CN1441507A - Prepn of polyvinylidene difluoride film for secondary lithium ion battery - Google Patents
Prepn of polyvinylidene difluoride film for secondary lithium ion battery Download PDFInfo
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- CN1441507A CN1441507A CN02151621A CN02151621A CN1441507A CN 1441507 A CN1441507 A CN 1441507A CN 02151621 A CN02151621 A CN 02151621A CN 02151621 A CN02151621 A CN 02151621A CN 1441507 A CN1441507 A CN 1441507A
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- Y02E60/10—Energy storage using batteries
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Abstract
This invention relates to a method for preparing PVDF film used in Li ion secondary battery, mixing TFH with acetone to complex component solvent then mixing water with alcohol to complex component unsolvent, mixing the two solvents in 84:8 weight ratio evenly, then to mix PVDF-HFP with the mixture of the two solvents according to 8:92 weight ratio to get this invented PVDF film after stirring up, coating and dry. This invented electrolyte film has small aperture, unregular network structure good for absorbing electrolyte, stable chemical and electric chemical performance and good ionic conductivity.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery.
Technical background
Lithium ion battery has specific energy height, operating voltage height, in light weight, characteristics such as self discharge is little, have extended cycle life, discharge performance is stable, memory-less effect, environmental pollution are little.The lithium ion battery product is shell with the metal mainly at present, and when reduced thickness, because volume reduces, the amount of active material reduces in the housing, will cause the specific energy of battery to descend.Adopt flexible package, can not only make that battery is very thin, specific energy is higher, and can reduce size arbitrarily, exterior design freedom, internal pressure that can also buffer battery, the fail safe that improves battery.Adopt the film lithium ion battery of flexible package mainly to refer to polymer Li-ion battery and flexible package liquid lithium ionic cell, wherein the most representative with polymer Li-ion battery.To have higher energy density, flexible design, space availability ratio height, fail safe good because of it for polymer Li-ion battery, series of advantages such as memory-less effect and be subjected to people's extensive concern.The key technology of polymer Li-ion battery is the preparation polymer electrolyte diaphragm.Because the carbon-fluorine bond bond energy is stronger, and chemical property is more stable, the better mechanical property after the film forming is considered to desirable membrane material in the Kynoar (PVDF).1994; the Bellcore company of the U.S. announces that it develops a kind of lithium ion battery of novel PVDF base polymer electrolyte; it is to make porous membrane with the copolymer of Kynoar-hexafluoropropylene (PVDF-HFP); behind the absorption electrolyte; have higher conductivity and favorable mechanical performance; but need extracting pore creating material dibutyl phthalate in preparation process, it is unfavorable to bring to large-scale production.The 7th the 4th phase of volume of " electrochemistry " November calendar year 2001 is delivered people's such as Ren Xumei article " phase inversion method prepares the condition of porous PVDF film and explores ", and this article is by changing the proportioning between polymer and solvent, the non-solvent; Control temperature, solvent evaporates speed, the conditions such as time in non-solvent is bathed obtain a series of porous PVDF films, have studied the influence of the concentration of solvent and non-solvent in the coating solution to the structure and the character of PVDF film.But this article has only been inquired into the influence to filming performance of the solvent of single component and non-solvent.Experiment showed, the increase along with water content in the colloidal sol, the pick up that makes film increases gradually, and the aperture of micropore increases gradually in the film simultaneously.But for the electrolytic thin-membrane that is used for polymer Li-ion battery, not only require pick up higher, also require the reasonable pore distribution in the microcellular structure, the aperture is little, porosity wants high.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery, the aperture is little in the film pick up height that requirement makes, the microcellular structure, porosity is high.
For achieving the above object, the present invention adopts following technical scheme:
The preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery, Kynoar-hexafluoropropylene (PVDF-HFP) is mixed by a certain percentage with solvent, non-solvent, stirred 2-6 hour at 40 ℃-70 ℃ following constant temperature, scrape or coating process through being coated with again, allow solvent and non-solvent volatilize naturally, film after doing is taken off the environment of putting into 40 ℃-70 ℃ dried 10-30 hour, described solvent and non-solvent, one of them is two kinds of composite components that composition mixes at least.
Described compounding ingredients solvent is the mixture of acetone and oxolane (THF), and the compounding ingredients non-solvent is the mixture of water and ethanol.
When acetone mixed as double solvents with oxolane (THF), its weight ratio was (1-1.5): 1.
