CN104022250B - A kind of lithium ion battery separator and preparation method thereof - Google Patents
A kind of lithium ion battery separator and preparation method thereof Download PDFInfo
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- CN104022250B CN104022250B CN201410292541.6A CN201410292541A CN104022250B CN 104022250 B CN104022250 B CN 104022250B CN 201410292541 A CN201410292541 A CN 201410292541A CN 104022250 B CN104022250 B CN 104022250B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a kind of lithium ion battery separator and preparation method thereof, described ion battery barrier film, including barrier film base material, be coated with polyolefin coating on barrier film substrate surface, the coating thickness of described polyolefin coating is 1 ~ 4um；The lithium ion battery separator of the present invention is owing to being coated with polyolefin coating on barrier film base material; the effect reducing closed pore temperature can be played; such that it is able to prevent thermal runaway from aggravating; can pass through at very first time cut-out electric current when the temperature of inside lithium ion cell reaches closed pore temperature; play the effect of protection lithium ion battery, and the percent thermal shrinkage after 150 DEG C of bakings 1 hour is less than 5%；Compared to uncoated lithium ion battery separator, its imbibition increment rate is 10 ~ 28%, can further improve the charge and discharge cycles efficiency of lithium ion battery.
Description
Technical field
The present invention relates to a kind of macromolecular material plastic sheeting, particularly to a kind of lithium ion battery separator and preparation side thereof
Method.
Background technology
Closed pore temperature and the broken film temperature of lithium ion battery separator have important impact to the security of battery, typically come
Saying, closed pore temperature is low prevents inside battery thermal runaway to be further exacerbated by, and broken film temperature height can prevent barrier film from high temperature melting
Or rupture and cause large area short circuit.Therefore the difference of broken film temperature and closed pore temperature is to weigh the important finger of security of battery
Mark, on the premise of not affecting other performances, the security of the biggest battery of difference is the highest.The closed pore temperature of lithium ion battery separator
Degree and broken film temperature depend on the masking raw material selected, and as a example by polyalkene diaphragm, the closed pore temperature of wet method PE barrier film is general
At 120 DEG C ~ 130 DEG C, broken film temperature is typically at 140 ~ 150 DEG C；The closed pore temperature of dry method PP barrier film is typically at 150 ~ 160 DEG C, broken
Film temperature is typically at 170 ~ 180 DEG C.The broken film temperature of bi-material and closed pore temperature difference are 10 ~ 30 DEG C, the safety to battery
Property exist huge hidden danger and limit its use.Although the PP/PE/PP trilamellar membrane of Celgard company of the U.S. is at 135 DEG C of tools at present
There is closed pore effect to keep the broken film temperature of PP barrier film simultaneously, but the high-temperature hot of barrier film is shunk and affected very greatly by PE layer, 150
DEG C/percent thermal shrinkage about 35 ~ 40% of 30min；On wet method PE barrier film coating one layer aluminum oxide coating layer is had also been proposed, though
So can improve the thermal contraction of 135 DEG C, but still can melt to 140 DEG C of barrier films, and closed pore temperature also can improve.
Summary of the invention
In order to solve, existing lithium ion battery separator closed pore temperature is high, broken film temperature low and high temperature percent thermal shrinkage is big and imbibition
The undesirable technical problems such as rate is low, the primary and foremost purpose of the present invention is to provide one, and closed pore temperature is low, broken film temperature is high, high temperature
The lithium ion battery separator that the performance such as percent thermal shrinkage is little and pick up is high is the most excellent.
It is a further object of the present invention to provide the preparation method of above-mentioned lithium ion battery separator.
The present invention is achieved by the following technical solutions:
A kind of lithium ion battery separator, including barrier film base material, is coated with polyolefin coating on barrier film substrate surface, described
The coating thickness of polyolefin coating is 1 ~ 4um.
Further, it is coated with nano ceramic material to be coated with on the described same surface of barrier film base material or another surface simultaneously
Layer, the coating thickness of described nano ceramic material coating is 2 ~ 6um.
Preferably, the polyolefin of described polyolefin coating is selected from ethylene copolymer, polyethylene, polyacrylic one or several
Kind；Described ethylene copolymer is preferably ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer
One or more, described polyethylene is preferably crosslinked polyethylene, ultra-high molecular weight polyethylene, oxidic polyethylene, high-density polyethylene
Alkene, medium density polyethylene, low density polyethylene (LDPE) one or more, described polypropylene is common selected from atactic copolymerized polypropene, block
Poly-polypropylene, HOPP one or more.
Preferably, the nano ceramic material of described nano ceramic material coating is selected from aluminum oxide, zirconium oxide, titanium dioxide
One or more.
Preferably, described barrier film base material is selected from polyalkene diaphragm.
Wherein, the polyolefin of described polyolefin coating can play the temperature of closed pore effect is 95 ~ 140 DEG C.
Broken film temperature can be improved to 200 ~ 253 DEG C by the nano ceramic material of described nano ceramic material coating.
Membrane contrast after coating above-mentioned two coating increases Numerical Control at 100s/ in the air permeability of blank substrates
Within 100ml.
