CN103208604A - Electrospinning composite diaphragm with thermal hole sealing function - Google Patents
Electrospinning composite diaphragm with thermal hole sealing function Download PDFInfo
- Publication number
- CN103208604A CN103208604A CN2013100853495A CN201310085349A CN103208604A CN 103208604 A CN103208604 A CN 103208604A CN 2013100853495 A CN2013100853495 A CN 2013100853495A CN 201310085349 A CN201310085349 A CN 201310085349A CN 103208604 A CN103208604 A CN 103208604A
- Authority
- CN
- China
- Prior art keywords
- composite diaphragm
- point polymer
- melting point
- low melting
- electrospinning composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- Cell Separators (AREA)
Abstract
The invention discloses an electrospinning composite diaphragm with a thermal hole sealing function and relates to lithium ion batteries. By the electrospinning composite diaphragm, the secondary thermal hole sealing function can be realized, direct contact of positive and negative electrodes of lithium ion batteries due to thermal inertia is avoided, and safety of the lithium ion batteries is remarkably improved. The electrospinning composite diaphragm comprises polyimide nano fibers and low-melting-point polymer nano fibers, wherein the low-melting-point polymer nano fibers contain bismaleimide and azodisobutyronitrile, and the polyimide nano fibers and the low-melting-point polymer nano fibers are interwoven in stagger manner. The thickness of the electrospinning composite diaphragm with the thermal hole sealing function ranges from 10 micrometers to 50 micrometers. The melting point of the low-melting-point polymer nano fibers is 90-110 DEG C. Components of the low-melting-point polymer nano fibers can be ethylene-vinyl acetate copolymer, poly-succinic acid glycol ester and the like.
Description
Technical field
The present invention relates to lithium ion battery, especially relate to a kind of electrospinning composite diaphragm with hot closed pore function that adopts the preparation of electrospinning method.
Background technology
Lithium ion battery is because having energy density height, power density height, long service life and characteristics such as environmentally friendly are widely used in the consumer electronics product, yet the existing potential safety hazard of lithium ion battery has seriously hindered the expansion of lithium ion battery applications scope, as hybrid vehicle, electric automobile etc.Thermal runaway is to cause the main cause of cell safety hidden danger, and thermal runaway mainly because overcharge, inside or external short circuit or high thermal shock etc. cause.
The means that solve lithium ion battery security are mainly carried out from battery electrode material, electrolyte, electrolysis additive and barrier film aspect at present, wherein realize that by barrier film the high security of battery is the emphasis of current research, and the barrier film with hot closed pore function is the most important means of guaranteeing battery security.Chinese patent CN101794870A and CN102544414A all disclose characteristics such as high temperature resistant, the stable chemical performance of utilizing inorganic particle (as aluminium oxide) and have improved the barrier film heat-resistant stability, it has improved the fail safe of battery to a certain extent, but does not relate to hot closed pore problem.Present commercial barrier film mainly contains PP, PE and PP/PE/PP barrier film, and its hot closed pore temperature is about 165 ℃, 135 ℃, 135 ℃ respectively.In order to improve the fail safe of barrier film, patent JP7304110A, JP8250097A, GB2298817A and US5691007A disclose the technology of the hot closed pore barrier film of different making respectively and have realized hot closed pore function, and hot closed pore temperature is respectively 135～140 ℃, 124 ℃, 135 ℃ and 132 ℃.Operating temperature range when document A review on the key issues for lithium-ion battery management in electric vehicles points out most of battery charging and discharging is respectively-20～55 ℃ and 0～45 ℃, when battery temperature rises to 90～120 ℃, solid electrolyte interface film (SEI) beginning exothermic decomposition; When temperature surpassed 120 ℃, the SEI film was disintegrated fully, and electrode directly contacts and produce side reaction with electrolyte, and along with the rising of temperature, electrolyte, electrode decompose, and finally cause thermal runaway, so the hot closed pore temperature of barrier film should design in 90～120 ℃ of scopes; It is three layers of barrier film manufacture craft of 115 ℃ that patent US6080507A discloses a kind of hot closed pore temperature, points out that the hot closed pore temperature of barrier film should be lower than 120 ℃, preferably controls in 95～115 ℃ of scopes.
Above-mentioned patent has all improved the fail safe of barrier film to a certain extent, but because the effect of thermal inertia, the temperature of inside battery still might continue to rise behind hot closed pore and surpass the fusing point of barrier film composition, make the barrier film fusing cause the direct contact of lithium ion battery positive and negative electrode, make the inside battery generation thermal runaway that heats up rapidly, and finally might be explosion caused.
Summary of the invention
The object of the present invention is to provide and to realize the hot closed pore function of secondary, avoid causing because of the effect of thermal inertia the direct contact of lithium ion battery positive and negative electrode, significantly improve a kind of electrospinning composite diaphragm with hot closed pore function of lithium ion battery security.
Described electrospinning composite diaphragm with hot closed pore function is nonwoven fabric construct, comprises polyimides (PI) nanofiber and low melting point polymer nanofiber; Described low melting point polymer nanofiber is for containing the low melting point polymer nanofiber of bismaleimides (BMI) and azodiisobutyronitrile (AIBN), and the assorted order of polyimides (PI) nanofiber and low melting point polymer nanofiber is staggered.
Described thickness with electrospinning composite diaphragm of hot closed pore function can be 10～50 μ m.
The fusing point of described low melting point polymer nanofiber can be 90～110 ℃.The composition of described low melting point polymer nanofiber can be ethylene-vinyl acetate copolymer, polyethylene glycol succinate etc.
Press mass ratio, the ratio of described polyimides (PI) nanofiber content and low melting point polymer nanofiber content can be (3～1): 1; Press mass ratio, described bismaleimides (BMI) can be 15%～25% with the ratio of azodiisobutyronitrile (AIBN) content sum and described low melting point polymer nanofiber content, and wherein the ratio of bismaleimides (BMI) content and azodiisobutyronitrile (AIBN) content can be (60～40): 1.
Compared with the prior art, operation principle of the present invention and beneficial effect are as follows:
When the present invention prepares, each components in certain proportion is made into electrospinning solution, adopts existing electric spinning equipment, can obtain by the method for electrostatic spinning preparation.The desired thickness of electrospinning composite diaphragm can obtain by hot-pressing processing.The present invention is as lithium ion battery separator, it is the hot closed pore function first time of utilizing the fusing realization barrier film of low melting point polymer nanofiber, form polymer insulation layer behind the hot closed pore for the first time, after temperature continues to raise, this polymer insulation layer fusing, BMI and AIBN then are released in the lithium-ion battery electrolytes fully, form new even phase electrolyte system, but last PI fiber and the BMI in-situ polymerization under the inducing of AIBN in low melting point polymer insulating barrier fusing back, form solid insulator, thereby realize the hot closed pore function second time of barrier film.In addition, resulting PI high polymer is the high-temperature stability material behind PI nanofiber and the BMI monomer in-situ polymerization, is the important assurance that realizes battery security.Will make that resulting PI high polymer is more stable behind the BMI monomer in-situ polymerization because internal temperature of battery rises, to solidify the solid insulator that the back forms even therefore exist thermal inertia also can not destroy by new even phase electrolyte system.
Description of drawings
Fig. 1 is the fibr tissue schematic diagram of electrospinning composite diaphragm of the present invention.
Fig. 2 is the electrospinning composite diaphragm of the present invention hot closed pore process of secondary schematic diagram when using.
Fig. 3 is BMI monomer polymerization principle schematic of the present invention.
Embodiment
Referring to Fig. 1, described electrospinning composite diaphragm is nonwoven fabric construct, and the electrospinning composite diaphragm comprises polyimides (PI) nanofiber 15 and low melting point polymer nanofiber 16; Described low melting point polymer nanofiber 16 is for containing the low melting point polymer nanofiber of bismaleimides (BMI) and azodiisobutyronitrile (AIBN), and polyimides (PI) nanofiber 15 is staggered with low melting point polymer nanofiber 16 assorted orders.
Again through follow-up hot-pressing processing, make film thickness is 10～50um to described electrospinning composite diaphragm after the electric spinning equipment preparation.The fusing point of described low melting point polymer nanofiber 16 is 90～110 ℃.
Press mass ratio, the ratio of described polyimides (PI) nanofiber content and low melting point polymer nanofiber content is (3～1): 1; By mass percentage, described bismaleimides (BMI) is 15%～25% with the ratio of azodiisobutyronitrile (AIBN) content sum and described low melting point polymer nanofiber content, wherein the mass ratio of bismaleimides (BMI) content and azodiisobutyronitrile (AIBN) content is (60～40): 1.
Referring to Fig. 2, lithium ion battery mainly is made up of positive pole, barrier film/electrolyte and negative pole.In Fig. 2, mark 21 is electrolyte system; Mark 22 is the electrospinning composite diaphragm; The polymer insulation layer that mark 23 formed behind the hot closed pore for the first time; Mark 24 is released to the new even phase electrolyte system that forms behind the electrolyte fully for polymer insulation layer fusing back BMI and AIBN; Mark 25 is the last PI fibrage in low melting point polymer insulating barrier fusing back; The solid insulator that mark 26 forms behind in-situ polymerization under the inducing of AIBN for BMI.
The hot closed pore process of secondary during 22 work of composite electrospun barrier film is as described below:
1) when lithium ion battery discharges and recharges under normal operation circumstances, internal temperature of battery is far below 90 ℃, lithium ion electrolyte inside system 21 normal (referring to Fig. 2 (a), mark 22 is the electrospinning composite diaphragm).
2) when temperature rises to 90 ℃～110 ℃, the softening and fusing of low melting point polymer nanofiber, release portion BMI and AIBN absorb heat in fusion process simultaneously, tentatively slow down internal temperature of battery and rise; The space between the unfused PI nanofiber is stopped up in low melting point polymer nanofiber fusing back, forms polymer insulation layer 23, isolated ion transfer (i.e. the first time hot closed pore) (referring to Fig. 2 (b), mark 21 is electrolyte system).
3) when temperature continues to rise owing to reasons such as thermal inertias but is no more than 120 ℃, destroyed by the insulating barrier that low melting point polymer forms, BMI and AIBN are discharged fully, form new even phase electrolyte system 24(ginseng Fig. 2 (c), mark 25 is the last PI fibrage in low melting point polymer insulating barrier fusing back).
4) after temperature continues to rise above 120 ℃, the BMI monomer is in-situ polymerization under the AIBN action of evocating, make new even phase electrolyte system 24 be converted into solid-state by liquid state, realize for the second time isolated ion transfer (i.e. the second time hot closed pore) (referring to Fig. 2 (d)), the solid insulator that mark 26 forms behind in-situ polymerization under the inducing of AIBN for BMI; BMI monomer polymerization principle as shown in Figure 3.
Provide 1 specific embodiment of preparation electrospinning composite diaphragm below:
Polyimide powder is dissolved in the dimethylacetamide solvent, and the control solution concentration is 20wt%.Select fusing point at 90～100 ℃ polyethylene glycol oxide powder (PEO) as low melting point polymer, 12wt%PEO powder, 3wt%BMI and 0.05wt%AIBN are dissolved in together in the mixed solvent (mass ratio of deionized water and absolute ethyl alcohol is 3: 1) of deionized water and absolute ethyl alcohol, stir to make and treat electrospinning solution.Utilize existing electric spinning equipment can prepare described electrospinning composite diaphragm then, dimethylacetamide solvent volatilizees fully in preparation process.Stepping motor by the control electric spinning equipment can be realized gathering-device at the reciprocating motion of Y-direction and the intermittent rectilinear motion of directions X, thereby can obtain the electrospinning composite diaphragm (composite cellulosic membrane) of uniform large-area.The feed flow speed of solution feed pump by the control electric spinning equipment can realize that the mass ratio to PI nanofiber in the electrospinning composite diaphragm (composite cellulosic membrane) and PEO composite nano fiber is the accurate control of 3:1.The electrospinning composite diaphragm that makes is passed through finally to obtain the thick composite electrospun barrier film of 25 μ m after the pressure hot pressing of 5MPa.
Claims (5)
1. the electrospinning composite diaphragm with hot closed pore function is characterized in that described electrospinning composite diaphragm is nonwoven fabric construct, and the electrospinning composite diaphragm comprises polyimide nano-fiber and low melting point polymer nanofiber; Described low melting point polymer nanofiber is the low melting point polymer nanofiber that contains bismaleimides and azodiisobutyronitrile, and the assorted order of polyimide nano-fiber and low melting point polymer nanofiber is staggered.
2. a kind of electrospinning composite diaphragm with hot closed pore function as claimed in claim 1, the thickness that it is characterized in that described electrospinning composite diaphragm is 10～50 μ m.
3. a kind of electrospinning composite diaphragm with hot closed pore function as claimed in claim 1, the fusing point that it is characterized in that described low melting point polymer nanofiber is 90～110 ℃.
4. a kind of electrospinning composite diaphragm with hot closed pore function as claimed in claim 3, the composition that it is characterized in that described low melting point polymer nanofiber is ethylene-vinyl acetate copolymer or polyethylene glycol succinate.
5. a kind of electrospinning composite diaphragm with hot closed pore function as claimed in claim 1 is characterized in that by mass ratio, and the ratio of described polyimide nano-fiber content and low melting point polymer nanofiber content is 3～1: 1; Press mass ratio, the ratio of described bismaleimides and azodiisobutyronitrile content sum and described low melting point polymer nanofiber content is 15%～25%, and wherein the ratio of bismaleimide amine content and azodiisobutyronitrile content is 60～40: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310085349.5A CN103208604B (en) | 2013-03-18 | 2013-03-18 | Electrospinning composite diaphragm with thermal hole sealing function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310085349.5A CN103208604B (en) | 2013-03-18 | 2013-03-18 | Electrospinning composite diaphragm with thermal hole sealing function |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103208604A true CN103208604A (en) | 2013-07-17 |
| CN103208604B CN103208604B (en) | 2015-06-03 |
Family
ID=48755750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310085349.5A Active CN103208604B (en) | 2013-03-18 | 2013-03-18 | Electrospinning composite diaphragm with thermal hole sealing function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103208604B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103541149A (en) * | 2013-08-29 | 2014-01-29 | 天津工业大学 | Method for enhancing electrostatic spinning nanofiber membrane |
| CN103824988A (en) * | 2014-02-24 | 2014-05-28 | 东华大学 | Composite nanofiber lithium battery diaphragm and making method thereof |
| CN108666506A (en) * | 2018-05-07 | 2018-10-16 | 苏州睿烁环境科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof with compound resin |
| CN111933879A (en) * | 2020-07-21 | 2020-11-13 | 清华大学 | Lithium ion battery |
| CN112751136A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Lithium ion battery diaphragm with staggered fiber heterosequence and preparation method thereof |
| CN114079076A (en) * | 2020-08-11 | 2022-02-22 | 北京小米移动软件有限公司 | Battery module manufacturing process, battery module and electronic equipment |
| CN114566760A (en) * | 2020-11-27 | 2022-05-31 | 中国石油化工股份有限公司 | Lithium ion battery diaphragm containing polymer electrospun fibers and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469488A (en) * | 2013-09-29 | 2013-12-25 | 天津工业大学 | Preparation method of reinforced electrostatic spinning nano-fiber lithium-ion battery separator |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424340A (en) * | 2002-12-27 | 2003-06-18 | 中国科学院长春应用化学研究所 | Preparation of polyimide moulded by casting |
| CN101584077A (en) * | 2007-01-16 | 2009-11-18 | 株式会社Lg化学 | Electrolyte comprising eutectic mixture and secondary battery using the same |
| CN102272977A (en) * | 2008-12-30 | 2011-12-07 | 株式会社Lg化学 | Separator with a porous coating layer, and electrochemical device comprising same |
| CN102544413A (en) * | 2010-12-22 | 2012-07-04 | 财团法人工业技术研究院 | Battery separator, method for manufacturing same, and secondary battery using same |
| CN102947499A (en) * | 2010-06-21 | 2013-02-27 | 可隆株式会社 | Porous nanoweb and method for manufacturing the same |
-
2013
- 2013-03-18 CN CN201310085349.5A patent/CN103208604B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424340A (en) * | 2002-12-27 | 2003-06-18 | 中国科学院长春应用化学研究所 | Preparation of polyimide moulded by casting |
| CN101584077A (en) * | 2007-01-16 | 2009-11-18 | 株式会社Lg化学 | Electrolyte comprising eutectic mixture and secondary battery using the same |
| CN102272977A (en) * | 2008-12-30 | 2011-12-07 | 株式会社Lg化学 | Separator with a porous coating layer, and electrochemical device comprising same |
| CN102947499A (en) * | 2010-06-21 | 2013-02-27 | 可隆株式会社 | Porous nanoweb and method for manufacturing the same |
| CN102544413A (en) * | 2010-12-22 | 2012-07-04 | 财团法人工业技术研究院 | Battery separator, method for manufacturing same, and secondary battery using same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103541149A (en) * | 2013-08-29 | 2014-01-29 | 天津工业大学 | Method for enhancing electrostatic spinning nanofiber membrane |
| CN103824988A (en) * | 2014-02-24 | 2014-05-28 | 东华大学 | Composite nanofiber lithium battery diaphragm and making method thereof |
| CN108666506A (en) * | 2018-05-07 | 2018-10-16 | 苏州睿烁环境科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof with compound resin |
| CN112751136A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Lithium ion battery diaphragm with staggered fiber heterosequence and preparation method thereof |
| CN111933879A (en) * | 2020-07-21 | 2020-11-13 | 清华大学 | Lithium ion battery |
| CN114079076A (en) * | 2020-08-11 | 2022-02-22 | 北京小米移动软件有限公司 | Battery module manufacturing process, battery module and electronic equipment |
| CN114566760A (en) * | 2020-11-27 | 2022-05-31 | 中国石油化工股份有限公司 | Lithium ion battery diaphragm containing polymer electrospun fibers and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103208604B (en) | 2015-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103208604B (en) | Electrospinning composite diaphragm with thermal hole sealing function | |
| Uddin et al. | A low-cost, environment-friendly lignin-polyvinyl alcohol nanofiber separator using a water-based method for safer and faster lithium-ion batteries | |
| Zhu et al. | Aramid nanofibers/polyphenylene sulfide nonwoven composite separator fabricated through a facile papermaking method for lithium ion battery | |
| Boriboon et al. | Cellulose ultrafine fibers embedded with titania particles as a high performance and eco-friendly separator for lithium-ion batteries | |
| Li et al. | Tri-layer nonwoven membrane with shutdown property and high robustness as a high-safety lithium ion battery separator | |
| EP2689484B1 (en) | Battery separator and method for preparing the same | |
| CN102969471B (en) | A kind of high-temperature resistant aromatic polysulfonamide base lithium ion battery diaphragm | |
| Wang et al. | A single-ion gel polymer electrolyte based on polymeric lithium tartaric acid borate and its superior battery performance | |
| CN101562243B (en) | Method for manufacturing electrospinning of high-performance polyarylether resin lithium battery diaphragm | |
| CN107819095B (en) | A kind of high security complex lithium electric separator and preparation method thereof | |
| CN103081183B (en) | Battery with nonaqueous electrolyte | |
| CN104466231B (en) | A kind of lithium rechargeable battery and preparation method thereof | |
| Huang et al. | Review on advanced functional separators for lithium-sulfur batteries | |
| CN105449263B (en) | Lithium ion secondary battery | |
| Dong et al. | In situ reinforcing: ZrO2-armored hybrid polyimide separators for advanced and safe lithium-ion batteries | |
| CN104538577A (en) | Composite diaphragm and preparation method thereof | |
| CN101826606A (en) | Polytetrafluoroethylene lithium-ion battery separator and preparation method thereof | |
| Guo et al. | Flexible core-shell PAN/CNTs@ PVDF-HFP/Uio-66-NH2 hybrid nanofibers membrane for advanced lithium-ion batteries separator | |
| CN107819151A (en) | A kind of non-ignitable hybrid solid-state polymer dielectric and its application in solid secondary batteries | |
| CN103618056A (en) | Preparation method of nano-fiber membrane with three-dimensional porous structure for lithium ion battery diaphragm | |
| CN103378331A (en) | Lithium battery diaphragm and preparation method thereof | |
| CN103594680A (en) | Preparation method for electroactive self-supported nitrogen-doped carbon-film high-capacity electrode | |
| CN106450444B (en) | A kind of lithium-sulfur cell electrolyte and preparation method thereof | |
| Yusuf et al. | Toward a New Generation of Fire‐Safe Energy Storage Devices: Recent Progress on Fire‐Retardant Materials and Strategies for Energy Storage Devices | |
| CN105514324A (en) | PET non-woven cloth-based composite lithium ion battery diaphragm with nano aperture and preparation method of PET non-woven cloth-based composite lithium ion battery diaphragm |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 363000 the southern tip of Xiamen University Zhangzhou campus, Zhangzhou, Fujian Patentee after: XIAMEN University Address before: Xiamen City, Fujian Province, 361005 South Siming Road No. 422 Patentee before: XIAMEN University |