CN206505967U - A kind of barrier film and lithium ion battery for lithium ion battery - Google Patents

A kind of barrier film and lithium ion battery for lithium ion battery Download PDF

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Publication number
CN206505967U
CN206505967U CN201720025034.5U CN201720025034U CN206505967U CN 206505967 U CN206505967 U CN 206505967U CN 201720025034 U CN201720025034 U CN 201720025034U CN 206505967 U CN206505967 U CN 206505967U
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Prior art keywords
barrier film
lithium ion
ion battery
utility
battery
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CN201720025034.5U
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Chinese (zh)
Inventor
汪超
蔡雅男
武强
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Shenzhen Kang Mo Technology Co Ltd
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Shenzhen Kang Mo Technology Co Ltd
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The utility model proposes a kind of barrier film for lithium ion battery, it is arranged between described lithium ion cell positive and negative pole, described barrier film has the mixed coating of polyolefin porous separator basic unit and the high temperature resistance being arranged in described polyolefin porous separator basic unit.The utility model also proposed a kind of lithium ion battery, lithium ion battery separator and battery of the present utility model are by one layer of high-temperature-resistant layer containing inorganic ceramic and aramid fiber (paraphenylene terephthalamide's m-phenylene diamine (MPD)) and PVDF (Kynoar) three kinds of compositions, and the battery oxidation resistance under high-voltage state that charges is far superior to existing simple polyolefin (PP or PE) barrier film.

