CN104037379A - Composite polymer fiber diaphragm and preparation method thereof - Google Patents
Composite polymer fiber diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN104037379A CN104037379A CN201410248682.8A CN201410248682A CN104037379A CN 104037379 A CN104037379 A CN 104037379A CN 201410248682 A CN201410248682 A CN 201410248682A CN 104037379 A CN104037379 A CN 104037379A
- Authority
- CN
- China
- Prior art keywords
- ketone
- polyether
- barrier film
- filler
- electrostatic spinning
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 229920005594 polymer fiber Polymers 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 34
- 238000009987 spinning Methods 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000004888 barrier function Effects 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 239000011324 bead Substances 0.000 claims description 20
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 17
- 229920002530 polyetherether ketone Polymers 0.000 claims description 17
- -1 poly(ethylene oxide) Polymers 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000006193 liquid solution Substances 0.000 claims description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000292 calcium oxide Substances 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 10
- 229910002113 barium titanate Inorganic materials 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 150000002576 ketones Chemical class 0.000 claims description 10
- 229920002480 polybenzimidazole Polymers 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 9
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 9
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 7
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 abstract description 25
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 239000010954 inorganic particle Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 2
- 238000007590 electrostatic spraying Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 24
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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
- H01M50/44—Fibrous material
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a composite polymer fiber diaphragm and a preparation method thereof. The composite polymer fiber diaphragm is characterized in that the preparation method comprises the following steps: dissolving polymer matrix into solvent to prepare a polymer matrix solution with certain concentration, and adding filler which is not dissolved in the polymer matrix solution into the solution, wherein the filler comprises polymer particles with melting temperature of more than 180 DEG C and inorganic particles; and magnetically stirring the polymer matrix solution, to which the filler is added, at 800-1,000rpm for 8h to enable the filler to be uniformly dispersed in the polymer matrix solution to obtain dispersion liquid, and carrying out electrostatic spinning and spraying on the dispersion liquid to obtain the diaphragm, wherein the electrostatic spinning conditions are as follows: the voltage is 18-22kV, the collecting distance is 17-18cm, and the spinning speed is 0.08-0.1mL; furthermore, the large-area diaphragm can be obtained through a simultaneous spinning method by an array needle. The composite polymer fiber diaphragm has high porosity and facilitates diffusion transmission of electrolyte ions; when the temperature of inside of a battery continuously rises, the polymer particles are in a melting state, the electrolyte ion transmission can be further prevented, the chemical reaction of the battery is reduced and the battery safety is improved.
Description
Technical field
The present invention relates to a kind of composite polymer fibers barrier film and preparation method thereof, belong to technical field of new energies, be applied to the barrier film of automobile power cell.
Background technology
Energy-conservation and the new-energy automobile such as hybrid electric vehicle, pure electric automobile and fuel-cell vehicle becomes reasonable evolutionary path.Yet security reliability, life-span, continual mileage, cost and public facility etc. have greatly limited the fast development of new-energy automobile, this is wherein especially the most key with technological break-through and the scale application of electrokinetic cell.Lithium ion battery has that specific energy is high, operating voltage is high, self-discharge rate is little, advantages of environment protection, is new-energy automobile ideal power battery.But owing to using liquid electrolyte solution, make lithium ion battery have potential safety hazard, limited its large-scale promotion on automobile.As one of critical component of barrier film lithium battery, the security performance of battery is played an important role.
Barrier film between both positive and negative polarity has electrolyte ion transmission channel, prevents the effect of both positive and negative polarity contact short circuit.Yet current used TPO barrier film melting closed porosity when battery temperature is too high, intercepts the transmission of electrolyte ion, reduces security risk; But because the heat resistance of polyolefin itself is poor, along with the sharply rising of temperature, the protection that polyolefin polymers forms is destroyed, and loses defencive function; And after polyalkene diaphragm itself punctured by impurity (or Zhi Jing) etc., can make equally potential safety hazard sharply increase.
