CN103456908A - High security diaphragm and high capacity lithium ion power battery using high security diaphragm - Google Patents
High security diaphragm and high capacity lithium ion power battery using high security diaphragm Download PDFInfo
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- CN103456908A CN103456908A CN2012101669837A CN201210166983A CN103456908A CN 103456908 A CN103456908 A CN 103456908A CN 2012101669837 A CN2012101669837 A CN 2012101669837A CN 201210166983 A CN201210166983 A CN 201210166983A CN 103456908 A CN103456908 A CN 103456908A
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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 belongs to the technical field of batteries, and relates to a high security diaphragm and a high capacity lithium ion power battery using the high security diaphragm. The high security diaphragm comprises two parts comprising a substrate layer and a coating layer, the coating layer is double-sided, the diaphragm structure is coating layer-substrate layer-coating layer, the mass ratio of the substrate layer to the coating layer is 1:1-2, , a material for the substrate layer is polyolefin, a material for the coating layer is inorganic nano ceramic particles, and the substrate layer and the coating layer are fixed through an adhesive. According to the high security diaphragm, the surface of the polyolefin diaphragm is coated with the double-layer high-temperature-resistant inorganic nano ceramic particles, the security of the diaphragm can be essentially improved, when the battery is in an abuse state, even if the polymer substrate is melted, the high-temperature-resistant inorganic ceramic particles still can effectively prevent short circuit between positive and negative electrodes to greatly improve security performances. The diaphragm has excellent thermal stability, when the diaphragm is placed in the condition of 120 DEG for 1h, the transverse thermal contraction is 0%, and the longitudinal thermal shrinkage is 1.0-2.0%.
Description
Technical field
The invention belongs to the battery technology field, relate to a kind of high security barrier film and adopt the high-capacity lithium-ion electrokinetic cell of this barrier film.
Background technology
In recent years, the application of lithium-ion-power cell on the main equipments such as electric tool, electric bicycle, LEV (Light Electric Vehicle) day by day receives publicity and studies, high-capacity lithium-ion power battery, in the utilization process of electric automobile, needs primary factor and the technical problem considered are how to guarantee the fail safe of battery.Can the solution safety issue is related to lithium ion battery become electric automobile power battery, and finally makes electric automobile sail one of key factor of common people family into.Barrier film plays a part the most key to the fail safe of lithium ion battery.(inner partial short-circuit, external short circuit, overcharge etc.) is easy to induce inside battery high temperature to large-scale lithium ion battery at abuse during state, cause the barrier film of battery to shrink, melt, and then cause the short circuit of inside battery large tracts of land, the aggravation thermal accumlation, cause thermal runaway, produce the inside battery hyperbar, cause battery burning or blast.In order to meet the needs of high capacity lithium ion battery development, to develop resistant to elevated temperatures high security barrier film, it is the active demand that improves the electrokinetic cell security performance.
In recent years, barrier film manufacturer developed the high security barrier film one after another both at home and abroad, and there has been matured product in part producer.Relatively external, domestic producer's exploitation is relatively slow, mostly in development, large-scale matured product do not occur so far.Patent CN 101626095A is disclosed a kind of for improving the method for modifying of lithium ion battery security, in the technical process of manufacturing lithium ion battery, barrier film is heat-treated to technique, to improve the thermal stability of barrier film, but this method has certain limitation, barrier film fail safe after Overheating Treatment does not obtain the lifting of internal, still can not meet the requirement of electrokinetic cell high safety performance; Patent 101567434A discloses a kind of lithium-ion membrane and application thereof, barrier film be take polymer as matrix, contain homodisperse inorganic filler, the fail safe of barrier film and mechanical strength obtain certain raising, but do not embody advantage in the application aspect the high power capacity electrokinetic cell and security performance.
Summary of the invention
The object of the present invention is to provide a kind of high security lithium ion battery separator with good thermal stability.
The present invention also provides the high-capacity lithium-ion electrokinetic cell that adopts this barrier film, and this battery has good security performance, not on fire under abuse conditions, does not explode.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of high security barrier film, described barrier film is comprised of substrate layer and coat two parts, and described coat is two-sided, and the structure of barrier film is coat-substrate layer-coat; The mass ratio of substrate layer and coat is 1:1 ~ 2, and the material of substrate layer is polyolefin, and the material of coat is the inorganic nano ceramic particle; Between described substrate layer and coat, by binding agent, fix.High security barrier film of the present invention, by at the double-deck resistant to elevated temperatures inorganic nano ceramic particle of polyalkene diaphragm surface-coated, from having promoted in essence the fail safe of barrier film, when battery under the abuse state, even polymeric matrix melts, the existence of high temperature resistant inorganic ceramic particle still can effectively prevent the short circuit between both positive and negative polarity, thereby greatly improves security performance; Adopt the high-capacity lithium-ion electrokinetic cell of this barrier film, under the abuse state, fail safe has obtained remarkable lifting, for the high power capacity electrokinetic cell, in application and the popularization of electric automobile, provides safety guarantee.This barrier film has good thermal stability, under 120 ℃ of conditions, shelves 1h, and laterally thermal contraction is 0%, and vertically thermal contraction is 1.0 ~ 2.0%.
