CN103367674A - Lithium ion battery with polyvinylidene fluoride-hexafluoropropylene microporous membrane - Google Patents
Lithium ion battery with polyvinylidene fluoride-hexafluoropropylene microporous membrane Download PDFInfo
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- CN103367674A CN103367674A CN2013103137209A CN201310313720A CN103367674A CN 103367674 A CN103367674 A CN 103367674A CN 2013103137209 A CN2013103137209 A CN 2013103137209A CN 201310313720 A CN201310313720 A CN 201310313720A CN 103367674 A CN103367674 A CN 103367674A
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- hexafluoropropylene
- kynoar
- ion battery
- lithium ion
- supercritical
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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
The invention provides a lithium ion battery with a polyvinylidene fluoride-hexafluoropropylene microporous membrane. The microporous membrane is prepared by a supercritical fluid phase separation method.
Description
Technical field
The present invention relates to a kind of lithium ion battery, especially a kind of lithium ion battery with Kynoar-hexafluoropropylene micro-pore septum.
Background technology
Lithium ion battery is high with its energy density, have extended cycle life and the electrical property of the high excellence of voltage and obtained rapidly development.The electronic product fields such as mobile phone, portable computer, camera, video camera have been widely used at present.Lithium ion battery is divided into again liquid lithium ionic cell and solid lithium ion battery, solid lithium ion battery generally is called polymer Li-ion battery or plastic lithium-ion battery, its operation principle is identical with liquid lithium ionic cell, the electrolyte of different is polymer Li-ion battery is not free electrolyte, but gel electrolyte or solid electrolyte.Polymer dielectric not only has high ionic conductivity, long cycle life, minimum pollution level and good processing characteristics, the flexibility that has again simultaneously better fail safe, configuration design, it is used for replacing liquid electrolyte, can overcome the problem that the liquid electrolyte lithium ion battery exists at aspects such as capacity, security performances, for lithium ion battery provides advantage to all solid state, ultrathin development.Thereby this battery become the focus of the research and development of chemical power source in recent years, and extraordinary development prospect is arranged.
At present, polymer lithium ion battery electrolyte membrane properties quality directly affects optimization and the raising of polymer Li-ion battery performance.To the preparation of this class microporous polymer electrolyte barrier film, mainly contain at present the methods such as immersion precipitation is separated and thermic is separated.The disadvantage of immersion precipitation is the film that is difficult to obtain symmetrical configuration, and finger-like pore occurs easily, and this is unfavorable for contacting between barrier film and the electrode.Studying in recent years more is thermally induced phase separation, its advantage is that pore-size distribution is narrow, symmetrical configuration, without finger-like pore, shortcoming is that to present easily between blind hole structure, hole connectivity poor, thereby be unfavorable for that ion passes through, and in preparation process, need to use a large amount of solvents, easily cause the problems such as environmental pollution.
Summary of the invention
The objective of the invention is the deficiency for above-mentioned preparation method, a kind of lithium ion battery with Kynoar-hexafluoropropylene micro-pore septum is provided.
The technical solution used in the present invention is: a kind of lithium ion battery with Kynoar-hexafluoropropylene micro-pore septum, comprise negative pole, positive pole, electrolyte, barrier film, and its septation adopts the following methods preparation:
(1) Kynoar-hexafluoropropylene is placed on freeze-day with constant temperature 10～15h in the drying box, to remove moisture content wherein, that dried Kynoar-hexafluoropropylene sealing is for subsequent use;
(2) with the accurate weighing Kynoar of electronic balance-hexafluoropropylene particle, and add the organic solvent of dissolving Kynoar-hexafluoropropylene, be made into mass concentration and be 25% casting solution;
(3) after Kynoar-hexafluoropropylene dissolves fully and stirs, the sealing black out leaves standstill a period of time, removes gas remaining in the solution; Striking Kynoar-hexafluoropropylene solution film thickness is 200～300 μ m;
(4) setting bath temperature is 50～80 ℃, keeps constant after, open compressor and setting pressure, then opening high pressure gas cylinder and lasting several seconds, to blow away ducted air, close again gas cylinder;
The casting film dish that (5) will be loaded with casting solution is inserted in the autoclave rapidly and is sealed;
(6) gas in the gas cylinder is pressurized the pump pressure contracting, sends into first preheater and carries out preheating, is pressed into autoclave again, pressure setting is 20～30MPa, make the gas in the autoclave be in supercriticality, become supercritical fluid, the dwell time is 50～80min;
(7) control valve of device for opening outlet purges continuously to autoclave, at last system is carried out slow pressure release, and the gas flow during pressure release is controlled at 0～0.3m
3/ h;
(8) last opening high pressure still takes out the barrier film sample of preparation.
