CN103408975A - Coating material for lithium ion battery diaphragm - Google Patents
Coating material for lithium ion battery diaphragm Download PDFInfo
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- CN103408975A CN103408975A CN2013103566280A CN201310356628A CN103408975A CN 103408975 A CN103408975 A CN 103408975A CN 2013103566280 A CN2013103566280 A CN 2013103566280A CN 201310356628 A CN201310356628 A CN 201310356628A CN 103408975 A CN103408975 A CN 103408975A
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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 relates to a coating material for a lithium ion battery diaphragm. According to the invention, an organic-inorganic composite coating system is adopted, an inorganic ingredient and an organic ingredient are uniformly dispersed to form the coating material, and the coating material has good malleability on the surface of a polyolefin material and can form an uniform organic-inorganic composite coating on the outer surface of the lithium ion battery diaphragm and on the inner surfaces of tunnels after curing. Through coating of the coating material, a porous structure of the polyolefin diaphragm is kept, and electrolyte solution wellability and conservation rate, electrochemical stability, mechanical strength and heat stability of the diaphragm are improved. The diaphragm coated with the coating material can improve cycling stability, safety and a service life of the lithium ion battery.
Description
Technical field
The present invention relates to a kind of lithium ion battery separator coated material.
Background technology
China has been now global battery manufacture big country, and the output of battery and export volume all occupy the first in the world.China's lithium ion battery industrialization starts from the later stage in 1997, reaches 800,000,000 in 2004, surges to 38% in the market share of world market, is only second to Japan.In 2005 ~ 2008 years, the lithium ion battery world market share of China was stabilized in 34% left and right.
Lithium ion battery mainly contains four parts and forms, and is respectively positive electrode material, negative material, barrier film and electrolytic solution.
In the structure of lithium cell, barrier film is one of crucial interior layer assembly.The performance of barrier film has determined the interface structure, internal resistance of battery etc., directly affects the characteristics such as capacity, circulation and safety performance of battery, and the barrier film of excellent performance has important effect to the over-all properties that improves battery.
The Main Function of barrier film is that the positive and negative electrode of battery is separated, and prevents the two poles of the earth contacts and short circuit has the function that electrolyte ion is passed through in addition.The barrier film material is nonconducting, and its physicochemical property have a great impact the performance of battery.The kind difference of battery, the barrier film of employing are also different.
Battery diaphragm has played vital effect in battery, so barrier film need to possess and have excellent mechanical property, thermostability, chemical stability and relatively inexpensive characteristics.
But, no matter polyalkene diaphragm prepared by current dry method or wet method still exists thermostability bad, having caused the safety issue of battery, battery explosion or combustion incident many times appearred in life.Barrier film is poor to the wetting property of electrolytic solution simultaneously, causes battery electrical property and cycle performance poor.And, due to bad to electrolytical wetting property, make polyalkene diaphragm Shortcomings on battery charging and discharging speed and cycle life, to the large size battery, its defect is particularly evident.
Summary of the invention
The purpose of this invention is to provide a kind of lithium ion battery separator coated material, with the thermostability of the business-like polyalkene diaphragm that improves current use with to electrolytical wetting property.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of lithium ion battery separator coated material is characterized in that the composition of this coated material and quality percentage composition are:
Inorganic component 1～24%
Organic constituent 0.4～6%
Solvent 70～97%
Additive 0.1 ~ 1.2%
Described inorganic component is: at least a in Nano particles of silicon dioxide, aluminium sesquioxide nanoparticle, zirconium dioxide nanoparticles, titanium dioxide nano-particle, cerium dioxide, yttrium oxide;
Described organic constituent is: polyvinylidene difluoride (PVDF) PVdF, polyvinylidene difluoride (PVDF)-R 1216 PVdF-HFP, polymetylmethacrylate, the poly-acetimide of polyvinylpyrrolidone PVP, PEI, at least a in PVAC polyvinylalcohol, polyene third class amine PAH, polyacrylic acid PAA;
Described additive is at least a in diethanolamine, Dopamine HCL, catechol, citric acid, oxysuccinic acid, oxyacetic acid, γ-(methacryloxypropyl) propyl trimethoxy silicane, water.
