CN104157811A - Lithium ion battery composite diaphragm and preparation method and application thereof - Google Patents

Lithium ion battery composite diaphragm and preparation method and application thereof Download PDF

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Publication number
CN104157811A
CN104157811A CN201310673490.7A CN201310673490A CN104157811A CN 104157811 A CN104157811 A CN 104157811A CN 201310673490 A CN201310673490 A CN 201310673490A CN 104157811 A CN104157811 A CN 104157811A
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China
Prior art keywords
lithium ion
composite diaphragm
ion battery
polymer microsphere
inorganic ceramic
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CN201310673490.7A
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Chinese (zh)
Inventor
白莉
怀永建
王海文
张海峰
张国军
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Upper Ingression Energy Novel Material Science And Technology Ltd
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China Aviation Lithium Battery Co Ltd
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Priority to CN201310673490.7A priority Critical patent/CN104157811A/en
Publication of CN104157811A publication Critical patent/CN104157811A/en
Pending legal-status Critical Current

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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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a lithium ion battery composite diaphragm and a preparation method and an application thereof, belonging to the technical field of lithium ion batteries. The composite diaphragm comprises a polyolefin microporous membrane, a polymer microsphere based coating on one side surface of the polyolefin microporous membrane, and an inorganic ceramic-based coating on the other side surface of the polyolefin microporous membrane. The lithium ion battery composite diaphragm has good air permeability, liquid retaining capability and high-temperature resistance and can remarkably improve the security and the circulation property of the battery. The melting point or softening point of the polymer microsphere-based coating in the composite diaphragm is 90-140 DEG C, and when the temperature of the battery is increased, the polymer microsphere based coating is molten or swelled within a short time, then the apertures of the polyolefin microporous membrane are blocked rapidly, the thermal turn-off effect of the diaphragm is achieved, a lithium ion conveying channel is cut off, and short circuit inside the battery is prevented; meanwhile as ceramic grains inside the inorganic ceramic-based coating have the high-temperature resistance property, the polyolefin microporous membrane is effectively prevented from shrinkage, and the situation that positive and negative films directly come into contact to cause short circuit of the battery.

Description

A kind of lithium ion battery composite diaphragm, preparation method and application
Technical field
The present invention is specifically related to a kind of lithium ion battery composite diaphragm, also relates to the preparation method and application of this composite diaphragm simultaneously, belongs to technical field of lithium ion.
Background technology
Battery diaphragm refers to the thin porous material of one deck between anode and negative pole, is part very crucial in battery, and the fail safe of battery and cost are had a direct impact.The mechanical strength that it need to have macroion permeability to become reconciled, and to system for example in the electrolyte of battery chemical substance used and solvent there are long-time stability.In battery, barrier film must make negative electrode and anode electrode isolation completely, but makes electrolyte see through simultaneously, and it also must have lasting elasticity.
At present, the organic polymer films that traditional battery diaphragm is porous, typical organic barrier film is microporous polyolefin film, as polyethene microporous membrane and microporous polypropylene membrane.Yet microporous polyolefin film is for battery diaphragm, mainly there are the following problems: (1) polyolefin is as non-polar material, and poor with the electrolyte compatibility of strong polarity, the liquid-keeping property of barrier film is poor; (2) microporous polyolefin film adopts mechanical stretching pore more, or organic solvent extraction pore after mechanical stretching, then makes by thermal finalization, this film has shape memory effect, when temperature is higher, barrier film trends towards recovering the shape of stretching cephacoria, and heat-shrinkable strengthens.Although polyolefinic fusion temperature is lower, base material easily surpasses 165 ℃ of above generations in temperature and melts, and micropore is disappeared, and blocking-up ionic conduction is so-called fuse protection effect.But while there is fusing due to microporous polyolefin film, be also accompanied by volume contraction, membrane area dwindles, and makes barrier film lose the iris action between both positive and negative polarity, thereby causes inside battery both positive and negative polarity to be short-circuited, cause even blast of battery burning, produce potential safety hazard.
The fail safe that how to improve lithium ion battery is the important topic of current research.And the main cause of potential safety hazard appears in lithium ion battery, be that battery irreversible electrochemistry side reaction occurs has produced thermal runaway.Therefore, improve the thermal stability of barrier film, it is the important leverage that improves lithium ion battery security that a kind of barrier film high temperature resistant and that be at high temperature difficult for shrinking is provided.
