CN103094514A - Diaphragm for lithium ion batteries and preparation method thereof - Google Patents
Diaphragm for lithium ion batteries and preparation method thereof Download PDFInfo
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- CN103094514A CN103094514A CN2011103427058A CN201110342705A CN103094514A CN 103094514 A CN103094514 A CN 103094514A CN 2011103427058 A CN2011103427058 A CN 2011103427058A CN 201110342705 A CN201110342705 A CN 201110342705A CN 103094514 A CN103094514 A CN 103094514A
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- barrier film
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- ion battery
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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
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Abstract
Relating to the field of new energy, the invention discloses a diaphragm for lithium ion batteries and a preparation method thereof. In the invention, the problems of low porosity, poor permeability and poor safety in diaphragms for lithium ion batteries are solved mainly through a simple process. The diaphragm for lithium ion batteries provided in the invention mainly comprises: polyolefin, a high melting-point polymer (accounting for 0-70% of a total polymer amount), and a high boiling-point small molecule compound solvent (accounting for 50%-95% of a total polymer and solvent amount). The preparation method of the diaphragm for lithium ion batteries consists of: raw material charging, thick diaphragm sheet preparation, thin diaphragm sheet preparation, and post-treatment of the thin diaphragm sheet. Through the preparation method of the diaphragm for lithium ion batteries provided in the invention, the prepared diaphragm for lithium ion batteries has porosity of 40-80%, air permeability of 120-500s/100ml, and a total thickness of 10-50 micrometers. Thus, the method disclosed in the invention not only enhances the porosity and air permeability of the diaphragm for lithium ion batteries, but also improves the safety of the lithium-ion battery diaphragm.
Description
Technical field
The present invention relates to new energy field, relate in particular to that a kind of porosity is high, good permeability and safe lithium ion be with barrier film and preparation method thereof.
Background technology
In the lithium battery field, barrier film is to be one of crucial interior layer assembly in the lithium ion structure.The performance of barrier film has determined the interfacial structure, internal resistance of battery etc., directly affects the characteristics such as capacity, circulation and security performance of battery, and the barrier film of excellent performance has important effect to the combination property that improves battery.
Up to the present, multiple lithium battery, lithium ion battery separator have been developed.The applicant notices in research process: these commercial polyalkene diaphragms have individual layer or three layers of barrier film (with three layers of superimposed hot pressing of microporous barrier together, forming the PE/PP/PE structure); Adopt on production method by producing the method for hard elastic fibre, prepare high oriented polypropylene or the polyethylene film of low-crystallinity, obtain the oriented film of high-crystallinity at high annealing.Cryogenic tensile forms microdefect, under high temperature, defective is pulled open, and forms micropore; Or by add the beta crystal improver with nucleation in polypropylene, utilize the difference of density between the polypropylene different phase, crystal transfer occurs in drawing process form micropore, for the production of the PP film; Or high boiling hydrocarbon liquids or low-molecular-weight material are mixed with vistanex, heating is dissolved mixture and melt is layered on thin slice, then cooling is separated, then with vertical or twin shaft to thin slice is done orientation process, at last with volatile solvent extraction liquid acquisition film.
Existing lithium battery diaphragm manufacture method and technique all can not reach the requirement with low-cost production high-performance barrier film.There is following shortcoming in the barrier film manufacture method at present: (1) adopts crystallization to form microdefect, under high temperature, defective is pulled open, and forms micropore; Or adding the beta crystal improver with nucleation, the barrier film of the method manufacturing that utilizing stretches forms micropore is difficult to obtain high porosity and better gas permeability, satisfies less than higher requirement.(2) although the fail safe of adopting the mode of three layers of combination to solve barrier film, but the material of three layers of basement membrane is different, the pore-forming technique difference is large, need to be heat sealing at together in stack after moulding respectively, will increase equipment investment like this, increase the complexity of production control and management, increase production cost, can not produce thickness less than three layers of barrier film of 20 μ m, cause the limitation of use.
Summary of the invention
The invention provides a kind of good permeability, safe lithium ion barrier film.Its raw material is calculated by weight percentage and is comprised following component: (1) polyolefin; (2) high-melting-point polymer, content account for the 0-70% of polymer total amount; (3) higher boiling point micromolecular compound solvent accounts for the 50%-95% of polymer and solvent total amount.
Preferably, polyolefin is polyethylene, polypropylene etc., can be one or more mixing.
