CN108428843A - A kind of high safety nonwoven fabric base composite diaphragm and preparation method thereof - Google Patents
A kind of high safety nonwoven fabric base composite diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN108428843A CN108428843A CN201711310070.7A CN201711310070A CN108428843A CN 108428843 A CN108428843 A CN 108428843A CN 201711310070 A CN201711310070 A CN 201711310070A CN 108428843 A CN108428843 A CN 108428843A
- Authority
- CN
- China
- Prior art keywords
- nonwoven fabric
- fabric base
- preparation
- diaphragm
- composite diaphragm
- 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
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920000620 organic polymer Polymers 0.000 claims abstract description 23
- 239000004697 Polyetherimide Substances 0.000 claims abstract description 9
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 4
- 229920002635 polyurethane Polymers 0.000 claims abstract description 4
- 239000004814 polyurethane Substances 0.000 claims abstract description 4
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 3
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 18
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229920002334 Spandex Polymers 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000004759 spandex Substances 0.000 claims description 3
- KZRXPHCVIMWWDS-AWEZNQCLSA-N (4S)-4-amino-5-dodecanoyloxy-5-oxopentanoic acid Chemical compound CCCCCCCCCCCC(=O)OC(=O)[C@@H](N)CCC(O)=O KZRXPHCVIMWWDS-AWEZNQCLSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 claims description 2
- 229960004419 dimethyl fumarate Drugs 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 229940071085 lauroyl glutamate Drugs 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229960002415 trichloroethylene Drugs 0.000 claims description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- 150000001413 amino acids Chemical class 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 229920002994 synthetic fiber Polymers 0.000 claims 1
- 238000002955 isolation Methods 0.000 abstract description 11
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 5
- 239000004744 fabric Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- H01M50/403—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)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a kind of high safety nonwoven fabric base composite diaphragm and preparation method thereof, the high safety nonwoven fabric base composite diaphragm, including nonwoven fabric base bottom are filled with high-melting-point organic polymer in the surface at the nonwoven fabric base bottom and hole；The high-melting-point organic polymer is at least one of polymethyl methacrylate, polyamic acid, polyetherimide, aromatic diamine, aromatic dianhydride, polyurethane, polyether sulfone.The present invention coats nonwoven fabric base bottom using special high-melting-point organic polymer, not only assigns the good electronic isolation of nonwoven cloth diaphragm and excellent thermal stability, and the nonwoven fabric base composite diaphragm obtained helps to improve the safety of battery.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of high safety nonwoven fabric base composite diaphragm and its system
Preparation Method.
Background technology
Diaphragm plays isolation positive and negative electrode as one of lithium ion battery critical material, and transmits the effect of ion.Polyene
Hydro carbons diaphragm is to be commercialized the diaphragm generally used now, have high mechanical strength, porosity it is suitable, it is cheap, prepare work
Skill is simple and the advantages such as stable electrochemical property.However with the rapid development in the fields such as new-energy automobile, people are to battery
Security requirement is higher and higher, and polyolefins diaphragm is easy to happen big face at high temperature since intrinsic fusing point only has 130-170 DEG C
Product shrinks and leads to internal short-circuit of battery, causes safety accident, it is difficult to meet requirement of the emerging field to battery security.In order to
The safety for improving polyalkene diaphragm, by being current general method in its surface coated ceramic particle, and it is prepared poly-
Although alkene ceramic diaphragm can improve the safety of diaphragm to a certain extent, ask there is also ceramic particle is caducous
Topic, it is often more important that inherently fusing point is relatively low for polyolefine material, limits the further development and application of such diaphragm.
Nonwoven cloth diaphragm has many advantages, such as that high temperature resistant, high hole, simple production process, cost are relatively low, is expected to become next
For lithium ion battery separator.But due to the limitation of its production technology, membrane pore size is larger, and be unevenly distributed, electrical isolation
Difference, it is difficult to apply in actual battery, need compound other materials that can use.Coated ceramic particle is also on nonwoven cloth diaphragm
Current general solution, but the technical barrier of ceramic layer uniformity is higher, the relevant technologies are monopolized by foreign countries, and produce valence
Lattice are higher, remain to be further improved.