In order to change this because barrier film destroys the safety problem causing, people have carried out a series of research, on the one hand, to existing diagram modification, improve barrier film mechanical performance and heat resistance, for example membrane surface coating inorganic particle or polymer and inorganic particulate are made composite material (US 8409746 B2 for example, EP 2528139 A2, EP 2528142 A2, US7691529 B2, US 20130065132 A1); On the other hand, higher with temperature resistant grade, the better polymer of mechanical performance is prepared barrier film (for example publication number CN 101645497A, publication number CN 101420018A, application publication number CN 101752539 A, application publication number CN 101752540 A), as the polymeric material of barrier film itself, can there is the reaction (for example publication number US2012/0295154 A1) of similar closed pore effect, or add other polymer that can realize closed pore effect etc. (for example publication number CN 101656306A, publication number US2013/0022858 A1).
Summary of the invention
The object of this invention is to provide a kind of composite polymer fibers barrier film and preparation method thereof, it adopts electrostatic spinning technique that polymeric matrix and polymer beads or polymer beads and inorganic particulate are mixed and made into barrier film, the polymer beads adding has improved the mechanical performance of barrier film, the barrier film obtaining has higher porosity, is conducive to the diffusion transport of electrolyte ion; When internal temperature of battery continues to raise, polymer beads, in molten condition, can further stop the transmission of electrolyte ion, reduces the chemical reaction of battery, the fail safe that improves battery.
Technical scheme of the present invention is achieved in that a kind of composite polymer fibers barrier film, it is characterized in that its preparation method, concrete steps are as follows: polymeric matrix is dissolved in solvent and makes certain density Polymers liquid solution, the mass ratio of polymeric matrix and solvent is 0.01～0.19, in Polymers liquid solution, add the filler that is insoluble to this solution, filler is 180 ℃ of above polymer beads and inorganic particulates of melt temperature, the mass ratio of polymer beads and polymeric matrix is 0.07～2.5, and the mass ratio of inorganic particulate and polymer beads is 0.10～2.5; Add the Polymers liquid solution after filler to pass through magnetic agitation, magnetic agitation speed is 800～1000rpm, time is 8h, uniform filling is dispersed in Polymers liquid solution, and then obtains dispersion liquid, and dispersion liquid is sprayed and made barrier film by electrostatic spinning, electrostatic spinning condition is, voltage is 18kV ~ 22kV, and collecting distance is 17cm ~ 18cm, and spinning speed is 0.08mL ~ 0.1mL; Further, can obtain large-area barrier film by the method for array syringe needle spinning simultaneously.
Described polymeric matrix can be a kind of in poly(ethylene oxide), Kynoar, Kynoar-hexafluoropropylene, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, Sodium Polyacrylate, sodium carboxymethylcellulose, polyether sulfone, polyimides or their combination, particularly, poly(ethylene oxide)/Kynoar/Kynoar-hexafluoropropylene/polyacrylonitrile/polymethyl methacrylate/polyvinyl alcohol/Sodium Polyacrylate/sodium carboxymethylcellulose/polyether sulfone/polyimides=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
Described polymer beads can be polyether-ketone, polyether-ether-ketone, polyether ether ketone ketone, a kind of in polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazoles, polyphenylene sulfide or their combination, particularly, its ratio is polyether-ketone/polyether-ether-ketone/polyether ether ketone ketone/polyetherketoneetherketoneketone/polybenzothiozole/polybenzimidazoles/polyphenylene sulfide=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
Described inorganic particulate is a kind of in alundum (Al2O3), silicon dioxide, titanium dioxide, calcium oxide, barium titanate or their combination, particularly, its ratio is alundum (Al2O3)/earth silicon/titanic oxide/calcium oxide/barium titanate=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
Good effect of the present invention is that it adopts electrostatic spinning technique that polymeric matrix and polymer beads or polymer beads and inorganic particulate are mixed and made into barrier film, the polymer beads adding has improved the mechanical performance of barrier film, the barrier film obtaining has higher porosity, is conducive to the diffusion transport of electrolyte ion; When internal temperature of battery continues to raise, polymer beads, in molten condition, can further stop the transmission of electrolyte ion, reduces the chemical reaction of battery, the fail safe that improves battery.
