CN103915593B - Preparation method of a kind of polyimide nano lithium ion battery separator and products thereof - Google Patents
Preparation method of a kind of polyimide nano lithium ion battery separator and products thereof Download PDFInfo
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- CN103915593B CN103915593B CN201410147627.XA CN201410147627A CN103915593B CN 103915593 B CN103915593 B CN 103915593B CN 201410147627 A CN201410147627 A CN 201410147627A CN 103915593 B CN103915593 B CN 103915593B
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- preparation
- barrier film
- polyamic acid
- lithium ion
- ion battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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 discloses preparation method of a kind of polyimide nano lithium ion battery separator and products thereof, its preparation method comprises the following steps: the preparation of polyamic acid solution: by 4,4 ˊ mono-diaminodiphenyl ethers and the two phthalic anhydride of 4,4 ˊ mono-oxygen obtain in the middle polycondensation of dimethylacetylamide (DMAc) by a certain percentage; The preparation of melt: resulting polymers solution is solidified at a certain temperature and obtains solidfied material, then solidfied material is melted within the scope of 20-30 DEG C below its fusing point, obtain hypocrystalline melt; Prepared by barrier film: the melt obtained is obtained nanometer barrier film through melt spinning, recrystallization, cold and hot stretching and the process of thermal finalization series of process; Barrier film reprocessing: comprise the diluent in removal barrier film and some residual solvent, in a vacuum dry polyamic acid barrier film; Imidization process: high temperature imidization process is carried out to the polyamic acid nanometer barrier film prepared and obtains polyimide nano barrier film.Obtained excellent product performance, processes easy.
Description
Technical field
Preparation method that the present invention relates to lithium ion battery separator and products thereof.
Background technology
Barrier film, as one of most important parts of lithium ion battery, is referred to as " the 3rd pole " of battery, and major function is that isolation both positive and negative polarity directly contacts, and prevents short circuit, simultaneously for the reciprocating motion of lithium ion provides passage.The barrier film being widely used in lithium ion battery is at present mainly polyalkene diaphragm, and its preparation technology divides dry method and wet method two kinds.The maximum defect of polyalkene diaphragm is that the contact of itself and organic electrolyte is poor, is not easily soaked by electrolyte, has a strong impact on the raising of ionic conductivity.Existing a lot of patent Introduction dry method and wet-layer preparation individual layer or double-deck polyalkene diaphragm and various modified diaphragm.But along with the development of new-energy automobile industry, market it is also proposed higher requirement to power lithium-ion battery.How to improve the power density of power lithium-ion battery, charge/discharge rates, high temperature resistant and cycle performance seem particularly important.
Polyimides has been widely used in the fields such as electronic apparatus, barrier film, composite material and space flight and aviation as the high performance special engineering plastics of one.Polyimide nano materials application is also just being caused increasing concern in battery diaphragm field.Polyimide nano film not only has common nano material small-size effect and skin effect, also demonstrates it as macromolecular material high temperature resistant, the high pressure resistant and puncture strength characteristic excellent in battery diaphragm field simultaneously.The preparation method of current battery barrier film mainly contains dry method and wet method two kinds, but the raw material of two kinds of method employings is all generally PE (polyethylene), and produce battery diaphragm all directly not there is nano material characteristic, often need by modification as: add polymer nano granules.
Chinese patent CN103085442A discloses a kind of preparation method of lithium battery nano fiber diaphragm, it is characterized in that: described preparation method comprises the following steps: 1), by PET based polyalcohol dissolve in organic solvent, the wherein mass volume ratio concentration 10:25% of PET based polyalcohol, stir and obtain PET based polymer solution, the mensuration viscosity of described solution is between 300 ~ 400mPa.S; 2), using PP nonwoven fabrics as substrate, the PET based polymer solution prepared is carried out continuous electrostatic spinning at nanofiber spinning-drawing machine, obtain PP/PET nano-fiber composite film, the condition of described electrostatic spinning is: temperature 20 ~ 40 DEG C, and voltage 20 ~ 50KV, spinning speed are every meter of wide cut per minute 1 ~ 5 gram; 3) tunica fibrosa obtained after, spinning being completed carries out reprocessing: first hot-forming by 100 ~ 140 DEG C of rollers, again at 60 ~ 80 DEG C of vacuumize 10 ~ 20h, after removing solvent residual in described tunica fibrosa, obtain the nano fibrous membrane for lithium ion battery separator.