When water mixed as compound non-solvent with ethanol, its weight ratio was (1-1.5): 1.
Preferred version is: Kynoar-hexafluoropropylene (PVDF-HFP) is 8: 42: 42 with the weight ratio of oxolane, acetone, water, ethanol: 4: 4.
Above-mentioned solvent is the mixture of acetone and oxolane, and non-solvent is a water.This moment, preferred version was: Kynoar-hexafluoropropylene (PVDF-HFP) is 8: 42: 42 with the weight ratio of oxolane, acetone, water: 8.
Above-mentioned solvent is an acetone, and non-solvent is the mixture of water and ethanol.This moment, preferred version was: Kynoar-hexafluoropropylene (PVDF-HFP) is 8: 84: 4 with the weight ratio of acetone, water, ethanol: 4.
It below is the suction liquid fraction contrast of the electrolytic thin-membrane that makes of the PVDF-HFP colloidal sol of different proportionings
| Colloidal sol proportioning (WT) | Film pick up (WT%) |
| PVDF-HFP: THF: acetone: water=8: 42: 42: 8 | ?273.9 |
| PVDF-HFP: acetone: water: ethanol=8: 84: 4: 4 | ?305.5 |
| PVDF-HFP: THF: acetone: water: ethanol=8: 42: 42: 4: 4 | ?297.2 |
As seen from the above comparison, the pick up of the polymer electrolyte film that compounding ingredients makes is all very high, can satisfy the barrier film requirement of polymer Li-ion battery, and the aperture of the polymer electrolyte film that makes in this way is also different, the aperture of mixed solvent+electrolytic thin-membrane that single non-solvent makes is bigger, about about 10 microns; The aperture of single solvent+electrolytic thin-membrane that the mixing non-solvent makes is about about 6 microns; The aperture of mixed solvent+electrolytic thin-membrane that the mixing non-solvent makes is less, about about 3 microns; And the pore structure irregularity, network-like, more help Electolyte-absorptive.With PVDF-HFP: THF: acetone: water: ethanol=8: 42: 42: the film of preparation in 4: 4 is that positive pole, MCMB are that negative pole has been assembled the 650mAH polymer Li-ion battery as barrier film, LiCoO2, and electrolyte is selected EC for use: DMC=1: 1 (vol) 1MliPF6.Discharge curve when analyzing battery charge curve, 130mA and 650mA discharging current, discharge cut-off voltage is 3.0V, and the electric current that charging is adopted is 130mA, and the charging cut-ff voltage is 4.2V, and the 4.2V constant voltage time is 120 minutes.By analyzing as can be known, the charge-discharge performance of battery is similar with conventional liquid lithium ionic cell, and in the voltage range of 4.2V, prepared barrier film has better chemical and electrochemical stability at 3.0V; Adopting AC impedance to record the internal resistance of cell is 45m Ω; From the discharge curve of different electric currents also as can be seen, the 1C discharge capacity is 97.2% of a 0.2C discharge capacity, this illustrates that this battery can bear heavy-current discharge, and the electrolytic thin-membrane in the battery has ionic conductivity preferably, meets the requirement of polymer Li-ion battery to membrane properties.
Embodiment
Embodiment 1
At first oxolane (THF) and acetone are mixed into the compounding ingredients solvent according to 1: 1 weight ratio, again water and ethanol are mixed into the compounding ingredients non-solvent according to 1: 1 weight ratio, after solvent and non-solvent mixed according to 84: 8 weight ratio, according to Kynoar-hexafluoropropylene (PVDF-HFP): the weight ratio of the mixture of blending ingredients solvent and blending ingredients non-solvent=8: 92 is mixed, stirred 2-6 hour at 40 ℃-70 ℃ following constant temperature, obtain clarifying the colloidal sol of thickness, blade coating or on coating machine be the carrier coating on bright and clean glass plate with the aluminium foil, allow solvent and non-solvent volatilize naturally, the film after doing is taken off put into 60 ℃ of environment oven dry and promptly obtained polyvinylidene difluoride film of the present invention in 24 hours.