Description

A kind of barrier film and lithium ion battery for lithium ion battery
Technical field
The utility model is related to barrier film field, more particularly to a kind of barrier film and lithium ion battery for lithium ion battery.
Background technology
In the structure of lithium battery, barrier film is one of crucial interior layer assembly.The performance of barrier film determines the interface of battery Structure, internal resistance etc., directly affect the characteristics such as capacity, circulation and the security performance of battery, the barrier film of excellent performance is to improving electricity The combination property in pond has important effect.The main function of barrier film is that the positive and negative electrode for making battery is separated, and prevents the two poles of the earth from connecing Touch and it is short-circuit, additionally with the function that can pass through electrolyte ion.Barrier film material is nonconducting, its physicochemical properties Performance to battery has a great impact.The species of battery is different, and the barrier film of use is also different.
The barrier film of routine is simple poly- polyolefin (dry method PP or wet method PE) barrier film on the market at present, of the prior art Lithium battery isolation membrane can usually go out the problem of lithium battery explodes, its main cause is lithium battery often due to technology is not mature enough There is very big deficiency in terms of high temperature resistant.
Utility model content
In order to solve the technical problem of the above, the utility model provides a kind of resistant to elevated temperatures barrier film for lithium ion battery And lithium ion battery.
The utility model is achieved through the following technical solutions:
The utility model discloses a kind of barrier film for lithium ion battery, be arranged at described lithium ion cell positive and Between negative pole, described barrier film has polyolefin porous separator basic unit and is arranged in described polyolefin porous separator basic unit The mixed coating of high temperature resistance.
Further, the thickness of described mixed coating is:3 μm~4 μm.
Further, described mixed coating includes the ceramics layer for being close to described polyolefin porous separator basic unit, if The first PVDF layers be placed on described ceramics layer.
Further, described polyolefin porous separator groundwork thickness is:9μm、12μm、16μm、20μm.
Further, described positive pole, which is close to the one side of described barrier film, has the 2nd PVDF layers, described first PVDF layers with the 2nd PVDF layers mutually merge.
The utility model discloses a kind of lithium ion battery, including barrier film, described barrier film is barrier film as described above.
Implement a kind of barrier film and lithium ion battery for lithium ion battery of the present utility model, with following technical characteristic And beneficial technique effect:
The resistant to elevated temperatures performance of lithium ion battery separator for being different from prior art is not enough, and the utility model is contained by one layer The high-temperature-resistant layer of inorganic ceramic and aramid fiber (paraphenylene terephthalamide's m-phenylene diamine (MPD)) and PVDF (Kynoar) three kinds of compositions, electricity Oxidation resistance is far superior to existing simple polyolefin (PP or PE) barrier film under pond charging high-voltage state.
Brief description of the drawings
, below will be to embodiment in order to illustrate more clearly of the utility model embodiment or technical scheme of the prior art Or the accompanying drawing used required in description of the prior art is briefly described, it should be apparent that, drawings in the following description are only It is some embodiments of the present utility model, for those of ordinary skill in the art, before creative labor is not paid Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation of the utility model embodiment lithium ion battery separator.
Fig. 2 is the utility model embodiment lithium ion battery decomposition texture schematic diagram.
Embodiment
Below in conjunction with the accompanying drawing in the utility model embodiment, the technical scheme in the utility model embodiment is carried out Clearly and completely describe, it is clear that described embodiment is only a part of embodiment of the utility model, rather than whole Embodiment.Based on the embodiment in the utility model, those of ordinary skill in the art are not under the premise of creative work is made The every other embodiment obtained, belongs to the scope of the utility model protection.
Fig. 1 and Fig. 2 is referred to, a kind of preferred embodiment of the present utility model, barrier film 1 for lithium ion battery is set Between lithium ion cell positive 5 and negative pole 10, barrier film 1 has polyolefin porous separator basic unit 11 and is arranged at polyolefin porous The mixed coating 12 of high temperature resistance in barrier film basic unit 11.
The thickness of mixed coating 12 is:3 μm~4 μm.
Mixed coating 12 includes the ceramics layer 120 for being close to polyolefin porous separator basic unit 11, is arranged at ceramics layer 120 On the first PVDF layers 122.
The inorganic ceramic and aramid fiber (paraphenylene terephthalamide's m-phenylene diamine (MPD)) and PVDF contained in the utility model coating is (poly- Vinylidene) three kinds of composition heat-resisting abilities are far superior to simple simple polyolefin (PP or PE) barrier film.
The thickness of polyolefin porous separator basic unit 11 is:9μm、12μm、16μm、20μm.
The one side that positive pole 5 is close to barrier film 1 has the 2nd PVDF layers 51, the first PVDF layers 122 and the phase of the 2nd PVDF layers 51 Mutually fusion.
Barrier film energy density prepared by prior art is low, and cycle life is short.The utility model in mixed coating 12 due to containing Have PVDF layers, can be fused together in cell manufacturing process with the PVDF in positive plate, thus reduce cell thickness and by This improves battery energy density.
Referring to Fig. 2, a kind of lithium ion battery, including barrier film, barrier film is barrier film 1 as described above, and barrier film 1 is arranged at lithium Between ion battery positive pole 5 and negative pole 10.
It is detailed below.
This lithium battery diaphragm includes polyolefin porous separator basic unit, is coated on the ceramics of polyolefin porous separator substrate surface Material and aramid fiber (paraphenylene terephthalamide's m-phenylene diamine (MPD)) and PVDF (Kynoar) mixed coating.Mixed coating thickness is 3- 4 μm, the thickness of polyolefin (PP or PE) porous septum basic unit is respectively 9 μm, 12 μm, 16 μm, 20 μm.Thickness of the present utility model For 12 μm of common type on the market, 16 μm, 20 μm, 24 μm.
