CN103915593A - Preparation method of polyimide nanometer lithium ion battery diaphragm and product thereof - Google Patents
Preparation method of polyimide nanometer lithium ion battery diaphragm and product thereof Download PDFInfo
- Publication number
- CN103915593A CN103915593A CN201410147627.XA CN201410147627A CN103915593A CN 103915593 A CN103915593 A CN 103915593A CN 201410147627 A CN201410147627 A CN 201410147627A CN 103915593 A CN103915593 A CN 103915593A
- Authority
- CN
- China
- Prior art keywords
- preparation
- lithium ion
- ion battery
- polyamic acid
- battery separator
- 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
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a preparation method of a polyimide nanometer lithium ion battery diaphragm and a product thereof. The preparation method comprises the following steps: preparing a polyamide acid solution, namely, performing condensation polymerization on 4,4'-diaminodiphenyl ether and 4,4'-oxydiphthalic anhydride in dimethylacetamide (DMAc) in a certain ratio; preparing a melt, namely, curing the obtained polymer solution at a certain temperature to obtain a condensate, and melting the condensate within the range of 20-30 DEG C below a melting point to obtain a semi-crystalline melt; preparing a diaphragm, namely, treating the obtained melt through a series of process including melt spinning, recrystallization, cold and thermal stretching and heat setting to obtain a nanometer diaphragm; carrying out diaphragm post-treatment, namely, removing a diluent and a part of remaining solvent in the diaphragm, and drying a polyamide acid diaphragm in vacuum; carrying out imidization treatment, namely, performing high-temperature imidization treatment on the prepared polyamide acid nanometer diaphragm to obtain the polyimide nanometer diaphragm. The prepared product is excellent in performance, and easy and convenient to process.
Description
Technical field
The present invention relates to preparation method of lithium ion battery separator and products thereof.
Background technology
Barrier film, as one of most important parts of lithium ion battery, is known as " the 3rd utmost point " 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 that is widely used at present lithium ion battery is mainly polyalkene diaphragm, and its preparation technology divides two kinds of dry method and wet methods.The defect of polyalkene diaphragm maximum is that the contact of itself and organic electrolyte is poor, is difficult for being soaked by electrolyte, has a strong impact on the raising of ionic conductivity.Existing a lot of patent Introduction dry method and wet method are prepared individual layer or double-deck polyalkene diaphragm and various modified diaphragm.But along with the development of new-energy automobile industry, also have higher requirement to power lithium-ion battery in market.How to improve power lithium-ion battery power density, discharge and recharge speed, high temperature resistant and cycle performance seems 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 material is applied to battery diaphragm field and is also just causing increasing concern.Polyimide nano film not only has common nano material small-size effect and skin effect, also demonstrates it simultaneously as macromolecular material high temperature resistant, the high pressure resistant and puncture strength characteristics good in battery diaphragm field.The preparation method of current battery barrier film mainly contains two kinds of dry method and wet methods, but the raw material of two kinds of method employings is all generally PE (polyethylene), and produce battery diaphragm all directly do 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), PET based polyalcohol is dissolved in organic solvent, the wherein mass volume ratio concentration 10:25% of PET based polyalcohol, stir and obtain PET based polyalcohol solution, the mensuration viscosity of described solution is between 300 ~ 400mPa.S; 2), using PP nonwoven fabrics as substrate, the PET based polyalcohol solution preparing is carried out to continuous electrostatic spinning at nanofiber spinning-drawing machine, obtain PP/PET nano-fiber composite film, the condition of described electrostatic spinning is: 20 ~ 40 ℃ of temperature, and voltage 20 ~ 50KV, spinning speed are 1 ~ 5 gram of every meter of wide cut per minute; 3) tunica fibrosa, obtaining after spinning is completed carries out reprocessing: first hot-forming by 100 ~ 140 ℃ of rollers, again at 60 ~ 80 ℃ of vacuumize 10 ~ 20h, remove after solvent residual in described tunica fibrosa, make the nano fibrous membrane for lithium ion battery separator.
Chinese patent CN103383996A discloses a kind of preparation method of polyimides micro-pore septum, comprise the following steps: adopt flexible monomer, prepare soluble polyimide with one-step method, and form polyimide solution, comprise: under protective atmosphere, add organic solvent to form mixed liquor dianhydride monomer and diamine monomer, after stirring this mixed liquor this dianhydride monomer and diamine monomer being dissolved in this organic solvent, add catalyst, fully reaction at 160 ℃ to 200 ℃ temperature, generate polyimides, and gained polyimides is dissolved in to organic solvent is configured to polyimide solution, inorganic template is provided, and this inorganic template is inorganic nanoparticles, in organic solvent, by surface conditioning agent, this inorganic template is carried out to surface treatment, and inorganic template is dispersed in this organic solvent, forms inorganic template dispersion liquid, this polyimide solution and inorganic template dispersion liquid are mixed and ultrasonic processing, form preparation liquid, this preparation liquid is coated in to substrate surface and dries, form organic/inorganic composite film, and this organic/inorganic composite film is placed in to template removes agent solution, the inorganic template in this organic/inorganic composite film removes agent with this template and reacts, thereby removes the inorganic template in this organic/inorganic composite film, obtains this polyimides micro-pore septum.
