, choose 80 parts of polyethylene, 19.5 parts of polyethylene glycol adipate and 0.5 part and answer
Antioxidant is closed, with 2250r/min speed mixed at high speed in high-speed mixer, incorporation time is 13min；Then it will mix
Material put into extruding pelletization carried out into double screw extruder, obtain the pre- modified polyethylene resin particles of blending, will be pre-
Modified polyethylene resin particles are added in hopper, then come out from die head die orifice, are cooled down through vane, after inflation, by foam stabilizing
Frame collapser carry-over pinch rolls are batched, then finished films are rolled into cylinder, obtain polyethylene film；The polyethylene film of above-mentioned preparation is placed in
Irradiation bottle in, after being vacuumized to it, then be passed through argon gas, the above-mentioned closed irradiation devices full of argon gas be placed in gamma-rays
Irradiated in irradiation source chamber, exposure time is the polyethylene film that 25min produces pre- modification；After the completion of to be irradiated, then by bottle
Middle argon gas gas is detached, and forms vacuum pressure for -0.08MPa, under negative pressure state, by the polyethylene film of pre- modification and poly-
Ethylene glycol adipate mass ratio is 5:1 ratio, adds polyethylene glycol adipate, and ensure the polyethylene of pre- modification is thin
Film is submerged；Plasma radiofrequency frequency is set, radio-frequency power supply is opened, the irradiation bottle of the polyethylene film with pre- modification is in and penetrates
The centre at frequency the two poles of the earth, the argon gas formation plasma bodily form in 400kw discharge power, processing bottle is added in processing between outer electrode
State, processing time is that 2min obtains the polyethylene film after the processing of pre-irradiation plasma grafting；Last device for opening takes out pre-irradiation
Polyethylene film after plasma grafting processing, polyethylene film is rinsed with deionized water 4 times, removes surface homopolymer
Afterwards, 4h is dried under vacuum, that is, obtains a kind of polyethylene surface grafting polyethylene glycol adipate lithium battery diaphragm；It is wherein closed
Irradiation devices radiation dose rate is 6kGy/h, and irradiation dose is 300kGy；Each area's temperature of double screw extruder is that an area is 183
DEG C, 2nd area are 187 DEG C, and 3rd area are 192 DEG C, extruder rotating speed 50r/min；The each several part parameter of blown film machine：Screw diameter is
Ф 45mm, screw slenderness ratio 28：1, screw speed is 56r/min, a diameter of Ф 62mm of head film mouthful, and diameter of traction-roller is Ф
650mm, traction linear velocity is 26m/min, and film folding footpath width is 365mm, a diameter of Ф 450mm of vane；Composite antioxidant is
Four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and three [2,4- di-tert-butyl-phenyls] phosphite esters are pressed
Mass ratio 1:3 are mixed with and form.
The lithium battery diaphragm prepared is placed between positive pole and negative pole, the service life of barrier film extends original
50%, good to electrolyte compatibility, security performance is high.
Example 3
Count by weight first, choose 95 parts of polyethylene, 4.5 parts of polyethylene glycol adipate and 0.5 part and answer
Antioxidant is closed, with 2500r/min speed mixed at high speed in high-speed mixer, incorporation time is 15min；Then it will mix
Material put into extruding pelletization carried out into double screw extruder, obtain the pre- modified polyethylene resin particles of blending, will be pre-
Modified polyethylene resin particles are added in hopper, then come out from die head die orifice, are cooled down through vane, after inflation, by foam stabilizing
Frame collapser carry-over pinch rolls are batched, then finished films are rolled into cylinder, obtain polyethylene film；The polyethylene film of above-mentioned preparation is placed in
Irradiation bottle in, after being vacuumized to it, then be passed through argon gas, the above-mentioned closed irradiation devices full of argon gas be placed in gamma-rays
Irradiated in irradiation source chamber, exposure time is the polyethylene film that 30min produces pre- modification；After the completion of to be irradiated, then by bottle
Middle argon gas gas is detached, and forms vacuum pressure for -0.08MPa, under negative pressure state, by the polyethylene film of pre- modification and poly-
Ethylene glycol adipate mass ratio is 5:1 ratio, adds polyethylene glycol adipate, and ensure the polyethylene of pre- modification is thin
Film is submerged；Plasma radiofrequency frequency is set, radio-frequency power supply is opened, the irradiation bottle of the polyethylene film with pre- modification is in and penetrates
The centre at frequency the two poles of the earth, the argon gas formation plasma bodily form in 500kw discharge power, processing bottle is added in processing between outer electrode
State, processing time is that 2min obtains the polyethylene film after the processing of pre-irradiation plasma grafting；Last device for opening takes out pre-irradiation
Polyethylene film after plasma grafting processing, polyethylene film is rinsed with deionized water 5 times, removes surface homopolymer
Afterwards, 5h is dried under vacuum, that is, obtains a kind of polyethylene surface grafting polyethylene glycol adipate lithium battery diaphragm；It is wherein closed
Irradiation devices radiation dose rate is 6kGy/h, and irradiation dose is 300kGy；Each area's temperature of double screw extruder is that an area is 185
DEG C, 2nd area are 190 DEG C, and 3rd area are 195 DEG C, extruder rotating speed 50r/min；The each several part parameter of blown film machine：Screw diameter is
Ф 45mm, screw slenderness ratio 28：1, screw speed is 100r/min, a diameter of Ф 75mm of head film mouthful, and diameter of traction-roller is Ф
650mm, traction linear velocity is 50m/min, and film folding footpath width is 600mm, a diameter of Ф 450mm of vane；Composite antioxidant is
Four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and three [2,4- di-tert-butyl-phenyls] phosphite esters are pressed
Mass ratio 1:3 are mixed with and form.