Preferably, high-melting-point polymer is polyethylene terephthalate, Merlon, Nomex, PETG, polyarylate, Kynoar, polytetrafluoroethylene, poly(4-methyl-1-pentene) etc., can be one or more mixing.
Preferably, higher boiling point micromolecular compound solvent is one or more mixtures wherein such as n-dodecane, atoleine, castor oil, 18 alcohol, glycerol.
The invention provides a kind of lithium ion preparation method of barrier film, comprise the following steps:
The first step, raw material charging: polyolefin, high-melting-point polymer and higher boiling point micromolecular compound solvent are carried out respectively accurate measurement, and add simultaneously same extruder;
Second step, barrier film sheet processed: extruder carries out melt extruded and super plastics processing, and sends into die head and extrude after fondant filter, measuring pump and melt mixer, becomes the barrier film sheet of 0.3-3mm through the slab roller water cooling;
The 3rd step, barrier film thin slice processed: described sheet is become the barrier film thin slice of 10-50 μ m after carrying out unidirectional or biaxial tension after heating;
The 4th step, the reprocessing of barrier film thin slice: described barrier film thin slice is carried out the dry heat typing and cuts processing after detergent washing.
Preferably, extruder is twin (double) screw extruder.
Preferably, the temperature of melt extruded is 165-295 ℃.
Preferably, the stretching ratio of stretching is 8-12 times, and the temperature of stretching is 100-160 ℃.
Preferably, washing agent is the easy volatile solvent such as hexane, heptane, carrene, ethers.
Preferably, the temperature of dry heat typing is 100-150 ℃.
Therefore, use the technical scheme of the embodiment of the present invention, as 40-80%, gas permeability is 120-500s/100ml to the lithium ion battery that goes out take simple and direct stable explained hereafter with the porosity of barrier film, the gross thickness of barrier film is 10-50 μ m.Not only improved porosity and the gas permeability of lithium ion battery with barrier film, and the fail safe that has improved lithium ion battery separator.
Embodiment
Describe the present invention in detail below in conjunction with accompanying drawing and specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1:
High density polyethylene (HDPE) (HDPE with 28% percentage by weight, 134 ℃ of fusing points) and the atoleine of 72% percentage by weight join twin (double) screw extruder (diameter 72mm by the metering device of special use respectively, L/D=52) in, the twin (double) screw extruder temperature is 225 ℃, screw rod outlet melt pressure (pressure before measuring pump) remains on 5mpa(and automatically regulates) under condition, after melting, the mixed solution that obtains is extruded from die head after by measuring pump, filter and melt mixer, and obtaining thickness is the barrier film sheet of 480 μ m; The barrier film sheet with greater than the cooldown rate of 50 ℃/min by being cooled to room temperature through slab roller and tank, the barrier film sheet is then (vertical 10 times of 120 ℃ of lower biaxial tensiones, horizontal 5 times of stretchings), and by washing (heptane wash), drying and carry out thermal finalization under 120 ℃, obtain at last the porous septum thin slice of 16 μ m.Result of the test sees Table 1.
Embodiment 2:
high density polyethylene (HDPE) (HDPE with 20% percentage by weight, 134 ℃ of fusing points) and 8% polypropylene (PP, 168 ℃ of fusing points) and the metering device of the atoleine of 72% percentage by weight by special use join respectively twin (double) screw extruder (diameter 72mm, L/D=52), the twin (double) screw extruder temperature is 235 ℃, screw rod outlet melt pressure (pressure before measuring pump) remains on 5mpa(and automatically regulates) under condition, after melting, the mixed solution that obtains passes through measuring pump, extrude from die head after filter and melt mixer, obtaining thickness is the barrier film sheet of 480 μ m, the barrier film sheet with greater than the cooldown rate of 50 ℃/min by being cooled to room temperature through slab roller and tank, the barrier film sheet is then (vertical 10 times of 120 ℃ of lower biaxial tensiones, horizontal 5 times of stretchings), by washing (washed with dichloromethane), dry and 120 ℃ under carry out thermal finalization, obtain at last the porous septum thin slice of 16 μ m.Result of the test sees Table 1.