Chinese patent CN103383996A discloses a kind of preparation method of polyimide micro-pore diaphragm, comprise the following steps: adopt flexible unit, soluble polyimide is prepared with one-step method, and form polyimide solution, comprise: under protective atmosphere, dianhydride monomer and diamine monomer are added organic solvent and form mixed liquor, stir after this mixed liquor makes this dianhydride monomer and diamine monomer dissolve in this organic solvent, add catalyst, fully react at 160 DEG C to 200 DEG C temperature, generate polyimides, and gained polyimides is dissolved in organic solvent is configured to polyimide solution, there is provided inorganic template agent, this inorganic template agent is inorganic nanoparticles, carries out surface treatment in organic solvent by surface conditioning agent to this inorganic template agent, makes inorganic template agent be dispersed in this organic solvent, forms inorganic template agent dispersing liquid, this polyimide solution and inorganic template agent dispersing liquid are mixed and ultrasonic process, forms preparation liquid, this preparation liquid be coated in substrate surface and dry, forming organic/inorganic composite film, and this organic/inorganic composite film is placed in template removes agent solution, the inorganic template agent in this organic/inorganic composite film and this template remove agent and react, thus remove the inorganic template agent in this organic/inorganic composite film, obtain this polyimide micro-pore diaphragm.
US4588633 discloses a kind of lithium ion battery separator preparation method, and the method comprises ultra-high molecular weight polyethylene and mineral oil to add by a certain percentage in mixer carries out stirring and dissolving, and wherein, mineral oil and poly ratio are 10 ~ 99:1.Above-mentioned formula enhances film strength, and barrier film also meets the requirement of lithium ion battery to barrier film substantially, but there is following defect: the diaphragm micro-hole aperture of formation is uneven, and then affects its performance in the battery.
At present, the kind of lithium ion battery separator be mainly polyolefin film and Kynoar and with the blend film of respective compound or the Modified Membrane of adding inorganic nanoparticles, and nanometer barrier film and preparation thereof rarely have existence.
Chinese patent CN103147253A discloses a kind of High Strength Polyimide nano fiber porous film, described polyimide nano-fiber perforated membrane porosity is 70 ~ 85%, the average diameter in hole is 100 ~ 250nm, glass transition temperature is 260 ~ 400 DEG C, hot strength is 8 ~ 70MPa, high temperature 200 DEG C of heat treatments after 1 hour dimensional contraction rate be less than 0.3%; The chemical composition of described polyimide nano-fiber perforated membrane is copolyimide or blended polyimides.But this barrier film processed complex, performance is also not ideal.
Summary of the invention
The technical problem to be solved in the present invention is the deficiency overcoming prior art existence, provides preparation method of a kind of polyimide nano lithium ion battery separator of excellent performance and products thereof.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A preparation method for polyimide nano lithium ion battery separator, its preparation method comprises the following steps:
A) preparation of polyamic acid solution: 4,4' mono-diaminodiphenyl ether and the two phthalic anhydride of 4,4' mono-oxygen are obtained in the middle polycondensation of dimethylacetylamide (DMAc) by a certain percentage;
B) preparation of melt: resulting polymers solution is solidified at a certain temperature and obtains solidfied material, then solidfied material is melted within the scope of 20-30 DEG C below its fusing point, obtain hypocrystalline melt;
C) barrier film preparation: the melt obtained is obtained polyimide nano barrier film through melt spinning, recrystallization, cold and hot stretching and the process of thermal finalization series of process;
D) barrier film reprocessing: comprise the diluent in removal barrier film and some residual solvent, in a vacuum dry polyimide nano barrier film;
E) imidization process: high temperature imidization process is carried out to the polyamic acid nanometer barrier film prepared and obtains polyimide nano barrier film.
