CN104022250A - Lithium ion battery diaphragm and preparation method - Google Patents
Lithium ion battery diaphragm and preparation method Download PDFInfo
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- CN104022250A CN104022250A CN201410292541.6A CN201410292541A CN104022250A CN 104022250 A CN104022250 A CN 104022250A CN 201410292541 A CN201410292541 A CN 201410292541A CN 104022250 A CN104022250 A CN 104022250A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium ion battery diaphragm and a preparation method thereof. The ion battery diaphragm comprises a diaphragm base material, wherein the surface of the diaphragm base material is coated with a polyolefin coating, and the coating thickness of the polyolefin coating is 1 to 4 micrometers. The diaphragm base material is coated with the polyolefin coating, and an effect for reducing the obturator temperature can be realized, so that the worsening of a thermal runaway can be prevented, when the temperature in a lithium ion battery reaches the obturator temperature, current can be disconnected at the first time, an effect for protecting the lithium ion battery can be realized, the thermal shrinkage rate of the lithium ion battery diaphragm after being roasted for 1h under the temperature of 150DEG C is less than 5 percent; compared with a non-coated lithium ion battery diaphragm, for the lithium ion battery diaphragm disclosed by the invention, the liquid absorption addition rate is 10 to 28 percent, and the charging-discharging cycling efficiency of the lithium ion battery can be further improved.
Description
Technical field
The present invention relates to a kind of macromolecular material plastic film, particularly a kind of lithium ion battery separator and preparation method thereof.
Background technology
The closed pore temperature of lithium ion battery separator and broken film temperature have important impact to the fail safe of battery, in general, closed pore temperature is low prevents that inside battery thermal runaway from further aggravating, and broken film temperature height can prevent that barrier film from high temperature melting or break and cause large area short circuit.Therefore the difference of broken film temperature and closed pore temperature is to weigh the fail safe important indicator of battery, is not affecting under the prerequisite of other performances, and the fail safe of the larger battery of difference is just higher.The closed pore temperature of lithium ion battery separator and broken film temperature depend on the masking raw material of selecting, and taking polyalkene diaphragm as example, the closed pore temperature of wet method PE barrier film is generally at 120 DEG C ~ 130 DEG C, and broken film temperature is generally at 140 ~ 150 DEG C; The closed pore temperature of dry method PP barrier film is generally at 150 ~ 160 DEG C, and broken film temperature is generally at 170 ~ 180 DEG C.The broken film temperature of bi-material and closed pore temperature difference are 10 ~ 30 DEG C, and the fail safe of battery is existed huge hidden danger and limits its use.Although the PP/PE/PP trilamellar membrane of Celgard company of the U.S. has at 135 DEG C the broken film temperature that closed pore effect keeps PP barrier film at present simultaneously, the impact that the high temperature thermal contraction of barrier film is subject to PE layer is very large, the percent thermal shrinkage of 150 DEG C/30min approximately 35 ~ 40%; Also someone proposes to apply one deck aluminum oxide coating layer on wet method PE barrier film in addition, although can improve the thermal contraction of 135 DEG C, still can melt, and closed pore temperature also can improve to 140 DEG C of barrier films.
Summary of the invention
In order to solve that existing lithium ion battery separator closed pore temperature is high, broken film temperature low and high temperature percent thermal shrinkage is large and the undesirable technical problem such as pick up is low, primary and foremost purpose of the present invention is to provide the more good lithium ion battery separator of performance such as a kind of closed pore temperature is low, broken film temperature is high, high temperature percent thermal shrinkage is little and pick up is high.
Another object of the present invention is 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, comprises barrier film base material, on barrier film substrate surface, is coated with polyolefin coating, and the coating thickness of described polyolefin coating is 1 ~ 4um.
Further, be coated with nano ceramic material coating on the same surface of described barrier film base material or another surface, the coating thickness of described nano ceramic material coating is 2 ~ 6um simultaneously.
Preferably, the polyolefin of described polyolefin coating be selected from ethylene copolymer, polyethylene, polyacrylic one or more; Described ethylene copolymer is preferably one or more of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, described polyethylene is preferably one or more of crosslinked polyethylene, ultra-high molecular weight polyethylene, oxidic polyethylene, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), and described polypropylene is selected from one or more of atactic copolymerized polypropene, block copolymerization polypropylene, HOPP.