Xiao W. etc. are in document " Preparation and electrochemical performance of
ZrO2nanoparticle embedded nonwoven composite separator for lithium-ion
In batteries " using PVDF-HFP as binder the compound ZrO on polyethylene terephthalate (PET)2.Although comparing
In conventional polyolefins diaphragm, prepared diaphragm has better safety and electrolyte wetability, but this diaphragm was using
Binder PVDF-HFP can be swollen in journey, easily cause ZrO2Particle falls off, to cause battery short circuit.
Application publication number is that the Chinese invention patent application document of CN104766938A discloses one kind by non-woven fabrics base material
The compound diaphragm of layer, electrostatic spinning layer, polyalcohol stephanoporate coating, the diaphragm have higher safety, excellent electrochemistry
Can, but the preparation method is more complex, cost is more expensive, is not easy large-scale production.
Application publication number is that the Chinese invention patent application document of CN103887464A discloses a kind of lithium ion battery use
Diaphragm and preparation method thereof and lithium ion battery, the diaphragm include nonwoven fabric base bottom and are filled in the hole at the nonwoven fabric base bottom
In thermoplastic organic polymer particle；Preparation method includes, by thermoplastic organic polymer particle and binder according to one
Certainty ratio prepares solution, after mechanical agitation, non-woven fabrics is impregnated certain time in the solution, is taken out, drying at room temperature and vacuum are dry
It is dry, obtain diaphragm for lithium ion battery.The suitable aperture of the diaphragm reduces the risk of battery short circuit, improves the body of battery
Product specific capacity；But the diaphragm is because using thermoplastic organic polymer particle so that diaphragm poor heat resistance is unfavorable for diaphragm in height
Use under warm environment.
Therefore, it is necessary to which the improvement to Non-woven fabrics diaphragm is further probed into, simplify preparation method, improves diaphragm
Can, to meet the market requirement and large-scale production.
Invention content
The present invention provides a kind of high safety nonwoven fabric base composite diaphragm and preparation method thereof, the nonwoven fabric base composite diaphragms
It can assign nonwoven cloth diaphragm good electronic isolation, excellent thermal stability improves the safety of battery；The system of the diaphragm
Preparation Method is simple, is conducive to large-scale production.
The concrete scheme of the present invention is as follows：
A kind of high safety nonwoven fabric base composite diaphragm, including nonwoven fabric base bottom, the surface at the nonwoven fabric base bottom and hole
In be filled with high-melting-point organic polymer；The high-melting-point organic polymer is polymethyl methacrylate, polyamic acid, polyethers
At least one of acid imide, aromatic diamine, aromatic dianhydride, polyurethane, polyether sulfone.
The above-mentioned non-woven fabric compounded diaphragm of high safety (hereinafter referred to as " composite diaphragm ") can be made compound using non-woven fabrics as substrate
Diaphragm has good ion transporting and structural stability；And by high-melting-point organic polymer be filled in non-woven fabrics surface and
Diaphragm electronic isolation can be assigned in hole so that it can be applied in actual battery, and improve the safety of diaphragm, simultaneously
Also the thermal stability of composite diaphragm can be improved.
Preferably, the high-melting-point organic polymer is polyamic acid, polyetherimide, aromatic diamine, fragrance
At least one of race's dianhydride and polyurethane.
It is further preferred that the high-melting-point organic polymer is polyamic acid or polyetherimide.
Further, the nonwoven fabric base bottom be cellulose, polyphenylene sulfide, polyethylene terephthalate, poly- pair
At least one of terephtha-late, polysulfones, polyamide, polyacrylonitrile, aramid fiber and spandex.
Preferably, the nonwoven fabric base bottom is polyethylene terephthalate, polybutylene terephthalate, polyamides
At least one of amine, polyacrylonitrile, aramid fiber and spandex.
Preferably, the thickness at the nonwoven fabric base bottom is 9~15 μm；Porosity is 60~80%.
The present invention also provides a kind of preparation methods of the high safety nonwoven fabric base composite diaphragm, including：
(1) high-melting-point organic polymer is dissolved in organic solvent, adds surfactant, obtain mixed solution；
(2) mixed solution is compounded on the nonwoven fabric base bottom, after drying, obtains the high safety nonwoven fabric base
Composite diaphragm.
