CN104362275A - Manufacturing method of lithium ion battery diaphragm as well as battery diaphragm prepared by manufacturing method and battery - Google Patents
Manufacturing method of lithium ion battery diaphragm as well as battery diaphragm prepared by manufacturing method and battery Download PDFInfo
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- CN104362275A CN104362275A CN201410714344.9A CN201410714344A CN104362275A CN 104362275 A CN104362275 A CN 104362275A CN 201410714344 A CN201410714344 A CN 201410714344A CN 104362275 A CN104362275 A CN 104362275A
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- lithium ion
- ceramic
- ion battery
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- battery
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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
- H01M50/443—Particulate material
-
- 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 manufacturing method of a lithium ion battery diaphragm as well as the battery diaphragm prepared by the manufacturing method and a battery. The manufacturing method comprises the following steps: a. covering the surface of ceramic power by one organic high molecular material layer through a solid-phase covering or liquid-phase covering manner to obtain ceramic grain powder covered with the organic high molecular material layer, and sieving the dried and granulated powder for later use; b. adding a solvent, glue and an impregnating compound into the ceramic powder coated in the last step to prepare ceramic slurry; and c. coating a lithium ion battery diaphragm base material by the ceramic slurry to prepare the lithium ion battery diaphragm. The ceramic is firstly covered with the high molecular material layer, and the enough rigidity of the lithium ion battery, and especially a thin, long and wide battery produced by the lithium ion battery diaphragm can be guaranteed; the shrinking percentage is low when the battery is heated, the diaphragm breaking temperature of the diaphragm is improved and the safety of the battery is improved; and the high molecular material layer only needs to be coated for one time, so that the cost is obviously reduced and the efficiency is improved by at least one time.
Description
Technical field
The present invention relates to field of lithium ion battery technology, refer in particular to a kind of lithium ion battery separator manufacture method and obtained battery diaphragm thereof and battery.
Background technology
Be that the fossil resource of representative reduces day by day with oil, also bring the environment gone from bad to worse to us using oil while the automobile of raw material offers convenience to us, the mankind are at the clean alternative energy source of the searching of doing one's utmost.Lithium ion battery has that volume is little, quality is light, energy density advantages of higher can use as clean energy resource on electric automobile.The barrier film of lithium ion battery plays partition positive/negative plate in the battery, usual lithium ion battery separator is that macromolecular material is as polyethylene, polypropylene or polyethylene and polypropylene composite material, these materials in manufacture barrier film process to draw high or extracting process preparation has more hole film, can store electrolyte in these micropores, these electrolyte are the carrier that lithium ion moves around at both positive and negative polarity.Lithium ion battery is as can the battery of repeatedly charge and discharge cycles, its electrolyte can consume gradually at charge and discharge process, can not meet lithium ion between both positive and negative polarity during normal movement when electrolyte content is depleted to, the performance of lithium ion battery will become deterioration, causes maintaining normal discharge and recharge.Diaphragm material is porous polymer materials in addition, and when being heated, material can shrink rupture of membranes and causes positive/negative plate short circuit and the security incident that catching fire occurs.
In lithium ion battery, duricrust can be divided into pack, as box hat and aluminum-shell battery according to the manner of packing of battery core; Another kind of manner of packing is the flexible package mode of packing with aluminum-plastic composite membrane, the battery of flexible package mode due to fail safe high, battery size is flexible and changeable accounts for main flow in lithium ion battery.Because smart mobile phone and panel computer become the generally use of modern network means of information communication, these electronic equipments also be beneficial to light, thin etc. portable in development, this just requires that the lithium ion battery be used in wherein also will design to thin and wide direction, only has flexible-packed battery to have thin design advantage.But in order to ensure the stand-by time of electronic equipment, battery needs to design enough capacity, this makes battery length and Width need to increase, and another drawback that this design brings is that battery can be very soft, and easily distortion causes battery performance to worsen.In order to increase the hardness of battery, current solution is dissolved in organic solvent by the barrier film PVDF-HFP (vinylidene fluoride-hexafluoropropylene copolymer) of battery, then be coated on barrier film in the mode of dip-coating, then in technical process, cling by hot complex method and anode pole piece the hardness improving battery, make the drawback brought in this way be that PVDF-HFP can enter in the hole of barrier film with solvent, cause battery charging and discharging degradation.
In order to solve safety and the stiffness issue of battery, also have a kind of implementation on barrier film, first apply the ceramic layer of one deck 2 ~ 6um, and then apply one deck PVDF-HFP (vinylidene fluoride-hexafluoropropylene copolymer), this layer of PVDF-HFP layer is corresponding with anode pole piece, then in the mode having use under electrolyte effect to heat compound, coat and anode pole piece are bonded together and improve the hardness of battery, make barrier film in this way will apply 2 times, especially for very thin barrier film base material, coating difficulty itself, and coating repeatedly more can cause, and quality is bad to be increased greatly with quality hidden danger, and need quiescence in high temperature after battery powered solution liquid, complex process, cost is high.