As preferably, the thickness of this barrier film is 30 ~ 40 μ m, and wherein substrate layer thickness is 25 ~ 35 μ m, and every layer of coat thickness is 2.5 ~ 4 μ m.Thickness range is moderate, for electrokinetic cell, has both guaranteed that battery has good chemical property, had guaranteed the security performance of battery simultaneously.
As preferably, described polyolefin is polyethylene, polypropylene, both copolymers or both mixtures.Lithium ion battery separator is generally used polyolefine material at present, the raw material wide material sources, and technology is relatively ripe.
As preferably, described inorganic nano pottery is one or more the mixture in silicon dioxide, alundum (Al2O3), zirconia.Inorganic nano ceramic particle material stable in properties, and there are good high temperature resistant, anticorrosion properties.
As preferably, described binding agent is Kynoar or butadiene-styrene rubber.This two binding agent is current lithium battery field binding agent commonly used, high comprehensive performance.
A kind of preparation method of described high security barrier film, comprise the steps:
A, slurrying: auxiliary agent, binding agent and inorganic nano ceramic particle are added in the high speed planetary ball mill successively, add zirconium oxide balls to carry out ball milling simultaneously, obtaining viscosity is 25 ~ 50 mPas, the inorganic nano ceramic size that fineness is 15 ~ 20 μ m;
B, coating: the inorganic nano ceramic size that the mode of employing intaglio printing obtains step a is applied to the substrate layer surface;
C, oven dry: bake out temperature, at 80 ~ 90 ℃, is dried be controlled at<1000ppm of metacneme moisture.
As preferably, the mass ratio of described auxiliary agent, binding agent and inorganic nano ceramic particle is 1.5 ~ 2.0:4 ~ 5:100.
The high-capacity lithium-ion electrokinetic cell that a kind of described high security barrier film makes.As preferably, it is square soft-package battery.As preferably, the cell capacity of this battery is 20 ~ 50Ah.The high-capacity lithium-ion electrokinetic cell that the present invention obtains, through the acupuncture abuse test, cell voltage remains unchanged, and surface temperature is without significant change, and battery is not on fire, does not explode.Shelve 30min in 150 ℃ of baking ovens, cell voltage reduces by 0.1 ~ 0.2mV, and battery is not on fire, does not explode.
High security lithium ion battery diaphragm of the present invention, by the double-deck inorganic nano ceramic particle that applies on the substrate layer surface, greatly improved the thermal stability of barrier film, on the high power capacity electrokinetic cell, has great application prospect; Be conducive to the high power capacity electrokinetic cell in electric automobile application and universal.The high-capacity lithium-ion electrokinetic cell made by this barrier film, its capacity is 20 ~ 50Ah, is applicable to battery for electric automobile, battery is under abuse conditions, not on fire, does not explode, and has high security, meets the demand of electric automobile for high security.
The accompanying drawing explanation
Fig. 1 is structural representation of the present invention;
In figure: 1, substrate layer, 2, coat.
Embodiment
Below by specific embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is described in further detail.Should be appreciated that enforcement of the present invention is not limited to the following examples, any pro forma accommodation that the present invention is made and/or change all will fall into protection range of the present invention.
In the present invention, if not refer in particular to, all part, percentages are unit of weight, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.
The high security barrier film, be comprised of substrate layer 1 and coat 2 two parts as shown in Figure 1, and described coat is two-sided, and, in two surface distributed of substrate layer 1, the structure of barrier film is coat-substrate layer-coat; The mass ratio of substrate layer and coat is 1:2, and the material of substrate layer is polyolefin, and the material of coat is the inorganic nano ceramic particle; Between described substrate layer and coat, by binding agent, fix.The thickness of barrier film is 30 μ m, and wherein substrate layer thickness is 25 μ m, and every layer of coat thickness is 2.5 μ m.
In the present embodiment, the inorganic nano ceramic particle is nano ceramics alundum (Al2O3) particle, and the preparation method is shown in embodiment 4, and the material of substrate layer is polyethylene.