Preferably, described step a) in, the material preparing polyamide acid solution has 4, the two phthalic anhydride (ODPA) of 4' mono-diaminodiphenyl ether (ODA), 4,4' mono-oxygen and dimethylacetylamide (DMAc), wherein 4,4' mono-diaminodiphenyl ether (ODA) and 4, the amount of substance ratio of the two phthalic anhydride (ODPA) of 4' mono-oxygen is 1:1, and dimethylacetylamide is reaction medium, and polyamic acid solid content is in the solution 20wt%.
Preferably, described step b) in, polymer solution is polyamic acid solution, it is made up of polyamic acid, diluent and additive, diluent can be one in N-dimethylacetylamide (DMAc), dibutyl phthalate (DBP), 1-METHYLPYRROLIDONE or its combination in any, and additive is surfactant.
Preferably, the mixed proportion of polyamic acid and diluent is: 5:95 to 30:70, and the quality of all additives accounts for 0.5%-5% of polyamic acid and diluent gross mass.
Preferably, described step c) in, draft temperature is at 120 ± 10 DEG C, and draw ratio is got between 2.5-3.
Preferably, described step c) in, the blank film thickness obtained is 80-100nm.
Preferably, described steps d) in, the extractant of removing diluent is organic solvent or its mixtures such as n-hexane, cyclohexane, absolute ethyl alcohol, methyl alcohol, toluene, dimethylbenzene.
Preferably, described steps d) in, the polyamide nano barrier film obtained at 60 DEG C vacuumize 5h to remove residual solvent.
Preferably, described step e) in, dried battery diaphragm is carried out high temperature imidization in a nitrogen atmosphere, and high temperature imidization is as follows: 1) 5 DEG C/min is warming up to 100 DEG C and processes 40min; 2) 5 DEG C/min is warming up to 200 DEG C of process 40min; 3) 5 DEG C/min is warming up to 300 DEG C and processes 40min.
A kind of polyimide nano lithium ion battery separator, it adopts the preparation method of above-mentioned polyimide nano lithium ion battery separator to obtain.
Compared with prior art, polyimide nano lithium ion battery separator of the present invention is all excellent than conventional membrane at aspect of performances such as electrochemical stability, thermal contraction, porosity, withstand voltage, tightness and melting temperatures, significantly can promote the life-span of lithium ion battery, and process easy.
Embodiment
Below by way of specific embodiment, the present invention is described in further detail.
Originally be embodied as a kind of preparation method of polyimide nano lithium ion battery separator, it comprises the steps:
A) preparation of polyamic acid solution: the material preparing polyamide acid solution has 4,4' mono-diaminodiphenyl ether (ODA), 4, the two phthalic anhydride (ODPA) of 4' mono-oxygen and dimethylacetylamide (DMAc), wherein 4,4' mono-diaminodiphenyl ether (ODA) and 4, the amount of substance ratio of the two phthalic anhydride (ODPA) of 4' mono-oxygen is 1:1, and dimethylacetylamide is reaction medium, and polyamic acid solid content is in the solution 20wt%.At room temperature, a certain amount of ODA is dissolved in DMAC, continuous stirring, until ODA dissolves completely and becomes colourless transparent solution, then joined in solution by the ODPA of equivalent, when reaching equivalent point soon, the viscosity of polyamic acid increases rapidly in batches, continue to stir 2.2h, make its viscosity reach stable.Adopting Ubbelohde viscometer to record polyamic acid solution the viscosity of 25 DEG C is 2.43dLg
-1;
B) preparation of melt: when temperature 60 C, it is 15:85 that embodiment step soluble polyamide acid solution (PAA) DMAc obtained played in 1 is diluted to PAA:DMAc, and add absolute ethyl alcohol, its amount is 1% of total amount, the polyamic acid solution obtained is prepared into polyamic acid melt;
C) barrier film preparation: the polyamic acid melt obtained is stretched under 120 ± 10 DEG C of conditions, prepares polyamic acid (PAA) nano-lithium ion cell barrier film;
D) barrier film reprocessing: the PAA nanometer barrier film obtained at 60 DEG C vacuumize 5h to remove residual solvent;
E) imidization process: dried battery diaphragm is carried out high temperature imidization in a nitrogen atmosphere.PAA nanometer barrier film ladder-elevating temperature by obtaining: 1) 50C/min is warming up to 150 DEG C and processes 40min; 2) 5 DEG C/min is warming up to 200 DEG C of process 40min; 3) 5 DEG C/min is warming up to 300 DEG C and processes 40min.Finally obtain polyimides (PI) nanometer barrier film.