The preparation method of above-mentioned lithium ion battery separator, comprises the steps:
A) polyolefin being configured to polyolefin coatings, the weight percent proportioning of this coating is: the polyolefin of 20 ~ 30%, 2 ~ 4%
Acrylic resin, the organic silicone oil of 0.1 ~ 0.5%, the polyoxyethylene ether of 0.1 ~ 0.2%, the hydroxy propyl cellulose of 0.03 ~ 0.05%
Element sodium and the deionized water of surplus；Nano ceramic material is configured to nano ceramic material coating, the weight hundred of this coating simultaneously
Distribution ratio is: the nano ceramic material of 38 ~ 42%, the styrene-butadiene emulsion of 0.9 ~ 1.0%, the acrylic resin of 0.4 ~ 0.8%, 0.25 ~
The epoxy resin of 0.35%, the polyether-modified polysiloxane of 0.1 ~ 0.15%, the calgon of 0.1 ~ 0.15%, 0.1 ~
The sodium carboxymethylcellulose of 0.13% and the deionized water of surplus；
B) polyolefin coatings, the nano ceramic material coating that step a) are obtained utilize micro-gravure coater to be coated on simultaneously
Barrier film base material one side or be respectively coated at barrier film base material two-sided；
C) utilizing roll-type drying unit to be dried by coated barrier film, drying temperature is 40 ~ 70 DEG C, live-roller speed
It is 5 ~ 30 ms/min, i.e. obtains above-mentioned lithium ion battery separator.
The present invention compared with prior art, has the advantages that
1) lithium ion battery separator of the present invention is owing to being coated with polyolefin coating on barrier film base material, can play reduction and close
The effect of hole temperature, such that it is able to prevent thermal runaway from aggravating, when the temperature of inside lithium ion cell reaches closed pore temperature can be
One time cut off electric current and passes through, and played the effect of protection lithium ion battery；
2) lithium ion battery separator of the present invention is owing to being coated with nano ceramic material coating, energy on barrier film base material simultaneously
Play the effect improving broken film temperature, thus ensure that this barrier film remains to keep after toasting 10 minutes under 200 ~ 250 DEG C of high temperature
Whole film form, without melted or fracture phenomena, effectively prevents the positive and negative electrode bump contact of lithium ion battery during high temperature from causing tight
Weight short circuit；
3) the high-temperature hot shrinkage factor of the lithium ion battery separator of the present invention is little, the percent thermal shrinkage after toasting 1 hour at 150 DEG C
Less than 5%；
4) lithium ion battery separator of the present invention has good pick up, compared to uncoated lithium ion battery separator,
Its imbibition increment rate is 10 ~ 28%, can further improve the charge and discharge cycles efficiency of lithium ion battery.
Detailed description of the invention
Further illustrating the present invention below by detailed description of the invention, following example are the present invention preferably embodiment party
Formula, but embodiments of the present invention are not limited by following embodiment.
Now the component used by embodiment and comparative example is done as described below, but is not limited to these materials:
In embodiment 1 ~ 3 and embodiment 10:
Barrier film base material, select Foshan City to be full of 20um dry method PP film that Bracco skill Co., Ltd produces, its air penetrability is
365.2s/100ml, the percent thermal shrinkage of 150 DEG C/1h is 24.5%；
Polyolefin: select 105 DEG C of ethylene-propylene copolymers that can play closed pore effect；
Nano ceramic material: select aluminum oxide.
In embodiment 4 ~ 6:
Barrier film base material: selecting the 16um dry method PP film that Celgard company of the U.S. produces, its air penetrability is 230.6s/
100ml, the percent thermal shrinkage of 150 DEG C/1h is 21.0%；
Polyolefin: select 110 DEG C of crosslinked polyethylenes that can play closed pore effect；
Nano ceramic material: select zirconium oxide.
In embodiment 7 ~ 9:
Barrier film base material: selecting the 25um dry method PP film that Zhongke Science-Technology Co., Ltd., Xinxiang produces, its air penetrability is
428.2s/100ml, the percent thermal shrinkage of 150 DEG C/1h is 28.5%；
Polyolefin: select 140 DEG C of atactic copolymerized polypropenes that can play closed pore effect；
Nano ceramic material: select titanium dioxide.
Embodiment 1
A kind of lithium ion battery separator, is configured to second by the ethylene-propylene copolymer that can play closed pore effect at 105 DEG C
Alkene-propylene copolymer coating, the weight percent proportioning of this coating is: the ethylene-propylene copolymer of 20%, the acrylic resin of 2%,
The polyoxyethylene ether of 0.1%, the organic silicone oil of 0.1%, the HPMC of 0.05% and the deionized water of surplus；Simultaneously
Aluminum oxide is configured to aluminum oxide coating, and the weight percent proportioning of this coating is: the aluminum oxide of 38%, the styrene-butadiene emulsion of 0.9%,
The acrylic resin of 0.4%, the epoxy resin of 0.25%, the polyether-modified polysiloxane of 0.1%, the calgon of 0.1%,
The sodium carboxymethylcellulose of 0.13% and the deionized water of surplus；First micro-gravure coater is utilized to be coated with the aluminum oxide coating obtained
Cloth forms aluminum oxide coating layer at the one side of 20um dry method PP film, utilizes roll-type drying unit to be dried by coated barrier film,
Drying temperature is 60 DEG C, and transmission speed is 20 ms/min；Second in the coating of micro-gravure coater is utilized again on this aluminum oxide coating layer
Alkene-propylene copolymer coating forms ethylene-propylene copolymer coating, utilizes roll-type drying unit to be dried by coated barrier film
Dry, drying temperature is 50 DEG C, and live-roller speed is 5 ms/min, obtain the ethylene-propylene copolymer/aluminum oxide of one side coating/
PP lithium ion battery separator；Wherein the coating thickness of aluminum oxide coating layer is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um,
Coating thickness corresponding to ethylene-propylene copolymer coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um.
By the ethylene-propylene copolymer/aluminum oxide/PP lithium ion battery separator of five kinds of one sides coating obtained above, warp
Crossing 105 DEG C of baking 10s, air penetrability, broken film temperature, percent thermal shrinkage and imbibition increment rate after test baking are as shown in table 1.