US4588633 discloses a kind of lithium ion battery separator preparation method, and the method comprises ultra-high molecular weight polyethylene and mineral oil are added by a certain percentage and in mixer, stirs and dissolve, and wherein, mineral oil and poly ratio are 10 ~ 99:1.Above-mentioned formula has strengthened film strength, and barrier film also meets the requirement of lithium ion battery to barrier film substantially, but has following defect: the barrier film micropore size of formation is inhomogeneous, and then affects its performance in 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 ℃, hot strength is 8～70MPa, 200 ℃ of heat treatments of high temperature after 1 hour dimensional contraction rate be less than 0.3%; The chemical composition of described polyimide nano-fiber perforated membrane is copolyimide or blend 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 to overcome the deficiency that prior art exists, and preparation method of a kind of polyimide nano lithium ion battery separator of excellent performance and products thereof is provided.
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: by two to 4,4', mono-diaminodiphenyl ether and 4,4', mono-oxygen phthalic anhydrides by a certain percentage in dimethylacetylamide (DMAc) polycondensation make;
B) preparation of melt: resulting polymers solution is solidified and obtains solidfied material at a certain temperature, then solidfied material is melted within the scope of its 20-30 below fusing point ℃, obtain hypocrystalline melt;
C) barrier film preparation: the melt obtaining is obtained to polyimide nano barrier film through melt spinning, recrystallization, cold and hot stretching and the processing of thermal finalization series of process;
D) barrier film reprocessing: comprise diluent and the part residual solvent removed in barrier film, in a vacuum dry polyimide nano barrier film;
E) imidization processing: the polyamic acid nanometer barrier film preparing is carried out to high temperature imidization processing and obtain polyimide nano barrier film.
Preferably, described step a) in, the material of preparing polyamide acid solution has 4,4' mono-diaminodiphenyl ether (ODA), 4, the two phthalic anhydrides (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 anhydrides (ODPA) of 4' mono-oxygen is 1:1, and dimethylacetylamide is reaction medium, and the solid content of polyamic acid in solution is 20 wt%.
Preferably, described step b) in, polymer solution is polyamic acid solution, it is made up of polyamic acid, diluent and additive, diluent can be a kind of or its combination in any in N-dimethylacetylamide (DMAc), dibutyl phthalate (DBP), 1-METHYLPYRROLIDONE, and additive is surfactant.
Preferably, the mixed proportion of polyamic acid and diluent is: 5:95 is 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 ℃, draw ratio is got between 2.5-3.
Preferably, described step c) in, the blank film thickness obtaining is 80-100nm.
Preferably, described steps d) in, removing the extractant that diluent uses 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 obtaining at 60 ℃ vacuumize 5h to remove residual solvent.
Preferably, described step e) in, dried battery diaphragm is carried out under nitrogen atmosphere to high temperature imidization, high temperature imidization process is as follows: 1) 5 ℃/min is warming up to 100 ℃ and process 40 min; 2) 5 ℃/min is warming up to 200 ℃ and processes 40 min; 3) 5 ℃/min is warming up to 300 ℃ and process 40 min.
A kind of polyimide nano lithium ion battery separator, it adopts the preparation method of above-mentioned polyimide nano lithium ion battery separator to make.
Compared with prior art, polyimide nano lithium ion battery separator of the present invention at aspect of performances such as electrochemical stability, thermal contraction, porosity, withstand voltage, tightness and melting temperatures all than conventional membrane excellence, can significantly promote the life-span of lithium ion battery, and process easy.
Embodiment
By specific embodiment, the present invention is described in further detail below.