Preferably, the nano ceramic material of described nano ceramic material coating is selected from one or more of aluminium oxide, zirconia, titanium dioxide.
Preferably, described barrier film base material is selected from polyalkene diaphragm.
Wherein, to play the temperature of closed pore effect be 95 ~ 140 DEG C to the polyolefin of described polyolefin coating.
The nano ceramic material of described nano ceramic material coating can be increased to broken film temperature 200 ~ 253 DEG C.
Be coated with the air permeability that barrier film after above-mentioned two coatings in contrast to blank base material and increase Numerical Control in 100s/100ml.
The preparation method of above-mentioned lithium ion battery separator, comprises the steps:
A) polyolefin is mixed with to polyolefin coatings, the weight percent proportioning of this coating is: 20 ~ 30% polyolefin, 2 ~ 4% acrylic resin, 0.1 ~ 0.5% organic silicone oil, 0.1 ~ 0.2% polyoxyethylene ether, 0.03 ~ 0.05% HPMC and the deionized water of surplus; Nano ceramic material is mixed with to nano ceramic material coating simultaneously, the weight percent proportioning of this coating is: 38 ~ 42% nano ceramic material, 0.9 ~ 1.0% styrene-butadiene emulsion, 0.4 ~ 0.8% acrylic resin, 0.25 ~ 0.35% epoxy resin, 0.1 ~ 0.15% polyether-modified polysiloxane, 0.1 ~ 0.15% calgon, 0.1 ~ 0.13% sodium carboxymethylcellulose and the deionized water of surplus;
B) polyolefin coatings, nano ceramic material coating step a) being obtained utilizes nick version coating machine to be coated on barrier film base material one side simultaneously or to be coated on respectively barrier film base material two-sided;
C) utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 40 ~ 70 DEG C, and live-roller speed is 5 ~ 30 ms/min, obtains above-mentioned lithium ion battery separator.
The present invention compared with prior art, has following beneficial effect:
1) lithium ion battery separator of the present invention is owing to being coated with polyolefin coating on barrier film base material, can play the effect that reduces closed pore temperature, thereby can prevent thermal runaway aggravation, can cut off electric current in the very first time and pass through when the temperature of inside lithium ion cell reaches closed pore temperature, play 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 on barrier film base material simultaneously, can play the effect that improves broken film temperature, thereby ensure still can keep complete film form after this barrier film toasts 10 minutes under 200 ~ 250 DEG C of high temperature, without melting or fracture phenomena, the positive and negative electrode large area of lithium ion battery contact while effectively preventing high temperature and cause serious short circuit;
3) the high temperature percent thermal shrinkage of lithium ion battery separator of the present invention is little, and the percent thermal shrinkage 150 DEG C of bakings after 1 hour is less than 5%;
4) lithium ion battery separator of the present invention has good pick up, and than 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.
Embodiment
Further illustrate the present invention below by embodiment, following examples are preferably execution mode of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
Now embodiment and comparative example component used are done to following explanation, but are not limited to these materials:
In embodiment 1 ~ 3 and embodiment 10:
Barrier film base material, select Foshan City be full of Bracco skill Co., Ltd produce 20um dry method PP film, 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 aluminium oxide.
In embodiment 4 ~ 6:
Barrier film base material: the 16um dry method PP film of selecting Celgard company of the U.S. to produce, 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 zirconia.
In embodiment 7 ~ 9:
Barrier film base material: the 25um dry method PP film of selecting Zhongke Science-Technology Co., Ltd., Xinxiang to produce, 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, the ethylene-propylene copolymer that can play closed pore effect at 105 DEG C is mixed with to ethylene-propylene copolymer coating, and the weight percent proportioning of this coating is: 20% ethylene-propylene copolymer, 2% acrylic resin, 0.1% polyoxyethylene ether, 0.1% organic silicone oil, 0.05% HPMC and the deionized water of surplus; Aluminium oxide is mixed with to aluminium oxide coating simultaneously, the weight percent proportioning of this coating is: 38% aluminium oxide, 0.9% styrene-butadiene emulsion, 0.4% acrylic resin, 0.25% epoxy resin, 0.1% polyether-modified polysiloxane, 0.1% calgon, 0.13% sodium carboxymethylcellulose and the deionized water of surplus; The one side that first the aluminium oxide coating obtaining is utilized nick version coating machine to be coated on 20um dry method PP film forms aluminum oxide coating layer, utilizes roll-type drying unit that coated barrier film is dried, and bake out temperature is 60 DEG C, and transmission speed is 20 ms/min; On this aluminum oxide coating layer, utilize again ethylene-propylene copolymer coating in the coating of nick version coating machine to form ethylene-propylene copolymer coating, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 50 DEG C, live-roller speed is 5 ms/min, obtains ethylene-propylene copolymer/aluminium oxide/PP lithium ion battery separator of one side coating; Wherein the coating thickness of aluminum oxide coating layer is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um, and coating thickness corresponding to ethylene-propylene copolymer coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um.