Summary of the invention
Main purpose of the present invention is to provide a kind of lithium ion battery separator manufacture method and obtained battery diaphragm thereof and battery, and its ceramic layer only needs coating once, and technique is simple, and has better discharge cycles performance, security performance and battery hardness performance.
For achieving the above object, the present invention adopts following technical scheme:
A kind of lithium ion battery separator manufacture method, comprises following processing step:
A. by the mode of the coated or liquid phase coating of solid phase at ceramic powder Surface coating one deck high-molecular organic material layer, obtain the ceramic particle powder of coated organic polymer material layer, by stand-by for the powder screening after this drying-granulating;
B. the ceramic powder solubilizer of coated for above-mentioned steps mistake, glue and size are configured to ceramic size;
C. foregoing ceramic slurry is coated on lithium ion battery separator base material, obtained a kind of lithium ion battery separator.
As a kind of preferred version, described liquid phase coating process comprises following step and gathers:
A1. high-molecular organic material is dissolved in solvent by agitating mode, forms organic macromolecule material solution; The solvent of this high-molecular organic material of solubilized can be NMP, acetone or water equal solvent.
A2. in aforementioned high-molecular organic material solution, add ceramic powder, be uniformly mixed;
A3. fall the solvent in abovementioned steps a2 in mixture by mode of heating evaporation drying or spraying dry, obtain the ceramic particle powder of coated organic polymer material layer.
As a kind of preferred version, the coated process of described solid phase comprises following step and gathers: by high-molecular organic material powder and ceramic powder stirrings, ball milling, that mechanical fusion mode carries out solid phase is coated, then by heating for dissolving method at ceramic powder surperficial formation skim coating layer.
As a kind of preferred version, high-molecular organic material content in described high-molecular organic material solution is 5% ~ 50%, and in described step a, high-molecular organic material is one or several mixtures in phenolic resins, epoxy resin, polyvinylidene fluoride resin, epoxy resin, polyacrylic acid, butadiene-styrene rubber; Add in described step b that ceramic powder consumption accounts for high-molecular organic material solution in step a 50 ~ 95%.
As a kind of preferred version, described ceramic powder is oxide or the inorganic salts of electronic isolation, and described oxide is alundum (Al2O3) or titanium oxide, and described inorganic salts is barium sulfate.
As a kind of preferred version, in described step b, each ceramic particle D50 of ceramic powder is 0.1 ~ 10 micron.
As a kind of preferred version, the high-molecular organic material layer thickness of described ceramic particle outer cladding is 0.05 ~ 2 micron; The described ceramic size be coated on barrier film base material, the thickness after oven dry is 0.5 ~ 20 micron.
A kind of lithium ion battery separator, includes barrier film base material, this barrier film base material is attached with a ceramic layer, and this ceramic layer is ceramic particle layer, each ceramic particle is coated with high-molecular organic material layer.
As a kind of preferred version, the high-molecular organic material layer thickness of described ceramic particle outer cladding is 0.05 ~ 2 micron; The described ceramic layer thickness be coated on barrier film base material is 0.5 ~ 10 micron.
A kind of lithium ion battery, includes battery pole piece, this battery pole piece is pasted with the battery diaphragm according to any one of aforementioned claim 1 to 9.
The present invention compared with prior art has obvious advantage and beneficial effect, specifically, as shown from the above technical solution, on the one hand, its pottery is first coated high-molecular organic material layer, this layer of coating layer has and anode pole piece binding function, reaches the hardness that battery needs, and the lithium ion battery produced with this kind of lithium ion battery separator is especially thin and long and wide battery can ensure enough hardness; On the other hand, shrinkage when it is heated is low, and the ceramic layer being coated on membrane surface can form skeleton and support barrier film when barrier film is heated, and the broken film temperature of barrier film is improved, and increases the fail safe of battery; Moreover it makes in battery diaphragm process, only needs coating once, coating operation decreases half, and greatly can avoid repeatedly applying the quality caused in operation bad, cost is obviously lower, and efficiency improves at least one times.
For more clearly setting forth architectural feature of the present invention, technological means and the specific purposes reached thereof and function, below in conjunction with accompanying drawing and specific embodiment, the present invention is described in further detail:
Accompanying drawing explanation
Fig. 1 is the enlarged diagram of a ceramic particle in the embodiment of the present invention.