The performance test results of the ethylene-propylene copolymer/aluminum oxide/PP lithium ion battery separator of table 1 one side coating
Embodiment 2
A kind of lithium ion battery separator, is configured to second by the ethylene-propylene copolymer that can play closed pore effect at 105 DEG C
Alkene-propylene copolymer coating, the weight percent proportioning of this coating is: the ethylene-propylene copolymer of 20%, the acrylic resin of 2%,
The polyoxyethylene ether of 0.1%, the organic silicone oil of 0.1%, the HPMC of 0.05% and the deionized water of surplus；Simultaneously
Aluminum oxide is configured to aluminum oxide coating, and the weight percent proportioning of this coating is: the aluminum oxide of 38%, the styrene-butadiene emulsion of 0.9%,
The acrylic resin of 0.4%, the epoxy resin of 0.25%, the polyether-modified polysiloxane of 0.1%, the calgon of 0.1%,
The sodium carboxymethylcellulose of 0.13% and the deionized water of surplus；First the ethylene-propylene copolymer coating obtained is utilized nick version
Coating machine is coated on the one side of 20um dry method PP film and forms ethylene-propylene copolymer coating, utilizes roll-type drying unit to be coated with
Good barrier film is dried, and drying temperature is 50 DEG C, and live-roller speed is 5 ms/min；It is coated with at this ethylene-propylene copolymer again
Utilize the upper aluminum oxide coating of micro-gravure coater coating to form aluminum oxide coating layer on Ceng, utilize roll-type drying unit by coated
Barrier film is dried, and drying temperature is 60 DEG C, and transmission speed is 20 ms/min；Obtain the aluminum oxide/ethene-the third of one side coating
Alkene copolymer/PP lithium ion battery separator；Wherein the coating thickness of ethylene-propylene copolymer coating be respectively 0.8um, 1.0um,
2.0um, 4.0um, 5.0um, the coating thickness that aluminum oxide coating layer is corresponding be respectively 1.8um, 2.0um, 4.0um, 6.0um,
7.0um。
By the aluminum oxide/ethylene-propylene copolymer/PP lithium ion battery separator of five kinds of one sides coating obtained above, warp
Crossing 105 DEG C of baking 10s, air penetrability, broken film temperature, percent thermal shrinkage and imbibition increment rate after test baking are as shown in table 2.
The performance test results of the aluminum oxide/ethylene-propylene copolymer/PP lithium ion battery separator of table 2 one side coating
Embodiment 3
A kind of lithium ion battery separator, is configured to second by the ethylene-propylene copolymer that can play closed pore effect at 105 DEG C
Alkene-propylene copolymer coating, the weight percent proportioning of this coating is: the ethylene-propylene copolymer of 20%, the acrylic resin of 2%,
The polyoxyethylene ether of 0.1%, the organic silicone oil of 0.1%, the HPMC of 0.05% and the deionized water of surplus；Simultaneously
Aluminum oxide is configured to aluminum oxide coating, and the weight percent proportioning of this coating is: the aluminum oxide of 38%, the styrene-butadiene emulsion of 0.9%,
The acrylic resin of 0.4%, the epoxy resin of 0.25%, the polyether-modified polysiloxane of 0.1%, the calgon of 0.1%,
The sodium carboxymethylcellulose of 0.13% and the deionized water of surplus；First the ethylene-propylene copolymer coating obtained is utilized nick version
Coating machine is coated on the one side of 20um dry method PP film and forms ethylene-propylene copolymer coating, utilizes roll-type drying unit to be coated with
Good barrier film is dried, and drying temperature is 50 DEG C, and live-roller speed is 5 ms/min；Again at another of this 20um dry method PP film
Face utilizes micro-gravure coater upper aluminum oxide coating of coating to form aluminum oxide coating layer, utilize roll-type drying unit by coated every
Film is dried, and drying temperature is 60 DEG C, and transmission speed is 20 ms/min；Obtain the ethylene-propylene copolymer of double spread/
PP/ aluminum oxide lithium ion battery separator；Wherein the coating thickness of ethylene-propylene copolymer coating be respectively 0.8um, 1.0um,
2.0um, 4.0um, 5.0um, the coating thickness that aluminum oxide coating layer is corresponding be respectively 1.8um, 2.0um, 4.0um, 6.0um,
7.0um。
By the ethylene-propylene copolymer of five kinds of double spreads obtained above/PP/ aluminum oxide lithium ion battery separator, warp
Crossing 105 DEG C of baking 10s, air penetrability, broken film temperature, percent thermal shrinkage and imbibition increment rate after test baking are as shown in table 3.
The performance test results of the ethylene-propylene copolymer of table 3 double spread/PP/ aluminum oxide lithium ion battery separator
Embodiment 4
A kind of lithium ion battery separator, is configured to cross-link poly-second by the crosslinked polyethylene that can play closed pore effect at 110 DEG C
Alkene coating, the weight percent proportioning of this coating is: the crosslinked polyethylene of 30%, the acrylic resin of 4%, the organic silicone oil of 0.4%,
The polyoxyethylene ether of 0.1%, the HPMC of 0.05% and the deionized water of surplus；Zirconium oxide is configured to oxygen simultaneously
Change zirconium coating, the weight percent proportioning of this coating is: the zirconium oxide of 40%, the styrene-butadiene emulsion of 1.0%, the acrylic resin of 0.7%,
The epoxy resin of 0.35%, the polyether-modified polysiloxane of 0.15%, the calgon of 0.15%, 0.1% carboxymethyl fine
Dimension element sodium and the deionized water of surplus；First micro-gravure coater is utilized to be coated on 16um dry method PP film the zirconium oxide coating obtained
One side formed zirconia coating, utilize roll-type drying unit to be dried by coated barrier film, dry temperature be 65 DEG C, pass
Dynamic speed is 15 ms/min；Utilize micro-gravure coater coating crosslinked polyethylene coating to be formed again on this zirconia coating to hand over
Connection polyethylene coating, utilizes roll-type drying unit to be dried by coated barrier film, and drying temperature is 55 DEG C, live-roller speed
It it is 5 ms/min；Obtain the crosslinked polyethylene/zirconium oxide/PP lithium ion battery separator of one side coating；Wherein zirconia coating
Coating thickness is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um, the coating thickness difference that crosslinked polyethylene coating is corresponding
For 0.8um, 1.0um, 2.0um, 4.0um, 5.0um.