In the prior art, the fusing point of the organic polymer for coating nonwoven fabric base bottom is relatively low so that composite diaphragm
Thermal stability is poor, influences the use scope of diaphragm；And the viscosity of such organic polymer is poor, and it is viscous to generally require additional addition
Agent is tied, can be smoothly coated on non-woven fabrics, and Swelling easily occurs for binder during diaphragm use, causes organic poly-
It closes object to fall off from non-woven fabrics, and then influences the electronic isolation of diaphragm.
The present invention is dissolved in corresponding organic using the high-melting-point organic polymer specifically with certain viscosity
Coating liquid is obtained in solvent, which can be compounded on nonwoven fabric base bottom, both solve that organic polymer is low-melting to ask
Topic, also avoids the use of binder, improves the thermal stability and electronic isolation of composite diaphragm.
Further, in step (1), the temperature of the dissolving is 50~120 DEG C.
Preferably, in step (1), the solid content of active ingredient is 1~50% in the high-melting-point organic polymer；It should
Solid content refers to mass fraction.
Further, the organic solvent be dimethylbenzene, trichloro ethylene, naphthane, decahydronaphthalene, N-Methyl pyrrolidone,
At least one of dimethylacetylamide, dimethylformamide and dimethyl fumarate.
Further, the surfactant is the stupid sodium sulfonate of straight chained alkyl, alkylsulfonate, ethylene glycol amide, poly- second
At least one of glycol, ethylene glycol monobutyl ether and lauroyl glutamate.
Further, in step (2), described is complex as dip-coating, spraying or coating.
Preferably, in step (2), the temperature of the drying is 50~150 DEG C, and the time is 8~48h.
Compared with prior art, the invention has the advantages that：
(1) present invention coats nonwoven fabric base bottom using special high-melting-point organic polymer, the high safety of acquisition
Nonwoven fabric base composite diaphragm not only increases the safety of battery, and has good electronic isolation and excellent thermostabilization
Property.
(2) not only preparation process is simple for the method for the present invention, but also dissolves high-melting-point by adding specific organic solvent
Organic polymer, obtained coating liquid can uniformly be coated in nonwoven fabric base bottom material in the case where not adding binder
On, further improve the electronic isolation and thermal stability of non-woven fabrics.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the composite diaphragm of PET base used in embodiment 1 and preparation；
Wherein, A is PET base；B is composite diaphragm.
Fig. 2 is the charging curve of the battery using PET base used in embodiment 1 and the assembling of the composite diaphragm of preparation.
Fig. 3 is the dimensional drawing of the composite diaphragm for preparing after high-temperature process in embodiment 1.
Specific implementation mode
Embodiment 1
A kind of preparation method of high safety nonwoven fabric base composite diaphragm, is as follows：
(1) 5g polyetherimide particles are taken, it is 95g to be slowly added into quality, and the dimethylformamide that temperature is 120 DEG C tries
In agent, after stirring is completely dissolved to polyetherimide particle, solution temperature is cooled to 80 DEG C, and 3 drop ethylene glycol lists are added thereto
Butyl ether stirs evenly, and obtains coating solution；
(2) PET base that thickness is 15 μm, porosity is 70% is completely submerged in 2min in the mixed solution, taken
Go out PET composite diaphragms, after 20 μm of scraper of spacing removes PET composite diaphragm surface residual solution, natural air drying in air
30min, then the vacuum drying 12h at 120 DEG C obtain high safety nonwoven fabric base composite diaphragm.
Performance detection is carried out to the high safety nonwoven fabric base composite diaphragm of above-mentioned preparation, it is as a result as follows：
As shown in Figure 1, PET membrane surfaces pore-size distribution is uneven, and there is apparent macropore；And the surface of composite diaphragm is without apparent
Macropore.As shown in Fig. 2, micro-short circuit phenomenon occurs in the battery of former PET base assembling, illustrate that former PET base electronic isolation is poor；And
Composite diaphragm can charge normal, have good electronic isolation, illustrate by PET compound polyetherimide can make
Composite diaphragm is applied in actual battery.