Described supercritical fluid is selected from supercritical carbon dioxide, supercritical methane, overcritical ethane, supercritical propane, overcritical ethene, supercritical n pentane.
Described organic solvent is selected from methyl alcohol, ethanol, acetone, benzene, toluene, 1-METHYLPYRROLIDONE, DMF, oxolane, polyvinylpyrrolidone, dimethyl sulfoxide (DMSO), sulfolane.
The invention has the beneficial effects as follows: this being separated with supercritical fluid prepares membrane for polymer technique, utilize supercritical fluid can the swelling most polymers, can dissolve many micromolecular characteristics again, with the non-solvent of supercritical fluid as the casting film system, exchange by supercritical fluid and organic solvent makes supercritical fluid enter into polymer solution, and solution is separated, thereby obtain needed barrier film, this process is the supercritical fluid preparation membrane process that is separated.This preparation technology's advantage is: 1) supercritical fluid not only makes polymer solution be separated, also can play " drying " effect to formed microporous barrier (polymer-rich phase), thereby being separated in traditional L-S method united two into one with thereafter drying process; 2) because supercritical fluid can not produce vapour-liquid interface (without phase transformation) to the dry run of film, thereby avoided the structural collapse problem that in the film dry run, very easily occurs; 3) organic solvent that dissolves each other with supercritical fluid can be by recycling after the simple decompression separation operation, so that whole film preparation process becomes the enclosed type technical process of a kind of " green "; 4) this technique has been introduced pressure as extra variable, also can regulate the phase process of system by the pressure that changes supercritical fluid, thus can the Effective Regulation Membrane Morphology.
Embodiment
Below by specific embodiment technical scheme of the present invention and the effect that reaches thereof are described further, but following instance does not consist of limitation of the invention.
A kind of lithium ion battery with Kynoar-hexafluoropropylene micro-pore septum comprises negative pole, positive pole, electrolyte, barrier film, and its septation adopts the following methods preparation:
(1) Kynoar-hexafluoropropylene is placed on freeze-day with constant temperature 10～15h in the drying box, to remove moisture content wherein, that dried Kynoar-hexafluoropropylene sealing is for subsequent use;
(2) with the accurate weighing Kynoar of electronic balance-hexafluoropropylene particle, and add the organic solvent of dissolving Kynoar-hexafluoropropylene, be made into mass concentration and be 25% casting solution;
(3) after Kynoar-hexafluoropropylene dissolves fully and stirs, the sealing black out leaves standstill a period of time, removes gas remaining in the solution; Striking Kynoar-hexafluoropropylene solution film thickness is 200～300 μ m;
(4) setting bath temperature is 50～80 ℃, keeps constant after, open compressor and setting pressure, then opening high pressure gas cylinder and lasting several seconds, to blow away ducted air, close again gas cylinder;
The casting film dish that (5) will be loaded with casting solution is inserted in the autoclave rapidly and is sealed;
(6) gas in the gas cylinder is pressurized the pump pressure contracting, sends into first preheater and carries out preheating, is pressed into autoclave again, pressure setting is 20～30MPa, make the gas in the autoclave be in supercriticality, become supercritical fluid, the dwell time is 50～80min;
(7) control valve of device for opening outlet purges continuously to autoclave, at last system is carried out slow pressure release, and the gas flow during pressure release is controlled at 0～0.3m
3/ h;
(8) last opening high pressure still takes out the barrier film sample of preparation.
(9) the micropore polymer diaphragm sample that takes out is dried, obtain final product.
