CN103236510B - A kind of corona treatment process of membrane for polymer of lithium rechargeable battery - Google Patents
A kind of corona treatment process of membrane for polymer of lithium rechargeable battery Download PDFInfo
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- CN103236510B CN103236510B CN201310135842.3A CN201310135842A CN103236510B CN 103236510 B CN103236510 B CN 103236510B CN 201310135842 A CN201310135842 A CN 201310135842A CN 103236510 B CN103236510 B CN 103236510B
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- 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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- 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
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Abstract
A kind of corona treatment process of membrane for polymer of lithium rechargeable battery, with polymer molecule barrier film for substrate, utilize the various ions that high frequency, electrion condition air ionization produce, accelerate under highfield effect and impact barrier film, make polymer molecule chemical bond rupture and degrade, increase membrane surface roughness and surface area, improve stock surface-clinging ability.The a large amount of strong oxidizer ozone utilizing air ionization to produce, membrane polymer molecular oxidation is produced carbonyl and the stronger group of peroxide isopolarity, raising membrane surface can increase it and protect liquid measure to the wetability of polar solvent and barrier film, increases ion permeability and fail safe.The porous gel barrier film lithium battery of application corona treatment, liquid measure protected by the battery that can improve 2 ~ 3% while having excellent high rate performance and less internal resistance, promotes battery performance.
Description
Technical field
The present invention relates to a kind of corona treatment process of membrane for polymer of lithium rechargeable battery, be specifically related to high-frequency and high-voltage corona process polymer molecule barrier film and improve its structure to improve the process of battery performance.
Background technology
Current in the accumulation power supply such as lithium rechargeable battery and ultracapacitor, membrane for polymer, because can significantly improve cycle life and the energy density of accumulation power supply, has good processability and is widely applied.Accumulation power supply using polymer molecule barrier film, can not only improve the leakage of power supply, the problems such as burning and blast, and can make to significantly improve its high-energy, high rate during charging-discharging, can be widely applied to new-energy automobile in the future, in peak load regulation network and electronics.
Battery diaphragm basis material mainly comprises polypropylene, polythene material and additive, barrier film adopt basis material to barrier film mechanical property and and the wettability of electrolyte have and directly contact.Basis material is polypropylene or poly barrier film, because polymer molecule degree of crystallinity is high and polarity is little, is unfavorable for the infiltration of electrolyte solution, thus can only only leans on the electrolyte embedded in diaphragm micro-hole to conduct electricity.Meanwhile, for polypropylene material, belong to difficult sticky material, and it is bonding to be unfavorable between positive and negative electrode, between barrier film and electrode, interface cohesion is tight, greatly will affect energy density and the fail safe of battery.
Corona discharge is the local self-maintained discharge of gas medium in non-uniform electric field.Near the point electrode that radius of curvature is very little, because local electric field strength exceedes ionisation of gas field intensity, make gas that ionization and excitation occur, thus occur corona discharge.Corona discharge can produce tiny intensive hyacinthine spark, make air ionization and produce various ion, ion is under the effect of highfield, accelerate and impact to need polymeric material to be processed, molecular chemistry bond fission can be made and degrade, increase surface roughness and surface area, increase the adhesive ability on stock surface.Also can produce a large amount of ozone during electric discharge, ozone is a kind of strong oxidizer, and polymer molecule can be made to be oxidized, and produces the group that carbonyl and peroxide isopolarity are stronger, thus raising surface energy polymer increases its wetability to polar solvent.
Summary of the invention
The object of the invention is to provide a kind of corona treatment process of membrane for polymer of lithium rechargeable battery, by improving membrane configuration, increases membrane for polymer surface area, improves electrolyte wetability and protects liquid measure, thus promoting battery performance, improving cell safety characteristic.