Accompanying drawing explanation
Fig. 1 is that barrier film of the present invention is prepared schematic diagram.
Fig. 2 is the SEM of embodiments of the invention 1.
Fig. 3 is the state diagram that the barrier film of embodiments of the invention 1 respectively heats 1h under 90 ℃, 135 ℃, 165 ℃ environment.
Embodiment
Below in conjunction with drawings and Examples, to of the present invention, be further described, claim includes but not limited to described embodiment content: as shown in Figure 1, a kind of composite polymer fibers barrier film, it is characterized in that its preparation method, concrete steps are as follows: polymeric matrix is dissolved in solvent and makes certain density Polymers liquid solution, the mass ratio of polymeric matrix and solvent is 0.01～0.19, in Polymers liquid solution, add the filler that is insoluble to this solution, filler is 180 ℃ of above polymer beads and inorganic particulates of melt temperature, the mass ratio of polymer beads and polymeric matrix is 0.07～2.5, the mass ratio of inorganic particulate and polymer beads is 0.10～2.5, add the Polymers liquid solution after filler to pass through magnetic agitation, magnetic agitation speed is 800～1000rpm, time is 8h, uniform filling is dispersed in Polymers liquid solution, and then obtains dispersion liquid, and dispersion liquid is sprayed and made barrier film by electrostatic spinning, electrostatic spinning condition is, voltage is 18kV ~ 22kV, and collecting distance is 17cm ~ 18cm, and spinning speed is 0.08mL ~ 0.1mL, further, can obtain large-area barrier film by the method for array syringe needle spinning simultaneously.
Described polymeric matrix can be a kind of in poly(ethylene oxide), Kynoar, Kynoar-hexafluoropropylene, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, Sodium Polyacrylate, sodium carboxymethylcellulose, polyether sulfone, polyimides or their combination, particularly, poly(ethylene oxide)/Kynoar/Kynoar-hexafluoropropylene/polyacrylonitrile/polymethyl methacrylate/polyvinyl alcohol/Sodium Polyacrylate/sodium carboxymethylcellulose/polyether sulfone/polyimides=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
Described polymer beads can be polyether-ketone, polyether-ether-ketone, polyether ether ketone ketone, a kind of in polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazoles, polyphenylene sulfide or their combination, particularly, its ratio is polyether-ketone/polyether-ether-ketone/polyether ether ketone ketone/polyetherketoneetherketoneketone/polybenzothiozole/polybenzimidazoles/polyphenylene sulfide=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
Described inorganic particulate is a kind of in alundum (Al2O3), silicon dioxide, titanium dioxide, calcium oxide, barium titanate or their combination, particularly, its ratio is alundum (Al2O3)/earth silicon/titanic oxide/calcium oxide/barium titanate=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
Embodiment 1
(1) Kynoar-hexafluoropropylene copolymer of 6.0g is dissolved in 40g acetone, through heating, strong stirring, treats that it fully dissolves; (2) the ultra-fine polyether-ether-ketone ketone powder 0.60g and the 0.60g silicon dioxide that to (1), add, continuation heating, 800rpm stir 8h and obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 18KV, collecting distance is 18cm, and flow velocity is under 0.1mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 70 ℃ of vacuum drying 2h.The barrier film of preparing with this embodiment has carried out heat shrinkage test.As shown in Figure 3, this barrier film, under 90 ℃ and 135 ℃ of conditions, does not shrink; At 165 ℃, transverse and longitudinal is 0.1%, and this barrier film thermal endurance is good as seen, can improve the security performance of battery.As shown in Figure 2, there is higher porosity, can improve like this imbibition/liquid-keeping property of this barrier film, be conducive to improve conductivity.
