CN103066230B - A kind of composite polymer electrolytes and preparation method thereof - Google Patents
A kind of composite polymer electrolytes and preparation method thereof Download PDFInfo
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- CN103066230B CN103066230B CN201210582514.3A CN201210582514A CN103066230B CN 103066230 B CN103066230 B CN 103066230B CN 201210582514 A CN201210582514 A CN 201210582514A CN 103066230 B CN103066230 B CN 103066230B
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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 discloses a kind of composite polymer electrolytes, it is characterized in that: it is made up of polyolefin base membrane and the film on polyolefin base membrane surface, and described film is made up of the raw material of following mass fraction: the DMF of PVDF, 90-120 part of PI, 6-9 part of 1-4 part.A preparation method for composite polymer electrolytes, comprises the following steps: 1) by various raw material mix and blend, heat aging, and vacuum stirring de-soak makes colloidal film forming liquid; 2) film forming liquid is coated in the surface of polyolefin base membrane, obtains wet film; 3) wet film is carried out immersion process; 4) wet film is taken out, dry.Barrier film resistance to elevated temperatures prepared by the present invention is obvious, exceeds more than 20% than business PE; Adopt the battery that barrier film of the present invention is made, it is high temperature resistant and specific discharge capacity and cycle performance thereof are all better than the battery that adopts business-like barrier film made; The preparation method of barrier film of the present invention is easy, saves manufacturing cost.
Description
Technical field
The present invention relates to a kind of composite polymer electrolytes and preparation method thereof.
Background technology
Lithium battery forms primarily of positive pole, negative pole, barrier film and electrolyte.Barrier film is the important part of lithium battery, and its performance determines the interfacial structure, internal resistance etc. of battery, directly affects the characteristics such as the capacity of battery, cycle performance, and the barrier film of excellent performance has important effect to the combination property improving battery.At present, business-like barrier film adopts polyethylene (PE) or polypropylene (PP) barrier film mostly, and it has higher porosity, lower resistance, higher tearing toughness, good antiacid alkali ability, good elasticity and the retention to aprotic solvent.But also there is following shortcoming in it: porosity is not high, limited strength, percent thermal shrinkage are not good, fail safe that is material exists limitation.Therefore, increasing enterprise tests improving membrane properties.
Summary of the invention
The object of this invention is to provide a kind of composite polymer electrolytes and preparation method thereof.
The technical solution used in the present invention is:
A kind of composite polymer electrolytes, it is made up of polyolefin base membrane and the film on polyolefin base membrane surface, and described film is made up of the raw material of following mass fraction: the DMF of PVDF, 90-120 part of PI, 6-9 part of 1-4 part.
The mass ratio of PI and PVDF is 3:7 or 2:8.
Described polyolefin base membrane is polyethylene film or polypropylene screen.
The thickness of described basement membrane is 5-20 μm.
The thickness of described film is 5-9 μm.
A preparation method for composite polymer electrolytes, comprises the following steps:
1) by various raw material mix and blend, heat aging, vacuum stirring de-soak, makes colloidal film forming liquid;
2) film forming liquid is coated in the surface of polyolefin base membrane, obtains wet film;
3) wet film is carried out immersion process;
4) wet film is taken out, dry.
Described heat aging temperature is 40-60 DEG C.
The temperature of described heat drying is 40-60 DEG C.
The invention has the beneficial effects as follows: 1. resistance to elevated temperatures is obvious, exceeds more than 20% than business PE.
2. adopt the battery that is made of barrier film of the present invention, it is high temperature resistant and specific discharge capacity and cycle performance thereof are all better than the battery that adopts business-like barrier film made.
3. the preparation method of barrier film of the present invention is easy, saves manufacturing cost.
Accompanying drawing explanation
The voltage buckleing electricity-specific volume spirogram that Fig. 1 makes for barrier film with sample 1.
The voltage buckleing electricity-specific volume spirogram that Fig. 2 makes for barrier film with sample 4.
Voltage-specific volume the spirogram of what Fig. 3 made using PE as barrier film buckle electricity.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further:
embodiment 1:
This composite polymer electrolytes, the basement membrane selected is polyethylene film, and thickness is 16 microns.
The preparation method of this composite polymer electrolytes:
1) take polyimides 3.1581 grams, Kynoar (PVDF-761) 7.3695 grams as solute, dimethyl formamide (DMF) 100 milliliters is as solvent; Three's mixing and at room temperature stirring and dissolving, be more fully uniformly mixed in heating under vacuum to 40-60 DEG C, slaking to the film forming liquid forming homogeneous colloids shape, then set aside for use;
2) by coating equipment (scraper or coating machine etc.), the above-mentioned film forming liquid made is coated in the surface (one side) of basement membrane under room temperature, forms wet film, the thickness of coating (film forming liquid) is controlled by coating equipment;
3) under room temperature, wet film immersion is left standstill 0.5 hour;
4) take out wet film, heat drying (temperature is 50 degree) 0.5-2 hour, film forming liquid is formed and is attached to epilamellar outer membrane, finally obtains described composite polymer electrolytes.
