CN103515563A - Method for manufacturing ceramic diaphragm for high-safety lithium ion battery - Google Patents
Method for manufacturing ceramic diaphragm for high-safety lithium ion battery Download PDFInfo
- Publication number
- CN103515563A CN103515563A CN201310481960.XA CN201310481960A CN103515563A CN 103515563 A CN103515563 A CN 103515563A CN 201310481960 A CN201310481960 A CN 201310481960A CN 103515563 A CN103515563 A CN 103515563A
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- Prior art keywords
- ceramic
- lithium ion
- suspension
- ion battery
- diaphragm
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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
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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
- 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
-
- 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
A method for manufacturing a ceramic diaphragm for a high-safety lithium ion battery relates to the technical field of manufacturing methods of ceramic diaphragms for lithium ion batteries, and overcomes the technical defect that a conventional diaphragm for the lithium ion battery cannot be thinned to be 16 micrometers. The method comprises the following steps: 1) batching: at first, dissolving PVDF-HFP in NMP to form a glue solution with the solid content of 5-10%, then adding ceramic powder accounting for 1-3% of the weight of the glue solution in the glue solution, stirring to form a suspension, and adding acetone while stirring, diluting till the total solid content is 1-3%, and at last, forming a suspension for standby application through a sand grinding machine; 2) coating: coating the prepared suspension from the step 1) on a polyolefine film through adopting an infiltrating and lifting method; 3) curing: at first, preliminarily drying the coated suspension coating at the drying temperature of 50-80 DEG C, and then extracting NMP in an extraction solvent slot to obtain a ceramic layer with the thickness of 2-4 micrometers through stacking. The strength and the size stability of the diaphragm can be kept, the ceramic is a bad thermal conductor; when a certain point of the battery is short-circuited, heat cannot be diffused to the whole battery, without causing fires and explosion.
Description
Technical field
The present invention relates to the manufacture method technical field of ceramic diaphragm for lithium ion battery.
Background technology
Along with the universal development of intelligent mobile phone battery, the lifting of lithium ion battery energy density is proposed to more and more higher requirement, the important one side of hoist capacity is exactly to reduce the volume of inert matter, and the use of thin membrane is important direction.The barrier film of existing lithium ion battery is after being thinner than 16 μ m, and the security performance such as the overcharging of battery, stove heat, short circuit is seriously deteriorated.
Summary of the invention
In sum, the barrier film that the object of the invention is to solve existing lithium ion battery cannot accomplish to be thinner than the technical deficiency of 16 μ m, and proposes the manufacture method of ceramic diaphragm for a kind of high security lithium ion battery.
For solving technical problem proposed by the invention, the technical scheme of employing is: the manufacture method of ceramic diaphragm for a kind of high security lithium ion battery, is characterized in that described manufacture method includes following steps:
1) batching, first PVDF-HFP is dissolved in NMP, form the glue of solid content 5-10%, then in glue, add the ceramic powders that accounts for glue weight 1-3%, and stir formation suspension, more then add while stirring acetone, being diluted to total solid content is 1-3%, finally the logical sand mill of going over, forms suspension stand-by;
2) applying, adopt and infiltrate the method that lifts by the 1st) suspension that makes of step is coated on polyolefin film;
3) solidify, first, the suspension coating preliminarily dried to coating under the baking temperature of 50 ℃-80 ℃; Then, through extractant groove, NMP is extracted, obtain piling up the thick ceramic layer of formation 2-4 μ m.
Described ceramic powders is selected the ceramic particle of particle size range or class ball-type spherical at 300nm-700nm.
The extractant of described extractant groove is selected its one or more kinds of mixtures in methyl alcohol, ethanol and water.
Beneficial effect of the present invention is: the ceramic layer that applies 2-4 μ m on the barrier film that method of the present invention is produced, can keep every film strength and dimensionally stable, and pottery is hot non-conductor, during battery one-point short circuit, heat can not diffuse to whole battery, can not cause blast on fire.Because PVDF-HFP dissolves difficulty in acetone, generally adopt heating for dissolving, this scheme can cause acetone strongly to volatilize, and fills a prescription unstable; Solvent of the present invention adopts the mixed solution of NMP and acetone, can keep the stable of dicyandiamide solution.The present invention selects the component in electrolyte to be used as pore former, lower boiling material is methyl formate (MF), Ethyl formate (MA), ethyl acetate (EA), high boiling substance is EC, and lower boiling material is to be allowed to condition at the pore-forming that volatilizees when First lifts rear preliminarily dried.High boiling material is to be allowed to condition at pore-forming in the process of extraction.The material adopting is the LITHIUM BATTERY material in battery operation, can not introduce new impurity, economical simply again.