By the crosslinked polyethylene/zirconium oxide/PP lithium ion battery separator of five kinds of one sides coating obtained above, through 110
DEG C baking 10s, test baking after air penetrability, broken film temperature, percent thermal shrinkage and imbibition increment rate as shown in table 4.
The performance test results of the crosslinked polyethylene/zirconium oxide/PP lithium ion battery separator of table 4 one side coating
Embodiment 5
A kind of lithium ion battery separator, is configured to cross-link poly-second by the crosslinked polyethylene that can play closed pore effect at 110 DEG C
Alkene coating, the weight percent proportioning of this coating is: the crosslinked polyethylene of 30%, the acrylic resin of 4%, the organic silicone oil of 0.4%,
The polyoxyethylene ether of 0.1%, the HPMC of 0.05% and the deionized water of surplus；Zirconium oxide is configured to oxygen simultaneously
Change zirconium coating, the weight percent proportioning of this coating is: the zirconium oxide of 40%, the styrene-butadiene emulsion of 1.0%, the acrylic resin of 0.7%,
The epoxy resin of 0.35%, the polyether-modified polysiloxane of 0.15%, the calgon of 0.15%, 0.1% carboxymethyl fine
Dimension element sodium and the deionized water of surplus；First micro-gravure coater is utilized to be coated on 16um dry method the crosslinked polyethylene coating obtained
The one side of PP film forms crosslinked polyethylene coating, utilizes roll-type drying unit to be dried by coated barrier film, dries temperature
Being 55 DEG C, live-roller speed is 5 ms/min；Utilize in this crosslinked polyethylene coating again and aoxidize in the coating of micro-gravure coater
Zirconium coating forms zirconia coating, utilizes roll-type drying unit to be dried by coated barrier film, and drying temperature is 65 DEG C, passes
Dynamic speed is 15 ms/min；Obtain the zirconium oxide/crosslinked polyethylene/PP lithium ion battery separator of one side coating；Wherein zirconium oxide
The coating thickness of coating is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um, the coating thickness that crosslinked polyethylene coating is corresponding
Degree is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um.
By the zirconium oxide/crosslinked polyethylene/PP lithium ion battery separator of five kinds of one sides coating obtained above, through 110
DEG C baking 10s, test baking after air penetrability, broken film temperature, percent thermal shrinkage and imbibition increment rate as shown in table 5.
The performance test results of the zirconium oxide/crosslinked polyethylene/PP lithium ion battery separator of table 5 one side coating
Embodiment 6
A kind of lithium ion battery separator, it is configured to cross-link poly-second by the crosslinked polyethylene that can play closed pore effect at 110 DEG C
Alkene coating, the weight percent proportioning of this coating is: the crosslinked polyethylene of 30%, the acrylic resin of 4%, the organic silicone oil of 0.4%,
The polyoxyethylene ether of 0.1%, the HPMC of 0.05% and the deionized water of surplus；Zirconium oxide is configured to oxygen simultaneously
Change zirconium coating, the weight percent proportioning of this coating is: the zirconium oxide of 40%, the styrene-butadiene emulsion of 1.0%, the acrylic resin of 0.7%,
The epoxy resin of 0.35%, the polyether-modified polysiloxane of 0.15%, the calgon of 0.15%, 0.1% carboxymethyl fine
Dimension element sodium and the deionized water of surplus；First micro-gravure coater is utilized to be coated on 16um dry method the crosslinked polyethylene coating obtained
The one side of PP film forms crosslinked polyethylene coating, utilizes roll-type drying unit to be dried by coated barrier film, dries temperature
Being 55 DEG C, live-roller speed is 5 ms/min；Another side at this 16um dry method PP film utilizes in the coating of micro-gravure coater again
Zirconium oxide coating forms zirconia coating, utilizes roll-type drying unit to be dried by coated barrier film, and drying temperature is 65
DEG C, transmission speed is 15 ms/min；Obtain the crosslinked polyethylene/PP/ zirconium oxide lithium ion battery separator of double spread；Wherein
The coating thickness of crosslinked polyethylene coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um, and zirconia coating is corresponding
Coating thickness is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um.
By the crosslinked polyethylene/PP/zirconium oxide lithium ion battery separator of five kinds of double spreads obtained above, through 110
DEG C baking 10s, test baking after air penetrability, broken film temperature, percent thermal shrinkage and imbibition increment rate as shown in table 6.