By ethylene-propylene copolymer/aluminium oxide/PP lithium ion battery separator of five kinds of one sides coating obtained above, through 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 ethylene-propylene copolymer/aluminium oxide/PP lithium ion battery separator of table 1 one side coating
embodiment 2
A kind of lithium ion battery separator, the ethylene-propylene copolymer that can play closed pore effect at 105 DEG C is mixed with to ethylene-propylene copolymer coating, and the weight percent proportioning of this coating is: 20% ethylene-propylene copolymer, 2% acrylic resin, 0.1% polyoxyethylene ether, 0.1% organic silicone oil, 0.05% HPMC and the deionized water of surplus; Aluminium oxide is mixed with to aluminium oxide coating simultaneously, the weight percent proportioning of this coating is: 38% aluminium oxide, 0.9% styrene-butadiene emulsion, 0.4% acrylic resin, 0.25% epoxy resin, 0.1% polyether-modified polysiloxane, 0.1% calgon, 0.13% sodium carboxymethylcellulose and the deionized water of surplus; The one side that first the ethylene-propylene copolymer coating obtaining is utilized nick version coating machine to be coated on 20um dry method PP film forms ethylene-propylene copolymer coating, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 50 DEG C, and live-roller speed is 5 ms/min; In this ethylene-propylene copolymer coating, utilize aluminium oxide coating in the coating of nick version coating machine to form aluminum oxide coating layer again, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 60 DEG C, and transmission speed is 20 ms/min; Obtain aluminium oxide/ethylene-propylene copolymer/PP lithium ion battery separator of one side coating; Wherein the coating thickness of ethylene-propylene copolymer coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um, and the coating thickness that aluminum oxide coating layer is corresponding is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um.
By aluminium oxide/ethylene-propylene copolymer/PP lithium ion battery separator of five kinds of one sides coating obtained above, through 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 aluminium oxide/ethylene-propylene copolymer/PP lithium ion battery separator of table 2 one side coating
embodiment 3
A kind of lithium ion battery separator, the ethylene-propylene copolymer that can play closed pore effect at 105 DEG C is mixed with to ethylene-propylene copolymer coating, and the weight percent proportioning of this coating is: 20% ethylene-propylene copolymer, 2% acrylic resin, 0.1% polyoxyethylene ether, 0.1% organic silicone oil, 0.05% HPMC and the deionized water of surplus; Aluminium oxide is mixed with to aluminium oxide coating simultaneously, the weight percent proportioning of this coating is: 38% aluminium oxide, 0.9% styrene-butadiene emulsion, 0.4% acrylic resin, 0.25% epoxy resin, 0.1% polyether-modified polysiloxane, 0.1% calgon, 0.13% sodium carboxymethylcellulose and the deionized water of surplus; The one side of first the ethylene-propylene copolymer coating obtaining being utilized nick version coating machine to be coated on 20um dry method PP film forms ethylene-propylene copolymer coating, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 50 DEG C, and live-roller speed is 5 ms/min; Utilize aluminium oxide coating in the coating of nick version coating machine to form aluminum oxide coating layer at the another side of this 20um dry method PP film again, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 60 DEG C, and transmission speed is 20 ms/min; Obtain ethylene-propylene copolymer/PP/ aluminium oxide lithium ion battery separator of double spread; Wherein the coating thickness of ethylene-propylene copolymer coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um, and the coating thickness that aluminum oxide coating layer is corresponding is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um.
