CN105789532A - Polyvinylidene fluoride-hexafluoropropylene-based lithium-ion battery composite membrane - Google Patents
Polyvinylidene fluoride-hexafluoropropylene-based lithium-ion battery composite membrane Download PDFInfo
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- CN105789532A CN105789532A CN201410826701.0A CN201410826701A CN105789532A CN 105789532 A CN105789532 A CN 105789532A CN 201410826701 A CN201410826701 A CN 201410826701A CN 105789532 A CN105789532 A CN 105789532A
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- kynoar
- hexafluoropropene
- supercritical
- ion battery
- autoclave
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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 polyvinylidene fluoride-hexafluoropropylene-based lithium-ion battery composite membrane, which is mainly applied to a lithium-ion battery. A polyvinylidene fluoride-hexafluoropropylene microporous membrane is prepared by a supercritical fluid phase separation method; and Al2O3 particles and PS microspheres are respectively compounded at two sides of the polyvinylidene fluoride-hexafluoropropylene microporous membrane to prepare a polyvinylidene fluoride-hexafluoropropylene lithium-ion battery composite membrane. The prepared lithium-ion battery composite membrane has good air permeability, electrolyte retention property and high temperature resistance; and the safety and the cycle performance of the battery can be significantly improved.
Description
Technical field
The present invention relates to a kind of lithium ion battery composite separation membrane based on Kynoar-hexafluoropropene, it is mainly used in lithium ion battery.
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 obtain rapid development.Have been widely used for the electronics field such as mobile phone, portable computer, photographing unit, video camera at present.Lithium ion battery is divided into again liquid lithium ionic cell and solid lithium ion battery, solid lithium ion battery is commonly referred to as polymer Li-ion battery or plastic lithium-ion battery, its operation principle is identical with liquid lithium ionic cell, the difference is that the electrolyte of 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, there is again the motility of better safety, configuration design simultaneously, it is used for replacing liquid electrolyte, liquid electrolyte lithium ion battery Problems existing in capacity, security performance etc. can be overcome, provide advantage for lithium ion battery to development all solid state, ultrathin.Thus this battery has become the focus of electrochmical power source research and development in recent years, there is extraordinary development prospect.
At present, polymer lithium ion battery electrolyte membrane properties quality directly affects optimization and the raising of polymer Li-ion battery performance.Preparation to this kind of microporous polymer electrolyte barrier film, currently mainly has immersion precipitation to be separated and the method such as Thermal inactive.The disadvantage of immersion precipitation is difficult to obtain the film of symmetrical configuration, and finger-like pore easily occurs, and this is unfavorable for contacting between barrier film with electrode.Studying more in recent years is thermally induced phase separation, its advantage is that pore-size distribution is narrow, symmetrical configuration, without finger-like pore, shortcoming is that easily to present connectivity between closed pore structures, hole poor, thus being unfavorable for that ion passes through, and need to use a large amount of solvent, easily cause the problems such as environmental pollution in preparation process.
Summary of the invention
It is an object of the invention to the deficiency for above-mentioned preparation method, it is provided that a kind of lithium ion battery composite separation membrane based on Kynoar-hexafluoropropene.
The technical solution used in the present invention is: a kind of lithium ion battery composite separation membrane based on Kynoar-hexafluoropropene, adopts following methods to prepare:
1, Kynoar-hexafluoropropene microporous membrane is prepared
(1) it is placed in drying baker by Kynoar-hexafluoropropene freeze-day with constant temperature 10～15h, to remove moisture content therein, dried Kynoar-hexafluoropropene is sealed standby；
(2) use electronic balance precise Kynoar-hexafluoropropene granule, and add the organic solvent of dissolving Kynoar-hexafluoropropene, be made into the casting solution that mass concentration is 15%；
(3) after Kynoar-hexafluoropropene is completely dissolved and stirs, seal black out and stand a period of time, remove the gas of remaining in solution；Striking Kynoar-hexafluoropropene solution film thickness is 100～150 μm；
(4) set bath temperature as 50～80 DEG C, keep constant after, open compressor setting pressure, then open gas cylinder persistently several seconds, to blow away the air in pipeline, turn off gas cylinder；
(5) the casting film dish being loaded with casting solution is inserted rapidly in autoclave and seal；
(6) gas in gas cylinder is pressurized pump pressure contracting, first sends into preheater and preheats, then is pressed into autoclave, pressure setting is 20～30MPa, making the gas in autoclave be in supercriticality, become supercritical fluid, the dwell time is 50～80min；
(7) the control valve of device for opening outlet, purges continuously autoclave, finally system is carried out slow pressure release, and gas flow during pressure release controls at 0～0.3m3/h；
(8) finally open autoclave, take out the microporous membrane sample of preparation.