Crosslinked polyethylene/the PP of table 6 double spread/zirconium oxide lithium ion battery separator the performance test results
Embodiment 7
A kind of lithium ion battery separator, is configured to random being total to by the atactic copolymerized polypropene playing closed pore effect at 140 DEG C of energy
Poly-polypropylerie paint, the weight percent proportioning of this coating is: the atactic copolymerized polypropene of 30%, the acrylic resin of 3.2%, 0.4%
Organic silicone oil, the polyoxyethylene ether of 0.1%, the sodium carboxymethylcellulose of 0.046% and the deionized water of surplus；Simultaneously by two
Titanium oxide is configured to titania coating, and the weight percent proportioning of this coating is: the titanium dioxide of 41%, the styrene-butadiene emulsion of 1.0%,
The acrylic resin of 0.8%, the epoxy resin of 0.25%, the polyether-modified polysiloxane of 0.15%, the hexa metaphosphoric acid of 0.15%
Sodium, the sodium carboxymethylcellulose of 0.1% and the deionized water of surplus；First nick version is utilized to be coated with the titania coating obtained
Machine is coated on the one side of 25um dry method PP film and forms coating of titanium dioxide, utilizes roll-type drying unit to be carried out by coated barrier film
Drying, drying temperature is 70 DEG C, and transmission speed is 30 ms/min, then utilizes micro-gravure coater on this coating of titanium dioxide
In coating, atactic copolymerized polypropene coating forms atactic copolymerized polypropene coating, utilizes roll-type drying unit by coated barrier film
Drying, drying temperature is 62 DEG C, and live-roller speed is 16 ms/min；Obtain atactic copolymerized polypropene/bis-of one side coating
Titanium oxide/PP lithium ion battery separator；Wherein the coating thickness of coating of titanium dioxide be respectively 1.8um, 2.0um, 4.0um,
6.0um, 7.0um, coating thickness corresponding to atactic copolymerized polypropene coating be respectively 0.8um, 1.0um, 2.0um, 4.0um,
5.0um。
By the atactic copolymerized polypropene/titanium dioxide/PP lithium ion battery separator of five kinds of one sides coating obtained above, warp
Crossing 140 DEG C of baking 10s, air penetrability, broken film temperature, percent thermal shrinkage and imbibition increment rate after test baking are as shown in table 7.
The performance test results of the atactic copolymerized polypropene/titanium dioxide/PP lithium ion battery separator of table 7 one side coating
Embodiment 8
A kind of lithium ion battery separator, is configured to random being total to by the atactic copolymerized polypropene playing closed pore effect at 140 DEG C of energy
Poly-polypropylerie paint, the weight percent proportioning of this coating is: the atactic copolymerized polypropene of 30%, the acrylic resin of 3.2%, 0.4%
Organic silicone oil, the polyoxyethylene ether of 0.1%, the sodium carboxymethylcellulose of 0.046% and the deionized water of surplus；Simultaneously by two
Titanium oxide is configured to titania coating, and the weight percent proportioning of this coating is: the titanium dioxide of 41%, the styrene-butadiene emulsion of 1.0%,
The acrylic resin of 0.8%, the epoxy resin of 0.25%, the polyether-modified polysiloxane of 0.15%, the hexa metaphosphoric acid of 0.15%
Sodium, the sodium carboxymethylcellulose of 0.1% and the deionized water of surplus；First the atactic copolymerized polypropene coating obtained is utilized nick
Version coating machine is coated on the one side of 25um dry method PP film and forms atactic copolymerized polypropene coating, utilizes roll-type drying unit to be coated with
Good barrier film is dried, and drying temperature is 62 DEG C, and live-roller speed is 16 ms/min；It is coated with at this atactic copolymerized polypropene again
Utilize the upper titania coating of micro-gravure coater coating to form coating of titanium dioxide on Ceng, utilize roll-type drying unit to be coated with
Good barrier film is dried, and drying temperature is 70 DEG C, and transmission speed is 30 ms/min；The random copolymerization obtaining one side coating gathers
Propylene/titanium dioxide/PP lithium ion battery separator；Wherein the coating thickness of coating of titanium dioxide be respectively 1.8um, 2.0um,
4.0um, 6.0um, 7.0um, coating thickness corresponding to atactic copolymerized polypropene coating be respectively 0.8um, 1.0um, 2.0um,
4.0um、5.0um。
By the titanium dioxide/atactic copolymerized polypropene/PP lithium ion battery separator of five kinds of one sides coating obtained above, warp
Crossing 140 DEG C of baking 10s, air penetrability, broken film temperature, percent thermal shrinkage and imbibition increment rate after test baking are as shown in table 8.
The performance test results of the titanium dioxide/atactic copolymerized polypropene/PP lithium ion battery separator of table 8 one side coating
Embodiment 9
A kind of lithium ion battery separator, is configured to random being total to by the atactic copolymerized polypropene playing closed pore effect at 140 DEG C of energy
Poly-polypropylerie paint, the weight percent proportioning of this coating is: the atactic copolymerized polypropene of 30%, the acrylic resin of 3.2%, 0.4%
Organic silicone oil, the polyoxyethylene ether of 0.1%, the sodium carboxymethylcellulose of 0.046% and the deionized water of surplus；Simultaneously by two
Titanium oxide is configured to titania coating, and the weight percent proportioning of this coating is: the titanium dioxide of 41%, the styrene-butadiene emulsion of 1.0%,
The acrylic resin of 0.8%, the epoxy resin of 0.25%, the polyether-modified polysiloxane of 0.15%, the hexa metaphosphoric acid of 0.15%
Sodium, the sodium carboxymethylcellulose of 0.1% and the deionized water of surplus；First the atactic copolymerized polypropene coating obtained is utilized nick
Version coating machine is coated on the one side of 25um dry method PP film and forms atactic copolymerized polypropene coating, utilizes roll-type drying unit to be coated with
Good barrier film is dried, and drying temperature is 62 DEG C, and live-roller speed is 16 ms/min；Another at this 25um dry method PP film again
One side utilizes the upper titania coating of micro-gravure coater coating to form coating of titanium dioxide, utilizes roll-type drying unit by coating
Good barrier film is dried, and drying temperature is 70 DEG C, and transmission speed is 30 ms/min；The random copolymerization obtaining double spread gathers
Propylene/PP titanium dioxide lithium ion battery separator；Wherein the coating thickness of atactic copolymerized polypropene coating be respectively 0.8um,
1.0um, 2.0um, 4.0um, 5.0um, the coating thickness that coating of titanium dioxide is corresponding be respectively 1.8um, 2.0um, 4.0um,
6.0um、7.0um。
By the atactic copolymerized polypropene of five kinds of double spreads obtained above/PP/ titanium dioxide lithium ion battery separator, warp
Crossing 140 DEG C of baking 10s, air penetrability, broken film temperature, percent thermal shrinkage and imbibition increment rate after test baking are as shown in table 9.