Accompanying drawing explanation
Fig. 1 is the picture of existing ceramic diaphragm on the market;
Fig. 2 is according to the picture of the resulting ceramic diaphragm of the inventive method;
Fig. 3 is the picture of the barrier film produced of the inventive method under sweep electron microscope.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
Manufacture method includes following steps:
1) batching, first using PVDF-HFP(polyvinylidene fluoride-hexafluoropropylene) as adhesive, be dissolved in NMP(N-methyl pyrrolidone) in, form the glue of solid content 5-10%, then in glue, add the ceramic powders that accounts for glue weight 1-3%, and stir formation suspension, more then add while stirring acetone, being diluted to total solid content is 1-3%, finally the logical sand mill of going over, forms suspension stand-by; Described ceramic powders is selected the ceramic particle of particle size range or class ball-type spherical at 300nm-700nm.Solvent of the present invention adopts the mixed solution of NMP and acetone, can keep the stable of dicyandiamide solution.
2) applying, adopt and infiltrate the method that lifts by the 1st) suspension that makes of step is coated on polyolefin film.
3) solidify, first, the suspension coating preliminarily dried to coating under the baking temperature of 50 ℃-80 ℃; Then, through extractant groove, NMP is extracted, obtain piling up the thick ceramic diaphragm of formation 2-4 μ m.The extractant of described extractant groove is selected its one or more kinds of mixtures in methyl alcohol, ethanol and water.In order not damage barrier film, dry temperature 50 C-80 ℃, and the boiling point of mixed solvent is far above 80 ℃, therefore the present invention through preliminary being dried, through an extractant groove, both can extract not volatile NMP after lifting, all right forming section hole, is conducive to lithium ion and passes through.The inventive method makes aperture more many, is more evenly distributed, and can not affects battery performance.
Because ceramic layer is blocked up, every film strength and good stability of the dimension, still can reduce the chemical property of lithium ion battery.Too thin or configuration of surface is bad, size and intensity are bad again.The present invention's ceramic particle particle size range is spherical at 300nm-700nm or class ball-type is attached on polyolefin film by binding agent, through closs packing, forms 2-4 μ m ceramic layer.Closs packing makes ceramic layer form the effect of skeleton, and the transparent performance that thin coating can deteriorated barrier film, can not make the electrical property of battery decline.
Physical property
Upper table is after adopting the barrier film of 16 μ m to apply the pottery of 4 μ m and the data of 20 μ m barrier films contrast.As can be seen from the table, ceramic diaphragm dimensional contraction at high temperature obviously diminishes, and air permeability does not almost increase.Illustrate that pore-creating is comparatively perfect.
Chemical property
Adopt 503759(lamination process 1200mAh), with conventional ceramic barrier film as a comparison
Capacity and internal resistance
Ceramic diaphragm of the present invention does not reduce capacity, increases internal resistance.
Multiplying power
| Conservation rate | Pottery 1 | Pottery 2 | Contrast |
| 0.5C | 100.0% | 100.0% | 100.0% |
| 1C | 97.7% | 97.3% | 96.3% |
| 2C | 73.8% | 67.7% | 64.4% |
| 3A | 57.2% | 49.6% | 46.9% |
Ceramic diaphragm high rate performance of the present invention is better than comparative run.
Cycle performance
| Cycle-index | This law 1 | This law 2 | Comparative run |
| 100 | 95.1% | 93.8% | 95.2% |
| 300 | 90.6% | 90.0% | 83.2% |
Adopt ceramic diaphragm cycle performance of the present invention to be obviously better than comparative run, because this law barrier film pore-forming is even, and hole is many, and shown in Fig. 1, Fig. 2 and Fig. 3, Fig. 1 has a lot of nonuniform depositions, the ，You space and Fig. 2 is evenly distributed.
Security performance
Security performance test, barrier film of the present invention, 60 ℃ of short circuits, clashes into, and roll side, acupuncture, 130 ℃ of 1h, embody obvious advantage in 150 ℃ of 30min.
Claims (3)
1. the manufacture method of ceramic diaphragm for high security lithium ion battery, is characterized in that described manufacture method includes following steps:
1) batching, first PVDF-HFP is dissolved in NMP, form the glue of solid content 5-10%, then in glue, add the ceramic powders that accounts for glue weight 1-3%, and stir formation suspension, more then add while stirring acetone, being diluted to total solid content is 1-3%, finally the logical sand mill of going over, forms suspension stand-by;
2) applying, adopt and infiltrate the method that lifts by the 1st) suspension that makes of step is coated on polyolefin film;
3) solidify, first, the suspension coating preliminarily dried to coating under the baking temperature of 50 ℃-80 ℃; Then, through extractant groove, NMP is extracted, obtain piling up the thick ceramic diaphragm of formation 2-4 μ m.