Originally the preparation method who is embodied as a kind of polyimide nano lithium ion battery separator, it comprises the steps:
A) preparation of polyamic acid solution: the material of preparing polyamide acid solution has 4,4' mono-diaminodiphenyl ether (ODA), 4, the two phthalic anhydrides (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 anhydrides (ODPA) of 4' mono-oxygen is 1:1, and dimethylacetylamide is reaction medium, and the solid content of polyamic acid in solution is 20 wt%.At room temperature, a certain amount of ODA is dissolved in DMAC, constantly stir, until ODA dissolves completely and becomes colourless transparent solution, then the ODPA of equivalent is joined in solution in batches, in the time reaching equivalent point soon, the viscosity of polyamic acid increases rapidly, continue to stir 2.2h, make its viscosity reach stable.Adopting Ubbelohde viscometer to record polyamic acid solution is 2.43dL g the viscosity of 25 ℃
-1;
B) preparation of melt: the in the situation that of temperature 60 C, embodiment step is played to soluble polyamide acid solution (PAA) DMAc obtaining in 1, and to be diluted to PAA:DMAc be 15:85, and add absolute ethyl alcohol, its amount, for 1% of total amount, is prepared into polyamic acid melt by the polyamic acid solution obtaining;
C) barrier film preparation: the polyamic acid melt obtaining is stretched under 120 ± 10 ℃ of conditions, prepare polyamic acid (PAA) nano-lithium ion cell barrier film;
D) barrier film reprocessing: the PAA nanometer barrier film obtaining at 60 ℃ vacuumize 5h with remove residual solvent;
E) imidization processing: dried battery diaphragm is carried out under nitrogen atmosphere to high temperature imidization.PAA nanometer barrier film ladder-elevating temperature by obtaining: 1) 5 0C/min are warming up to 150 ℃ and process 40 min; 2) 5 ℃/min is warming up to 200 ℃ and processes 40 min; 3) 5 ℃/min is warming up to 300 ℃ and process 40 min.Finally obtain polyimides (PI) nanometer barrier film.
The performance of lithium ion battery test and the contrast step that are assembled by above-mentioned polyimide nano barrier film are as follows:
I) PP/PE/PP barrier film is chosen: adopt the PP/PE/PP barrier film that Celgard company comparatively advanced and generally application provides in the market to carry out performance comparison test;
II) battery assembling: assembled battery adopts LiCoO
2for positive pole, lithium metal is negative pole, the 1.0 M LiPF that electrolyte provides for Dongguan China fir China fir
6-ethylene carbonate (EC)/dimethyl carbonate (DMC)/ethyl methyl carbonate (EMC) (1:1:1, v/v/v);
III) battery physics and electrochemical property test: mainly comprise the test of 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.
With respect 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, improved 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 solve 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, also should be considered as protection scope of the present invention not departing from the improvement and the conversion that obtain under the technology of the present invention design prerequisite.
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 anhydrides by a certain percentage in dimethylacetylamide polycondensation make;
B) preparation of melt: resulting polymers solution is solidified and obtains solidfied material at a certain temperature, then solidfied material is melted within the scope of its 20-30 below fusing point ℃, obtain hypocrystalline melt;
C) barrier film preparation: the melt obtaining is obtained to polyamic acid nanometer barrier film through melt spinning, recrystallization, cold and hot stretching and the processing of thermal finalization series of process;
D) barrier film reprocessing: comprise diluent and the part residual solvent removed in barrier film, in a vacuum dry polyamic acid nanometer barrier film;
E) imidization processing: the polyamic acid nanometer barrier film preparing is carried out to high temperature imidization processing and obtain 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 of preparing polyamide acid solution has 4,4' mono-diaminodiphenyl ether, 4, the two phthalic anhydrides of 4' mono-oxygen and dimethylacetylamide, wherein 4,4' mono-diaminodiphenyl ether and 4, the amount of substance ratio of the two phthalic anhydrides of 4' mono-oxygen is 1:1, and dimethylacetylamide is reaction medium, and the solid content of polyamic acid in solution is 20 wt%.
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 a kind of or its combination in any in N-dimethylacetylamide, dibutyl phthalate, 1-METHYLPYRROLIDONE, 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 is to 30:70, and 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 ℃, 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 obtaining 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, removing the extractant that diluent uses 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 polyamide nano barrier film obtaining at 60 ℃ vacuumize 5h with 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 battery diaphragm is carried out under nitrogen atmosphere to high temperature imidization, high temperature imidization process is as follows: 1) 5 ℃/min is warming up to 100 ℃ and process 40 min; 2) 5 ℃/min is warming up to 200 ℃ and processes 40 min; 3) 5 ℃/min is warming up to 300 ℃ and process 40 min.