Technical scheme of the present invention is as follows:
A corona treatment process for the membrane for polymer of lithium rechargeable battery take membrane for polymer as target body, utilizes frequency range 50 ~ 1000Hz, voltage range 5000 ~ 15000V/m
2high-frequency and high-voltage alternating current, control power output 10 ~ 30%, the discharging condition of discharge process time 0.5 ~ 10m/min make air ionization produce various ion, acceleration shock membrane for polymer under highfield effect, then dry; Described membrane for polymer thickness is 0.1-100 μm, and structure is at least one deck; (this membrane for polymer can be the structure of one deck or multilayer)
Every layer of material comprises any one in following three kinds:
1) polyolefin substrate material, Kynoar matrix material or cellulose composite membrane material;
2) by the 1st) plant formation dipped by diaphragm material barrier film through organic solvent, organic solvent used is one or more in acetone, 1-METHYLPYRROLIDONE, dimethyl carbonate, Merlon and ethyl cellulose;
3) by the 1st) plant diaphragm material by dipping other polymer molecule colloids formation barrier film; Other described polymer molecules comprise Kynoar, polytetrafluoroethylene, polyvinyl chloride, polystyrene, hexafluoropropylene, styrene, acrylonitrile, methacrylic acid, polyacrylamide, one or more in methyl esters polyformaldehyde, Merlon, poly-inkstone, polyimides, polyarylether, Nomex and fluoro containing polymers, boracic macromolecule;
Described corona treatment process need carries out in dust-collecting air; Preferably at 0 ~ 50 DEG C, carry out in the dust-collecting air of RH range 20 ~ 50%.
Barrier film drying condition after above-mentioned corona treatment can be natural drying at room temperature, forced air drying, vacuumize.Preferred vacuumize.
The invention provides a kind of corona treatment process of membrane for polymer of lithium rechargeable battery, with polymer molecule diaphragm material for target body, utilize high frequency, electrion condition makes air ionization produce various ion, and under highfield effect acceleration shock barrier film, make polymer molecule chemical bond rupture and degrade, increase membrane surface roughness and surface area, improve stock surface-clinging ability.The a large amount of strong oxidizer ozone simultaneously utilizing air ionization to produce, membrane polymer molecular oxidation is produced carbonyl and the stronger group of peroxide isopolarity, improve membrane surface and can increase it to the wetability of polar solvent and guarantor's liquid measure, increase ion permeability and fail safe.
Accompanying drawing explanation
Fig. 1 is 20 μm of thick polyethylene lithium battery diaphragm surfaces;
Fig. 2 is 20 μm of thick polyethylene lithium battery diaphragm surface scan Electronic Speculum figure;
Fig. 3 is 30% power output corona treatment membrane for polymer surface;
Fig. 4 is 30% power output corona treatment membrane for polymer surface scan Electronic Speculum figure;
Fig. 5 is 20% power output corona treatment membrane for polymer surface scan Electronic Speculum figure;
Fig. 6 is untreated barrier film, and 20% power corona process barrier film and 30% power corona process barrier film soak 60 days metacneme surfaces in the electrolytic solution.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described further.
Embodiment 1
Corona treatment provides 50Hz, 5000V/m
2alternating voltage, adopt 20 μm of thick polyethylene lithium battery diaphragm materials as processing sample, and with the speed of 1m/min through corona treatment.Measuring corona treatment device space temperature is 25 DEG C, and relative humidity is 20%.Corona treatment output power, 30%, carries out one side Corona discharge Treatment to transmission diaphragm material.As shown in Figure 1, scanning electron microscope (SEM) photograph as shown in Figure 2 for polyethylene battery membrane surface outside drawing.As shown in Figure 3, scanning electron microscope (SEM) photograph as shown in Figure 4 for membrane surface outside drawing after corona treatment.Upper figure shows the Corona discharge Treatment through 30% power, membrane surface is even needle prick shape, illustrate that now corona power output has caused slight barrier film to puncture for used 20 μm of thick polyethylene lithium battery diaphragms, make its surface texture there occurs larger change, degree of roughness and specific surface increase simultaneously.Calling corona treatment power output is 20%, and the identical lower process polyethylene battery barrier film of other conditions, its scanning electron microscope (SEM) photograph as shown in Figure 5.Comparison diagram 4 and Fig. 5 can find, can be improved for 20 μm of thick polyethylene barrier films its degree of roughness after the corona treatment of 20% and 30% power, but watt level on its degree of roughness to affect difference little.Carry out determination of moisture to the polyethylene lithium battery diaphragm material before and after corona treatment, untreated diaphragm material moisture average is-375ppm, and 20% power corona process barrier film moisture average is-128ppm, and 30% power corona process barrier film moisture average is 22ppm.Illustrate that polymer molecule barrier film makes its water absorbing capacity strengthen because surface creates the stronger group of polarity after corona treatment, and corona degree is larger, water absorption is stronger.