By ethylene-propylene copolymer/PP/ aluminium oxide lithium ion battery separator of five kinds of double spreads obtained above, through 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 ethylene-propylene copolymer/PP/ aluminium oxide lithium ion battery separator of table 3 double spread
embodiment 4
A kind of lithium ion battery separator, the crosslinked polyethylene that can play closed pore effect at 110 DEG C is mixed with to crosslinked polyethylene coating, and the weight percent proportioning of this coating is: 30% crosslinked polyethylene, 4% acrylic resin, 0.4% organic silicone oil, 0.1% polyoxyethylene ether, 0.05% HPMC and the deionized water of surplus; Zirconia is mixed with to zirconia coating simultaneously, the weight percent proportioning of this coating is: 40% zirconia, 1.0% styrene-butadiene emulsion, 0.7% acrylic resin, 0.35% epoxy resin, 0.15% polyether-modified polysiloxane, 0.15% calgon, 0.1% sodium carboxymethylcellulose and the deionized water of surplus; The one side that first the zirconia coating obtaining is utilized nick version coating machine to be coated on 16um dry method PP film forms zirconia coating, utilizes roll-type drying unit that coated barrier film is dried, and bake out temperature is 65 DEG C, and transmission speed is 15 ms/min; On this zirconia coating, utilize nick version coating machine coating crosslinked polyethylene coating to form crosslinked polyethylene coating again, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 55 DEG C, and live-roller speed is 5 ms/min; Obtain crosslinked polyethylene/zirconia/PP lithium ion battery separator of one side coating; Wherein the coating thickness of zirconia coating is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um, and coating thickness corresponding to crosslinked polyethylene coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um.
By crosslinked polyethylene/zirconia/PP lithium ion battery separator of five kinds of one sides coating obtained above, through 110 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 4.
The performance test results of crosslinked polyethylene/zirconia/PP lithium ion battery separator of table 4 one side coating
embodiment 5
A kind of lithium ion battery separator, the crosslinked polyethylene that can play closed pore effect at 110 DEG C is mixed with to crosslinked polyethylene coating, and the weight percent proportioning of this coating is: 30% crosslinked polyethylene, 4% acrylic resin, 0.4% organic silicone oil, 0.1% polyoxyethylene ether, 0.05% HPMC and the deionized water of surplus; Zirconia is mixed with to zirconia coating simultaneously, the weight percent proportioning of this coating is: 40% zirconia, 1.0% styrene-butadiene emulsion, 0.7% acrylic resin, 0.35% epoxy resin, 0.15% polyether-modified polysiloxane, 0.15% calgon, 0.1% sodium carboxymethylcellulose and the deionized water of surplus; The one side that first the crosslinked polyethylene coating obtaining is utilized nick version coating machine to be coated on 16um dry method PP film forms crosslinked polyethylene coating, utilizes roll-type drying unit that coated barrier film is dried, and bake out temperature is 55 DEG C, and live-roller speed is 5 ms/min; In this crosslinked polyethylene coating, utilize zirconia coating in the coating of nick version coating machine to form zirconia coating again, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 65 DEG C, and transmission speed is 15 ms/min; Obtain zirconia/crosslinked polyethylene/PP lithium ion battery separator of one side coating; Wherein the coating thickness of zirconia coating is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um, and coating thickness corresponding to crosslinked polyethylene coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um.
By zirconia/crosslinked polyethylene/PP lithium ion battery separator of five kinds of one sides coating obtained above, through 110 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 5.
The performance test results of zirconia/crosslinked polyethylene/PP lithium ion battery separator of table 5 one side coating
embodiment 6
A kind of lithium ion battery separator, the crosslinked polyethylene that can play closed pore effect at 110 DEG C is mixed with to crosslinked polyethylene coating, and the weight percent proportioning of this coating is: 30% crosslinked polyethylene, 4% acrylic resin, 0.4% organic silicone oil, 0.1% polyoxyethylene ether, 0.05% HPMC and the deionized water of surplus; Zirconia is mixed with to zirconia coating simultaneously, the weight percent proportioning of this coating is: 40% zirconia, 1.0% styrene-butadiene emulsion, 0.7% acrylic resin, 0.35% epoxy resin, 0.15% polyether-modified polysiloxane, 0.15% calgon, 0.1% sodium carboxymethylcellulose and the deionized water of surplus; The one side of first the crosslinked polyethylene coating obtaining being utilized nick version coating machine to be coated on 16um dry method PP film forms crosslinked polyethylene coating, utilizes roll-type drying unit that coated barrier film is dried, and bake out temperature is 55 DEG C, and live-roller speed is 5 ms/min; Utilize zirconia coating in the coating of nick version coating machine to form zirconia coating at the another side of this 16um dry method PP film again, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 65 DEG C, and transmission speed is 15 ms/min; Obtain crosslinked polyethylene/PP/ zirconia 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 the coating thickness that zirconia coating is corresponding is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um.