Described supercritical fluid is selected from supercritical carbon dioxide, supercritical methane, supercritical ethane, supercritical propane, supercritical ethylene, supercritical n pentane.
Described organic solvent is selected from methanol, ethanol, acetone, benzene, toluene, N-Methyl pyrrolidone, N,N-dimethylformamide, oxolane, polyvinylpyrrolidone, dimethyl sulfoxide, sulfolane.
2, composite diaphragm is prepared
(1) the Al2O3 granule (particle diameter 0.01～2.0 μm) of certain mass ratio is mixed with binding agent, be uniformly dispersed, prepare side of the positive electrode coating paste；
(2) just PS base (styrene-divinylbenzene copolymerization) microsphere of certain mass ratio mixes with binding agent, is uniformly dispersed, and prepares negative side coating paste；
(3) adopting continuous gravure coating process to be respectively coated in the both sides of Kynoar-hexafluoropropene by the coating paste prepared in above-mentioned steps (1) and step (2), it is 8～15 μm that coating layer thickness is, and dries and prepares composite diaphragm.
Described binding agent is one or more in the conventional binders such as Kynoar (PVDF), esters of acrylic acid, acrylic compounds, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyurethane.
The invention has the beneficial effects as follows: lithium ion battery composite separation membrane obtained in the present invention has good breathability, protects fluidity and resistance to elevated temperatures, can significantly improve safety and the cycle performance of battery.Adopt supercritical fluid to be separated and prepare membrane for polymer technique, utilize supercritical fluid can swelling most polymers, many micromolecular characteristics can be dissolved again, non-solvent using supercritical fluid as casting film system, supercritical fluid is made to enter in polymer solution by the exchange of supercritical fluid Yu organic solvent, and make solution be separated, thus obtain required barrier film.
Detailed description of the invention
Embodiment 1
1, Kynoar-hexafluoropropene microporous membrane is prepared
(1) it is placed in drying baker by Kynoar-hexafluoropropene freeze-day with constant temperature 10～15h, to remove moisture content therein, dried Kynoar-hexafluoropropene is sealed standby；
(2) use electronic balance precise Kynoar-hexafluoropropene granule, and add the organic solvent of dissolving Kynoar-hexafluoropropene, be made into the casting solution that mass concentration is 15%；
(3) after Kynoar-hexafluoropropene is completely dissolved and stirs, seal black out and stand a period of time, remove the gas of remaining in solution；Striking Kynoar-hexafluoropropene solution film thickness is 100～150 μm；
(4) set bath temperature as 50～80 DEG C, keep constant after, open compressor setting pressure, then open gas cylinder persistently several seconds, to blow away the air in pipeline, turn off gas cylinder；
(5) the casting film dish being loaded with casting solution is inserted rapidly in autoclave and seal；
(6) gas in gas cylinder is pressurized pump pressure contracting, first sends into preheater and preheats, then is pressed into autoclave, pressure setting is 20～30MPa, making the gas in autoclave be in supercriticality, become supercritical fluid, the dwell time is 50～80min；
(7) the control valve of device for opening outlet, purges continuously autoclave, finally system is carried out slow pressure release, and gas flow during pressure release controls at 0～0.3m3/h；
(8) finally open autoclave, take out the microporous membrane sample of preparation.
Described supercritical fluid is selected from supercritical carbon dioxide, supercritical methane, supercritical ethane, supercritical propane, supercritical ethylene, supercritical n pentane.
Described organic solvent is selected from methanol, ethanol, acetone, benzene, toluene, N-Methyl pyrrolidone, N,N-dimethylformamide, oxolane, polyvinylpyrrolidone, dimethyl sulfoxide, sulfolane.
2, composite diaphragm is prepared
(1) the Al2O3 granule (particle diameter 0.01～2.0 μm) that mass ratio is 97:3 is mixed with binding agent (carboxymethyl cellulose), be uniformly dispersed, prepare side of the positive electrode coating paste；
(2) PS base (styrene-divinylbenzene copolymerization) microsphere that mass ratio is 95:5 is mixed with binding agent (polyvinyl alcohol), be uniformly dispersed, prepare negative side coating paste；
(3) continuous gravure coating process is adopted to be respectively coated in the both sides of Kynoar-hexafluoropropene microporous membrane by the coating paste prepared in above-mentioned steps (1) and step (2), it is 8～15 μm that coating layer thickness is, and dries and prepares composite diaphragm.