10. a polyimide nano lithium ion battery separator, is characterized in that: it is to adopt the preparation method of the arbitrary described polyimide nano lithium ion battery separator of claim 1 to 9 to make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410147627.XA CN103915593B (en) | 2014-04-14 | 2014-04-14 | Preparation method of a kind of polyimide nano lithium ion battery separator and products thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410147627.XA CN103915593B (en) | 2014-04-14 | 2014-04-14 | Preparation method of a kind of polyimide nano lithium ion battery separator and products thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103915593A true CN103915593A (en) | 2014-07-09 |
| CN103915593B CN103915593B (en) | 2016-01-20 |
Family
ID=51041108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410147627.XA Expired - Fee Related CN103915593B (en) | 2014-04-14 | 2014-04-14 | Preparation method of a kind of polyimide nano lithium ion battery separator and products thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103915593B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111106293A (en) * | 2018-10-25 | 2020-05-05 | 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 |
| CN115149211A (en) * | 2022-08-09 | 2022-10-04 | 四川大学 | Double-layer composite diaphragm, preparation method thereof and HNTs @ PI-PP double-layer composite diaphragm |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110129104A (en) * | 2010-05-25 | 2011-12-01 | 코오롱패션머티리얼 (주) | Polyimide porous nanofiber web and method for manufacturing the same |
| CN102618964A (en) * | 2012-04-11 | 2012-08-01 | 北京化工大学 | Polyimide/polyacrylonitrile blended fiber and preparation method thereof |
-
2014
- 2014-04-14 CN CN201410147627.XA patent/CN103915593B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110129104A (en) * | 2010-05-25 | 2011-12-01 | 코오롱패션머티리얼 (주) | Polyimide porous nanofiber web and method for manufacturing the same |
| CN102618964A (en) * | 2012-04-11 | 2012-08-01 | 北京化工大学 | Polyimide/polyacrylonitrile blended fiber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 向红兵: "聚酰亚胺纤维及其纺丝工艺研究进展", 《高分子通报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111106293A (en) * | 2018-10-25 | 2020-05-05 | 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 |
| CN115149211A (en) * | 2022-08-09 | 2022-10-04 | 四川大学 | Double-layer composite diaphragm, preparation method thereof and HNTs @ PI-PP double-layer composite diaphragm |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103915593B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102251307B (en) | Polyimide-base nano fibrous membrane, and preparation method and application thereof | |
| CN102277648B (en) | Inorganic/organic composite polyimide nanometer fibrous film, preparation method thereof and application thereof | |
| Li et al. | Preparation and performance of aramid nanofiber membrane for separator of lithium ion battery | |
| Chen et al. | Improved performance of lithium ion battery separator enabled by co-electrospinnig polyimide/poly (vinylidene fluoride-co-hexafluoropropylene) and the incorporation of TiO2-(2-hydroxyethyl methacrylate) | |
| Zhang et al. | High thermal resistance polyimide separators prepared via soluble precusor and non-solvent induced phase separation process for lithium ion batteries | |
| Wang et al. | Electrospun polyimide-based fiber membranes as polymer electrolytes for lithium-ion batteries | |
| CN102891335B (en) | Preparation method of full-solid-state nano composite polymer electrolyte | |
| Cao et al. | Performance evaluation of electrospun polyimide non-woven separators for high power lithium-ion batteries | |
| CN102230257B (en) | Coaxial compound nanometre fibre film as well as preparation method and application thereof | |
| Liu et al. | A Core@ sheath nanofibrous separator for lithium ion batteries obtained by coaxial electrospinning | |
| CN103915593B (en) | Preparation method of a kind of polyimide nano lithium ion battery separator and products thereof | |
| Kang et al. | A thermostability gel polymer electrolyte with electrospun nanofiber separator of organic F-doped poly-m-phenyleneisophthalamide for lithium-ion battery | |
| Li et al. | Effects of fluorinated SiO2 nanoparticles on the thermal and electrochemical properties of PP nonwoven/PVdF-HFP composite separator for Li-ion batteries | |
| CN108346765A (en) | A kind of composite lithium ion cell diaphragm and preparation method thereof | |
| CN107994256B (en) | Polymer electrolyte membrane containing POSS-based quaternary ammonium salt ionic liquid and preparation method thereof | |
| Wang et al. | Electrospun melamine resin-based multifunctional nonwoven membrane for lithium ion batteries at the elevated temperatures | |
| CN103383996A (en) | Preparation method of polyimide micro-pore diaphragm | |
| Zhao et al. | The significant effect of octa (aminophenyl) silsesquioxane on the electrospun ion-selective and ultra-strong poly-m-phenyleneisophthalamide separator for enhanced electrochemical performance of lithium-sulfur battery | |
| CN104183806B (en) | Composite lithium battery diaphragm and preparation method thereof | |
| CN105585732A (en) | Ultraviolet crosslinking polyaryletherketone porous membrane, preparation method and application of ultraviolet crosslinking polyaryletherketone porous membrane | |
| CN106229445A (en) | A kind of lithium ion battery separator and preparation method thereof and lithium ion battery | |
| CN101638490B (en) | Polyimide porous membrane and preparation method and lithium ion battery thereof | |
| CN101752540A (en) | Polyimide diaphragm for lithium ion secondary battery and lithium ion battery | |
| JPWO2016098659A1 (en) | Polymer ion permeable membrane, composite ion permeable membrane, battery electrolyte membrane and electrode composite | |
| JP2014240189A (en) | Aromatic polyamide/aromatic polyimide composite porous membrane, separator for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20160414 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |