CN105161762A - Preparation method of polymer electrolyte membrane and lithium-ion battery - Google Patents
Preparation method of polymer electrolyte membrane and lithium-ion battery Download PDFInfo
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- CN105161762A CN105161762A CN201510483022.2A CN201510483022A CN105161762A CN 105161762 A CN105161762 A CN 105161762A CN 201510483022 A CN201510483022 A CN 201510483022A CN 105161762 A CN105161762 A CN 105161762A
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- dielectric film
- polymer dielectric
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- electrolyte membrane
- pmma
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a preparation method of a polymer electrolyte membrane and a lithium-ion battery. In order to achieve the targets, with aramid non-woven as a support layer, a gel polymer electrolyte membrane skeleton is prepared by a method of coating the supporting layer with a polymer; a common diaphragm is replaced with the electrolyte membrane skeleton; a dry battery core is prepared by a winding or laminating technology; and the lithium-ion battery containing the polymer electrolyte membrane is obtained by the procedures of high-temperature baking, filling liquid electrolyte, standing, forming and packaging. The polymer electrolyte membrane disclosed by the invention is high in mechanical strength and excellent in electrochemical property; the safety performance of the battery is greatly improved when the electrochemical property is reduced hardly; and the polymer electrolyte membrane has high practical value.
Description
Technical field:
The present invention relates to a kind of preparation method and lithium ion battery of polymer dielectric film, belong to battery material technical field.
Background technology:
Along with the continuous expansion in lithium ion battery applications field, the especially following large-scale application in electric automobile field, the security performance of people to lithium ion battery proposes more and more stricter requirement.In view of the innate advantage in security performance, solid Li-ion battery becomes the developing direction in lithium ion battery future.But due to the restriction of the present art and working condition, the room-temperature conductivity of solid electrolyte still cannot reach level that can be practical.Therefore, people develop gel polymer electrolyte again, due to have solid electrolyte not easy-to-leak liquid concurrently advantage while, have again higher conductivity, gel polymer electrolyte becomes the study hotspot in this field in recent years.But gel electrolyte membrane mechanical strength prepared by current process is poor, is unfavorable for that battery is assembled.Meanwhile, directly to the gel electrolyte adding polymerisable monomer in liquid electrolyte and prepare, due to the existence of a large amount of polymerisable monomer, its chemical property is not satisfactory.
In view of this, be necessary to provide a kind of preparation method and the lithium ion battery with the gel-form solid polymer electrolyte film of higher mechanical strength and excellent electrochemical performance.
Summary of the invention:
The object of this invention is to provide a kind of with low cost, the preparation method of the simple polymer dielectric film of technique and lithium ion battery.For achieving the above object, the present invention selects aramid fiber nonwoven fabrics to be supporting layer, the method of coated polymer prepares gel polymer electrolyte film skeleton thereon, then this dielectric film skeleton is replaced common diaphragm, be prepared into dry battery core by winding or lamination process, through high-temperature baking, filling liquid electrolyte, leave standstill, change into packaging process after must containing the lithium ion battery of polymer dielectric film.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for polymer dielectric film, comprises step as follows:
(1) prepared polymer coating slurry: add a certain amount of SiO2 in solvent, ultrasonic agitation 40min, then add P (VDF-HFP) and PMMA successively, continues stirring after 4 ~ 6 hours, leaves standstill de-bubble, obtain homogeneous transparent slurry;
(2) with scraper by gained slurry in step (1), even blade coating, on aramid fiber nonwoven fabrics, after drying at room temperature 5 ~ 10min, is put into deionized water and is soaked, last 80 DEG C of oven dry, both must polymer dielectric film skeleton;
(3) above-mentioned polymer dielectric film skeleton is obtained polymer dielectric film after liquid electrolyte soaks.In described step (1), solvent is acetone and dimethyl formamide (DMF) mixed solvent of volume ratio 4: 1.
In described step (1), in coating slurry, P (VDF-HFP)/PMMA/SiO2 concentration is 15% ~ 35%.
In described step (1), the mass fraction of SiO2 in P (VDF-HFP)/PMMA/SiO2 is 8% ~ 15%.
In described step (1), the mass fraction of PMMA in P (VDF-HFP)/PMMA/SiO2 is 10% ~ 35%.
In described step (2), aramid fiber nonwoven fabrics material is PPTA, porosity ~ 70%, aperture ~ 30 μm.
Present invention also offers a kind of lithium ion battery, the polymer dielectric film comprising positive pole, negative pole and be placed between both positive and negative polarity.Preparation process is as follows: using above-mentioned polymer dielectric film skeleton as barrier film, obtains nude battery core by winding or lamination process, successively through fluid injection, leave standstill, change into, shaping, degasification operation obtain lithium ion battery.
Advantage of the present invention is: the technique preparing polymer dielectric film is simple, with low cost, the mechanical strength of obtained polymer dielectric film is high, electrochemical performance, can while reducing chemical property hardly, greatly improve the security performance of battery, there is very high practical value.Meanwhile, need hardly to change existing lithium ion battery production line, can commercial application be realized, be convenient to promote.
Embodiment:
For illustrating this aspect further, describe the preferred embodiments of the invention below in conjunction with specific embodiment, these describe just in order to further illustrate advantage of the present invention, instead of limiting to the claimed invention.
Embodiment:
Prepare gel polymer electrolyte skeleton: (1) adds a certain amount of SiO2 in the acetone and dimethyl formamide (DMF) mixed solvent of volume ratio 4: 1, ultrasonic agitation 40min, then P (VDF-HFP) and PMMA is added successively, continue stirring after 4 ~ 6 hours, leave standstill de-bubble, obtain homogeneous transparent slurry, P (VDF-HFP)/PMMA/SiO2 concentration is 20%, the mass fraction of SiO2 and PMMA in P (VDF-HFP)/PMMA/SiO2 is respectively 10%, 20%.
(2) with scraper by gained slurry in step (1), even blade coating, on aramid fiber nonwoven fabrics, after drying at room temperature 10min, is put into deionized water and is soaked, last 80 DEG C of oven dry, both must polymer dielectric film skeleton.
Preparation liquid electrolyte: after EC, PC, DEC, VC, PS being dewatered respectively, 30: 30: 35: 1.5: 1.5 mixing, stir, add appropriate LiPF6, obtain the liquid electrolyte that LiPF6 concentration is 1mol/L in mass ratio.
Preparation experiment battery: (1) take LiCoO2 as positive electrode, add bonding agent Kynoar (PVDF), conductive agent conductive black is sized mixing in 1-methyl-9-pyrrolidinone solvent, gained slurry double-faced uniform is coated on aluminium foil, drying, roll extrusion, obtain anode pole piece after cutting.
(2) take graphite as negative material, add butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC), graphite sizes mixing in deionized water, gained slurry double-faced uniform is coated on Copper Foil, drying, roll extrusion, obtains cathode pole piece after cutting.
(3) be clipped between both positive and negative polarity pole piece by above-mentioned gel polymer electrolyte film skeleton, by the dry battery core that reels to obtain, with laminated aluminum film, top side seal is placed in baking oven and toasts.
(4) above-mentioned liquid electrolyte is injected the dry battery core after baking, through leaving standstill, changing into, shaping, must lithium ion battery be tested after degasification.
Contrast:
Comparative example experimental cell, except replacing with except common PE barrier film by the gel polymer electrolyte film skeleton in embodiment, it is identical with step and embodiment
Effect detects:
Experimental cell in comparative example and embodiment is tested as follows:
Capacity and cycle performance are tested:
In 35 ± 2 DEG C of environment, by following program, experimental cell is tested, leave standstill 3min, 0.5C constant current charge to 4.2V, constant voltage is to 0.05C, leave standstill 3min, crossing current 0.5C is discharged to 3.0V, opens circulation in next week after leaving standstill 3min, so circulation 500 weeks, record first all discharge capacity D1 and circulation 500 weeks rear capability retention D500/D1, test result is as shown in table 1.
Pin prick test:
Completely filled by experimental cell, in 25 ± 5 DEG C of environment, use the rustless draw point of 3mm, with the speed breakthrough experiment battery center of 20mm/S, and keep 1min, record fiery number of batteries and maximum temperature Tmax, test result is as shown in table 1.
Table 1 embodiment and comparative example experimental cell test result
| Group | D1(mAh) | D500/D1 | Catch fire number/sum | Tmax(℃) |
| Embodiment | 1513 | 0.884 | 0/20 | 81 |
| Comparative example | 1517 | 0.907 | 17/20 | 122 |
As can be seen from Table 1, the capacity of embodiment battery and cycle performance slightly lower than comparative example battery, but the amplitude of reduction is minimum, and pin prick test result is far superior to comparative example battery.Illustrate that gel polymer electrolyte film provided by the invention while reducing chemical property hardly, can greatly improve the security performance of battery, there is very high practical value.
Claims (6)
1. a preparation method for polymer dielectric film, is characterized in that: comprise step as follows:
(1) prepared polymer coating slurry: add a certain amount of SiO2 in solvent, ultrasonic agitation 40min, then add P (VDF-HFP) and PMMA successively, continues stirring after 4 ~ 6 hours, leaves standstill de-bubble, obtain homogeneous transparent slurry;
(2) with scraper by gained slurry in step (1), even blade coating, on aramid fiber nonwoven fabrics, after drying at room temperature 5 ~ 10min, is put into deionized water and is soaked, last 80 DEG C of oven dry, both must polymer dielectric film skeleton;
(3) above-mentioned polymer dielectric film skeleton is obtained polymer dielectric film after liquid electrolyte soaks.
2. a lithium ion battery, it is characterized in that: the polymer dielectric film comprising positive pole, negative pole and be placed between both positive and negative polarity, its preparation process is as follows: using above-mentioned polymer dielectric film skeleton as barrier film, obtain nude battery core by winding or lamination process, successively through fluid injection, leave standstill, change into, shaping, degasification operation obtain lithium ion battery.
3. the preparation method of polymer dielectric film according to claim 1, is characterized in that: in described step (1), and solvent is acetone and dimethyl formamide (DMF) mixed solvent of volume ratio 4: 1.
4. the preparation method of polymer dielectric film according to claim 1, is characterized in that: in described step (1), and in coating slurry, P (VDF-HFP)/PMMA/SiO2 concentration is 15% ~ 35%.
5. the preparation method of polymer dielectric film according to claim 1, is characterized in that: in described step (1), and the mass fraction of SiO2 in P (VDF-HFP)/PMMA/SiO2 is 8% ~ 15%.
6. the preparation method of polymer dielectric film according to claim 1, is characterized in that: in described step (1), and the mass fraction of PMMA in P (VDF-HFP)/PMMA/SiO2 is 10% ~ 35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510483022.2A CN105161762A (en) | 2015-08-05 | 2015-08-05 | Preparation method of polymer electrolyte membrane and lithium-ion battery |
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| CN201510483022.2A CN105161762A (en) | 2015-08-05 | 2015-08-05 | Preparation method of polymer electrolyte membrane and lithium-ion battery |
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| CN105161762A true CN105161762A (en) | 2015-12-16 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470564A (en) * | 2016-01-22 | 2016-04-06 | 山东鸿正电池材料科技有限公司 | Solid electrolyte membrane, preparation method of solid electrolyte membrane and lithium ion battery |
| CN108110315A (en) * | 2017-12-08 | 2018-06-01 | 河北师范大学 | A kind of lithium ion battery self-healing polymers electrolyte preparation method |
| CN109888379A (en) * | 2019-01-11 | 2019-06-14 | 安徽鼎正包装材料有限公司 | Alkalinity polymer electrolyte thin films and preparation method thereof based on nonwoven carrier |
| 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 |
| CN112713301A (en) * | 2020-12-31 | 2021-04-27 | 广东微电新能源有限公司 | Energy storage device |
| CN112820939A (en) * | 2019-11-18 | 2021-05-18 | 青岛蓝科途膜材料有限公司 | Gel electrolyte and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101552359A (en) * | 2009-05-12 | 2009-10-07 | 湖南大学 | Micro-nano porous structure polymer electrolyte membrane used for lithium ion battery and method of producing the same |
| US20130183570A1 (en) * | 2004-09-02 | 2013-07-18 | Lg Chem, Ltd. | Organic/inorganic composite porous film and electrochemical device prepared thereby |
-
2015
- 2015-08-05 CN CN201510483022.2A patent/CN105161762A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20130183570A1 (en) * | 2004-09-02 | 2013-07-18 | Lg Chem, Ltd. | Organic/inorganic composite porous film and electrochemical device prepared thereby |
| CN101552359A (en) * | 2009-05-12 | 2009-10-07 | 湖南大学 | Micro-nano porous structure polymer electrolyte membrane used for lithium ion battery and method of producing the same |
Non-Patent Citations (1)
| Title |
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| 张国庆等: ""添加无机粒子的P(VDF-HFP)-PMMA复合聚合物电解质的性能"", 《材料科学与工程学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470564A (en) * | 2016-01-22 | 2016-04-06 | 山东鸿正电池材料科技有限公司 | Solid electrolyte membrane, preparation method of solid electrolyte membrane and lithium ion battery |
| CN108110315A (en) * | 2017-12-08 | 2018-06-01 | 河北师范大学 | A kind of lithium ion battery self-healing polymers electrolyte preparation method |
| CN108110315B (en) * | 2017-12-08 | 2019-12-31 | 河北师范大学 | Preparation method of self-repairing polymer electrolyte of lithium ion battery |
| CN109888379A (en) * | 2019-01-11 | 2019-06-14 | 安徽鼎正包装材料有限公司 | Alkalinity polymer electrolyte thin films and preparation method thereof based on nonwoven carrier |
| 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 |
| CN112820939A (en) * | 2019-11-18 | 2021-05-18 | 青岛蓝科途膜材料有限公司 | Gel electrolyte and lithium ion battery |
| CN112820939B (en) * | 2019-11-18 | 2024-03-12 | 青岛蓝科途膜材料有限公司 | Gel electrolyte and lithium ion battery |
| CN112713301A (en) * | 2020-12-31 | 2021-04-27 | 广东微电新能源有限公司 | Energy storage device |
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