Fig. 2 is the schematic diagram of line-of-sight course hardness test device in the embodiment of the present invention.
Accompanying drawing identifier declaration:
1, ceramic particle, 2, coating layer, 3, pressure device, 4, measured object.
Embodiment
Embodiment 1
A kind of lithium ion battery separator manufacture method, its processing step comprises:
A. the LBG-1 (a kind of Kynoar PVDF) of 5% content is added in acetone, open the high-molecular organic material solution that mixer stirring and dissolving is uniformly transparent.
B. in above-mentioned solution, add the ceramic powder that solid matter content accounts for this solution 30%, 50% accumulation diameter D50 in this ceramic powder domain size distribution is 0.5 micron, stirs.
C. said mixture mode of heating evaporation drying is fallen the solvent in mixture, make ceramic particle 1 Surface coating one deck polyvinylidene fluoride resin PVDF 2 (see accompanying drawing 1), coating layer 2 thickness is about 0.1 micron, obtains the ceramic particle powder of coated organic polymer material layer.
D, by above-mentioned coated after ceramic powder to add SBR (butadiene-styrene rubber) emulsion, CMC (carboxymethyl cellulose) and deionized water for stirring even.
E, the mode of above-mentioned ready slurry intaglio printing is coated in 9 micron thickness barrier film base material polypropylene diaphragm on and dry, after coating drying, coating layer thickness is 3 microns.
By this, a kind of lithium ion battery separator of the present embodiment can be obtained, this lithium ion battery separator gross thickness 12 microns, wherein, polypropylene screen 9 microns, particle type ceramic coating is 3 microns, each ceramic particle is coated with one deck polyvinylidene fluoride resin, the thickness of this coating layer is 0.1 microns.
Embodiment 2
A kind of lithium ion battery separator manufacture method, its processing step comprises:
A. the LBG-1 (a kind of Kynoar PVDF) of 10% content is added in acetone, open the solution that mixer stirring and dissolving is uniformly transparent.
B. in above-mentioned solution, add the ceramic powder that solid matter content accounts for this solution 30%, 50% accumulation diameter D50 in this ceramic powder domain size distribution is 0.5um, stirs.
C. said mixture spraying dry is fallen the solvent in mixture, make the coated one deck PVDF of ceramic grain surface (see accompanying drawing 1), coating thickness is about 0.2 micron.
D, by above-mentioned coated after ceramic powder to add SBR (butadiene-styrene rubber) emulsion, CMC (carboxymethyl cellulose) and deionized water for stirring even.
E, the mode of above-mentioned ready slurry intaglio printing is coated in 9 micron thickness barrier film base material polypropylene diaphragm on and dry, after coating drying, coating layer thickness is 3 microns.
By this, a kind of lithium ion battery separator of the present embodiment can be obtained, this lithium ion battery separator gross thickness 12 microns, wherein, polypropylene screen 9 microns, particle type ceramic coating is 3 microns, each ceramic particle is coated with one deck polyvinylidene fluoride resin, the thickness of this coating layer is 0.2 microns.
Embodiment 3
A kind of lithium ion battery separator manufacture method, its processing step comprises:
A, ceramic powder and LBG-1 (a kind of Kynoar PVDF) added in mechanical fusion equipment according to 75:25 mix;
B, by a walk in mixed material heating cool after 2 hours to 160 degree of stirrings, make LBG-1 form the coating layer of one deck about 0.1 micron thickness at ceramic grain surface;
C, by above-mentioned coated after ceramic powder add SBR (butadiene-styrene rubber) emulsion, CMC (carboxymethyl cellulose) and deionized water for stirring even.
D, the mode of above-mentioned ready slurry intaglio printing to be coated on 9 micron polypropylene barrier films and dry, after coating is dry, coating layer thickness is 3 microns.
By this, a kind of lithium ion battery separator of the present embodiment can be obtained, this lithium ion battery separator gross thickness 12 microns, wherein, polypropylene screen 9 microns, particle type ceramic coating is 3 microns, each ceramic particle is coated with one deck polyvinylidene fluoride resin, the thickness of this coating layer is 0.1 microns.
Cut into same widths with the uncoated barrier film of coated barrier film and same thickness in aforementioned three embodiments and carry out thermal contraction test, test result is as following table one.
Table one: diaphragm retracts Performance comparision
The coated barrier film obtained by aforementioned three embodiments and the barrier film of uncoated same thickness cut into the width of needs, battery core is wound into together with both positive and negative polarity, battery core model is 426090 (thick 4.2mm, wide 60mm, long 90mm), battery core through fluid injection, 85 degree of hot pressing, normal temperature cold pressing compound, change into, partial volume, encapsulated moulding.Battery is carried out use line-of-sight course hardness test (fix see accompanying drawing 2, two ends, middle applying pressure 3 runs a segment distance makes measured object 4 deformation to a certain degree, the size of the power required for test and comparison per stroke), compare test result is as following table two.