The lithium ion battery prepared using the utility model barrier film has high temperature resistant, high-energy-density, long circulating performance etc. Advantage.
Mixed coating is by ceramic material and aramid fiber (paraphenylene terephthalamide's m-phenylene diamine (MPD)) and PVDF (Kynoar) three Plant material composition.
Mixed coating preparation method can be:
Using flaky pottery particle as paste powder, ceramic powder is mixed in the slurry simultaneously with PVDF, aramid fiber fat granule PVDF and aramid fiber are dissolved completely in solvent, and ceramic powder is uniformly dispersed and is suspended in solvent, while also containing in slurry Pore creating material.In the drying course of follow-up slurry coating, the effect of pore-creating can be effectively played, the barrier film after coating has ceramic painting concurrently Cover barrier film (simple in polyolefin basic layer to apply ceramic layer) and PVDF coatings gelatin membrane (simple in polyolefin basic layer to apply PVDF layers) The performance characteristics of barrier film (simple in polyolefin basic layer to apply aramid layers), the close current pottery pure on the market of high rate performance are coated with aramid fiber The performance indications of porcelain coating, energy density reaches the performance indications of pure PVDF gel coatings barrier film, and security performance reaches pure aramid fiber The performance indications of barrier film.
What the technical solution of the utility model was realized in:A kind of lithium ion battery is modified the preparation side of coating barrier film Method, it is characterised in that comprise the following steps that:
A nano-grade ceramic powder) is prepared;
B nano-grade ceramic powder and PVDF mixed slurries) are prepared;
C slurry coated polymer porous septum) is used;
D) drying coating slurry prepares the equally distributed coat lithium ion battery barrier film in surface.
Wherein step A) the flaky pottery particle is tabular alumina, barium titanate, silica, magnesia, metatitanic acid One or more in magnesium, calcium titanate, zirconium oxide.
Nano-ceramic powder is pressed into following technique ball milling → colloid mill → Ball-stirring mill → vibromill → ultra micro air-flow crushing powder It is 50~200nm to D50, Dmax is less than 0.8 μm of flaky pottery powder.While purity >=99.95% of ceramic powder particles.
Wherein step B) slurry is aqueous cementitious slurry.
1. in its component, containing the group of hydrogen bond can be formed, while including following several compositions:
A. suspending agent:Carboxymethyl cellulose (CMC), ethyl cellulose (EC), carboxyethyl cellulose (HEC), carboxymethyl are fine One or more in dimension plain (HPC), carboxylic propyl methocel (HPMC);
B. the master of following composition divides solvent and a certain proportion of added solvent soluble in water.
Added solvent:Acetone, ethanol, isobutanol, propane diols, n-methlpyrrolidone (NMP), nitrogen-nitrogen dimethylacetamide One or more in amine (DMAC), nitrogen-nitrogen dimethylformamide (DMF), dimethyl sulfoxide (DMSO).
Main point of solvent:Dimethyl carbonate (DMC), nitrogen-nitrogen dimethyl acetamide (DMAC) and a certain proportion of dioxane Or petroleum ether, the two weight ratio of dimethyl carbonate (DMC) and nitrogen-nitrogen dimethyl acetamide (DMAC) is 1:1 ﹀ 1:3;
C. dispersant:Polyvinyl alcohol (PVA), polyethylene glycol (PE-200, PE-400, PE-600 etc.), polyvinylpyrrolidine Alkanone (PVP);
D. binding agent:Kynoar (PVDF) and polymethyl methacrylate (PMMA), polyacrylic acid (PA), poly- third One or more in e pioic acid methyl ester (PMMA), butadiene-styrene rubber, butyronitrile rubber are added by a certain percentage;
E. pore creating material:Added by a certain percentage less than 100 DEG C of volatile polyalcohol and highly branched chain alcohol including boiling point.
2. above-mentioned various composition is configured to uniform solution by a certain percentage.
3. above-mentioned uniform solution is mixed with a certain proportion of flaky pottery powder and deionized water by way of stirring Close uniform, form ceramics+PVDF mixed slurries.This slurry solid content is that between 20~50%, PVDF and aramid fiber weight ratio are 1:1 ~1:Between 2, PVDF and aramid fiber gross mass and ceramic powder weight ratio are 2:3~1:1. between slurry drying after PVDF and ceramic powder Total mass ratio be 90~50% between.The interphase interaction of various components can form stable hydrogen bond, be coated in membrane surface simultaneously And the compactness of coating is ensure that after drying.
Wherein step C) coating method be squash type spray, gravure roll transfer type coating, immersion type coating in one Kind, by slurry be uniformly coated to PE, PP or PE, PP composite diaphragms surface (including dry and wet, can one side coating it is also double Face is coated), coating thickness is 3~4 μm.
Wherein step D) described in drying mode for coating after dry immediately, and temperature no more than 60 DEG C need to be with blowing hot wind Form drying, after drying its water content be less than 600ppm.
Step B) in various solvents become volatile under interaction, it is to avoid when PE or PP barrier films are coated on surface Deformed because of high-temperature baking, arc spends height, the internal short-circuit of battery that positive/negative plate contact is caused in follow-up winding process.Coating Barrier film is appointed in battery core preparation process so uses Baking heat pressing process.
After Baking techniques, electrolyte enters inside two layers of PVDF mixed layer, whole battery core without substantially free electrolysis Liquid, so as to improve the security of battery.While two layers is combined into one layer and decreases the thickness of battery, so as to improve its energy Metric density.
The inorganic ceramic material being coated in simultaneously in polyolefin porous separator basic unit in mixed coating can improve barrier film Heat endurance and mechanical performance.
Furthermore oxidation resistance under high voltage (high electrode current potential) state of three kinds of compositions in coating when battery charges It is much better than simple polyolefin (PP or PE).
Therefore its cycle life is then much better than polyolefin (PP or PE) barrier film (either dry method (PP materials at present on the market Matter), or wet method (PE materials).
Specific embodiment described herein is only to the utility model objective explanation for example.The utility model institute Category those skilled in the art can make various modifications or supplement or using similar to described specific embodiment Mode substitute, but without departing from objective of the present utility model or surmount scope defined in appended claims.