The atactic copolymerized polypropene of table 9 double spread/PP/ titanium dioxide lithium ion battery separator the performance test results
Embodiment 10
A kind of lithium ion battery separator, is configured to second by the ethylene-propylene copolymer that can play closed pore effect at 105 DEG C
Alkene-propylene copolymer coating, the weight percent proportioning of this coating is: the ethylene-propylene copolymer of 20%, the acrylic resin of 2%,
The polyoxyethylene ether of 0.1%, the organic silicone oil of 0.1%, the HPMC of 0.05% and the deionized water of surplus；Will
To ethylene-propylene copolymer coating utilize micro-gravure coater be coated on 20um dry method PP film one side formed ethylene-propylene
Copolymer coated；Utilizing roll-type drying unit to be dried by coated barrier film, drying temperature is 50 DEG C, and live-roller speed is
5 ms/min；Obtain the ethylene-propylene copolymer/PP lithium ion battery separator of one side coating；Wherein ethylene-propylene copolymer is coated with
The coating thickness of layer is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um.
By the ethylene-propylene copolymer/PP lithium ion battery separator of five kinds of one sides coating obtained above, through 105 DEG C
Baking 10s, air penetrability, broken film temperature, percent thermal shrinkage and imbibition increment rate after test baking are as shown in table 10.
The performance test results of the ethylene-propylene copolymer/PP lithium ion battery separator of table 10 one side coating
Comparative example 1
Selection barrier film base material is: the PP/PE/PP three-layer membrane of Celgard company of the U.S., its thickness is 20um, air penetrability
For 455.3s/100ml, this barrier film base material is toasted 10s, 1min and 10min at 135 DEG C respectively, record breathing freely after baking
Rate and percent thermal shrinkage are as shown in table 11.
The performance test results of the Celgard three-layer membrane (PP/PE/PP) that table 11 is uncoated
Aluminum oxide is configured to aluminum oxide coating, and the weight percent proportioning of this coating is: the aluminum oxide of 38%, the fourth of 0.9%
Benzene emulsion, the acrylic resin of 0.4%, the epoxy resin of 0.25%, the polyether-modified polysiloxane of 0.1%, the six of 0.1% inclined
Sodium phosphate, the sodium carboxymethylcellulose of 0.13% and the deionized water of surplus；Nick version is utilized to be coated with the aluminum oxide coating obtained
Forming coating thickness on the surface of the PP/PE/PP barrier film that machine is coated on 20um Celgard is the aluminum oxide coating layer of 4um；Utilize
Coated barrier film is dried by roll-type drying unit, and drying temperature is 60 DEG C, and transmission speed is 20 ms/min；Obtain
Celgard three-layer membrane (PP/PE/PP)/aluminum oxide lithium ion battery separator；The air penetrability of gained barrier film is 457.67s/
100ml.
By Celgard three-layer membrane (PP/PE/PP)/aluminum oxide lithium ion battery separator obtained above, at 135 DEG C
Toast 10s, 1min and 10min respectively, record the air penetrability after baking and percent thermal shrinkage is as shown in table 12.
The performance test results of table 12 Celgard three-layer membrane (PP/PE/PP)/aluminum oxide lithium ion battery separator
Comparative example 2
Selection barrier film base material is: Asahi Kasei Corporation of Japan wet method PE barrier film, its thickness is 20um, and air penetrability is 326.6s/
100ml, toasts 10s, 1min and 10min at 135 DEG C respectively by this barrier film base material, records the air penetrability after baking and thermal contraction
Rate is as shown in table 13.
The performance test results of Asahi Chemical Industry's wet method PE film that table 13 is uncoated
Aluminum oxide is configured to aluminum oxide coating, and the weight percent proportioning of this coating is: the aluminum oxide of 38%, the fourth of 0.9%
Benzene emulsion, the acrylic resin of 0.4%, the epoxy resin of 0.25%, the polyether-modified polysiloxane of 0.1%, the six of 0.1% inclined
Sodium phosphate, the sodium carboxymethylcellulose of 0.13% and the deionized water of surplus；Nick version is utilized to be coated with the aluminum oxide coating obtained
It is the aluminum oxide coating layer of 4um that machine is coated on the surface of 20um Asahi Chemical Industry wet method PE film formation coating thickness；Roll-type is utilized to dry
Coated barrier film is dried by device, and drying temperature is 60 DEG C, and transmission speed is 20 ms/min；Ji get Asahi Chemical Industry wet method
PE film/aluminum oxide lithium ion battery separator；The air penetrability of gained barrier film is 341.7s/100ml.
By Asahi Chemical Industry obtained above wet method PE film/aluminum oxide lithium ion battery separator, toast respectively at 135 DEG C 10s,
1min and 10min, records the air penetrability after baking and percent thermal shrinkage is as shown in table 14.