Assembled by above-mentioned polyimide nano barrier film performance of lithium ion battery test and contrast step as follows:
I) PP/PE/PP barrier film is chosen: employing is comparatively advanced in the market and the PP/PE/PP barrier film that the Celgard company generally applied provides carries out performance comparison test;
II) battery assembling: assembled battery adopts LiCoO
2for positive pole, lithium metal is negative pole, the 1.0MLiPF that electrolyte provides for Dongguan China fir China fir
6-ethylenecarbonate (EC)/dimethylcarbonate (DMC)/ethylmethylcarbonate (EMC) (1:1:1, v/v/v);
III) battery physics and electrochemical property test: the test mainly comprising electrochemical stability, thermal contraction, porosity, withstand voltage, tightness and melting temperature etc.
Above-mentioned steps III) in, test condition is operating voltage 3.2V, static capacity 8Ah.Test result is as shown in the table.
Relative to jejune electrostatic spinning process, preparation method of the present invention utilizes traditional comparatively ripe barrier film preparation technology-fusion drawn method audaciously, under the control of strict technological parameter and condition, prepare new type lithium ion polyimide nano barrier film, prepare relatively simple, greatly reduce new types of diaphragm production cost, improve the stability of new types of diaphragm.And the polyimide nano lithium ion battery separator high porosity that this method obtains is higher, be conducive to the raising of lithium ion battery ionic conductivity, and there is excellent high temperature resistant and high rate capability, be conducive to solving batteries of electric automobile security performance and useful life.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is also not only confined to above-described embodiment.For those skilled in the art, do not departing from the improvement that obtains under the technology of the present invention concept thereof and conversion also should be considered as protection scope of the present invention.
Claims (10)
1. a preparation method for polyimide nano lithium ion battery separator, is characterized in that, its preparation method comprises the following steps:
A) preparation of polyamic acid solution: by two to 4,4' mono-diaminodiphenyl ether and 4,4' mono-oxygen phthalic anhydride by a certain percentage in dimethylacetylamide polycondensation obtain;
B) preparation of melt: resulting polymers solution is solidified at a certain temperature and obtains solidfied material, then solidfied material is melted within the scope of 20-30 DEG C below its fusing point, obtain hypocrystalline melt;
C) barrier film preparation: the melt obtained is obtained polyamic acid nanometer barrier film through melt spinning, recrystallization, cold and hot stretching and the process of thermal finalization series of process;
D) barrier film reprocessing: comprise the diluent in removal barrier film and some residual solvent, in a vacuum dry polyamic acid nanometer barrier film;
E) imidization process: high temperature imidization process is carried out to the polyamic acid nanometer barrier film prepared and obtains polyimide nano barrier film.
2. the preparation method of polyimide nano lithium ion battery separator according to claim 1, it is characterized in that: described step a) in, the material preparing polyamic acid solution has 4, the two phthalic anhydride of 4' mono-diaminodiphenyl ether, 4,4' mono-oxygen and dimethylacetylamide, wherein 4,4' mono-diaminodiphenyl ether and 4, the amount of substance ratio of the two phthalic anhydride of 4' mono-oxygen is 1:1, and dimethylacetylamide is reaction medium, and polyamic acid solid content is in the solution 20wt%.