Claims (5)

1. a kind of barrier film for lithium ion battery, is arranged between described lithium ion cell positive and negative pole, its feature exists In described barrier film has polyolefin porous separator basic unit and the high temperature resistance being arranged in described polyolefin porous separator basic unit Mixed coating.
2. barrier film according to claim 1, it is characterised in that the thickness of described mixed coating is:3 μm~4 μm.
3. barrier film according to claim 1 or 2, it is characterised in that described mixed coating includes being close to described polyene The ceramics layer of hydrocarbon porous septum basic unit, is arranged at the first PVDF layers on described ceramics layer.
4. barrier film according to claim 3, it is characterised in that the one side that described positive pole is close to described barrier film has 2nd PVDF layers, the described first PVDF layers with the 2nd PVDF layers mutually merge.
5. a kind of lithium ion battery, including barrier film, it is characterised in that described barrier film is described in any one of Claims 1-4 Barrier film.
CN201720025034.5U 2017-01-10 2017-01-10 A kind of barrier film and lithium ion battery for lithium ion battery Expired - Fee Related CN206505967U (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807806A (en) * 2018-08-23 2018-11-13 河北金力新能源科技股份有限公司 A kind of battery diaphragm and preparation method thereof
CN109181522A (en) * 2018-07-17 2019-01-11 河北金力新能源科技股份有限公司 Aramid fiber coating liquid, lithium ion battery separator and preparation method thereof
CN110635090A (en) * 2019-09-27 2019-12-31 宁德卓高新材料科技有限公司 Preparation method of high-heat-resistance vinylidene fluoride polymer mixed coating diaphragm
CN110707265A (en) * 2019-09-23 2020-01-17 河北金力新能源科技股份有限公司 Aramid fiber coating liquid, preparation method thereof, diaphragm based on aramid fiber coating liquid and application
CN111370625A (en) * 2020-03-22 2020-07-03 华南理工大学 Aramid fiber phase-transition coating lithium ion battery diaphragm and preparation method thereof
CN112290165A (en) * 2020-11-05 2021-01-29 青岛蓝科途膜材料有限公司 Lithium ion battery diaphragm, preparation method and lithium ion battery
CN113136121A (en) * 2021-04-14 2021-07-20 合肥利夫生物科技有限公司 Bio-based diaphragm coating liquid, preparation method thereof and application thereof in lithium battery
CN113394516A (en) * 2021-05-25 2021-09-14 惠州锂威电子科技有限公司 Lithium ion battery diaphragm, preparation method thereof and lithium ion battery
CN113675530A (en) * 2021-08-23 2021-11-19 长园泽晖新能源材料研究院(珠海)有限公司 PVDF (polyvinylidene fluoride) diaphragm taking nano silicon dioxide as filler

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109181522A (en) * 2018-07-17 2019-01-11 河北金力新能源科技股份有限公司 Aramid fiber coating liquid, lithium ion battery separator and preparation method thereof
CN109181522B (en) * 2018-07-17 2020-08-18 河北金力新能源科技股份有限公司 Aramid fiber coating liquid, lithium ion battery diaphragm and preparation method thereof
CN108807806A (en) * 2018-08-23 2018-11-13 河北金力新能源科技股份有限公司 A kind of battery diaphragm and preparation method thereof
CN110707265A (en) * 2019-09-23 2020-01-17 河北金力新能源科技股份有限公司 Aramid fiber coating liquid, preparation method thereof, diaphragm based on aramid fiber coating liquid and application
CN110635090A (en) * 2019-09-27 2019-12-31 宁德卓高新材料科技有限公司 Preparation method of high-heat-resistance vinylidene fluoride polymer mixed coating diaphragm
CN110635090B (en) * 2019-09-27 2022-04-29 宁德卓高新材料科技有限公司 Preparation method of high-heat-resistance vinylidene fluoride polymer mixed coating diaphragm
CN111370625A (en) * 2020-03-22 2020-07-03 华南理工大学 Aramid fiber phase-transition coating lithium ion battery diaphragm and preparation method thereof
CN112290165A (en) * 2020-11-05 2021-01-29 青岛蓝科途膜材料有限公司 Lithium ion battery diaphragm, preparation method and lithium ion battery
CN113136121A (en) * 2021-04-14 2021-07-20 合肥利夫生物科技有限公司 Bio-based diaphragm coating liquid, preparation method thereof and application thereof in lithium battery
CN113394516A (en) * 2021-05-25 2021-09-14 惠州锂威电子科技有限公司 Lithium ion battery diaphragm, preparation method thereof and lithium ion battery
CN113675530A (en) * 2021-08-23 2021-11-19 长园泽晖新能源材料研究院(珠海)有限公司 PVDF (polyvinylidene fluoride) diaphragm taking nano silicon dioxide as filler

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