Embodiment 2
(1) 0.4g sodium carboxymethylcellulose is dissolved in 40g water, through heating, strong stirring, treats that it fully dissolves; (2) to (1), add 0.4g polyether-ether-ketone superfine powder and 0.20g titanium dioxide, continuation heating, 1000rpm stir 8h, obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 22KV, collecting distance is 18cm, and flow velocity is under 0.08mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 80 ℃ of vacuum drying 2h.
Embodiment 3
(1) 1.0g poly(ethylene oxide) is dissolved in 40g water, through heating, strong stirring, treats that it fully dissolves; (2) to (1), add 1.0g polyether-ketone and 0.1g barium titanate, continuation heating, 900rpm stir 8h, obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 21KV, collecting distance is 17cm, and flow velocity is under 0.1mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 80 ℃ of vacuum drying 2h.
Embodiment 4
(1) 6.0g Kynoar-hexafluoropropylene is dissolved in 20g NMP and 20g acetone, through heating, strong stirring, treats that it fully dissolves; (2) to (1), add superfine powder mixture 0. 9 g and the 0.30g calcium oxide of polyphenylene sulfide and polybenzimidazoles, continuation heating, 1000rpm stir 8h, obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 20KV, collecting distance is 18cm, and flow velocity is under 0.1mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 75 ℃ of vacuum drying 2h.
Embodiment 5
(1) 6.0g Kynoar is dissolved in 38g DMF, through heating, strong stirring, treats that it fully dissolves; (2) to (1), add polyetherketoneetherketoneketone and polybenzothiozole superfine powder mixture 0.725g and 0.6g calcium oxide/barium titanate mixture (the two mass ratio 1/1), continuation heating, 1000rpm stir 8h, obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 18KV, collecting distance is 17.5cm, and flow velocity is under 0.1mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 75 ℃ of vacuum drying 2h.
Embodiment 6
(1) polyacrylonitrile of 6.0g is dissolved in 32gDMF, through heating, strong stirring, treats that it fully dissolves; (2) the ultra-fine polybenzimidazoles 0.60g and the 0.60g alundum (Al2O3) that to (1), add, continuation heating, 800rpm stir 8h and obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 18KV, collecting distance is 17.5cm, and flow velocity is under 0.08mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 70 ℃ of vacuum drying 2h.
Embodiment 7
(1) 0.4g polymethyl methacrylate is dissolved in 30g acetone, through heating, strong stirring, treats that it fully dissolves; (2) to (1), add 0.4g polyphenylene sulfide superfine powder and 0.20g barium titanate, continuation heating, 1000rpm stir 8h, obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 22KV, collecting distance is 18cm, and flow velocity is under 0.10mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 80 ℃ of vacuum drying 2h.
Embodiment 8
(1) by the alcoholysis of 0.4g polyethylene in 40g water, through heating, strong stirring, treat that it fully dissolves; (2) to (1), add 1.0g polybenzothiozole and 0.5g calcium oxide, continuation heating, 900rpm stir 8h, obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 21KV, collecting distance is 17.5cm, and flow velocity is under 0.08mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 80 ℃ of vacuum drying 2h.
Embodiment 9
(1) 0.8g Sodium Polyacrylate is dissolved in 40g water, through heating, strong stirring, treats that it fully dissolves; (2) to (1), add superfine powder mixture and the 0.30g calcium oxide of 0.3g Ju Ben Liu Mi ﹑ 0.3g polybenzimidazoles and 0.3g polybenzothiozole, continuation heating, 900rpm stir 8h, obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 20KV, collecting distance is 18cm, and flow velocity is under 0.1mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 75 ℃ of vacuum drying 2h.
Embodiment 10
(1) 3.0g polyimides is dissolved in 38g DMF, through heating, strong stirring, treats that it fully dissolves; (2) to (1), add superfine powder mixture and 0.4g alundum (Al2O3) and the 0.4g silicon dioxide of the poly-ether ketone ﹑ 0.3g polyethers ether copper ﹑ 0.3g polyether ether ketone ketone of 0.4g polyethers ether ketone ketone ketone ﹑ 0.3g, continuation heating, 1000rpm stir 8h, obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 18KV, collecting distance is 17.5cm, and flow velocity is under 0.1mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 75 ℃ of vacuum drying 2h.