Claims (3)
1. the lithium ion battery with Kynoar-hexafluoropropylene-hexafluoropropylene micro-pore septum comprises negative pole, positive pole, electrolyte, barrier film, it is characterized in that, Kynoar-hexafluoropropylene-hexafluoropropylene micro-pore septum adopts the following methods preparation:
1) Kynoar-hexafluoropropylene is placed on freeze-day with constant temperature 10～15h in the drying box, to remove moisture content wherein, that dried Kynoar-hexafluoropropylene sealing is for subsequent use;
2) with the accurate weighing Kynoar of electronic balance-hexafluoropropylene particle, and add the organic solvent of dissolving Kynoar-hexafluoropropylene, be made into mass concentration and be 25% casting solution;
3) after Kynoar-hexafluoropropylene dissolves fully and stirs, the sealing black out leaves standstill a period of time, removes gas remaining in the solution; Striking Kynoar-hexafluoropropylene solution film thickness is 200～300 μ m;
4) setting bath temperature is 50～80 ℃, keeps constant after, open compressor and setting pressure, then opening high pressure gas cylinder and lasting several seconds, to blow away ducted air, close again gas cylinder;
The casting film dish that 5) will be loaded with casting solution is inserted in the autoclave rapidly and is sealed;
6) gas in the gas cylinder is pressurized the pump pressure contracting, sends into first preheater and carries out preheating, is pressed into autoclave again, pressure setting is 20～30MPa, make the gas in the autoclave be in supercriticality, become supercritical fluid, the dwell time is 50～80min;
7) control valve of device for opening outlet purges continuously to autoclave, at last system is carried out slow pressure release, and the gas flow during pressure release is controlled at 0～0.3m
3/ h;
8) last opening high pressure still takes out the barrier film sample of preparation.
2. the lithium ion battery with Kynoar-hexafluoropropylene micro-pore septum claimed in claim 1, it is characterized in that described supercritical fluid is selected from supercritical carbon dioxide, supercritical methane, overcritical ethane, supercritical propane, overcritical ethene, supercritical n pentane.
3. the lithium ion battery with Kynoar-hexafluoropropylene micro-pore septum claimed in claim 1, it is characterized in that, described organic solvent is selected from methyl alcohol, ethanol, acetone, benzene, toluene, 1-METHYLPYRROLIDONE, DMF, oxolane, polyvinylpyrrolidone, dimethyl sulfoxide (DMSO), sulfolane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013103137209A CN103367674A (en) | 2013-07-24 | 2013-07-24 | Lithium ion battery with polyvinylidene fluoride-hexafluoropropylene microporous membrane |
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| CN2013103137209A CN103367674A (en) | 2013-07-24 | 2013-07-24 | Lithium ion battery with polyvinylidene fluoride-hexafluoropropylene microporous membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108134108A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of Kynoar-application of the hexafluoropropene diaphragm in flow battery |
| CN111944177A (en) * | 2020-08-20 | 2020-11-17 | 中山大学 | Polymer ultrathin film forming system and polymer ultrathin film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003213425A (en) * | 2002-01-24 | 2003-07-30 | Utec:Kk | Apparatus and method for forming film |
| CN1613548A (en) * | 2004-09-24 | 2005-05-11 | 浙江大学 | Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology |
| CN102070793A (en) * | 2010-12-22 | 2011-05-25 | 大连理工大学 | Process for preparing polymer lithium ion battery microporous membrane by supercritical fluid phase separation |
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2013
- 2013-07-24 CN CN2013103137209A patent/CN103367674A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003213425A (en) * | 2002-01-24 | 2003-07-30 | Utec:Kk | Apparatus and method for forming film |
| CN1613548A (en) * | 2004-09-24 | 2005-05-11 | 浙江大学 | Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology |
| CN102070793A (en) * | 2010-12-22 | 2011-05-25 | 大连理工大学 | Process for preparing polymer lithium ion battery microporous membrane by supercritical fluid phase separation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108134108A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of Kynoar-application of the hexafluoropropene diaphragm in flow battery |
| CN111944177A (en) * | 2020-08-20 | 2020-11-17 | 中山大学 | Polymer ultrathin film forming system and polymer ultrathin film |
| CN111944177B (en) * | 2020-08-20 | 2023-07-07 | 中山大学 | Polymer ultrathin film forming system and polymer ultrathin film |
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Application publication date: 20131023 |