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Membrane configuration is with embodiment 1, and difference is: the mass ratio of substrate layer and coat is 1:1.5, and the thickness of barrier film is 40 μ m, and wherein substrate layer thickness is 35 μ m, and every layer of coat thickness is 2.5 μ m.In the present embodiment, the inorganic nano ceramic particle is the nano ceramics silica dioxide granule, and the preparation method is shown in embodiment 5, and the material of substrate layer is polypropylene.
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embodiment 3
Membrane configuration is with embodiment 1, and difference is: the mass ratio of substrate layer and coat is 1:1.The thickness of barrier film is 40 μ m, and wherein substrate layer thickness is 32 μ m, and every layer of coat thickness is 4 μ m.In the present embodiment, the inorganic nano ceramic particle is the nano ceramics zirconia particles, and its preparation method, with embodiment 4, is only that the nano-aluminium oxide particle of embodiment 4 is replaced by the nano zircite particle.The material of substrate layer is the copolymer that polyethylene and polypropylene mix with the 1:1 ratio.
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embodiment 4the preparation of barrier film
1, slurrying: the PVDF(Kynoar that is 5:100 by mass ratio) and the nano-aluminium oxide particle join in the high speed planetary ball mill, and then add the NMP(N-methyl pyrrolidone) control solid content 42% ~ 45%, add zirconium oxide balls simultaneously, carry out the high speed ball milling, make the nano ceramics alundum (Al2O3) slurry with certain viscosity and fineness; Wherein slurry viscosity is controlled at 25 ~ 40 mPas, and fineness is controlled at 15 ~ 20 μ m.Wherein NMP is auxiliary agent, for dissolving binding agent PVDF.
2, coating: the nano ceramics alundum (Al2O3) slurry that the mode of employing intaglio printing obtains step 1 is applied to the substrate layer surface.
3, dry: bake out temperature, at 80 ~ 90 ℃, is dried be controlled at<1000ppm of metacneme moisture, and NMP content is controlled at and is less than 50ppm.
?
embodiment 5the preparation of barrier film
1. slurrying: the CMC(sodium carboxymethylcellulose that is 1.5:100:4 by mass ratio), nanometer silicon dioxide particle and SBR(butadiene-styrene rubber) add successively in the high speed planetary ball mill, add appropriate pure water to regulate solid content 40% ~ 43%, add zirconium oxide balls simultaneously, carry out the high speed ball milling, make the nano ceramics silica slurry with certain viscosity and fineness; Wherein slurry viscosity is controlled at 30 ~ 50 mPas; CMC is sagging inhibitor.
2. coating: the nano ceramics silica slurry that the mode of employing intaglio printing obtains step 1 is applied to the substrate layer surface.
3. dry: bake out temperature, at 80 ~ 90 ℃, is dried be controlled at<1000ppm of metacneme moisture.
the making of embodiment 6 electrokinetic cells
The barrier film that adopts embodiment 1-3 to make, using LiFePO4 as positive electrode, and Delanium is as negative material, carries out successively slurrying, is coated with, rolls, punching, assembling procedure, and after battery pole piece assemble, first 80 ℃ of battery liquid-filling toasts 6 ~ 10h; Then carry out fluid injection, find time, seal, change into by normal flow, the Soft Roll electrokinetic cell that the capacity of being made into is 20Ah.Electrokinetic cell be made as prior art, the emphasis that non-the present invention will study, the difference of the present embodiment only is the barrier film difference adopted, and therefore at this, does not elaborate.
After battery completes, randomly draw 10 batteries, carry out acupuncture, hot case safety experiment under full power state; Cell safety test, on fire, do not explode, security performance is ungood.
the making of embodiment 7 electrokinetic cells
The barrier film that adopts embodiment 1-3 to make, using LiFePO4 as positive electrode, and Delanium is as negative material, carries out successively slurrying, is coated with, rolls, punching, assembling procedure, and after battery pole piece assemble, first 80 ℃ of battery liquid-filling toasts 6 ~ 10h; Then carry out fluid injection, find time, seal, change into by normal flow, the Soft Roll electrokinetic cell that the capacity of being made into is 50Ah.
After battery completes, randomly draw 10 batteries, carry out acupuncture, hot case safety experiment under full power state; Cell safety test, on fire, do not explode, security performance is ungood.
relevant test data:
1, the thermal stability of high security barrier film:
Randomly draw the barrier film that 10 groups of embodiment 1-3 make, every group all is cut into two that size is 10cm*10cm, and wherein a slice is placed in 120 ℃ of baking ovens, keeps 1h, takes out barrier film, toasts metacneme longitudinal contraction average out to 1%, cross-direction shrinkage average out to 0%; Therefore, barrier film has good thermal stability.