Summary of the invention
The object of this invention is to provide a kind of lithium ion battery composite diaphragm.
Meanwhile, the present invention also provides a kind of preparation method of lithium ion battery composite diaphragm.
Finally, the present invention also provides the application of a kind of lithium ion battery composite diaphragm in lithium-ion-power cell.
In order to realize above object, the technical solution adopted in the present invention is:
A lithium ion battery composite diaphragm, comprises microporous polyolefin film, is coated in the polymer microsphere base coating on microporous polyolefin film one side and is coated in the inorganic ceramic base coating on microporous polyolefin film another side.
The thickness of described lithium ion battery composite diaphragm is 12～72 μ m; Wherein, the thickness of microporous polyolefin film is 8～60 μ m, and the thickness of polymer microsphere base coating is 2～6 μ m, and the thickness of inorganic ceramic base coating is 2～6 μ m.
Described microporous polyolefin film is conventional polyethylene, single-layer polypropylene, double-deck polypropylene, polypropylene, polyethylene/polypropylene composite materials microporous barrier etc.
Described polymer microsphere base coating is comprised of the component of following quality percentage composition: polymer microsphere 50～98%, binding agent 2～50%.
The softening point of described polymer microsphere or fusing point, lower than the hot melting temperature of microporous polyolefin film, are preferably 90～140 ℃, more preferably 100～130 ℃.In battery, during local overheating, polymer microsphere is melting or swelling rapidly, stops up the aperture of polyolefin film, reduces the thermal shutdown temperature of barrier film.Concrete, polymer microsphere can be polyacrylonitrile, polystyrene, polyvinyl alcohol, polyvinyl chloride, polyamide, polyimides, polyacrylate and vinylacetate class, one or more in the polymer microspheres such as polyethylene, polypropylene type and polypropylene, polyethylene copolymer, polypropylene/rubbery copolymer, polyethylene/rubbery copolymer.
The particle diameter of described polymer microsphere is 0.01～2.0 μ m, more preferably 0.07～1.5 μ m.When battery is normally used, polymer microsphere base coating can guarantee the unobstructed of polyolefin micropore membrane aperture, does not hinder effective transmission of lithium ion; When battery temperature raises, polymer microsphere is melting or swelling at short notice, and the micropore of fast blocking microporous polyolefin film is realized the heat of barrier film and turn-offed effect, cuts off lithium ion transmission channels, prevents internal short-circuit of battery.
Described binding agent is one or more in the conventional binding agents such as Kynoar (PVDF), esters of acrylic acid, acrylic compounds, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyurethane.
Described inorganic ceramic base coating is comprised of the component of following quality percentage composition: inorganic ceramic particle 60～95%, binding agent 5～40%.
Described inorganic ceramic particle is Al 2o 3, TiO 2, SiO 2, MgO, ZnO, ZrO 2, SnO 2in any one or multiple.The particle diameter of inorganic ceramic particle is 0.01～2.0 μ m, more preferably 0.05～1.5 μ m.
Described binding agent is the same.
A preparation method for lithium ion battery composite diaphragm, comprises the following steps:
(1) according to quality percentage composition, accurately get each component, polymer microsphere and binding agent are mixed, be dispersed in water, the sub-microsphere slurries that secures satisfactory grades is standby;
(2) inorganic ceramic particle and binding agent are mixed, be dispersed in water, obtain inorganic ceramic slurry standby;
(3) polymer microsphere slurry, inorganic ceramic slurry are coated in respectively to the two sides of microporous polyolefin film, dry and get final product at 60～85 ℃.
The solid content of described polymer microsphere slurry, inorganic ceramic slurry is respectively 15～65%.
In preparation process, can be first at a coating inorganic ceramic size of microporous polyolefin film, after oven dry, the another side in microporous polyolefin film applies polymer microsphere slurry again, dries and makes composite diaphragm; Also can, first at the one side coating polymer microsphere slurry of microporous polyolefin film, after oven dry, again at the another side coating inorganic ceramic size of microporous polyolefin film, dry and make composite diaphragm.
Described coating method is for shifting coating, comma blade coating, intaglio printing, spraying etc.
The application of lithium ion battery composite diaphragm in lithium-ion-power cell, described polymer microsphere base coating is positioned at composite diaphragm towards the side of battery cathode, and described inorganic ceramic base coating is the side towards anode in composite diaphragm.