The performance test results of table 14 Asahi Chemical Industry wet method PE film/aluminum oxide lithium ion battery separator
From the experimental data of embodiment 1 ~ 3 it can be seen that on the one hand, when needing to reach closed pore (i.e. air penetrability after baking
＞ 3000s/100ml) effect time, the thickness of ethylene-propylene copolymer coating must reach more than 1um, and closed pore performance is with second
The coating thickness of alkene-propylene copolymer coating increases and improves, and ethylene-propylene copolymer coating reaches 4um, through 105 DEG C of bakings
Breathing freely the most hardly after 10s, but be further added by its coating thickness after coating thickness reaches certain value, closed pore performance is without significantly carrying
High；On the other hand, when the effect needing broken film temperature to be more than 200 DEG C and 150 DEG C/1h percent thermal shrinkage ＜ 5%, aluminum oxide coating layer
Thickness must reach more than 2um, broken film temperature and thermal contraction performance to be increased with the thickness of aluminum oxide coating layer and improves, but when coating
Thickness is further added by its coating thickness, broken film temperature and thermal contraction performance without significantly improving after arriving 6um；Due to ethylene-propylene altogether
There is in polymers coating and aluminum oxide coating layer irregular space, the adsorption capacity to electrolyte can be strengthened, thus imbibition increases
Rate increases with the increase of the coating thickness of coating.In like manner, such rule can be from embodiment 4 ~ 6 and embodiment 7 ~ 9
Obtain.
From the experimental data of embodiment 10 it can be seen that be only coated with the barrier film of ethylene-propylene copolymer coating, have good
Closed pore effect, the regularity presented is consistent with embodiment 1 ~ 3；But owing to there is no the support of aluminum oxide coating layer, under broken film temperature
Being down to 175 DEG C, high-temperature hot shrinkage factor is close with the blank substrates not having coating, it was demonstrated that ethylene-propylene copolymer coating is to rupture of membranes
Temperature and high-temperature hot shrinkage do not improve；Further, since have irregular space pair in ethylene-propylene copolymer coating
Absorbent is improved.
From the experimental data of comparative example 1 it can be seen that uncoated Celgard company of U.S. PP/PE/PP three-layer membrane
Closed pore speed is slow, and 150 DEG C/1h longitudinal direction percent thermal shrinkage is big；The aluminum oxide being coated with one layer of 4um on the basis of three-layer membrane is coated with
Layer, though 150 DEG C/1h longitudinal direction percent thermal shrinkage has improvement, but is affected 150 DEG C/1h heat by PE layer in PP/PE/PP three-layer membrane and is received
Shrinkage is the biggest, and the aluminum oxide coating layer of coating has negative impact to the closed pore performance of PE layer.
Can draw from the experimental data of comparative example 2, uncoated Asahi Kasei Corporation's wet method PE film is 135 DEG C of bakings
10min just closed pore, and melt the most completely at 150 DEG C.Owing to the pure PE film 150 DEG C/1h heat when high temperature exceedes its fusing point is received
Shrinkage is big, and coating aluminum oxide coating layer does not has due effect, and significantly weakens the closed pore performance of this barrier film.
The tester of each performance and testing standard or method:
Thickness characterizes: Jinan blue streak CHY-C2 calibrator (GB/T6672-2001 plastic sheeting and the measuring machine of sheet thickness
Tool mensuration), (thickness of on-line measurement barrier film base material and the thickness of coating metacneme, with painting for U.S. NDC infrared thickness measurement online instrument
The thickness of the thickness=coating of the thickness barrier film base material of cloth metacneme)；
Temperature characterize: Dongguan stand a LY-645 accurate baking oven (GB/T2423.1-2008 test A " low-temperature test method ",
GB/T2423.2-2008 test B " high-temperature testing method ")
Closed pore performance characterization: U.S. Gurley air permeability instrument (air permeability ＞ 3000s/100ml it is believed that closed pore)
(ASTMD726 " standard test method of atresia paper gas permeability ")
Percent thermal shrinkage characterizes: the 15cm steel ruler (precision is 0.1mm) of calibrated mistake；Quote GB/T10003-2008 " common
Purposes bidirectional stretching polypropylene film " percent thermal shrinkage method of testing, the raising of measurer precision is changed into 0.1mm and baking condition
150℃/30min。
Imbibition increment rate characterizes: double outstanding electronic balances (precision is ten thousand/)；
Sanction quadrat method:
1, starting to cut out sample away from sample edge 50mm, sample keeps free from dust smooth, clean；
2, with tweezers, the sample cut out is placed on bag test in glassware；
3, whole test process sample does not allow to touch with hand,；
4, specimen size is: L=0.05m, W=0.05m.
Test environment:
1, temperature: 23 ± 2 DEG C；
2, relative humidity: 50 ± 5%；
3, indoor without strenuous vibration, without intense electromagnetic interference, room air flows without obvious air.
Step:
1, model is cut out sample according to above-mentioned sanction quadrat method；
2, by the weight of electronic balance weighing model, it is designated as M1；
3, model is put into propyl carbonate submergence, takes out model with tweezers after 2 hours, and blot surface liquid with filter paper
Stain, uses electronic balance weighing weight, is designated as M2；
4, the pick up of model is: P=(M2-M1/M1) X 100%
5, the imbibition increment rate of coating model is: △ P=P is coated with P base material.
Claims (7)
1. a lithium ion battery separator, including barrier film base material, it is characterised in that: on barrier film substrate surface, it is coated with polyolefin
Coating, the coating thickness of described polyolefin coating is 1 ~ 4 μm；
Meanwhile, on described polyolefin coating or another surface of described barrier film base material is coated with nano ceramic material coating,
The coating thickness of described nano ceramic material coating is 2 ~ 6 μm；
The preparation method of described lithium ion battery separator, comprises the steps:
A) polyolefin being configured to polyolefin coatings, the weight percent proportioning of this coating is: the polyolefin of 20 ~ 30%, the third of 2 ~ 4%
Olefin(e) acid resin, the organic silicone oil of 0.1 ~ 0.5%, the polyoxyethylene ether of 0.1 ~ 0.2%, the HPMC of 0.03 ~ 0.05%
Deionized water with surplus；Nano ceramic material is configured to nano ceramic material coating simultaneously, and the weight percent of this coating is joined
Ratio is: the nano ceramic material of 38 ~ 42%, the styrene-butadiene emulsion of 0.9 ~ 1.0%, the acrylic resin of 0.4 ~ 0.8%, 0.25 ~ 0.35%
Epoxy resin, the polyether-modified polysiloxane of 0.1 ~ 0.15%, the calgon of 0.1 ~ 0.15%, 0.1 ~ 0.13%
Sodium carboxymethylcellulose and the deionized water of surplus；
B) polyolefin coatings, the nano ceramic material coating that step a) are obtained utilize micro-gravure coater to be coated on barrier film base material
One side or be respectively coated at barrier film base material two-sided；
C) utilizing roll-type drying unit to be dried by coated barrier film, drying temperature is 40 ~ 70 DEG C, live-roller speed is 5 ~
30 ms/min, i.e. obtain above-mentioned lithium ion battery separator.