Above-mentioned solvent is at least a in methyl alcohol, ethanol, Virahol, acetone, butanone, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate etc.
Above-mentioned inorganic nano-particle particle diameter is 5 ~ 50 nm.
Above-mentioned lithium ion battery separator with organic and inorganic complex intensifying coating production is:
A) inorganic component, organic constituent are joined according to a certain percentage in the solvent that contains a certain amount of additive and disperse, the mechanically mixing such as that dispersing method can adopt is ultrasonic, high speed shear;
B) then at 20-30 ℃ of temperature, adopt the coating process film forming such as dip coating, casting method, the consumption of coating fluid is 2-20 g/m
2, finally adopt 40-60 ℃ of dry 0.5-2min.
The advantage of the inventive method is as described below:
(1) the present invention modifies polyalkene diaphragm by the compound high dispersive system of organic and inorganic system, composite diaphragm can keep the pore passage structure of original membrane, and not obvious increase membrane thicknesses, the barrier film porosity after coating modifying and the ratio of barrier film initial porosity are greater than 80%.
(2) coating material of the present invention's employing can infiltrate the barrier film duct, outside surface and duct internal surface at barrier film after solidifying form uniform organic and inorganic compound coating, thereby strengthened the mechanical property, thermostability of polyalkene diaphragm, to the liquid holdup of electrolytic solution, and electrochemistry stability.With the polyalkene diaphragm of strengthened coat modified, heat 1h at 150 ℃, shrinking percentage is less than 10%; Its liquid holdup is greater than 260%, and electrochemical stability window is brought up to 5.0 V.
(3) processing method of the present invention is simple, and the reaction conditions gentleness is convenient to production control and popularization.
The accompanying drawing explanation
Fig. 1 is the field emission electron scanning electron microscope (SEM) photograph of original state PE barrier film
Fig. 2 is for applying the field emission electron scanning electron microscope (SEM) photograph of strengthened coat PE barrier film.
Fig. 3 is the photo of original state PE barrier film.
Fig. 4 is for applying the photo of strengthened coat PE barrier film.
Fig. 5 is the photo of PE film after heating 0.5h under 150 ℃.
Fig. 6 is for applying the contractible graph of strengthened coat PE barrier film after heating 0.5h under 150 ℃.
Embodiment
Below by non-limiting examples, the present invention is described.
Embodiment 1:The SiO that particle diameter is about to 10 nm
2Nanoparticle 3.0g, PVDF 0.9g, γ-(methacryloxypropyl) propyl trimethoxy silicane 0.3g, catechol 0.1g, acetone 200 g.High speed shear is mixed 2h, then adopts dip coating to be coated with on the single-layer polypropylene barrier film.In the process of dip-coating film forming, the timed interval between dip-coating is 240s each time, and after immersing, the residence time is 10s, repeats dip-coating 3 times, then under 50 ℃ of heating, dries 1min, and coated weight is about 3 g/m
2.
Embodiment 2:The TiO that particle diameter is about to 30 nm
2Nanoparticle 5.0g, polyvinylpyrrolidone 6.0g, oxyacetic acid 0.4g, join in methyl alcohol 200g, ultrasonic mixing 0.5 h, then adopt dip coating film forming on the monolayer polyethylene barrier film.In the process of dip-coating film forming, the timed interval between dip-coating is 240s each time, and after immersing, the residence time is 10s, adopts under 50 ℃ of heating and dries 1min.Repeat dip-coating 2 times, then under 50 ℃ of heating, dry 1min, coated weight is about 4 g/m
2.