Embodiment 11
(1) 1.0g polyether sulfone is dissolved in 32gDMAc, through heating, strong stirring, treats that it fully dissolves; (2) to (1), add 0.1g polyether-ketone, 0.1g polyether-ether-ketone, 0.1g polyether ether ketone ketone, the superfine powder mixture of 0.1g polyetherketoneetherketoneketone, 0.1g polybenzothiozole, 0.1g polybenzimidazoles, 0.1g polyphenylene sulfide and 0.2g silicon dioxide, 0.2g titanium dioxide, 0.2g calcium oxide, 0.2g barium titanate and 0.2g alundum (Al2O3), continuation heating, 900rpm stir 8h, obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 20KV, collecting distance is 18cm, and flow velocity is under 0.1mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 75 ℃ of vacuum drying 2h.
Embodiment 12
(1) by 3.0g Kynoar and 2.0g Kynoar-hexafluoropropylene in 32g DMF, through heating, strong stirring, treat that it fully dissolves; (2) to (1), add superfine powder mixture and the 0.6g alundum (Al2O3) of 0.5g polyether-ketone and 0.5g polyethers ether copper, continuation heating, 1000rpm stir 8h, obtain dispersed electrostatic spinning solution preferably; (3) by the spinning solution in (2), at direct voltage, be 18KV, collecting distance is 17.5cm, and flow velocity is under 0.1mL/min condition, electrostatic spinning; (4) take off film by after its low temperature and pressure, at 75 ℃ of vacuum drying 2h.
Claims (4)
1. a composite polymer fibers barrier film, it is characterized in that its preparation method, concrete steps are as follows: polymeric matrix is dissolved in solvent and makes certain density Polymers liquid solution, the mass ratio of polymeric matrix and solvent is 0.01～0.19, in Polymers liquid solution, add the filler that is insoluble to this solution, filler is 180 ℃ of above polymer beads and inorganic particulates of melt temperature, the mass ratio of polymer beads and polymeric matrix is 0.07～2.5, and the mass ratio of inorganic particulate and polymer beads is 0.10～2.5; Add the Polymers liquid solution after filler to pass through magnetic agitation, magnetic agitation speed is 800～1000rpm, time is 8h, uniform filling is dispersed in Polymers liquid solution, and then obtains dispersion liquid, and dispersion liquid is sprayed and made barrier film by electrostatic spinning, electrostatic spinning condition is, voltage is 18kV ~ 22kV, and collecting distance is 17cm ~ 18cm, and spinning speed is 0.08mL ~ 0.1mL; Further, can obtain large-area barrier film by the method for array syringe needle spinning simultaneously.