Embodiment 2
At first oxolane (THF) and acetone are mixed into the compounding ingredients solvent according to 1: 1 weight ratio, after compounding ingredients solvent and water mixed according to 84: 8 weight ratio, according to Kynoar-hexafluoropropylene (PVDF-HFP): the weight ratio of the mixture of blending ingredients solvent and water=8: 92 is mixed, stirred 2-6 hour at 40 ℃-70 ℃ following constant temperature, obtain clarifying the colloidal sol of thickness, blade coating or on coating machine be the carrier coating on bright and clean glass plate with the aluminium foil, allow solvent and non-solvent volatilize naturally, the film after doing is taken off put into 60 ℃ of environment oven dry and promptly obtained polyvinylidene difluoride film of the present invention in 24 hours.。
Embodiment 3
At first water and ethanol are mixed into the compounding ingredients non-solvent according to 1: 1 weight ratio, after acetone and compounding ingredients non-solvent mixed according to 84: 8 weight ratio, according to Kynoar-hexafluoropropylene (PVDF-HFP): the weight ratio of the mixture of acetone and blending ingredients non-solvent=8: 92 is mixed, stirred 2-6 hour at 40 ℃-70 ℃ following constant temperature, obtain clarifying the colloidal sol of thickness, blade coating or on coating machine be the carrier coating on bright and clean glass plate with the aluminium foil, allow solvent and non-solvent volatilize naturally, the film after doing is taken off put into 60 ℃ of environment oven dry and promptly obtained polyvinylidene difluoride film of the present invention in 24 hours.。
Embodiment 4
At first oxolane (THF) and acetone are mixed into the compounding ingredients solvent according to 1: 1.5 weight ratio, again water and ethanol are mixed into the compounding ingredients non-solvent according to 1.5: 1 weight ratio, after solvent and non-solvent mixed according to 84: 8 weight ratio, according to Kynoar-hexafluoropropylene (PVDF-HFP): the weight ratio of the mixture of blending ingredients solvent and blending ingredients non-solvent=8: 92 is mixed, stirred 2-6 hour at 40 ℃-70 ℃ following constant temperature, obtain clarifying the colloidal sol of thickness, blade coating or on coating machine be the carrier coating on bright and clean glass plate with the aluminium foil, allow solvent and non-solvent volatilize naturally, the film after doing is taken off put into 60 ℃ of environment oven dry and promptly obtained polyvinylidene difluoride film of the present invention in 24 hours.
Embodiment 5
At first oxolane (THF) and acetone are mixed into the compounding ingredients solvent according to 1: 1.3 weight ratio, again water and ethanol are mixed into the compounding ingredients non-solvent according to 1: 1 weight ratio, after solvent and non-solvent mixed according to 84: 8 weight ratio, according to Kynoar-hexafluoropropylene (PVDF-HFP): the weight ratio of the mixture of blending ingredients solvent and blending ingredients non-solvent=8: 92 is mixed, stirred 2-6 hour at 40 ℃-70 ℃ following constant temperature, obtain clarifying the colloidal sol of thickness, blade coating or on coating machine be the carrier coating on bright and clean glass plate with the aluminium foil, allow solvent and non-solvent volatilize naturally, the film after doing is taken off put into 60 ℃ of environment oven dry and promptly obtained polyvinylidene difluoride film of the present invention in 24 hours.
Claims (9)
1, the preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery, Kynoar-hexafluoropropylene (PVDF-HFP) is mixed by a certain percentage with solvent, non-solvent, stirred 2-6 hour at 40 ℃-70 ℃ following constant temperature, scrape or coating process through being coated with again, allow solvent and non-solvent volatilize naturally, film after doing is taken off the environment of putting into 40 ℃-70 ℃ dried 10-30 hour, it is characterized in that: described solvent and non-solvent, one of them is two kinds of composite components that composition mixes at least.
2, the preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery according to claim 1, it is characterized in that: described compounding ingredients solvent is the mixture of acetone and oxolane (THF), and the compounding ingredients non-solvent is the mixture of water and ethanol.
3, the preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery according to claim 2 is characterized in that: the weight ratio of acetone and oxolane (THF) is (1-1.5): 1.
4, the preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery according to claim 2 is characterized in that: the weight ratio of water and ethanol is (1-1.5): 1.
5, the preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery according to claim 2 is characterized in that: Kynoar-hexafluoropropylene (PVDF-HFP) is 8: 42: 42 with the weight ratio of oxolane, acetone, water, ethanol: 4: 4.
6, the preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery according to claim 1 is characterized in that: described solvent is the mixture of acetone and oxolane, and non-solvent is a water.
7, the preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery according to claim 6 is characterized in that: Kynoar-hexafluoropropylene (PVDF-HFP) is 8: 42: 42 with the weight ratio of oxolane, acetone, water: 8.