Embodiment 2
Corona treatment provides environment and corona treatment time with described in embodiment 1.The barrier film that corona treatment completes leaves standstill respectively in different environments, the wettability test of line correlation of going forward side by side.Polyethylene diagrams is 69 degree without the contact angle of Corona discharge Treatment, and after 5%, 10%, 20%, 30% and 35% power corona discharge process, contact angle becomes 58 degree, 39 degree, 32 degree, 29 degree and 28 degree.Describe 20 μm of thick polyethylene lithium battery diaphragms through Corona discharge Treatment, membrane contacts angle diminishes, and surface tension increases, and wetability strengthens, and corona discharge power output has good effect for experiment barrier film between 10 ~ 30%.Again measure its contact angle after barrier film at room temperature places 5 days, untreated membrane contacts angle is 73 degree, and the membrane contacts angle after 20% power corona discharge process is 35 degree.Measure membrane contacts angle in dry environments, untreated membrane contacts angle is 66 degree, is 28 degree through the membrane contacts angle of 20% power corona discharge process.After ambient temperatare puts 30 days, undressed membrane contacts angle is 72 degree, is 39 degree through the membrane contacts angle of 20% power corona discharge process.Can be shown by above data, along with the increase of standing time, corona effects has the trend lost efficacy gradually, is more conducive to the preservation of Corona discharge Treatment barrier film under the environment of relatively dry, keeps corona treatment effect.
Embodiment 3
Corona treatment provides environment and corona treatment time with described in embodiment 1.Corona discharge Treatment barrier film soaks through electrolyte, protects liquid measure test after leaving standstill different time respectively at ambient temperature to it.Through 5%, the barrier film of 10%, 20%, 30%, 35% power output corona treatment, its water retainability is all necessarily improved, and liquid measure protected by corona treatment diaphragm cell increases about 0.01g, 0.08g, 0.1g, 0.12g, 0.12g respectively relative to untreated diaphragm cell.Protect liquid measure by contrast different capacity corona treatment diaphragm cell, corona discharge power will make a significant impact between 10 ~ 30%.Place 15 days after corona treatment barrier film under 10 ~ 30% power being soaked electrolyte under room temperature, barrier film still has good guarantor's fluidity, illustrates that corona effects is still effective.Fig. 6 is non-corona treatment barrier film, and 20% power corona process barrier film and 30% power corona process barrier film soak the appearance figure after 60 days respectively in the electrolytic solution.Measure by protecting liquid measure to barrier film, the barrier film that corona treatment is crossed is protected liquid measure and is obtained certain lifting, confirms that corona effects lost efficacy not yet after barrier film immersion in the electrolytic solution 60 days.
Embodiment 4
The 20 μm thick polyethylene lithium battery diaphragms of application without Corona discharge Treatment and the one side polyethylene diagrams through 20% power corona discharge process 1m/min make experiment battery core, contrast every electrical property difference.Experiment battery core selects lithium cobaltate cathode, graphite cathode, lithium hexafluorophosphate electrolyte solution, uses the diaphragm material before and after corona treatment, through homogenate coating, pole piece is die-cut, laminated sheet package, 80 DEG C of baking 12h, leave standstill 48h at 45 DEG C after fluid injection, preliminary filling, shear angle is bled 60s, changes into making.Test battery core is carried out preliminary filling under the same conditions and is changed into, and measure AC impedance (EIS) under full power state, charge with 1C electric current, 1.5C electric current carries out discharge cycles and high rate performance is tested, and normal temperature circulation carries out 100 weeks, measures the internal resistance of cell.The one side polyethylene diagrams that liquid measure uses 5% and 35% power corona discharge process 1m/min protected by diaphragm cell after corona treatment, adopts the positive pole of same material and consumption, negative pole, and electrolyte builds battery core and carries out the performance test of same steps battery core.By contrasting non-corona barrier film, the battery core the performance test results that 5%, 20% and 35% power corona discharge process barrier film builds, the full electric EIS of all battery cores, cycle performance, high rate performance, the parameters such as battery core internal resistance change after circulation (about increase 0.2m Ω) are more or less the same.But protect liquid measure to battery to carry out mensurations and find, protect liquid measure result through the diaphragm cell of 5% power corona discharge process and the battery of non-corona diaphragm cell close, and compare increase by 2% through 20% with the diaphragm cell guarantor liquid measure of 35% power corona process.Describe corona treatment diaphragm cell while guarantee battery performance normally plays, battery can be improved and protect liquid measure and security performance, and corona treatment power is advisable about 20%.