Embodiment 3:Particle diameter is about to 15 nm ZrO
2Nanoparticle 13.4g, PVDF-HFP 11.2g, diethanolamine 1.6g, water 0.8g, join in the mixed solvent of methyl alcohol 60.0g and acetone 100.0g, ultrasonic mixing 0.5h, then
AdoptBy dip coating film forming on the monolayer polyethylene barrier film.The timed interval between dip-coating is 240s each time, and after immersing, the residence time is 10s, adopts under 50 ℃ of heating and dries 2min.Repeat dip-coating 2 times, then under 50 ℃ of heating, dry 1min, coated weight is about 3 g/m
2.
Embodiment 4:Particle diameter is about to 20 nm SiO
2Nanoparticle 6.0g, citric acid 0.5g, γ-(methacryloxypropyl) propyl trimethoxy silicane 0.4g, PVDF-HFP 6.0g, join in the mixed solvent of methyl alcohol 60g and acetone 120g, ultrasonic mixing 0.5h, then adopt dip coating film forming on the monolayer polyethylene barrier film.The timed interval between dip-coating is 240s each time, and after immersing, the residence time is 10s, repeats dip-coating 2 times, then under 50 ℃ of heating, dries 0.5min.Coated weight is about 2 g/m
2.
Embodiment 5: particle diameter is about to 50 nm Al
2O
3Nanoparticle 6.0g, oxysuccinic acid 0.5g, γ-(methacryloxypropyl) propyl trimethoxy silicane 0.6g, PMMA 3.0g, join in the mixed solvent of methyl alcohol 100g and acetone 100g, ultrasonic mixing 1.0 h, then adopt casting method single face film forming on the single-layer polypropylene barrier film, the coating fluid extrusion capacity is 10g/min, after applying 5 times, dry 0.5min under 50 ℃ of heating, then on the uncoated another side of barrier film, repeat above-mentioned steps, coated weight is about 10 g/m
2.
Embodiment 6: the ZrO that particle diameter is about to 15 nm
2Nanoparticle 28.0g, particle diameter are about the SiO of 10 nm
2Nanoparticle 18.0g, PEI 10.0g, water 2.0g, join ethanol 140.0 g, ultrasonic mixing 2.0 h, then adopt casting method single face film forming on the monolayer polyethylene barrier film, the coating fluid extrusion capacity is 10g/min, after coating, dry 0.5min under 50 ℃ of heating, then on the uncoated another side of barrier film, repeat above-mentioned steps, coated weight is about 6.0 g/m
2.
Contrast Fig. 1 and Fig. 2 can find out that the PE barrier film that is coated with strengthened coat has kept original pore passage structure; Comparison diagram 3 and Fig. 5 can find out, simple PE barrier film poor heat resistance, 150
oUnder the C condition, shrink serious; And comparison diagram 4 and Fig. 6 can find out, strengthened coat can improve the thermostability of PE barrier film.
Claims (3)
1. lithium ion battery separator coated material is characterized in that the composition of this coated material and quality percentage composition are:
Inorganic component 1～24%
Organic constituent 0.4～6%
Solvent 70～97%
Additive 0.1 ~ 1.2%
Described inorganic component is: at least a in Nano particles of silicon dioxide, aluminium sesquioxide nanoparticle, zirconium dioxide nanoparticles, titanium dioxide nano-particle, cerium dioxide, yttrium oxide;
Described organic constituent is: polyvinylidene difluoride (PVDF) PVdF, polyvinylidene difluoride (PVDF)-R 1216 PVdF-HFP, polymetylmethacrylate, the poly-acetimide of polyvinylpyrrolidone PVP, PEI, at least a in PVAC polyvinylalcohol, polyene third class amine PAH, polyacrylic acid PAA;
Described additive is at least a in diethanolamine, Dopamine HCL, catechol, citric acid, oxysuccinic acid, oxyacetic acid, γ-(methacryloxypropyl) propyl trimethoxy silicane, water.
2. lithium ion battery separator coated material according to claim 1, is characterized in that described solvent is at least a in methyl alcohol, ethanol, Virahol, acetone, butanone, ethylene dichloride, tetrahydrofuran (THF), ethyl acetate etc.