2, the security performance of high power capacity electrokinetic cell
1) randomly draw 50Ah electrokinetic cell prepared by 10 groups of embodiment 1-3, carry out the acupuncture abuse test.
Test condition is: the thin 5mm of pin, and the syringe needle translational speed is 1.4 ~ 1.5cm/sec; Acupuncture abuse test result: battery is not on fire, does not smolder, by test;
2) hot case test: oven temperature is risen to 150 ℃, the 50Ah high power capacity electrokinetic cell of step 1) is put into, after the battery surface temperature reaches 150 ℃, keep 30min, take out battery, the battery slight expansion, cell voltage decline 0.1V, aluminum plastic film does not ftracture, and battery does not explode, not on fire, fail safe is good.
Above-described embodiment is a kind of preferably scheme of the present invention, not the present invention is done to any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim puts down in writing.
Claims (10)
1. a high security barrier film, it is characterized in that: described barrier film is comprised of substrate layer and coat two parts, and described coat is two-sided, and the structure of barrier film is coat-substrate layer-coat; The mass ratio of substrate layer and coat is 1:1 ~ 2, and the material of substrate layer is polyolefin, and the material of coat is the inorganic nano ceramic particle; Between described substrate layer and coat, by binding agent, fix.
2. high security barrier film according to claim 1, it is characterized in that: the thickness of this barrier film is 30 ~ 40 μ m, and wherein substrate layer thickness is 25 ~ 35 μ m, and every layer of coat thickness is 2.5 ~ 4 μ m.
3. high security barrier film according to claim 1, it is characterized in that: described polyolefin is polyethylene or polypropylene.
4. according to claim 1 or 2 or 3 described high security barrier films, it is characterized in that: described inorganic nano pottery is one or more the mixture in silicon dioxide, alundum (Al2O3), zirconia.
5. according to claim 1 or 2 or 3 described high security barrier films, it is characterized in that: described binding agent is Kynoar or butadiene-styrene rubber.
6. the preparation method of a high security barrier film claimed in claim 1, is characterized in that comprising the steps:
A, slurrying: auxiliary agent, binding agent and inorganic nano ceramic particle are added in the high speed planetary ball mill successively, add zirconium oxide balls to carry out ball milling simultaneously, obtaining viscosity is 25 ~ 50 mPas, the inorganic nano ceramic size that fineness is 15 ~ 20 μ m;
B, coating: the inorganic nano ceramic size that the mode of employing intaglio printing obtains step a is applied to the substrate layer surface;
C, oven dry: bake out temperature, at 80 ~ 90 ℃, is dried be controlled at<1000ppm of metacneme moisture.
7. preparation method according to claim 6, it is characterized in that: the mass ratio of described auxiliary agent, binding agent and inorganic nano ceramic particle is 1.5 ~ 2.0:4 ~ 5:100.
8. a high-capacity lithium-ion electrokinetic cell that adopts high security barrier film as claimed in claim 1 to make.
9. high-capacity lithium-ion electrokinetic cell according to claim 8 is characterized in that: it is square soft-package battery.
10. high-capacity lithium-ion electrokinetic cell according to claim 8, it is characterized in that: the cell capacity of this battery is 20 ~ 50Ah.
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| CN2012101669837A CN103456908A (en) | 2012-05-28 | 2012-05-28 | High security diaphragm and high capacity lithium ion power battery using high security diaphragm |
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| CN2012101669837A CN103456908A (en) | 2012-05-28 | 2012-05-28 | High security diaphragm and high capacity lithium ion power battery using high security diaphragm |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105449143A (en) * | 2014-10-13 | 2016-03-30 | 万向A一二三***有限公司 | Lithium ion battery coating diaphragm and preparation method therefor |
| CN105932196A (en) * | 2016-05-04 | 2016-09-07 | 合肥国轩高科动力能源有限公司 | Preparation method for butadiene-styrene-rubber-coated lithium ion battery ceramic diaphragm, and ceramic diaphragm |
| CN105932206A (en) * | 2016-07-13 | 2016-09-07 | 洛阳力容新能源科技有限公司 | Lithium supplement composite diaphragm, preparation method and application |
| CN106531941A (en) * | 2017-01-10 | 2017-03-22 | 天津理工大学 | Ceramic slurry for lithium battery separator and preparation method and application method of ceramic slurry |
| CN106602124A (en) * | 2016-12-22 | 2017-04-26 | 多氟多（焦作）新能源科技有限公司 | Stacked-type electrode assembly and preparation method thereof, lithium battery and battery module |
| CN107394278A (en) * | 2017-07-26 | 2017-11-24 | 王昌国 | A kind of manufacture method of lithium ion battery of electric automobile |
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| CN109360921A (en) * | 2018-09-17 | 2019-02-19 | 湖北江升新材料有限公司 | A kind of lithium ion battery ceramic diaphragm and manufacturing method |
| CN109659470A (en) * | 2018-11-30 | 2019-04-19 | 欣旺达电子股份有限公司 | A kind of preparation method of ceramic diaphragm, ceramic diaphragm and dynamic lithium battery |
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| CN111599968A (en) * | 2020-05-29 | 2020-08-28 | 珠海冠宇动力电池有限公司 | Diaphragm, preparation method thereof and lithium ion power battery comprising diaphragm |
| CN111900460A (en) * | 2020-08-28 | 2020-11-06 | 常州赛得能源科技有限公司 | Solid electrolyte with self-supporting structure, preparation method and application |
| CN112909429A (en) * | 2019-11-15 | 2021-06-04 | 珠海恩捷新材料科技有限公司 | Power battery diaphragm and lithium battery thereof |
| CN113823829A (en) * | 2020-06-12 | 2021-12-21 | 厦门大学 | High-temperature-resistant lithium ion battery system and charging and discharging method thereof |
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| CN105449143A (en) * | 2014-10-13 | 2016-03-30 | 万向A一二三***有限公司 | Lithium ion battery coating diaphragm and preparation method therefor |
| CN105932196A (en) * | 2016-05-04 | 2016-09-07 | 合肥国轩高科动力能源有限公司 | Preparation method for butadiene-styrene-rubber-coated lithium ion battery ceramic diaphragm, and ceramic diaphragm |
| CN105932206B (en) * | 2016-07-13 | 2020-08-28 | 洛阳力容新能源科技有限公司 | Lithium-supplementing composite diaphragm, preparation method and application |
| CN105932206A (en) * | 2016-07-13 | 2016-09-07 | 洛阳力容新能源科技有限公司 | Lithium supplement composite diaphragm, preparation method and application |
| CN106602124A (en) * | 2016-12-22 | 2017-04-26 | 多氟多（焦作）新能源科技有限公司 | Stacked-type electrode assembly and preparation method thereof, lithium battery and battery module |
| CN106531941A (en) * | 2017-01-10 | 2017-03-22 | 天津理工大学 | Ceramic slurry for lithium battery separator and preparation method and application method of ceramic slurry |
| CN107394278A (en) * | 2017-07-26 | 2017-11-24 | 王昌国 | A kind of manufacture method of lithium ion battery of electric automobile |
| CN109994691A (en) * | 2017-12-29 | 2019-07-09 | 宁德时代新能源科技股份有限公司 | Separator, method for preparing the same, and electrochemical device comprising the same |
| CN109994691B (en) * | 2017-12-29 | 2021-09-21 | 宁德时代新能源科技股份有限公司 | Separator, method for preparing the same, and electrochemical device comprising the same |
| CN108400336A (en) * | 2018-03-17 | 2018-08-14 | 东华理工大学 | A kind of high-safety polymer lithium ion battery anode glue size and preparation method thereof and lithium ion battery |
| CN109360921A (en) * | 2018-09-17 | 2019-02-19 | 湖北江升新材料有限公司 | A kind of lithium ion battery ceramic diaphragm and manufacturing method |
| CN109659470A (en) * | 2018-11-30 | 2019-04-19 | 欣旺达电子股份有限公司 | A kind of preparation method of ceramic diaphragm, ceramic diaphragm and dynamic lithium battery |
| CN112909429A (en) * | 2019-11-15 | 2021-06-04 | 珠海恩捷新材料科技有限公司 | Power battery diaphragm and lithium battery thereof |
| CN112909429B (en) * | 2019-11-15 | 2023-07-25 | 珠海恩捷新材料科技有限公司 | Power battery diaphragm and lithium battery thereof |
| CN111599968A (en) * | 2020-05-29 | 2020-08-28 | 珠海冠宇动力电池有限公司 | Diaphragm, preparation method thereof and lithium ion power battery comprising diaphragm |
| CN113823829A (en) * | 2020-06-12 | 2021-12-21 | 厦门大学 | High-temperature-resistant lithium ion battery system and charging and discharging method thereof |
| CN113823829B (en) * | 2020-06-12 | 2023-11-07 | 厦门大学 | High-temperature-resistant lithium ion battery system and charging and discharging method thereof |
| CN111900460A (en) * | 2020-08-28 | 2020-11-06 | 常州赛得能源科技有限公司 | Solid electrolyte with self-supporting structure, preparation method and application |
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