Composite diaphragm prepared by embodiment 1 is cut into the rectangle of 2cm × 2cm, then is heat-treated in 200 DEG C of baking ovens
Then 30min tests its size.As shown in figure 3, the size of composite diaphragm is still 2 × 2cm after high-temperature heat treatment, say
Bright prepared composite diaphragm has good high high-temp stability, helps to improve the safety of battery.
Embodiment 2
A kind of preparation method of high safety nonwoven fabric base composite diaphragm, is as follows：
(1) 10g polyamic acids are taken, it is 90g to be slowly added into quality, and temperature is in 100 DEG C of dimethylacetylamide reagent,
Solution temperature is cooled to 50 DEG C by stirring to uniform solution is formed, and 3 drop polyethylene glycol are added thereto, stirs evenly, is applied
Cover solution；
(2) the polyacrylonitrile substrate that thickness is 12 μm, porosity is 60% is completely submerged in the mixed solution
2min takes out polyacrylonitrile composite diaphragm, after 15 μm of scraper of spacing removes polyacrylonitrile composite diaphragm surface residual solution,
Natural air drying 30min in air, then the vacuum drying 12h at 120 DEG C obtain high safety nonwoven fabric base composite diaphragm.
Embodiment 3
A kind of preparation method of high safety nonwoven fabric base composite diaphragm, is as follows：
(1) 10g polyetherimide particles are taken, it is 90g, the N- crassitudes that temperature is 100 DEG C to be slowly added into quality
In ketone reagent, after stirring is completely dissolved to polyetherimide particle, solution temperature is cooled to 80 DEG C, and 3 drop second two are added thereto
Alcohol monobutyl ether, stirs evenly, and obtains coating solution；
(2) PET base that thickness is 12 μm, porosity is 80% is completely submerged in 2min in the mixed solution, taken
Go out PET composite diaphragms, after 15 μm of scraper of spacing removes PET composite diaphragm surface residual solution, natural air drying in air
30min, then vacuum drying for 24 hours, obtains high safety nonwoven fabric base composite diaphragm at 100 DEG C.
Claims (10)
1. a kind of high safety nonwoven fabric base composite diaphragm, including nonwoven fabric base bottom, which is characterized in that the table at the nonwoven fabric base bottom
High-melting-point organic polymer is filled in face and hole；The high-melting-point organic polymer is polymethyl methacrylate, polyamides
At least one of amino acid, polyetherimide, aromatic diamine, aromatic dianhydride, polyurethane, polyether sulfone.
2. high safety nonwoven fabric base composite diaphragm as described in claim 1, which is characterized in that the nonwoven fabric base bottom is fibre
Tie up element, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, polysulfones, polyamide, polyacrylonitrile, virtue
At least one of synthetic fibre and spandex.
3. high safety nonwoven fabric base composite diaphragm as described in claim 1, which is characterized in that the thickness at the nonwoven fabric base bottom
It is 9~15 μm；Porosity is 60~80%.
4. a kind of preparation method of such as claims 1 to 3 any one of them high safety nonwoven fabric base composite diaphragm, feature exist
In, including：
(1) high-melting-point organic polymer is dissolved in organic solvent, adds surfactant, obtain mixed solution；
(2) mixed solution is compounded on the nonwoven fabric base bottom, after drying, it is compound obtains the high safety nonwoven fabric base
Diaphragm.
5. preparation method as claimed in claim 4, which is characterized in that in step (1), the temperature of the dissolving is 50~120
℃。
6. preparation method as claimed in claim 4, which is characterized in that in step (1), have in the high-melting-point organic polymer
The solid content for imitating ingredient is 1~50%.
7. preparation method as claimed in claim 4, which is characterized in that the organic solvent is dimethylbenzene, trichloro ethylene, tetrahydrochysene
At least one of naphthalene, decahydronaphthalene, N-Methyl pyrrolidone, dimethylacetylamide, dimethylformamide and dimethyl fumarate.
8. preparation method as claimed in claim 4, which is characterized in that the surfactant be the stupid sodium sulfonate of straight chained alkyl,
At least one of alkylsulfonate, ethylene glycol amide, polyethylene glycol, ethylene glycol monobutyl ether and lauroyl glutamate.
9. preparation method as claimed in claim 4, which is characterized in that in step (2), it is described be complex as dip-coating, spraying or
Coating.