2. according to a kind of composite polymer fibers barrier film described in claim 1, it is characterized in that described polymeric matrix can be poly(ethylene oxide), Kynoar, Kynoar-hexafluoropropylene, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, Sodium Polyacrylate, sodium carboxymethylcellulose, polyether sulfone, a kind of in polyimides or their combination, particularly, poly(ethylene oxide)/Kynoar/Kynoar-hexafluoropropylene/polyacrylonitrile/polymethyl methacrylate/polyvinyl alcohol/Sodium Polyacrylate/sodium carboxymethylcellulose/polyether sulfone/polyimides=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
3. according to a kind of composite polymer fibers barrier film described in claim 1, it is characterized in that described polymer beads can be polyether-ketone, polyether-ether-ketone, polyether ether ketone ketone, a kind of in polyetherketoneetherketoneketone, polybenzothiozole, polybenzimidazoles, polyphenylene sulfide or their combination, particularly, its ratio is polyether-ketone/polyether-ether-ketone/polyether ether ketone ketone/polyetherketoneetherketoneketone/polybenzothiozole/polybenzimidazoles/polyphenylene sulfide=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
4. according to a kind of composite polymer fibers barrier film described in claim 1, it is characterized in that described inorganic particulate is a kind of in alundum (Al2O3), silicon dioxide, titanium dioxide, calcium oxide, barium titanate or their combination, particularly, its ratio is alundum (Al2O3)/earth silicon/titanic oxide/calcium oxide/barium titanate=0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1/0 ~ 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410248682.8A CN104037379A (en) | 2014-06-06 | 2014-06-06 | Composite polymer fiber diaphragm and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410248682.8A CN104037379A (en) | 2014-06-06 | 2014-06-06 | Composite polymer fiber diaphragm and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104037379A true CN104037379A (en) | 2014-09-10 |
Family
ID=51468070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410248682.8A Pending CN104037379A (en) | 2014-06-06 | 2014-06-06 | Composite polymer fiber diaphragm and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104037379A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104389174A (en) * | 2014-09-18 | 2015-03-04 | 上海联晟材料科技有限公司 | Spraying treatment method for non-woven fabric diaphragm |
| CN105206776A (en) * | 2015-10-19 | 2015-12-30 | 丁玉琴 | Preparation method of modified sodium polyacrylate doped aluminum oxide diaphragm for lithium battery |
| CN105552279A (en) * | 2016-01-29 | 2016-05-04 | 常州达奥新材料科技有限公司 | Method for preparing overcharge protection battery separator with high heat stability by electrospinning method |
| CN106012290A (en) * | 2015-03-25 | 2016-10-12 | 松下知识产权经营株式会社 | Non-woven fabric and carbon fiber non-woven fabric |
| CN106299429A (en) * | 2016-08-24 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | Alkaline anion exchange composite membrane for fuel cell and preparation method thereof |
| CN106868712A (en) * | 2015-12-14 | 2017-06-20 | 中国科学院过程工程研究所 | A kind of Membrane Materials nano fibrous membrane and preparation method thereof |
| CN108899459A (en) * | 2018-06-11 | 2018-11-27 | 合肥国轩高科动力能源有限公司 | Preparation method of lithium ion battery diaphragm |
| CN109060199A (en) * | 2018-06-25 | 2018-12-21 | 青岛大学 | A kind of preparation method of piezoelectric transducer and the application of piezoelectric transducer |
| CN109860720A (en) * | 2019-01-30 | 2019-06-07 | 浙江锋锂新能源科技有限公司 | A kind of preparation method and solid state battery of composite electrolyte layer |
| CN109868560A (en) * | 2019-02-18 | 2019-06-11 | 山东星火科学技术研究院 | The preparation method of phosphorylation sulfonated polyether-ether-ketone and Nano particles of silicon dioxide static spinning membrane |
| CN110326152A (en) * | 2017-02-22 | 2019-10-11 | 三星Sdi株式会社 | Electrode assembly produces its method and the secondary cell including it |
| CN111072950A (en) * | 2020-01-10 | 2020-04-28 | 深圳职业技术学院 | Synthesis method of polyaryletherketone polymer, preparation method and application of PAEK membrane and PAEK-Al2O3 composite membrane |