8, the preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery according to claim 1, it is characterized in that: described solvent is an acetone, non-solvent is the mixture of water and ethanol.
9, the preparation method who is used for the polyvinylidene difluoride film of lithium rechargeable battery according to claim 8 is characterized in that: Kynoar-hexafluoropropylene (PVDF-HFP) is 8: 84: 4 with the weight ratio of acetone, water, ethanol: 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN02151621A CN1441507A (en) | 2002-12-26 | 2002-12-26 | Prepn of polyvinylidene difluoride film for secondary lithium ion battery |
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|---|---|---|---|
| CN02151621A CN1441507A (en) | 2002-12-26 | 2002-12-26 | Prepn of polyvinylidene difluoride film for secondary lithium ion battery |
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| CN1441507A true CN1441507A (en) | 2003-09-10 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465225C (en) * | 2006-10-24 | 2009-03-04 | 北京科技大学 | Process for preparing hybridized porous lithium ion cell electrolyte film |
| CN102127243A (en) * | 2010-12-31 | 2011-07-20 | 南京大学 | Conductive and antibacterial polytetrafluoroethylene composite thin film and manufacturing method thereof |
| DE102013106021A1 (en) | 2013-06-10 | 2014-12-11 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Unfilled and filled casting compound, in particular for producing coated metal foils, and their use for electrodes or separators in accumulators |
| CN106299209A (en) * | 2016-10-19 | 2017-01-04 | 电子科技大学 | Lithium ion battery separator and preparation method thereof, lithium ion battery |
| CN109830630A (en) * | 2018-12-29 | 2019-05-31 | 深圳中兴新材技术股份有限公司 | Coating diaphragm with hierarchical porous structure and its preparation method and application |
| CN110225691A (en) * | 2019-06-05 | 2019-09-10 | 南京理工大学 | A kind of production method for strengthening the carbon-based composite membrane that radiates |
| CN110444803A (en) * | 2018-05-03 | 2019-11-12 | 苏州华骞时代新能源科技有限公司 | A kind of lithium ion battery structure of semisolid and preparation method thereof |
| CN110760225A (en) * | 2019-10-31 | 2020-02-07 | 深圳中科瑞能实业有限公司 | Production method of gel polymer electrolyte porous membrane |
| CN113683471A (en) * | 2021-08-17 | 2021-11-23 | 武汉理工大学 | Polyvinylidene fluoride coated micron aluminum composite powder and preparation method thereof |
-
2002
- 2002-12-26 CN CN02151621A patent/CN1441507A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465225C (en) * | 2006-10-24 | 2009-03-04 | 北京科技大学 | Process for preparing hybridized porous lithium ion cell electrolyte film |
| CN102127243A (en) * | 2010-12-31 | 2011-07-20 | 南京大学 | Conductive and antibacterial polytetrafluoroethylene composite thin film and manufacturing method thereof |
| CN102127243B (en) * | 2010-12-31 | 2013-10-09 | 南京大学 | Conductive and antibacterial polytetrafluoroethylene composite thin film and manufacturing method thereof |
| DE102013106021A1 (en) | 2013-06-10 | 2014-12-11 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Unfilled and filled casting compound, in particular for producing coated metal foils, and their use for electrodes or separators in accumulators |
| EP2819213A2 (en) | 2013-06-10 | 2014-12-31 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Unfilled and filled casting material, in particular for producing coated metal films, and their use for electrodes or separators in batteries |
| CN106299209A (en) * | 2016-10-19 | 2017-01-04 | 电子科技大学 | Lithium ion battery separator and preparation method thereof, lithium ion battery |
| CN110444803A (en) * | 2018-05-03 | 2019-11-12 | 苏州华骞时代新能源科技有限公司 | A kind of lithium ion battery structure of semisolid and preparation method thereof |
| CN109830630A (en) * | 2018-12-29 | 2019-05-31 | 深圳中兴新材技术股份有限公司 | Coating diaphragm with hierarchical porous structure and its preparation method and application |
| CN110225691A (en) * | 2019-06-05 | 2019-09-10 | 南京理工大学 | A kind of production method for strengthening the carbon-based composite membrane that radiates |
| CN110760225A (en) * | 2019-10-31 | 2020-02-07 | 深圳中科瑞能实业有限公司 | Production method of gel polymer electrolyte porous membrane |
| CN113683471A (en) * | 2021-08-17 | 2021-11-23 | 武汉理工大学 | Polyvinylidene fluoride coated micron aluminum composite powder and preparation method thereof |
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