Beneficial effect of the present invention:
Lithium ion battery composite diaphragm in the present invention has good gas permeability, protects fluidity and resistance to elevated temperatures, can significantly improve fail safe and the cycle performance of battery.In composite diaphragm, the fusing point of polymer microsphere base coating or softening point are 90～140 ℃, when battery temperature raises, polymer microsphere base coating is melting or swelling at short notice, stop up rapidly the aperture of microporous polyolefin film, realize the heat of barrier film and turn-off effect, cut off lithium ion transmission channels, prevent internal short-circuit of battery; In inorganic ceramic base coating, ceramic particle has resistance to elevated temperatures simultaneously, can effectively stop microporous polyolefin film to be shunk, and avoids both positive and negative polarity pole piece directly to contact and cause battery short circuit.In addition, the coating that is coated in composite diaphragm two sides all has space, can significantly improve the porosity of composite diaphragm, makes up microporous polyolefin film and the low defect of pole piece porosity, improves the liquid-keeping property of composite diaphragm, thereby increases the cycle performance of lithium ion battery.
Composite diaphragm in the present invention has the dual safety mechanism that ensures lithium-ion electric pool high temperature resistant and be at high temperature difficult for shrinking, be difficult for making battery to be short-circuited, even if inside is short-circuited, also can fast shut-off lithium ion transmission channels, prevent that short circuit on a large scale or superheating phenomenon from occurring.
Accompanying drawing explanation
Fig. 1 is the structural representation of lithium ion battery composite diaphragm in the embodiment of the present invention 1;
Fig. 2 is the SEM figure of lithium ion battery composite diaphragm polymer microsphere base coating in embodiment 1;
Fig. 3 is the SEM figure of lithium ion battery composite diaphragm inorganic ceramic base coating in embodiment 1;
Fig. 4 is the SEM figure of common PP barrier film;
Fig. 5 is the SEM of polymer microsphere base coating figure after 140 ℃/30min of composite diaphragm in test example 1;
Fig. 6 is the SEM of inorganic ceramic base coating figure after 140 ℃/30min of composite diaphragm in test example 1;
Fig. 7 is the figure of the SEM after 140 ℃/30min of common PP barrier film in test example 1.
Embodiment
Following embodiment is only described in further detail the present invention, but does not form any limitation of the invention.
Embodiment 1
Lithium ion battery composite diaphragm in the present embodiment, comprises microporous polyolefin film, is coated in the polymer microsphere base coating on microporous polyolefin film one side and is coated in the inorganic ceramic base coating on microporous polyolefin film another side.The thickness of described composite diaphragm is 27 μ m, and wherein the thickness of microporous polyolefin film is 20 μ m, and porosity is 40%, and the thickness of polymer microsphere base coating is 4 μ m, and the thickness of inorganic ceramic base coating is 3 μ m.The structural representation of composite diaphragm is shown in Fig. 1, and the SEM figure of each coating is shown in Fig. 2, Fig. 3, and the SEM figure of common PP film is shown in Fig. 4.In Fig. 1,1,3 are respectively polymer microsphere base coating and inorganic ceramic base coating, and 2 is microporous polyolefin film (microporous polypropylene membrane).
In the present embodiment, the preparation method of lithium ion battery composite diaphragm comprises the following steps:
(1) to adding particle diameter in deionized water, be the Al of 0.5 μ m 2o 3particle, high speed dispersor stirs 1h, then adds binding agent CMC, continues to stir 1h, makes inorganic ceramic slurry, wherein Al 2o 3with the mass ratio of binding agent CMC be 95:5, the solid content of inorganic ceramic slurry is 40%;
(2) to adding particle diameter in deionized water, be PS base (copolymerization of the styrene-divinylbenzene) microballoon of 0.7 μ m, high speed dispersor stirs 1h, add again binding agent PVA, continue to stir 1h, make polymer microsphere slurry, wherein the mass ratio of polystyrene-based microballoon and binding agent PVA is 90:10, and the solid content of polymer microsphere slurry is 15%;
(3) adopt continuous intaglio plate rubbing method that above-mentioned inorganic ceramic slurry is evenly coated on the microporous polypropylene membrane that thickness is 20 μ m (porosity is 40%), coating thickness is 3 μ m, repeating this operation is coated on polymer microsphere slurry on another side, coating thickness is 4 μ m, obtains the composite diaphragm that thickness is 27 μ m.