| CN112194978A (en) * | 2020-08-25 | 2021-01-08 | 河北金力新能源科技股份有限公司 | High-heat-resistant coating slurry, high-temperature-resistant diaphragm for lithium battery and preparation method of high-temperature-resistant diaphragm |
| US11380900B2 (en) | 2016-10-12 | 2022-07-05 | Samsung Sdi Co., Ltd. | Anode for lithium secondary battery and lithium secondary battery comprising same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101192681A (en) * | 2006-11-29 | 2008-06-04 | 中国科学院理化技术研究所 | Device and method for directly compounding nanofiber separator on electrode surface of lithium ion battery |
| WO2012018676A1 (en) * | 2010-08-02 | 2012-02-09 | Celgard, Llc | Ultra high melt temperature microporous high temperature battery separators and related methods |
| CN102668173A (en) * | 2009-11-03 | 2012-09-12 | 阿莫绿色技术有限公司 | Heat-resistant and high-tenacity ultrafine fibrous separation layer, method for manufacturing same, and secondary cell using same |
-
2014
- 2014-06-06 CN CN201410248682.8A patent/CN104037379A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101192681A (en) * | 2006-11-29 | 2008-06-04 | 中国科学院理化技术研究所 | Device and method for directly compounding nanofiber separator on electrode surface of lithium ion battery |
| CN102668173A (en) * | 2009-11-03 | 2012-09-12 | 阿莫绿色技术有限公司 | Heat-resistant and high-tenacity ultrafine fibrous separation layer, method for manufacturing same, and secondary cell using same |
| WO2012018676A1 (en) * | 2010-08-02 | 2012-02-09 | Celgard, Llc | Ultra high melt temperature microporous high temperature battery separators and related methods |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104389174B (en) * | 2014-09-18 | 2016-06-29 | 上海联晟材料科技有限公司 | A kind of spraying process for treating of non-woven fabrics barrier film |
| CN104389174A (en) * | 2014-09-18 | 2015-03-04 | 上海联晟材料科技有限公司 | Spraying treatment method for non-woven fabric diaphragm |
| CN106012290A (en) * | 2015-03-25 | 2016-10-12 | 松下知识产权经营株式会社 | Non-woven fabric and carbon fiber non-woven fabric |
| CN105206776A (en) * | 2015-10-19 | 2015-12-30 | 丁玉琴 | Preparation method of modified sodium polyacrylate doped aluminum oxide diaphragm for lithium battery |
| CN106868712B (en) * | 2015-12-14 | 2019-03-15 | 中国科学院过程工程研究所 | A kind of membrane distillation nano fibrous membrane and preparation method thereof |
| CN106868712A (en) * | 2015-12-14 | 2017-06-20 | 中国科学院过程工程研究所 | A kind of Membrane Materials nano fibrous membrane and preparation method thereof |
| CN105552279A (en) * | 2016-01-29 | 2016-05-04 | 常州达奥新材料科技有限公司 | Method for preparing overcharge protection battery separator with high heat stability by electrospinning method |
| CN105552279B (en) * | 2016-01-29 | 2017-10-10 | 深圳市沃能新能源有限公司 | A kind of method that method of electrostatic spinning prepares the anti-overcharge battery diaphragm of high thermal stability |
| CN106299429A (en) * | 2016-08-24 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | Alkaline anion exchange composite membrane for fuel cell and preparation method thereof |
| CN106299429B (en) * | 2016-08-24 | 2019-11-01 | 合肥国轩高科动力能源有限公司 | Alkaline anion exchange composite membrane for fuel cell and preparation method thereof |
| US11380900B2 (en) | 2016-10-12 | 2022-07-05 | Samsung Sdi Co., Ltd. | Anode for lithium secondary battery and lithium secondary battery comprising same |
| CN110326152A (en) * | 2017-02-22 | 2019-10-11 | 三星Sdi株式会社 | Electrode assembly produces its method and the secondary cell including it |
| CN110326152B (en) * | 2017-02-22 | 2023-01-10 | 三星Sdi株式会社 | Electrode assembly, method of producing the same, and secondary battery including the same |
| CN108899459A (en) * | 2018-06-11 | 2018-11-27 | 合肥国轩高科动力能源有限公司 | Preparation method of lithium ion battery diaphragm |
| CN109060199A (en) * | 2018-06-25 | 2018-12-21 | 青岛大学 | A kind of preparation method of piezoelectric transducer and the application of piezoelectric transducer |
| CN109860720A (en) * | 2019-01-30 | 2019-06-07 | 浙江锋锂新能源科技有限公司 | A kind of preparation method and solid state battery of composite electrolyte layer |