Table two: battery hardness ratio comparatively
From aforementioned table one and table two, the lithium battery diaphragm being coated with the pottery of coated organic material layer has less shrinkage and more excellent hardness performance.
The above, it is only preferred embodiment of the present invention, not technical scope of the present invention is imposed any restrictions, thus every above embodiment is done according to technical spirit of the present invention any trickle amendment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. a lithium ion battery separator manufacture method, is characterized in that: comprise following processing step:
A. by the mode of the coated or liquid phase coating of solid phase at ceramic powder Surface coating one deck high-molecular organic material layer, obtain the ceramic particle powder of coated organic polymer material layer, by stand-by for the powder screening after this drying-granulating;
B. the ceramic powder solubilizer of coated for above-mentioned steps mistake, glue and size are configured to ceramic size;
C. foregoing ceramic slurry is coated on lithium ion battery separator base material, obtained a kind of lithium ion battery separator.
2. lithium ion battery separator manufacture method according to claim 1, is characterized in that: described liquid phase coating process comprises following step and gathers:
A1. high-molecular organic material is dissolved in solvent by agitating mode, forms organic macromolecule material solution;
A2. in aforementioned high-molecular organic material solution, add ceramic powder, be uniformly mixed;
A3. fall the solvent in abovementioned steps a2 in mixture by mode of heating evaporation drying or spraying dry, obtain the ceramic particle powder of coated organic polymer material layer.
3. lithium ion battery separator manufacture method according to claim 1, it is characterized in that: the coated process of described solid phase comprises following step and gathers: by high-molecular organic material powder and ceramic powder stirrings, ball milling, that mechanical fusion mode carries out solid phase is coated, then by heating for dissolving method at ceramic powder surperficial formation skim coating layer.
4. lithium ion battery separator manufacture method according to claim 1, it is characterized in that: the high-molecular organic material content in described high-molecular organic material solution is 5% ~ 50%, in described step a, high-molecular organic material is one or several mixtures in phenolic resins, epoxy resin, polyvinylidene fluoride resin, epoxy resin, polyacrylic acid, butadiene-styrene rubber; Add in described step b that ceramic powder consumption accounts for high-molecular organic material solution in step a 50 ~ 95%.
5. lithium ion battery separator manufacture method according to claim 1, is characterized in that: described ceramic powder is oxide or the inorganic salts of electronic isolation, and described oxide is alundum (Al2O3) or titanium oxide, and described inorganic salts is barium sulfate.
6. lithium ion battery separator manufacture method according to claim 1, is characterized in that: in described step b, each ceramic particle D50 of ceramic powder is 0.1 ~ 10 micron.
7. lithium ion battery separator manufacture method according to claim 1, is characterized in that: the high-molecular organic material layer thickness of described ceramic particle outer cladding is 0.05 ~ 2 micron; The described ceramic size be coated on barrier film base material, the thickness after oven dry is 0.5 ~ 20 micron.
8. a lithium ion battery separator, includes barrier film base material, it is characterized in that: this barrier film base material is attached with a ceramic layer, and this ceramic layer is ceramic particle layer, each ceramic particle is coated with high-molecular organic material layer.
9. lithium ion battery separator according to claim 8, is characterized in that: the high-molecular organic material layer thickness of described ceramic particle outer cladding is 0.05 ~ 2 micron; The described ceramic layer thickness be coated on barrier film base material is 0.5 ~ 10 micron.
10. a lithium ion battery, includes battery pole piece, it is characterized in that: this battery pole piece is pasted with the battery diaphragm according to any one of aforementioned claim 1 to 9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410714344.9A CN104362275A (en) | 2014-12-01 | 2014-12-01 | Manufacturing method of lithium ion battery diaphragm as well as battery diaphragm prepared by manufacturing method and battery |
| PCT/CN2015/095583 WO2016086783A1 (en) | 2014-12-01 | 2015-11-26 | Method for manufacturing lithium ion battery diaphragm, battery diaphragm prepared thereby, and battery |
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| CN201410714344.9A CN104362275A (en) | 2014-12-01 | 2014-12-01 | Manufacturing method of lithium ion battery diaphragm as well as battery diaphragm prepared by manufacturing method and battery |
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| CN104362275A true CN104362275A (en) | 2015-02-18 |
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| WO2016086783A1 (en) * | 2014-12-01 | 2016-06-09 | 东莞市卓高电子科技有限公司 | Method for manufacturing lithium ion battery diaphragm, battery diaphragm prepared thereby, and battery |
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