In the present embodiment, the preparation method of lithium ion battery comprises the following steps:
(1) anodal preparation: to the conductive agent carbon black of active material LiNi1/3Co1/3Mn1/3O2,4wt% and the binding agent PVDF of 3wt% that add 93wt% in solvent NMP, mix and make tertiary cathode slurry, anode sizing agent is evenly coated on the plus plate current-collecting body Al paper tinsel that thickness is 20 μ m, be dried and obtain positive pole, roll-in is standby;
(2) preparation of negative pole: to the negative electrode active material graphite powder that adds 95wt% in solvent deionized water, the thickener CMC(sodium carboxymethylcellulose of the conductive agent carbon black of 2wt%, 1wt%) and the binding agent SBR(butadiene-styrene rubber of 2wt%), mix and obtain cathode size, cathode size is evenly coated on the negative current collector Cu paper tinsel that thickness is 10 μ m, be dried and obtain negative pole, roll-in is standby;
(3) assembling of lithium ion battery: composite diaphragm, positive pole and negative pole lamination are formed to assembly, and polymer microsphere base coating is positioned at composite diaphragm towards the side of battery cathode, and described inorganic ceramic base coating is the side towards anode in composite diaphragm;
(4) injection of electrolyte: inject electrolyte (dimethyl carbonate DMC/ ethylene carbonate EC/ methyl ethyl carbonate EMC, lithium hexafluoro phosphate LiPF to lithium ion battery assembly 6concentration be 1M), obtain lithium rechargeable battery.
Embodiment 2
Lithium ion battery composite diaphragm in the present embodiment, comprises microporous polyolefin film (microporous polypropylene membrane), is coated in the polymer microsphere base coating on microporous polyolefin film one side and is coated in the inorganic ceramic base coating on microporous polyolefin film another side.The thickness of described composite diaphragm is 27 μ m, and wherein the thickness of microporous polyolefin film is 20 μ m, and porosity is 40%, and the thickness of polymer microsphere base coating is 4 μ m, and the thickness of inorganic ceramic base coating is 3 μ m.
In the present embodiment, the preparation method of lithium ion battery composite diaphragm comprises the following steps:
(1) to adding particle diameter in deionized water, be the SiO of 0.9 μ m 2particle, high speed dispersor stirs 1h, then adds binding agent PVDF, continues to stir 1h, makes inorganic ceramic slurry, wherein SiO 2with the mass ratio of PVDF be 92:8, the solid content of inorganic ceramic slurry is 30%;
(2) to adding particle diameter in deionized water, be the polyacrylonitrile microballoon (AN-AE) of 0.7 μ m, high speed dispersor stirs 1h, add again binding agent LA132(polyacrylic acid analog copolymer), continue to stir 1h, make polymer microsphere slurry, wherein the mass ratio of polyacrylonitrile microballoon and binding agent LA132 is 93:7, and the solid content of polymer microsphere slurry is 15%;
(3) adopt continuous intaglio plate rubbing method that above-mentioned inorganic ceramic slurry is evenly coated on the microporous polypropylene membrane that thickness is 20 μ m (porosity is 40%), coating thickness is 3 μ m, repeating this operation is coated on polymer microsphere slurry on another side, coating thickness is 4 μ m, obtains the composite diaphragm that thickness is 27 μ m.
In the present embodiment, the preparation method of lithium ion battery is with embodiment 1.
Embodiment 3
Lithium ion battery composite diaphragm in the present embodiment, comprises microporous polyolefin film (microporous polypropylene membrane), is coated in the polymer microsphere base coating on microporous polyolefin film one side and is coated in the inorganic ceramic base coating on microporous polyolefin film another side.The thickness of described composite diaphragm is 27 μ m, and wherein the thickness of microporous polyolefin film is 20 μ m, and porosity is 40%, and the thickness of polymer microsphere base coating is 3 μ m, and the thickness of inorganic ceramic base coating is 4 μ m.
In the present embodiment, the preparation method of lithium ion battery composite diaphragm comprises the following steps:
(1) to adding particle diameter in deionized water, be the TiO of 1.0 μ m 2particle, high speed dispersor stirs 1h, then adds binding agent PVDF, continues to stir 1h, makes inorganic ceramic slurry, wherein TiO 2with the mass ratio of binding agent PVDF be 93:7, the solid content of inorganic ceramic slurry is 30%;
(2) to adding particle diameter in deionized water, be the EVA microballoon (ethylene-vinyl acetate copolymer) of 0.7 μ m, high speed dispersor stirs 1h, add again binding agent LA132, continue to stir 1h, make polymer microsphere slurry, wherein the mass ratio of EVA microballoon and binding agent LA132 is 90:10, and the solid content of polymer microsphere slurry is 15%;
(3) adopt continuous intaglio plate rubbing method that above-mentioned inorganic ceramic slurry is evenly coated on the microporous polypropylene membrane that thickness is 20 μ m (porosity is 40%), coating thickness is 4 μ m, repeating this operation is coated on polymer microsphere slurry on another side, coating thickness is 3 μ m, obtains the composite diaphragm that thickness is 27 μ m.