2. the manufacture method of ceramic diaphragm for a kind of high security lithium ion battery according to claim 1, is characterized in that: described ceramic powders is selected the ceramic particle of particle size range or class ball-type spherical at 300nm-700nm.
3. the manufacture method of ceramic diaphragm for a kind of high security lithium ion battery according to claim 1, is characterized in that: the extractant of described extractant groove is selected its one or more kinds of mixtures in methyl alcohol, ethanol and water.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310481960.XA CN103515563A (en) | 2013-10-15 | 2013-10-15 | Method for manufacturing ceramic diaphragm for high-safety lithium ion battery |
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| CN201310481960.XA CN103515563A (en) | 2013-10-15 | 2013-10-15 | Method for manufacturing ceramic diaphragm for high-safety lithium ion battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106099017A (en) * | 2016-06-29 | 2016-11-09 | 珠海光宇电池有限公司 | A kind of preparation method of lithium battery diaphragm |
| WO2018205980A1 (en) * | 2017-05-11 | 2018-11-15 | Shanghai Energy New Materials Technology Co., Ltd. | Coating slurries for preparing separators, separators for electrochemical devices and preparation methods therefor |
| CN108963163A (en) * | 2018-08-01 | 2018-12-07 | 河北金力新能源科技股份有限公司 | A kind of oiliness PVDF slurry, its preparation process and its coating method |
| CN109309186A (en) * | 2018-12-03 | 2019-02-05 | 河北金力新能源科技股份有限公司 | A kind of PVDF diaphragm and preparation method thereof |
| CN111584809A (en) * | 2020-04-30 | 2020-08-25 | 浙江金非新能源科技有限公司 | Slurry for lithium ion battery roll core and preparation method and gluing process thereof |
| CN114883745A (en) * | 2022-06-02 | 2022-08-09 | 中材锂膜(宁乡)有限公司 | Method for producing a separator, electrochemical cell using said separator, and electrical device |
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| 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 |
| CN101809801A (en) * | 2007-09-28 | 2010-08-18 | A123系统公司 | Battery with inorganic/organic porous films |
| CN102195092A (en) * | 2010-03-19 | 2011-09-21 | 深圳市比克电池有限公司 | Gel polymer lithium ion battery and preparation method thereof |
| CN102464803A (en) * | 2010-11-13 | 2012-05-23 | 微宏动力系统（湖州）有限公司 | Porous membrane and preparation method thereof |
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2013
- 2013-10-15 CN CN201310481960.XA patent/CN103515563A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN101809801A (en) * | 2007-09-28 | 2010-08-18 | A123系统公司 | Battery with inorganic/organic porous films |
| CN102195092A (en) * | 2010-03-19 | 2011-09-21 | 深圳市比克电池有限公司 | Gel polymer lithium ion battery and preparation method thereof |
| CN102464803A (en) * | 2010-11-13 | 2012-05-23 | 微宏动力系统（湖州）有限公司 | Porous membrane and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106099017A (en) * | 2016-06-29 | 2016-11-09 | 珠海光宇电池有限公司 | A kind of preparation method of lithium battery diaphragm |
| CN106099017B (en) * | 2016-06-29 | 2018-08-03 | 珠海光宇电池有限公司 | A kind of preparation method of lithium battery diaphragm |
| WO2018205980A1 (en) * | 2017-05-11 | 2018-11-15 | Shanghai Energy New Materials Technology Co., Ltd. | Coating slurries for preparing separators, separators for electrochemical devices and preparation methods therefor |
| CN108963163A (en) * | 2018-08-01 | 2018-12-07 | 河北金力新能源科技股份有限公司 | A kind of oiliness PVDF slurry, its preparation process and its coating method |
| CN108963163B (en) * | 2018-08-01 | 2021-08-10 | 河北金力新能源科技股份有限公司 | Oily PVDF slurry, preparation process and coating method thereof |
| CN109309186A (en) * | 2018-12-03 | 2019-02-05 | 河北金力新能源科技股份有限公司 | A kind of PVDF diaphragm and preparation method thereof |
| CN111584809A (en) * | 2020-04-30 | 2020-08-25 | 浙江金非新能源科技有限公司 | Slurry for lithium ion battery roll core and preparation method and gluing process thereof |
| CN111584809B (en) * | 2020-04-30 | 2022-08-26 | 浙江金非新能源科技有限公司 | Slurry for lithium ion battery roll core and preparation method and gluing process thereof |
| CN114883745A (en) * | 2022-06-02 | 2022-08-09 | 中材锂膜(宁乡)有限公司 | Method for producing a separator, electrochemical cell using said separator, and electrical device |
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Application publication date: 20140115 |