By the crosslinked polyethylene/PP of five kinds of double spreads obtained above/zirconia lithium ion battery separator, through 110 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 6.
Crosslinked polyethylene/PP/zirconia lithium ion battery separator the performance test results of table 6 double spread
embodiment 7
A kind of lithium ion battery separator, the atactic copolymerized polypropene that can play closed pore effect at 140 DEG C is mixed with to atactic copolymerized polypropene coating, and the weight percent proportioning of this coating is: 30% atactic copolymerized polypropene, 3.2% acrylic resin, 0.4% organic silicone oil, 0.1% polyoxyethylene ether, 0.046% sodium carboxymethylcellulose and the deionized water of surplus; Titanium dioxide is mixed with to titania coating simultaneously, the weight percent proportioning of this coating is: 41% titanium dioxide, 1.0% styrene-butadiene emulsion, 0.8% acrylic resin, 0.25% epoxy resin, 0.15% polyether-modified polysiloxane, 0.15% calgon, 0.1% sodium carboxymethylcellulose and the deionized water of surplus; The one side that first titania coating obtaining is utilized nick version coating machine to be coated on 25um dry method PP film forms coating of titanium dioxide, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 70 DEG C, transmission speed is 30 ms/min, on this coating of titanium dioxide, utilize again atactic copolymerized polypropene coating in the coating of nick version coating machine to form atactic copolymerized polypropene coating, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 62 DEG C, and live-roller speed is 16 ms/min; Obtain atactic copolymerized polypropene/titanium dioxide/PP lithium ion battery separator of one side coating; Wherein the coating thickness of coating of titanium dioxide is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um, and coating thickness corresponding to atactic copolymerized polypropene coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um.
By atactic copolymerized polypropene/titanium dioxide/PP lithium ion battery separator of five kinds of one sides coating obtained above, through 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 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, the atactic copolymerized polypropene that can play closed pore effect at 140 DEG C is mixed with to atactic copolymerized polypropene coating, and the weight percent proportioning of this coating is: 30% atactic copolymerized polypropene, 3.2% acrylic resin, 0.4% organic silicone oil, 0.1% polyoxyethylene ether, 0.046% sodium carboxymethylcellulose and the deionized water of surplus; Titanium dioxide is mixed with to titania coating simultaneously, the weight percent proportioning of this coating is: 41% titanium dioxide, 1.0% styrene-butadiene emulsion, 0.8% acrylic resin, 0.25% epoxy resin, 0.15% polyether-modified polysiloxane, 0.15% calgon, 0.1% sodium carboxymethylcellulose and the deionized water of surplus; The one side that first the atactic copolymerized polypropene coating obtaining is utilized nick version coating machine to be coated on 25um dry method PP film forms atactic copolymerized polypropene coating, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 62 DEG C, and live-roller speed is 16 ms/min; In this atactic copolymerized polypropene coating, utilize titania coating in the coating of nick version coating machine to form coating of titanium dioxide again, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 70 DEG C, and transmission speed is 30 ms/min; Obtain atactic copolymerized polypropene/titanium dioxide/PP lithium ion battery separator of one side coating; Wherein the coating thickness of coating of titanium dioxide is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um, and coating thickness corresponding to atactic copolymerized polypropene coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um.
By titanium dioxide/atactic copolymerized polypropene/PP lithium ion battery separator of five kinds of one sides coating obtained above, through 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 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, the atactic copolymerized polypropene that can play closed pore effect at 140 DEG C is mixed with to atactic copolymerized polypropene coating, and the weight percent proportioning of this coating is: 30% atactic copolymerized polypropene, 3.2% acrylic resin, 0.4% organic silicone oil, 0.1% polyoxyethylene ether, 0.046% sodium carboxymethylcellulose and the deionized water of surplus; Titanium dioxide is mixed with to titania coating simultaneously, the weight percent proportioning of this coating is: 41% titanium dioxide, 1.0% styrene-butadiene emulsion, 0.8% acrylic resin, 0.25% epoxy resin, 0.15% polyether-modified polysiloxane, 0.15% calgon, 0.1% sodium carboxymethylcellulose and the deionized water of surplus; The one side of first the atactic copolymerized polypropene coating obtaining being utilized nick version coating machine to be coated on 25um dry method PP film forms atactic copolymerized polypropene coating, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 62 DEG C, and live-roller speed is 16 ms/min; Utilize titania coating in the coating of nick version coating machine to form coating of titanium dioxide at the another side of this 25um dry method PP film again, utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 70 DEG C, and transmission speed is 30 ms/min; Obtain atactic copolymerized polypropene/PP titanium dioxide lithium ion battery separator of double spread; Wherein the coating thickness of atactic copolymerized polypropene coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um, and the coating thickness that coating of titanium dioxide is corresponding is respectively 1.8um, 2.0um, 4.0um, 6.0um, 7.0um.