In the present embodiment, the preparation method of lithium ion battery is with embodiment 1.
Test example
(1) permeability of composite diaphragm under different temperatures
Get the lithium ion battery composite diaphragm of embodiment 1～3 preparation, be placed in temperature and be the vacuum drying oven 30min of 80 ℃, 120 ℃, 125 ℃, 140 ℃, measure the ventilative value of composite diaphragm under different temperatures, the results detailed in following table 1.Wherein, the composite diaphragm of embodiment 1 SEM figure of each coating after 140 ℃ of vacuum drying oven 30min is shown in Fig. 5, Fig. 6, and the SEM figure of common PP film is shown in Fig. 7.
The permeability of composite diaphragm under table 1 different temperatures
As can be seen from Table 1, the lithium ion battery composite diaphragm of embodiment 1～3 preparation plug-hole completely at 125 ℃.Illustrate that polymer microsphere melts fast and infiltrates basement membrane micropore 120～125 ℃ of temperature ranges, cause barrier film duct to be stopped up, reach closed pore effect.And common PP film 140 ℃ of processing afterwards ventilative value with respect to former film, double, just barrier film base material is softening, aperture impact not quite.Hence one can see that, and the softening point temperature of polymer microsphere, lower than the closed pore temperature of barrier film, will be conducive to the raising of battery security.
(2) heat-shrinkable of composite diaphragm under different temperatures
Get the lithium ion battery composite diaphragm of embodiment 1～3 preparation, be placed in temperature and be the baking oven 2h of 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, measure the percent thermal shrinkage of composite diaphragm under different temperatures, the results detailed in following table 2.
The heat-shrinkable of composite diaphragm under table 2 different temperatures
As can be seen from Table 2, the lithium ion battery composite diaphragm that prepared by embodiment 1～3 is all obviously better than common PP film at heat-shrinkable at each temperature.When temperature is during lower than 120 ℃, because the thermal endurance of inorganic ceramic particle in inorganic ceramic base coating is stronger, composite diaphragm is and occurs shrinkage phenomenon; After temperature is higher than 120 ℃, there is slight shrinkage in composite diaphragm, but polymer microsphere melting stops composite diaphragm further to shrink; When temperature reaches 160 ℃, the percent thermal shrinkage of composite diaphragm is still less than 2.5%, and the fusing completely of common PP film.
(3) absorbent of different barrier films
The lithium ion battery composite diaphragm of getting common PP film and embodiment 1～3 preparation, is placed in respectively electrolyte and soaks 30min, weighs the weight of barrier film before and after soaking, and the liquid absorption of unit of account area barrier film, the results detailed in following table 3.
The absorbent of the different barrier films of table 3
As can be seen from Table 3, the absorbent of the lithium ion battery composite diaphragm of embodiment 1～3 preparation is obviously better than common PP film.Owing to being coated in the coating on composite diaphragm two sides, all there is space, can significantly improve the porosity of composite diaphragm, make up microporous polyolefin film and the low defect of pole piece porosity, improve the liquid-keeping property of composite diaphragm, thereby increase the cycle performance of lithium ion battery.
(4) apply the cycle performance of the lithium ion battery of different barrier films
Get the lithium ion battery of embodiment 1～3 preparation and the lithium ion battery that adopts common PP film preparation, measure the capability retention of the different cycle periods of lithium ion battery, the results detailed in following table 4.
The cycle performance of the lithium ion battery of the different barrier films of table 4 application
As can be seen from Table 4, the life-span that embodiment 1～3 prepares lithium ion battery, capability retention reached more than 90% after circulation 500 weeks, and the capability retention of common PP film lithium ion battery only 79.4%.Illustrate that embodiment 1～3 lithium ion battery composite diaphragm of preparation and the wettability of electrolyte are better, thereby make battery there is superior cycle performance.