The lithium battery diaphragm prepared is placed between positive pole and negative pole, the service life of barrier film extends original
50%, good to electrolyte compatibility, security performance is high.
Claims (3)
1. a kind of method that polyethylene surface grafting polyethylene glycol adipate prepares lithium battery diaphragm, it is characterised in that specific system
It is for step：
(1) count by weight, choose 75~95 parts of polyethylene, 4.5~24.5 parts of polyethylene glycol adipate and 0.5 part
Composite antioxidant, with 2000~2500r/min speed mixed at high speed in high-speed mixer, incorporation time be 10~
15min；
(2) material mixed is put into and extruding pelletization is carried out into double screw extruder, obtain the pre- modified poly- second of blending
Olefine resin particle, pre- modified polyethylene resin particles are added in hopper, then are come out from die head die orifice, cold through vane
But, after inflation, batched by foam stabilizing frame collapser carry-over pinch rolls, then finished films are rolled into cylinder, obtain polyethylene film；Described double spiral shells
Each area's temperature of bar extruder is that an area is 180~185 DEG C, and 2nd area are 185~190 DEG C, and 3rd area are 190~195 DEG C, and extruder turns
Fast 50r/min；
(3) polyethylene film of above-mentioned preparation is placed in the irradiation bottle of closed irradiation devices, after being vacuumized to it, then led to
Enter argon gas, the above-mentioned closed irradiation devices full of argon gas are placed in gamma-ray irradiation source chamber and irradiated, exposure time is 20
~30min produces the polyethylene film of pre- modification；
(4) after the completion of to be irradiated, then argon gas gas in bottle detached, vacuum pressure is formed for -0.08MPa, in negative pressure state
Under, it is 5 by the polyethylene film and polyethylene glycol adipate mass ratio of pre- modification:1 ratio, adds polyadipate ethylene glycol
Ester, and ensure to submerge the polyethylene film of pre- modification；
(5) plasma radiofrequency frequency is set, radio-frequency power supply is opened, the irradiation bottle of the polyethylene film with pre- modification is in and penetrates
The centre at frequency the two poles of the earth, processing when outer electrode between add 300~500kw discharge power, processing bottle in argon gas formation etc. from
Daughter form, processing time is that 1~2min obtains the polyethylene film after the processing of pre-irradiation plasma grafting；
(6) device for opening takes out the polyethylene film after the processing of pre-irradiation plasma grafting, and poly- second is rinsed with deionized water
Alkene film 3~5 times, removes after the homopolymer of surface, 3~5h is dried under vacuum, that is, obtains a kind of polyethylene surface grafting and gather oneself
Naphthalate lithium battery diaphragm.
2. a kind of polyethylene surface grafting polyethylene glycol adipate according to claim 1 prepares the side of lithium battery diaphragm
Method, it is characterised in that：Described closed irradiation devices radiation dose rate is 6kGy/h, and irradiation dose is 300kGy.
3. a kind of polyethylene surface grafting polyethylene glycol adipate according to claim 1 prepares the side of lithium battery diaphragm
Method, it is characterised in that：Described composite antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters
With three [2,4- di-tert-butyl-phenyls] phosphite esters in mass ratio 1:3 are mixed with and form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510576216.7A CN105206775B (en) | 2015-09-11 | 2015-09-11 | A kind of method that polyethylene surface grafting polyethylene glycol adipate prepares lithium battery diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510576216.7A CN105206775B (en) | 2015-09-11 | 2015-09-11 | A kind of method that polyethylene surface grafting polyethylene glycol adipate prepares lithium battery diaphragm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105206775A CN105206775A (en) | 2015-12-30 |
| CN105206775B true CN105206775B (en) | 2017-10-17 |
Family
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735470A (en) * | 2009-11-26 | 2010-06-16 | 上海大学 | Method for preparing lithium ion battery membrane via radiation grafting modification by using polypropylene film |
| CN101948571A (en) * | 2010-08-20 | 2011-01-19 | 中国科学院上海应用物理研究所 | Grafting modified polymer material and preparation method and application thereof |
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| US6384100B1 (en) * | 1999-10-29 | 2002-05-07 | Hollingsworth + Vose Company | Graft polymerization, separators, and batteries including the separators |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735470A (en) * | 2009-11-26 | 2010-06-16 | 上海大学 | Method for preparing lithium ion battery membrane via radiation grafting modification by using polypropylene film |
| CN101948571A (en) * | 2010-08-20 | 2011-01-19 | 中国科学院上海应用物理研究所 | Grafting modified polymer material and preparation method and application thereof |
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Effective date of registration: 20180322 Address after: 410600 Jinshui East Road, Ningxiang high tech Industrial Park, Changsha City, Hunan Province, No. 188 Patentee after: Hunan lithium new Mstar Technology Ltd Address before: De Shan Zhen Qi Xing an Cun 415001 Hunan city in Changde Province Economic and Technological Development Zone 3 Taolin Road North Patentee before: HUNAN CHINALY NEW MATERIAL CO., LTD. |
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Address after: 410600 No.188 Jinshui East Road, Ningxiang high tech Industrial Park, Changsha City, Hunan Province Patentee after: Sinoma lithium film (Ningxiang) Co.,Ltd. Address before: 410600 No.188 Jinshui East Road, Ningxiang high tech Industrial Park, Changsha City, Hunan Province Patentee before: HUNAN CHINALY NEW MATERIAL TECHNOLOGY Co.,Ltd. |
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