Claims (4)
1., based on a lithium ion battery composite separation membrane for Kynoar-hexafluoropropene, adopt following methods to prepare:
(1) it is placed in drying baker by Kynoar-hexafluoropropene freeze-day with constant temperature 10～15h, to remove moisture content therein, dried Kynoar-hexafluoropropene is sealed standby；
(2) use electronic balance precise Kynoar-hexafluoropropene granule, and add the organic solvent of dissolving Kynoar-hexafluoropropene, be made into the casting solution that mass concentration is 15%；
(3) after Kynoar-hexafluoropropene is completely dissolved and stirs, seal black out and stand a period of time, remove the gas of remaining in solution；Striking Kynoar-hexafluoropropene solution film thickness is 100～150 μm；
(4) set bath temperature as 50～80 DEG C, keep constant after, open compressor setting pressure, then open gas cylinder persistently several seconds, to blow away the air in pipeline, turn off gas cylinder；
(5) the casting film dish being loaded with casting solution is inserted rapidly in autoclave and seal；
(6) gas in gas cylinder is pressurized pump pressure contracting, first sends into preheater and preheats, then is pressed into autoclave, pressure setting is 20～30MPa, making the gas in autoclave be in supercriticality, become supercritical fluid, the dwell time is 50～80min；
(7) the control valve of device for opening outlet, purges continuously autoclave, finally system is carried out slow pressure release, and gas flow during pressure release controls at 0～0.3m3/h；
(8) finally open autoclave, take out the microporous membrane sample of preparation.
(9) the Al2O3 granule (particle diameter 0.01～2.0 μm) of certain mass ratio is mixed with binding agent, be uniformly dispersed, prepare side of the positive electrode coating paste；
(10) PS base (styrene-divinylbenzene copolymerization) microsphere of certain mass ratio is mixed with binding agent, is uniformly dispersed, prepare negative side coating paste；
(11) continuous gravure coating process is adopted to be respectively coated in the both sides of Kynoar-hexafluoropropene microporous membrane by the coating paste prepared in above-mentioned steps (9) and step (10), it is 8～15 μm that coating layer thickness is, and dries and prepares composite diaphragm.
2. supercritical fluid described in claim 1 is selected from supercritical carbon dioxide, supercritical methane, supercritical ethane, supercritical propane, supercritical ethylene, supercritical n pentane.
3. organic solvent described in claim 1 is selected from methanol, ethanol, acetone, benzene, toluene, N-Methyl pyrrolidone, N,N-dimethylformamide, oxolane, polyvinylpyrrolidone, dimethyl sulfoxide, sulfolane.
4. the binding agent described in claim 1 is one or more in the conventional binders such as Kynoar (PVDF), esters of acrylic acid, acrylic compounds, polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), polyurethane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410826701.0A CN105789532A (en) | 2014-12-26 | 2014-12-26 | Polyvinylidene fluoride-hexafluoropropylene-based lithium-ion battery composite membrane |
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| CN201410826701.0A CN105789532A (en) | 2014-12-26 | 2014-12-26 | Polyvinylidene fluoride-hexafluoropropylene-based lithium-ion battery composite membrane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111911717A (en) * | 2020-07-13 | 2020-11-10 | 江苏海基新能源股份有限公司 | Fire extinguishing agent conveying pipe for lithium battery pack and preparation method thereof |
| CN111987275A (en) * | 2020-09-01 | 2020-11-24 | 厦门大学 | Preparation method and preparation device of lithium ion battery diaphragm |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104157811A (en) * | 2013-12-11 | 2014-11-19 | 中航锂电（洛阳）有限公司 | Lithium ion battery composite diaphragm and preparation method and application thereof |
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- 2014-12-26 CN CN201410826701.0A patent/CN105789532A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104157811A (en) * | 2013-12-11 | 2014-11-19 | 中航锂电（洛阳）有限公司 | Lithium ion battery composite diaphragm and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111911717A (en) * | 2020-07-13 | 2020-11-10 | 江苏海基新能源股份有限公司 | Fire extinguishing agent conveying pipe for lithium battery pack and preparation method thereof |
| CN111987275A (en) * | 2020-09-01 | 2020-11-24 | 厦门大学 | Preparation method and preparation device of lithium ion battery diaphragm |
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Application publication date: 20160720 |