Claims (1)
1. a corona treatment process for the membrane for polymer of lithium rechargeable battery, is characterized in that, is target body with membrane for polymer, utilizes frequency 50Hz, voltage 5000V/m
2high-frequency and high-voltage alternating current, control power output 20% and carry out corona treatment for condition, make air ionization produce various ion, acceleration shock membrane for polymer under highfield effect, then drying; During corona treatment, membrane for polymer is 1m/min through the speed of corona treatment, and described corona treatment process is 25 DEG C in temperature, and relative humidity is carry out in the dust-collecting air of 20%; Described membrane for polymer thickness is 20 μm, and structure is at least one deck;
Every layer of material comprises any one in following three kinds:
1) polyolefin substrate material, Kynoar matrix material or cellulose composite membrane material;
2) by the 1st) plant formation dipped by diaphragm material barrier film through organic solvent, organic solvent used is one or more in acetone, 1-METHYLPYRROLIDONE, dimethyl carbonate, Merlon and ethyl cellulose;
3) by the 1st) plant diaphragm material by dipping following colloid formation barrier film; Comprise one or more in Kynoar, polytetrafluoroethylene, polyvinyl chloride, polystyrene, hexafluoropropylene, styrene, acrylonitrile, methacrylic acid, polyacrylamide, Merlon, poly-inkstone, polyimides, polyarylether, Nomex and fluoro containing polymers, boracic macromolecule.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106848150B (en) * | 2016-11-23 | 2020-11-03 | 中山大学 | Preparation method of modified diaphragm for lithium battery |
| CN107046117A (en) * | 2017-03-10 | 2017-08-15 | 深圳中兴创新材料技术有限公司 | A kind of corona treatment plant and its application for lithium ion battery separator or basement membrane |
| CN110364659A (en) | 2018-03-26 | 2019-10-22 | 华硕电脑股份有限公司 | The manufacturing method of coiled battery |
| CN110148698B (en) * | 2019-05-28 | 2021-12-28 | 大连中比动力电池有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN111354903B (en) * | 2020-03-13 | 2020-09-11 | 烟台三新新能源科技有限公司 | Electrolyte membrane, production apparatus and production process thereof |
| CN112490589A (en) * | 2020-04-08 | 2021-03-12 | 万向一二三股份公司 | Diaphragm and lamination process using same |
| CN112117494A (en) * | 2020-10-09 | 2020-12-22 | 昆山聚创新能源科技有限公司 | Laminate, lamination method and application thereof |
| CN113640636A (en) * | 2021-08-25 | 2021-11-12 | 云南电网有限责任公司电力科学研究院 | Preparation method of film for corona discharge detection of power equipment |
| CN114274527A (en) * | 2021-11-25 | 2022-04-05 | 安徽墙煌彩铝科技有限公司 | Radiation refrigeration metal plate film coating process |
| CN114133613B (en) * | 2021-12-06 | 2023-07-14 | 中国电子科技集团公司第四十六研究所 | Surface activation treatment method for PTFE (polytetrafluoroethylene) substrate |
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| JP2001043843A (en) * | 1999-05-21 | 2001-02-16 | Oji Paper Co Ltd | Manufacture of separator for alkali battery |
| DE10319057B4 (en) * | 2003-04-25 | 2009-01-29 | Carl Freudenberg Kg | Process for the production of plasma-treated textile fabrics |
| CN102306727B (en) * | 2011-08-12 | 2013-01-02 | 沧州明珠塑料股份有限公司 | Polymer modification polyolefin lithium ion battery membrane and preparation method thereof |
| CN102306726A (en) * | 2011-08-12 | 2012-01-04 | 沧州明珠塑料股份有限公司 | Compound modified polyolefin lithium ion battery separator and manufacturing method thereof |
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