By atactic copolymerized polypropene/PP/ titanium dioxide lithium ion battery separator of five kinds of double spreads obtained above, through 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.
Atactic copolymerized polypropene/PP/ titanium dioxide lithium ion battery separator the performance test results of table 9 double spread
embodiment 10
A kind of lithium ion battery separator, the ethylene-propylene copolymer that can play closed pore effect at 105 DEG C is mixed with to ethylene-propylene copolymer coating, and the weight percent proportioning of this coating is: 20% ethylene-propylene copolymer, 2% acrylic resin, 0.1% polyoxyethylene ether, 0.1% organic silicone oil, 0.05% HPMC and the deionized water of surplus; The one side that utilizes nick version coating machine to be coated on 20um dry method PP film the ethylene-propylene copolymer coating obtaining forms ethylene-propylene copolymer coating; Utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 50 DEG C, and live-roller speed is 5 ms/min; Obtain ethylene-propylene copolymer/PP lithium ion battery separator of one side coating; Wherein the coating thickness of ethylene-propylene copolymer coating is respectively 0.8um, 1.0um, 2.0um, 4.0um, 5.0um.
By ethylene-propylene copolymer/PP lithium ion battery separator of five kinds of one sides coating obtained above, through 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 10.
The performance test results of ethylene-propylene copolymer/PP lithium ion battery separator of table 10 one side coating
comparative example 1
Select barrier film base material to be: tri-layers of barrier film of PP/PE/PP of Celgard company of the U.S., its thickness is 20um, air penetrability is 455.3s/100ml, and this barrier film base material is toasted respectively to 10s, 1min and 10min at 135 DEG C, records air penetrability and percent thermal shrinkage after baking as shown in table 11.
The performance test results of the uncoated tri-layers of barrier film of Celgard (PP/PE/PP) of table 11
Aluminium oxide is mixed with to aluminium oxide coating, the weight percent proportioning of this coating is: 38% aluminium oxide, 0.9% styrene-butadiene emulsion, 0.4% acrylic resin, 0.25% epoxy resin, 0.1% polyether-modified polysiloxane, 0.1% calgon, 0.13% sodium carboxymethylcellulose and the deionized water of surplus; Utilize nick version coating machine to be coated on the surface of PP/PE/PP barrier film of 20um Celgard the aluminium oxide coating obtaining and form the aluminum oxide coating layer that coating thickness is 4um; Utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 60 DEG C, and transmission speed is 20 ms/min; Obtain tri-layers of barrier film of Celgard (PP/PE/PP)/aluminium oxide lithium ion battery separator; The air penetrability of gained barrier film is 457.67s/100ml.
By tri-layers of barrier film of Celgard obtained above (PP/PE/PP)/aluminium oxide lithium ion battery separator, at 135 DEG C, toast respectively 10s, 1min and 10min, record air penetrability and percent thermal shrinkage after baking as shown in table 12.
The performance test results of tri-layers of barrier film of table 12 Celgard (PP/PE/PP)/aluminium oxide lithium ion battery separator
comparative example 2
Select barrier film base material to be: the Japanese wet method PE of Asahi Kasei Corporation barrier film, its thickness is 20um, air penetrability is 326.6s/100ml, and this barrier film base material is toasted respectively to 10s, 1min and 10min at 135 DEG C, records air penetrability and percent thermal shrinkage after baking as shown in table 13.