Embodiment 3:
high density polyethylene (HDPE) (HDPE with 10% percentage by weight, 134 ℃ of fusing points) and 18% polypropylene (PP, 168 ℃ of fusing points) and the metering device of the atoleine of 72% percentage by weight by special use join respectively twin (double) screw extruder (diameter 72mm, L/D=52), the twin (double) screw extruder temperature is 230 ℃, screw rod outlet melt pressure (pressure before measuring pump) remains on 5mpa(and automatically regulates) under condition, after melting, the mixed solution that obtains passes through measuring pump, extrude from die head after filter and melt mixer, obtain the barrier film sheet of thickness 480 μ m, the barrier film sheet with greater than the cooldown rate of 50 ℃/min by being cooled to room temperature through slab roller and tank, the barrier film sheet is then (vertical 10 times of 120 ℃ of lower biaxial tensiones, horizontal 5 times of stretchings), and by washing (washed with dichloromethane), dry and carry out thermal finalization under 120 ℃, obtain at last the porous septum thin slice of 16 μ m.Result of the test sees Table 1.
Embodiment 4:
high density polyethylene (HDPE) (HDPE with 14% percentage by weight, 134 ℃ of fusing points) and 14% Kynoar (PVDF, 174 ℃ of fusing points) and the atoleine of 72% percentage by weight and castor oil (weight ratio 1:1), metering device by special use joins respectively twin (double) screw extruder (diameter 72mm, L/D=52), the twin (double) screw extruder temperature is 235 ℃, screw rod outlet melt pressure (pressure before measuring pump) remains under 5mpa (automatically regulating) condition, after melting, the mixed solution that obtains passes through measuring pump, extrude from die head after filter and melt mixer, obtaining thickness is 480 μ m barrier film sheets, the barrier film sheet with greater than the cooldown rate of 50 ℃/min by being cooled to room temperature through slab roller and tank, the barrier film sheet is then (vertical 10 times of 120 ℃ of lower biaxial tensiones, horizontal 5 times of stretchings), and by washing (washed with dichloromethane), dry and carry out thermal finalization under 120 ℃, obtain at last the porous septum thin slice of 16 μ m.Result of the test sees Table 1.
Table 1 has only been listed the part sample, and lithium ion battery is 48-52% with the barrier film porosity, and gas permeability is 305-320s/100ml, and the gross thickness of barrier film is 16 μ m.According to the present invention different combined methods can prepare that porosity is high, good permeability and safe lithium ion barrier film.
Table 1 comparison of test results table
| The test batch | Thickness (μ m) | Puncture intensity (g) | Porosity (%) | Gas permeability (s/100ml) | Closed pore temperature (℃) | Broken film temperature (℃) |
| Embodiment 1 | 16 | 490 | 52 | 305 | 130 | 140 |
| Embodiment 2 | 16 | 510 | 50 | 315 | 131 | 150 |
| Embodiment 3 | 16 | 535 | 48 | 305 | 138 | 168 |
| Embodiment 4 | 16 | 530 | 48 | 320 | 134 | 165 |
The above technical scheme that the embodiment of the present invention is provided is described in detail, used specific case herein principle and the execution mode of the embodiment of the present invention are set forth, the explanation of above embodiment is only applicable to help to understand the principle of the embodiment of the present invention; Simultaneously, for one of ordinary skill in the art, according to the embodiment of the present invention, all will change on embodiment and range of application, in sum, this description should not be construed as limitation of the present invention.
Claims (10)
1. lithium ion battery barrier film, its raw material is calculated by weight percentage and is comprised following component: (1) polyolefin; (2) high-melting-point polymer, content account for the 0-70% of polymer total amount; (3) higher boiling point micromolecular compound solvent accounts for the 50%-95% of polymer and solvent total amount.
2. lithium ion battery barrier film according to claim 1, it is characterized in that: described polyolefin is polyethylene, polypropylene etc., can be one or more mixing.
3. lithium ion battery barrier film according to claim 1, it is characterized in that: described high-melting-point polymer is polyethylene terephthalate, Merlon, Nomex, PETG, polyarylate, Kynoar, polytetrafluoroethylene, poly(4-methyl-1-pentene) etc., can be one or more mixing.
4. lithium ion battery barrier film according to claim 1, it is characterized in that: described higher boiling point micromolecular compound solvent is one or more mixtures wherein such as n-dodecane, atoleine, castor oil, 18 alcohol, glycerol.
5. lithium ion battery with the preparation method of barrier film, comprises the following steps according to claim 1:
The first step, raw material charging: polyolefin, high-melting-point polymer and higher boiling point micromolecular compound solvent are carried out respectively accurate measurement, and add simultaneously same extruder;
Second step, barrier film sheet processed: extruder carries out melt extruded and super plastics processing, and sends into die head and extrude after fondant filter, measuring pump and melt mixer, becomes the barrier film sheet of 0.3-3mm through the slab roller water cooling;
The 3rd step, barrier film thin slice processed: described sheet is become the barrier film thin slice of 10-50 μ m after carrying out unidirectional or biaxial tension after heating;
The 4th step, the reprocessing of barrier film thin slice: described barrier film thin slice is carried out the dry heat typing and cuts processing after detergent washing.