Sample number into spectrum 1-3 in the table 1 of the corresponding embodiment 2 of several films prepared by the step of the present embodiment.
embodiment 2:
This composite polymer electrolytes, the basement membrane selected is polyethylene film, and thickness is 16 microns.
The preparation method of this composite polymer electrolytes:
1) polyimides 3.1581 grams, Kynoar (PVDF-761) 7.3695 grams is taken as solute, dimethyl formamide (DMF) 100 milliliters is as solvent, three's mixing and at room temperature stirring and dissolving, fully be uniformly mixed in heating under vacuum to 40-60 DEG C again, slaking extremely forms the film forming liquid of homogeneous colloids shape, then set aside for use;
2) by coating equipment (scraper or coating machine etc.), the above-mentioned film forming liquid made is coated in the surface (two-sided) of basement membrane under room temperature, forms wet film, the thickness of coating (film forming liquid) is controlled by coating equipment;
3) under room temperature, wet film immersion is left standstill 0.5 hour;
4) take out wet film, heat drying (temperature is 50 degree) 0.5-2 hour, film forming liquid is formed and is attached to epilamellar outer membrane, finally obtains described composite polymer electrolytes.
The each sample of sample number into spectrum 4-6(in the table 1 of the corresponding embodiment 2 of several films prepared by the step of the present embodiment is two-sided film, and identical for the thickness of single sample dual coating, the coating thickness of the every one side of sample 4-6 is followed successively by 5 μm, 7 μm, 9 μm).
Below for data compare:
table 1: the performance comparison of barrier film of the present invention and PE barrier film
Fig. 1-3 is respectively using the sample of sample number into spectrum 1 and 4 in sample 1,4(i.e. upper table), PE is as the voltage the buckleing electricity-specific volume spirogram of barrier film, in addition, it should be noted that, the formation of the button electricity that this test is used is: positive pole cobalt acid lithium, negative pole lithium sheet, barrier film is respectively barrier film sample 1,4 of the present invention and PE barrier film, electrolyte 1mol/LLiPF
6eC:DEC:EMC=2:3:1 (weight ratio), what button was electric is prepared as common practise in the industry.
As can be seen from Fig. 1-3, dual coating applies better effects if than one side, and this composite polymer electrolytes is made the voltage platform of battery and specific discharge capacity and cycle performance thereof and is better than PE barrier film.
Claims (4)
1. a composite polymer electrolytes, is characterized in that: it is made up of polyolefin base membrane and the film on polyolefin base membrane surface, and described film is made up of the raw material of following mass fraction: the DMF of PVDF, 90-120 part of PI, 6-9 part of 1-4 part; The mass ratio of PI and PVDF is 3:7 or 2:8; Described polyolefin base membrane is polyethylene film or polypropylene screen; The thickness of described basement membrane is 5-20 μm; The thickness of described film is 5-9 μm.
2. prepare the method for a kind of composite polymer electrolytes according to claim 1, it is characterized in that: comprise the following steps:
1) by various raw material mix and blend, heat aging, vacuum stirring de-soak, makes colloidal film forming liquid;
2) film forming liquid is coated in the surface of polyolefin base membrane, obtains wet film;
3) wet film is carried out immersion process;
4) wet film is taken out, dry.
3. the preparation method of a kind of composite polymer electrolytes according to claim 2, is characterized in that: described heat aging temperature is 40-60 DEG C.
4. the preparation method of a kind of composite polymer electrolytes according to claim 2, is characterized in that: the temperature of described drying is 40-60 DEG C.
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| CN110600657B (en) * | 2019-09-27 | 2022-04-19 | 宁德卓高新材料科技有限公司 | Preparation method of filamentous vinylidene fluoride polymer composite coating diaphragm |
| CN111117473A (en) * | 2019-12-25 | 2020-05-08 | 河北金力新能源科技股份有限公司 | Coating slurry based on linear aromatic polymer compound, preparation method and application thereof, and battery shell |
| WO2023226052A1 (en) * | 2022-05-27 | 2023-11-30 | 深圳市星源材质科技股份有限公司 | Coating slurry, separator, separator preparation method, and battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102487131A (en) * | 2010-12-06 | 2012-06-06 | 财团法人工业技术研究院 | Multilayer battery separator and method for manufacturing same |
| CN102810655A (en) * | 2011-05-30 | 2012-12-05 | 东莞新能源科技有限公司 | Lithium ion battery composite isolation membranes |
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| JP2005285385A (en) * | 2004-03-29 | 2005-10-13 | Sanyo Electric Co Ltd | Separator and nonaqueous electrolyte battery using the separator |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102487131A (en) * | 2010-12-06 | 2012-06-06 | 财团法人工业技术研究院 | Multilayer battery separator and method for manufacturing same |
| CN102810655A (en) * | 2011-05-30 | 2012-12-05 | 东莞新能源科技有限公司 | Lithium ion battery composite isolation membranes |
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