The performance test results of the uncoated wet method PE of the Asahi Chemical Industry film of table 13
Aluminium oxide is mixed with to aluminium oxide coating, the weight percent proportioning of this coating is: 38% aluminium oxide, 0.9% styrene-butadiene emulsion, 0.4% acrylic resin, 0.25% epoxy resin, 0.1% polyether-modified polysiloxane, 0.1% calgon, 0.13% sodium carboxymethylcellulose and the deionized water of surplus; Utilize nick version coating machine to be coated on the surface of the wet method PE of 20um Asahi Chemical Industry film the aluminium oxide coating obtaining and form the aluminum oxide coating layer that coating thickness is 4um; Utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 60 DEG C, and transmission speed is 20 ms/min; The wet method PE of Ji get Asahi Chemical Industry film/aluminium oxide lithium ion battery separator; The air penetrability of gained barrier film is 341.7s/100ml.
By the wet method PE of Asahi Chemical Industry film/aluminium oxide lithium ion battery separator obtained above, at 135 DEG C, toast respectively 10s, 1min and 10min, record air penetrability and percent thermal shrinkage after baking as shown in table 14.
The performance test results of the wet method PE of table 14 Asahi Chemical Industry film/aluminium oxide lithium ion battery separator
Can find out from the experimental data of embodiment 1 ~ 3: on the one hand, in the time need to reaching the effect of closed pore (i.e. air penetrability > 3000s/100ml after baking), more than the thickness of ethylene-propylene copolymer coating must reach 1um, closed pore performance increases and improves with the coating thickness of ethylene-propylene copolymer coating, ethylene-propylene copolymer coating reaches 4um, ventilative hardly after 105 DEG C of baking 10s, but after coating thickness reaches certain value, increase its coating thickness, closed pore performance is without significantly improving again; On the other hand, when needing broken film temperature to be greater than the effect of 200 DEG C and 150 DEG C/1h percent thermal shrinkage < 5%, more than the thickness of aluminum oxide coating layer must reach 2um, broken film temperature and thermal contraction performance increase and improve with the thickness of aluminum oxide coating layer, but after coating thickness arrives 6um, increase its coating thickness, broken film temperature and thermal contraction performance are without significantly improving again; Owing to thering is irregular space in ethylene-propylene copolymer coating and aluminum oxide coating layer, can strengthen the adsorption capacity to electrolyte, thereby imbibition increment rate increases with the increase of the coating thickness of coating.In like manner, such rule can obtain from embodiment 4 ~ 6 and embodiment 7 ~ 9.
Can find out from the experimental data of embodiment 10: be only coated with the barrier film of ethylene-propylene copolymer coating, have good closed pore effect, the regularity presenting is consistent with embodiment 1 ~ 3; But owing to there is no the support of aluminum oxide coating layer, broken film temperature drops to 175 DEG C, high temperature percent thermal shrinkage approaches with the blank base material of not coating, proves that ethylene-propylene copolymer coating does not improve broken film temperature and high temperature thermal contraction performance; In addition, owing to thering is irregular space in ethylene-propylene copolymer coating, absorbent is improved.
Can find out from the experimental data of comparative example 1: the closed pore speed of uncoated tri-layers of barrier film of the PP/PE/PP of Celgard company of the U.S. is slow, and the longitudinal percent thermal shrinkage of 150 DEG C/1h is large; On three layers of barrier film basis, be coated with the aluminum oxide coating layer of one deck 4um, though the longitudinal percent thermal shrinkage of 150 DEG C/1h is improved, but be subject to PE layer in tri-layers of barrier film of PP/PE/PP to affect 150 DEG C/1h percent thermal shrinkage still very large, 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, the uncoated wet method PE of Asahi Kasei Corporation film toasts just closed pores of 10min at 135 DEG C, and has melted completely at 150 DEG C.Because the 150 DEG C/1h percent thermal shrinkage of pure PE film in the time that high temperature exceedes its fusing point is large, coating aluminum oxide coating layer does not have due effect, and greatly 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 (the mensuration machinery mensuration of GB/T6672-2001 plastic film and sheet thickness), the infrared thickness measurement online instrument of U.S. NDC (thickness of the thickness of on-line measurement barrier film base material and coating metacneme, the thickness of the thickness=coating of thickness-barrier film base material of use coating metacneme);
Temperature characterizes: 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 ") is found in Dongguan
Closed pore performance characterization: U.S. Gurley air permeability instrument (air permeability > 3000s/100ml can think closed pore) (ASTMD726 " standard test method of atresia paper gas permeability ")
Percent thermal shrinkage characterizes: the 15cm steel ruler (precision is 0.1mm) through calibrating; Quote GB/T10003-2008 " general applications bidirectional stretching polypropylene film " percent thermal shrinkage method of testing, measurer precision is increased to 0.1mm and baking condition changes 150 DEG C/30min into.