Lithium ion battery separator the most according to claim 1, it is characterised in that the polyolefin of described polyolefin coating is selected from
Ethylene copolymer, polyethylene, polyacrylic one or more；Described ethylene copolymer selected from ethylene-propylene copolymer, ethene-
Butylene copolymer, ethylene-vinyl acetate copolymer one or more, described polyethylene be selected from crosslinked polyethylene, supra polymer
Weight northylen, oxidic polyethylene, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE) one or more, described poly-
Propylene selected from atactic copolymerized polypropene, block copolymerization polypropylene, HOPP one or more.
Lithium ion battery separator the most according to claim 1, it is characterised in that the nanometer of described nano ceramic material coating
Ceramic material selected from aluminum oxide, zirconium oxide, titanium dioxide one or more.
Lithium ion battery separator the most according to claim 1, it is characterised in that described barrier film base material selected from polyolefin every
Film.
Lithium ion battery separator the most according to claim 1 and 2, it is characterised in that described polyolefin coating can play and close
The temperature of hole effect is 95 ~ 140 DEG C.
Lithium ion battery separator the most according to claim 3, it is characterised in that described nano ceramic material coating can be by broken
Film temperature improves to 200 ~ 253 DEG C.
7. the preparation method of the lithium ion battery separator as described in any one of claim 1 ~ 3, comprises the steps:
A) polyolefin being configured to polyolefin coatings, the weight percent proportioning of this coating is: the polyolefin of 20 ~ 30%, the third of 2 ~ 4%
Olefin(e) acid resin, the organic silicone oil of 0.1 ~ 0.5%, the polyoxyethylene ether of 0.1 ~ 0.2%, the HPMC of 0.03 ~ 0.05%
Deionized water with surplus；Nano ceramic material is configured to nano ceramic material coating simultaneously, and the weight percent of this coating is joined
Ratio is: the nano ceramic material of 38 ~ 42%, the styrene-butadiene emulsion of 0.9 ~ 1.0%, the acrylic resin of 0.4 ~ 0.8%, 0.25 ~ 0.35%
Epoxy resin, the polyether-modified polysiloxane of 0.1 ~ 0.15%, the calgon of 0.1 ~ 0.15%, 0.1 ~ 0.13%
Sodium carboxymethylcellulose and the deionized water of surplus；
B) polyolefin coatings, the nano ceramic material coating that step a) are obtained utilize micro-gravure coater to be coated on barrier film simultaneously
Base material one side or be respectively coated at barrier film base material two-sided；
C) utilizing roll-type drying unit to be dried by coated barrier film, drying temperature is 40 ~ 70 DEG C, live-roller speed is 5 ~
30 ms/min, i.e. obtain above-mentioned lithium ion battery separator.
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| CN104900833B (en) * | 2015-07-07 | 2017-04-12 | 佛山市盈博莱科技股份有限公司 | Lithium ion battery separator and preparation method thereof |
| CN105140453B (en) * | 2015-08-26 | 2017-09-08 | 厦门大学 | A kind of Ceramic Composite barrier film and its application with Thermal shutdown function |
| CN107022209A (en) * | 2017-04-24 | 2017-08-08 | 合肥星源新能源材料有限公司 | A kind of lithium ion battery separator coating of high wellability |
| CN108807789A (en) * | 2018-05-28 | 2018-11-13 | 上海恩捷新材料科技股份有限公司 | Diaphragm and preparation method thereof for lithium ion battery |
| CN111224045A (en) * | 2018-11-27 | 2020-06-02 | 佛山市盈博莱科技股份有限公司 | Ceramic composite diaphragm with thermal shutdown function and preparation method thereof |
| CN109786620B (en) * | 2018-12-13 | 2022-03-15 | 武汉中兴创新材料技术有限公司 | Coating film and preparation method and application thereof |
| CN113437436B (en) * | 2021-06-29 | 2022-06-03 | 江苏厚生新能源科技有限公司 | High-flexibility lithium ion battery film and preparation method thereof |
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| CN103094517A (en) * | 2012-12-13 | 2013-05-08 | 深圳中兴创新材料技术有限公司 | Composite battery membrane and preparation method thereof |
| CN203386832U (en) * | 2013-06-20 | 2014-01-08 | 深圳中兴创新材料技术有限公司 | Three-layer membrane for lithium ion battery |
| CN103811702A (en) * | 2014-02-12 | 2014-05-21 | 佛山市金辉高科光电材料有限公司 | Novel ceramic coating polyolefin composite film and preparation method thereof |
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| CN103094517A (en) * | 2012-12-13 | 2013-05-08 | 深圳中兴创新材料技术有限公司 | Composite battery membrane and preparation method thereof |
| CN203386832U (en) * | 2013-06-20 | 2014-01-08 | 深圳中兴创新材料技术有限公司 | Three-layer membrane for lithium ion battery |
| CN103811702A (en) * | 2014-02-12 | 2014-05-21 | 佛山市金辉高科光电材料有限公司 | Novel ceramic coating polyolefin composite film and preparation method thereof |
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