| CN109860720B (en) * | 2019-01-30 | 2022-08-05 | 浙江锋锂新能源科技有限公司 | Preparation method of composite electrolyte layer and solid-state battery |
| CN109868560A (en) * | 2019-02-18 | 2019-06-11 | 山东星火科学技术研究院 | The preparation method of phosphorylation sulfonated polyether-ether-ketone and Nano particles of silicon dioxide static spinning membrane |
| CN111072950A (en) * | 2020-01-10 | 2020-04-28 | 深圳职业技术学院 | Synthesis method of polyaryletherketone polymer, preparation method and application of PAEK membrane and PAEK-Al2O3 composite membrane |
| CN112194978A (en) * | 2020-08-25 | 2021-01-08 | 河北金力新能源科技股份有限公司 | High-heat-resistant coating slurry, high-temperature-resistant diaphragm for lithium battery and preparation method of high-temperature-resistant diaphragm |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104037379A (en) | Composite polymer fiber diaphragm and preparation method thereof | |
| Shi et al. | Functional separator consisted of polyimide nonwoven fabrics and polyethylene coating layer for lithium-ion batteries | |
| Wang et al. | Self-assembly of PEI/SiO2 on polyethylene separators for Li-ion batteries with enhanced rate capability | |
| Zhang et al. | Progress in polymeric separators for lithium ion batteries | |
| Xu et al. | Layer-by-layer deposition of organic–inorganic hybrid multilayer on microporous polyethylene separator to enhance the electrochemical performance of lithium-ion battery | |
| Wei et al. | Enhanced cycle performance of lithium–sulfur batteries using a separator modified with a PVDF-C layer | |
| Shi et al. | Polyimide matrix-enhanced cross-linked gel separator with three-dimensional heat-resistance skeleton for high-safety and high-power lithium ion batteries | |
| CN103390741B (en) | Barrier film of organic/inorganic composite porous coating and preparation method thereof | |
| CN103682217B (en) | High-temperature resistant non-woven composite membrane for power lithium-ion battery and preparation method for high-temperature resistant non-woven composite membrane | |
| CN107316965A (en) | Lithium lanthanum zirconium oxygen nanofiber, preparation method of composite film and solid state battery application | |
| Naderi et al. | Activation of Passive Nanofillers in Composite Polymer Electrolyte for Higher Performance Lithium‐Ion Batteries | |
| CN101989651A (en) | Method for preparing cross-linked ceramic-coated separator containing ionic polymer, ceramic-coated separator prepared by the method, and lithium secondary battery using the same | |
| Wang et al. | Polydopamine hydrophilic modification of polypropylene separator for lithium ion battery | |
| CN103208604B (en) | Electrospinning composite diaphragm with thermal hole sealing function | |
| CN104051691B (en) | Preparation method of polydopamine-based modified composite polymer diaphragm | |
| Miao et al. | Superior thermal stability of PVA/cellulose composite membranes for lithium-ion battery separators prepared by impregnation method with noncovalent cross-linking of intermolecular multiple hydrogen-bonds | |
| Liu et al. | Hexagonal boron nitride-coated polyimide ion track etched separator with enhanced thermal conductivity and high-temperature stability for lithium-ion batteries | |
| CN109524597A (en) | A kind of preparation method of the polyethylene wax microballoon with automatic shutoff function/PVDF composite lithium ion cell diaphragm | |
| CN104022248B (en) | A kind of preparation method of high-performance lithium ion conductive membranes | |
| John et al. | Polymeric materials for lithium‐ion cells | |
| Zhang et al. | Enhanced thermostability and electrochemical performance of separators based on an organic-inorganic composite binder composed of polyvinyl alcohol and inorganic phosphate for lithium ion batteries | |
| CN104086797A (en) | Preparation method of high-melting-point resin composite diaphragm | |
| CN107658478A (en) | A kind of diaphragm of all-vanadium redox flow battery and preparation method thereof | |
| CN104031289B (en) | Polyolefin composite diaphragm and preparation method thereof, and lithium ion battery | |
| CN104091909A (en) | Hard plastic-containing composite polymer fiber 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140910 |