Imbibition increment rate characterizes: two outstanding electronic balances (precision be ten thousand/);
Cut out quadrat method:
1, starting to cut out sample apart from the sample limit 50mm of portion, sample keeps smooth, clean free from dust;
2, with tweezers, the sample cutting out is placed on to bag in glassware and tests;
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 is without obvious Air Flow.
Step:
1, model is cut out to sample according to above-mentioned sanction quadrat method;
2, by the weight of electronic balance weighing model, be designated as M1;
3, model is put into propyl carbonate submergence, after 2 hours, take out model with tweezers, and blot surperficial liquid with filter paper and steep, use electronic balance weigh, be 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 coating-P base material.
Claims (8)
1. a lithium ion battery separator, comprises barrier film base material, it is characterized in that: on barrier film substrate surface, be coated with polyolefin coating, the coating thickness of described polyolefin coating is 1 ~ 4um.
2. lithium ion battery separator according to claim 1, is characterized in that: be coated with nano ceramic material coating on the same surface of described barrier film base material or another surface, the coating thickness of described nano ceramic material coating is 2 ~ 6um simultaneously.
3. lithium ion battery separator according to claim 1, is characterized in that, the polyolefin of described polyolefin coating be selected from ethylene copolymer, polyethylene, polyacrylic one or more; Described ethylene copolymer is preferably one or more of ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, described polyethylene is preferably one or more of crosslinked polyethylene, ultra-high molecular weight polyethylene, oxidic polyethylene, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), and described polypropylene is selected from one or more of atactic copolymerized polypropene, block copolymerization polypropylene, HOPP.
4. lithium ion battery separator according to claim 2, is characterized in that, the nano ceramic material of described nano ceramic material coating is selected from one or more of aluminium oxide, zirconia, titanium dioxide.
5. lithium ion battery separator according to claim 1 and 2, is characterized in that, described barrier film base material is selected from polyalkene diaphragm.
6. according to the lithium ion battery separator described in claim 1 or 3, it is characterized in that, the temperature that described polyolefin coating can play closed pore effect is 95 ~ 140 DEG C.
7. according to the lithium ion battery separator described in claim 1 or 4, it is characterized in that, described nano ceramic material coating can be increased to broken film temperature 200 ~ 253 DEG C.
8. the preparation method of the lithium ion battery separator as described in claim 1 ~ 4 any one, comprises the steps:
A) polyolefin is mixed with to polyolefin coatings, the weight percent proportioning of this coating is: 20 ~ 30% polyolefin, 2 ~ 4% acrylic resin, 0.1 ~ 0.5% organic silicone oil, 0.1 ~ 0.2% polyoxyethylene ether, 0.03 ~ 0.05% HPMC and the deionized water of surplus; Nano ceramic material is mixed with to nano ceramic material coating simultaneously, the weight percent proportioning of this coating is: 38 ~ 42% nano ceramic material, 0.9 ~ 1.0% styrene-butadiene emulsion, 0.4 ~ 0.8% acrylic resin, 0.25 ~ 0.35% epoxy resin, 0.1 ~ 0.15% polyether-modified polysiloxane, 0.1 ~ 0.15% calgon, 0.1 ~ 0.13% sodium carboxymethylcellulose and the deionized water of surplus;
B) polyolefin coatings, nano ceramic material coating step a) being obtained utilizes nick version coating machine to be coated on barrier film base material one side simultaneously or to be coated on respectively barrier film base material two-sided;
C) utilize roll-type drying unit that coated barrier film is dried, bake out temperature is 40 ~ 70 DEG C, and live-roller speed is 5 ~ 30 ms/min, obtains above-mentioned lithium ion battery separator.
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| CN104900833A (en) * | 2015-07-07 | 2015-09-09 | 佛山市盈博莱科技有限公司 | Lithium ion battery separator and preparation method thereof |
| CN105140453A (en) * | 2015-08-26 | 2015-12-09 | 厦门大学 | Ceramic composite membrane with thermal-shutdown function and application thereof |
| 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 |
| CN109786620A (en) * | 2018-12-13 | 2019-05-21 | 武汉中兴创新材料技术有限公司 | A kind of coated film and its preparation method and application |
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| CN109786620A (en) * | 2018-12-13 | 2019-05-21 | 武汉中兴创新材料技术有限公司 | A kind of coated film and its preparation method and application |
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