3. lithium ion battery separator coated material according to claim 1, is characterized in that described inorganic nano-particle particle diameter is 5 ~ 50 nm.
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| CN2013103566280A CN103408975A (en) | 2013-08-16 | 2013-08-16 | Coating material for lithium ion battery diaphragm |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104051691A (en) * | 2014-06-06 | 2014-09-17 | 中国第一汽车股份有限公司 | Preparation method of polydopamine-based modified composite polymer diaphragm |
| CN104112833A (en) * | 2014-06-06 | 2014-10-22 | 珠海光宇电池有限公司 | Lithium ion battery separating membrane, preparing method thereof and applications of the separating membrane |
| CN104804569A (en) * | 2015-03-27 | 2015-07-29 | 上海大学 | Organic-inorganic hybrid coating material for polyolefin membrane of lithium ion battery |
| CN106654127A (en) * | 2016-12-23 | 2017-05-10 | 合肥星源新能源材料有限公司 | High-wettability lithium-ion battery separator and preparation method thereof |
| CN106928777A (en) * | 2017-02-23 | 2017-07-07 | 上海杰宁新能源科技发展有限公司 | The preparation method of adjustment hole structure coating material, coating coating method and coating |
| CN107845759A (en) * | 2017-11-01 | 2018-03-27 | 安徽安凯汽车股份有限公司 | A kind of preparation technology of new energy battery composite fibre barrier film |
| CN109119680A (en) * | 2018-08-27 | 2019-01-01 | 江苏中兴派能电池有限公司 | A kind of preparation method of lithium ion battery with high energy density |
| CN109244320A (en) * | 2018-09-17 | 2019-01-18 | 湖北江升新材料有限公司 | A kind of secure high performance lithium ion battery separator and preparation method thereof |
| WO2019104927A1 (en) * | 2017-11-28 | 2019-06-06 | 东莞理工学院 | Method for preparing carbon-coated cerium dioxide hollow sphere |
| WO2020107282A1 (en) * | 2018-11-28 | 2020-06-04 | 湖南中锂新材料有限公司 | Composite separator, preparation method therefor and lithium ion battery containing same |
| CN113555645A (en) * | 2021-06-01 | 2021-10-26 | 惠州锂威新能源科技有限公司 | Modified diaphragm, lithium ion battery and power consumption device |
| CN113851787A (en) * | 2021-09-29 | 2021-12-28 | 中材锂膜有限公司 | Composite diaphragm, preparation method thereof and secondary battery |
| CN114122620A (en) * | 2021-11-25 | 2022-03-01 | 江苏厚生新能源科技有限公司 | High-flame-retardant high-mechanical-strength high-adhesion lithium ion battery diaphragm and preparation method thereof |
| US11289770B2 (en) | 2018-02-19 | 2022-03-29 | Lg Energy Solution, Ltd. | Separator including separator base with coating layer including structural unit derived from sulfonic acid containing catechol/pyrogallol and dopamine, manufacturing method therefor, and lithium-sulfur battery comprising same |
| CN114335882A (en) * | 2021-12-09 | 2022-04-12 | 河北工程大学 | Modified PE-based lithium ion battery diaphragm and preparation method thereof |
| US11539099B2 (en) | 2017-12-06 | 2022-12-27 | Lg Energy Solution, Ltd. | Slurry composition for coating secondary battery separator and secondary battery separator prepared using same |
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| US20050084761A1 (en) * | 2002-02-26 | 2005-04-21 | Volker Hennige | Electric separator, method for the production and use thereof |
| CN101281961A (en) * | 2007-04-06 | 2008-10-08 | 比亚迪股份有限公司 | Coating composition for lithium ion battery diaphragm and method for making the same |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104112833A (en) * | 2014-06-06 | 2014-10-22 | 珠海光宇电池有限公司 | Lithium ion battery separating membrane, preparing method thereof and applications of the separating membrane |
| CN104051691A (en) * | 2014-06-06 | 2014-09-17 | 中国第一汽车股份有限公司 | Preparation method of polydopamine-based modified composite polymer diaphragm |
| CN104804569A (en) * | 2015-03-27 | 2015-07-29 | 上海大学 | Organic-inorganic hybrid coating material for polyolefin membrane of lithium ion battery |
| CN106654127A (en) * | 2016-12-23 | 2017-05-10 | 合肥星源新能源材料有限公司 | High-wettability lithium-ion battery separator and preparation method thereof |
| CN106928777A (en) * | 2017-02-23 | 2017-07-07 | 上海杰宁新能源科技发展有限公司 | The preparation method of adjustment hole structure coating material, coating coating method and coating |
| CN107845759B (en) * | 2017-11-01 | 2021-01-29 | 安徽安凯汽车股份有限公司 | Preparation process of new energy battery composite fiber diaphragm |
| CN107845759A (en) * | 2017-11-01 | 2018-03-27 | 安徽安凯汽车股份有限公司 | A kind of preparation technology of new energy battery composite fibre barrier film |
| WO2019104927A1 (en) * | 2017-11-28 | 2019-06-06 | 东莞理工学院 | Method for preparing carbon-coated cerium dioxide hollow sphere |
| US10654020B2 (en) | 2017-11-28 | 2020-05-19 | Dongguan University Of Technology | Preparation method of carbon-coated ceria hollow sphere |
| US11539099B2 (en) | 2017-12-06 | 2022-12-27 | Lg Energy Solution, Ltd. | Slurry composition for coating secondary battery separator and secondary battery separator prepared using same |
| US11289770B2 (en) | 2018-02-19 | 2022-03-29 | Lg Energy Solution, Ltd. | Separator including separator base with coating layer including structural unit derived from sulfonic acid containing catechol/pyrogallol and dopamine, manufacturing method therefor, and lithium-sulfur battery comprising same |
| CN109119680A (en) * | 2018-08-27 | 2019-01-01 | 江苏中兴派能电池有限公司 | A kind of preparation method of lithium ion battery with high energy density |
| CN109244320A (en) * | 2018-09-17 | 2019-01-18 | 湖北江升新材料有限公司 | A kind of secure high performance lithium ion battery separator and preparation method thereof |
| WO2020107282A1 (en) * | 2018-11-28 | 2020-06-04 | 湖南中锂新材料有限公司 | Composite separator, preparation method therefor and lithium ion battery containing same |
| CN113555645A (en) * | 2021-06-01 | 2021-10-26 | 惠州锂威新能源科技有限公司 | Modified diaphragm, lithium ion battery and power consumption device |
| CN113555645B (en) * | 2021-06-01 | 2023-09-05 | 惠州锂威新能源科技有限公司 | Modified diaphragm, lithium ion battery and power utilization device |
| CN113851787A (en) * | 2021-09-29 | 2021-12-28 | 中材锂膜有限公司 | Composite diaphragm, preparation method thereof and secondary battery |
| CN114122620A (en) * | 2021-11-25 | 2022-03-01 | 江苏厚生新能源科技有限公司 | High-flame-retardant high-mechanical-strength high-adhesion lithium ion battery diaphragm and preparation method thereof |
| CN114122620B (en) * | 2021-11-25 | 2023-09-01 | 江苏厚生新能源科技有限公司 | Lithium ion battery diaphragm with high flame retardance, high mechanical strength and high bonding performance and preparation method |
| CN114335882A (en) * | 2021-12-09 | 2022-04-12 | 河北工程大学 | Modified PE-based lithium ion battery diaphragm and preparation method thereof |
| CN114335882B (en) * | 2021-12-09 | 2024-01-30 | 河北工程大学 | Modified PE-based lithium ion battery diaphragm and preparation method thereof |
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Application publication date: 20131127 |