(4) apply the security performance of the lithium ion battery of different barrier films
Get the lithium ion battery of embodiment 1～3 preparation and the lithium ion battery that adopts common PP film preparation, measure respectively its security performance, the results detailed in following table 5.
The security performance of the lithium ion battery of the different barrier films of table 5 application
As can be seen from Table 5, the lithium ion battery of embodiment 1～3 preparation has superior security performance.

Claims (10)

1. a lithium ion battery composite diaphragm, is characterized in that: comprise microporous polyolefin film, be coated in the polymer microsphere base coating on microporous polyolefin film one side and be coated in the inorganic ceramic base coating on microporous polyolefin film another side.
2. lithium ion battery composite diaphragm according to claim 1, is characterized in that: the thickness of described lithium ion battery composite diaphragm is 12～72 μ m; Wherein, the thickness of microporous polyolefin film is 8～60 μ m, and the thickness of polymer microsphere base coating is 2～6 μ m, and the thickness of inorganic ceramic base coating is 2～6 μ m.
3. lithium ion battery composite diaphragm according to claim 1, is characterized in that: described polymer microsphere base coating is comprised of the component of following quality percentage composition: polymer microsphere 50～98%, binding agent 2～50%.
4. lithium ion battery composite diaphragm according to claim 3, is characterized in that: the softening point of described polymer microsphere or fusing point, lower than the hot melting temperature of microporous polyolefin film, are 90～140 ℃.
5. lithium ion battery composite diaphragm according to claim 4, it is characterized in that: described polymer microsphere is polyacrylonitrile, polystyrene, polyvinyl alcohol, polyvinyl chloride, polyamide, polyimides, polyacrylate and vinylacetate class, one or more in polyethylene, polypropylene type and polypropylene, polyethylene copolymer, polypropylene/rubbery copolymer, polyethylene/rubbery copolymer, particle diameter is 0.01～2.0 μ m.
6. lithium ion battery composite diaphragm according to claim 3, is characterized in that: described binding agent is one or more in Kynoar, esters of acrylic acid, acrylic compounds, polyvinyl alcohol, carboxymethyl cellulose, polyurethane.
7. according to the lithium ion battery composite diaphragm described in claim 1 or 3, it is characterized in that: described inorganic ceramic base coating is comprised of the component of following quality percentage composition: inorganic ceramic particle 60～95%, binding agent 5～40%.
8. lithium ion battery composite diaphragm according to claim 7, is characterized in that: described inorganic ceramic particle is Al 2o 3, TiO 2, SiO 2, MgO, ZnO, ZrO 2, SnO 2in any one or multiple, particle diameter is 0.01～2.0 μ m.
9. a preparation method for lithium ion battery composite diaphragm as claimed in claim 7, is characterized in that: comprise the following steps:
(1) according to quality percentage composition, accurately get each component, polymer microsphere and binding agent are mixed, be dispersed in water, the sub-microsphere slurries that secures satisfactory grades is standby;
(2) inorganic ceramic particle and binding agent are mixed, be dispersed in water, obtain inorganic ceramic slurry standby;
(3) polymer microsphere slurry, inorganic ceramic slurry are coated in respectively to the two sides of microporous polyolefin film, dry and get final product at 60～85 ℃.
10. a lithium ion battery composite diaphragm as claimed in claim 1 application in lithium-ion-power cell, it is characterized in that: described polymer microsphere base coating is positioned at composite diaphragm towards the side of battery cathode, described inorganic ceramic base coating is the side towards anode in composite diaphragm.
CN201310673490.7A 2013-12-11 2013-12-11 Lithium ion battery composite diaphragm and preparation method and application thereof Pending CN104157811A (en)

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CN113078412A (en) * 2019-12-17 2021-07-06 山东海科创新研究院有限公司 Flame-retardant composite diaphragm, preparation method thereof and lithium ion battery
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CN111785893A (en) * 2020-07-09 2020-10-16 合肥国轩高科动力能源有限公司 Low-closed-pore-temperature coated polypropylene diaphragm and preparation method thereof
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EP4040588A4 (en) * 2020-12-11 2023-03-08 Chongqing Jimat New Material Technology Co., Ltd. Safe lithium-ion battery separator, preparation method and lithium-ion battery
CN112751139A (en) * 2020-12-30 2021-05-04 珠海冠宇电池股份有限公司 Ceramic microsphere, diaphragm containing ceramic microsphere and lithium ion battery containing diaphragm
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