6. lithium ion battery is with the preparation method of barrier film according to claim 5, and it is characterized in that: described extruder is twin (double) screw extruder.
7. lithium ion battery is with the preparation method of barrier film according to claim 5, and it is characterized in that: the temperature of described melt extruded is 165-295 ℃.
8. lithium ion battery with the preparation method of barrier film, is characterized in that according to claim 5: the stretching ratio of described stretching be 8-12 doubly, the temperature of stretching is 100-160 ℃.
9. lithium ion is with the manufacture method of barrier film according to claim 5, and it is characterized in that: described washing agent is the easy volatile solvent such as hexane, heptane, carrene, ethers.
10. lithium ion is with the manufacture method of barrier film according to claim 5, and it is characterized in that: the temperature of described dry heat typing is 100-150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2011103427058A CN103094514A (en) | 2011-11-03 | 2011-11-03 | Diaphragm for lithium ion batteries and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011103427058A CN103094514A (en) | 2011-11-03 | 2011-11-03 | Diaphragm for lithium ion batteries and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161655A (en) * | 2015-06-26 | 2015-12-16 | 深圳市星源材质科技股份有限公司 | Heat-resistance lithium-ion battery diaphragm and preparation method thereof |
| CN105355814A (en) * | 2015-12-14 | 2016-02-24 | 苏州锂盾储能材料技术有限公司 | Preparation method of lithium-ion battery safe diaphragm material |
| CN111040236A (en) * | 2019-12-25 | 2020-04-21 | 乐凯胶片股份有限公司 | Polyethylene microporous membrane and preparation method thereof |
| CN111592717A (en) * | 2020-05-28 | 2020-08-28 | 四川大学 | Polypropylene microporous membrane containing polytetrafluoroethylene modifier and preparation method thereof |
| CN113394512A (en) * | 2021-05-20 | 2021-09-14 | 惠州锂威电子科技有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN113972435A (en) * | 2021-09-26 | 2022-01-25 | 中材锂膜有限公司 | Preparation method of high-porosity and high-permeability lithium ion battery base membrane |
Citations (2)
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| JP2004161899A (en) * | 2002-11-13 | 2004-06-10 | Tonen Chem Corp | Film with minute pore and its manufacturing method and use |
| CN1545742A (en) * | 2002-06-20 | 2004-11-10 | 索尼株式会社 | Electrode and cell comprising the same |
-
2011
- 2011-11-03 CN CN2011103427058A patent/CN103094514A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1545742A (en) * | 2002-06-20 | 2004-11-10 | 索尼株式会社 | Electrode and cell comprising the same |
| JP2004161899A (en) * | 2002-11-13 | 2004-06-10 | Tonen Chem Corp | Film with minute pore and its manufacturing method and use |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161655A (en) * | 2015-06-26 | 2015-12-16 | 深圳市星源材质科技股份有限公司 | Heat-resistance lithium-ion battery diaphragm and preparation method thereof |
| CN105355814A (en) * | 2015-12-14 | 2016-02-24 | 苏州锂盾储能材料技术有限公司 | Preparation method of lithium-ion battery safe diaphragm material |
| CN111040236A (en) * | 2019-12-25 | 2020-04-21 | 乐凯胶片股份有限公司 | Polyethylene microporous membrane and preparation method thereof |
| CN111040236B (en) * | 2019-12-25 | 2022-06-24 | 乐凯胶片股份有限公司 | Polyethylene microporous membrane and preparation method thereof |
| CN111592717A (en) * | 2020-05-28 | 2020-08-28 | 四川大学 | Polypropylene microporous membrane containing polytetrafluoroethylene modifier and preparation method thereof |
| CN113394512A (en) * | 2021-05-20 | 2021-09-14 | 惠州锂威电子科技有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN113972435A (en) * | 2021-09-26 | 2022-01-25 | 中材锂膜有限公司 | Preparation method of high-porosity and high-permeability lithium ion battery base membrane |
| CN113972435B (en) * | 2021-09-26 | 2023-01-03 | 中材锂膜有限公司 | Preparation method of high-porosity and high-permeability lithium ion battery base membrane |
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