3. the preparation method of polyimide nano lithium ion battery separator according to claim 1, it is characterized in that: described step b) in, polymer solution is polyamic acid solution, it is made up of polyamic acid, diluent and additive, diluent is one in dimethylacetylamide, dibutyl phthalate, 1-METHYLPYRROLIDONE or its combination in any, and additive is surfactant.
4. the preparation method of polyimide nano lithium ion battery separator according to claim 3, it is characterized in that: the mixed proportion of polyamic acid and diluent is: 5:95 to 30:70, the quality of all additives accounts for 0.5%-5% of polyamic acid and diluent gross mass.
5. the preparation method of polyimide nano lithium ion battery separator according to claim 1, is characterized in that: described step c) in, draft temperature is at 120 ± 10 DEG C, and draw ratio is got between 2.5-3.
6. the preparation method of polyimide nano lithium ion battery separator according to claim 1, is characterized in that: described step c) in, the polyamic acid nanometer membrane thicknesses obtained is 80-100nm.
7. the preparation method of polyimide nano lithium ion battery separator according to claim 1, it is characterized in that: described steps d) in, the extractant of removing diluent is n-hexane, cyclohexane, absolute ethyl alcohol, methyl alcohol, toluene, dimethylbenzene or its mixture.
8. the preparation method of polyimide nano lithium ion battery separator according to claim 1, is characterized in that: described steps d) in, the polyamic acid nanometer barrier film obtained at 60 DEG C vacuumize 5h to remove residual solvent.
9. the preparation method of polyimide nano lithium ion battery separator according to claim 1, it is characterized in that: described step e) in, dried polyamic acid nanometer barrier film is carried out high temperature imidization in a nitrogen atmosphere, and high temperature imidization is as follows: 1) 5 DEG C/min is warming up to 100 DEG C and processes 40min; 2) 5 DEG C/min is warming up to 200 DEG C of process 40min; 3) 5 DEG C/min is warming up to 300 DEG C and processes 40min.
10. a polyimide nano lithium ion battery separator, is characterized in that: it adopts the preparation method of the arbitrary described polyimide nano lithium ion battery separator of claim 1 to 9 to obtain.
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| CN108539097A (en) * | 2018-04-10 | 2018-09-14 | 深圳市摩码科技有限公司 | A kind of lithium battery diaphragm, preparation method and lithium battery |
| CN111106293B (en) * | 2018-10-25 | 2022-11-11 | 惠州比亚迪电池有限公司 | Porous diaphragm, preparation method thereof and lithium ion battery |
| CN113745761A (en) * | 2021-08-19 | 2021-12-03 | 中国科学院上海硅酸盐研究所 | Polyimide/silicon nitride whisker composite lithium ion battery diaphragm and preparation method thereof |
| CN113809476A (en) * | 2021-09-08 | 2021-12-17 | 北京化工大学常州先进材料研究院 | Polyimide diaphragm with thermal pore-closing function and preparation method thereof |
| CN115149211B (en) * | 2022-08-09 | 2023-07-14 | 四川大学 | Double-layer composite diaphragm, preparation method thereof and HNTs@PI-PP double-layer composite diaphragm |
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| CN102618964A (en) * | 2012-04-11 | 2012-08-01 | 北京化工大学 | Polyimide/polyacrylonitrile blended fiber and preparation method thereof |
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| KR101731802B1 (en) * | 2010-05-25 | 2017-05-02 | 코오롱패션머티리얼 (주) | Polyimide porous nanofiber web and Method for manufacturing the same |
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| CN102618964A (en) * | 2012-04-11 | 2012-08-01 | 北京化工大学 | Polyimide/polyacrylonitrile blended fiber and preparation method thereof |
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| Title |
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| 聚酰亚胺纤维及其纺丝工艺研究进展;向红兵;《高分子通报》;20110131(第1期);第40-50页 * |
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