10. preparation method as claimed in claim 4, which is characterized in that in step (2), the temperature of the drying is 50~150
DEG C, the time is 8~48 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711310070.7A CN108428843A (en) | 2017-12-11 | 2017-12-11 | A kind of high safety nonwoven fabric base composite diaphragm and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711310070.7A CN108428843A (en) | 2017-12-11 | 2017-12-11 | A kind of high safety nonwoven fabric base composite diaphragm and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108428843A true CN108428843A (en) | 2018-08-21 |
Family
ID=63155844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711310070.7A Pending CN108428843A (en) | 2017-12-11 | 2017-12-11 | A kind of high safety nonwoven fabric base composite diaphragm and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108428843A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110474009A (en) * | 2019-07-12 | 2019-11-19 | 大连恒超锂业科技有限公司 | A kind of lithium ion battery nonwoven fabric base composite diaphragm and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579553A (en) * | 2012-07-24 | 2014-02-12 | 海洋王照明科技股份有限公司 | Electrochemical power-supply composite membrane and preparation method thereof |
| CN104852006A (en) * | 2015-04-13 | 2015-08-19 | 江苏华东锂电技术研究院有限公司 | Composite diaphragm and preparation method therefor, and lithium ion battery |
| CN105336901A (en) * | 2015-09-25 | 2016-02-17 | 深圳市星源材质科技股份有限公司 | Preparation method of high-performance inter-porous coated diaphragm |
-
2017
- 2017-12-11 CN CN201711310070.7A patent/CN108428843A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103579553A (en) * | 2012-07-24 | 2014-02-12 | 海洋王照明科技股份有限公司 | Electrochemical power-supply composite membrane and preparation method thereof |
| CN104852006A (en) * | 2015-04-13 | 2015-08-19 | 江苏华东锂电技术研究院有限公司 | Composite diaphragm and preparation method therefor, and lithium ion battery |
| CN105336901A (en) * | 2015-09-25 | 2016-02-17 | 深圳市星源材质科技股份有限公司 | Preparation method of high-performance inter-porous coated diaphragm |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110474009A (en) * | 2019-07-12 | 2019-11-19 | 大连恒超锂业科技有限公司 | A kind of lithium ion battery nonwoven fabric base composite diaphragm and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104766938B (en) | A kind of compound lithium ion battery separator and preparation method thereof | |
| KR101301446B1 (en) | Secondary battery fibrous separation membrane and method thereof | |
| CN100514711C (en) | Electronic component separator and method for producing the same | |
| CN102969471B (en) | A kind of high-temperature resistant aromatic polysulfonamide base lithium ion battery diaphragm | |
| KR20210060611A (en) | Modified solid electrolyte membrane and its manufacturing method and lithium battery | |
| CN105355949B (en) | A kind of preparation method of micro nanometer fiber compound proton exchange membrane | |
| KR101676688B1 (en) | Micro porous hybrid separator, method for manufacturing the same and electrochemical device containing the same | |
| CN108914550B (en) | Preparation method of polyimide fiber membrane with surface coated with zirconium dioxide nano layer | |
| US20210135315A1 (en) | Coating slurries for preparing separators, separators for electrochemical devices and preparation methods therefor | |
| KR101470696B1 (en) | Manufacturing method of separator of lithium secondary battery and the separator manufactured thereby and the lithium secondary battery having the separator | |
| KR20110021217A (en) | Polymer electrolyte membrane for fuel cell and method of manufacturing the same | |
| KR102377721B1 (en) | Porous composite separator and manufacturing method thereof | |
| CN108807791B (en) | Composite diaphragm for lithium battery and preparation method thereof | |
| KR20110093714A (en) | Ultrafine fibrous separator with high heat-resistance and high strength and method of manufacturing the same | |
| CN107742688B (en) | Polyolefin lithium battery diaphragm and preparation method thereof | |
| KR20120052100A (en) | A porous separator having improved thermal resistance, manufacturing method thereof and electrochemical device comprising the same | |
| Chen et al. | The research progress of Li-ion battery separators with inorganic oxide nanoparticles by electrospinning: A mini review | |
| CN111192994A (en) | Heat-shrinkage-resistant polyethylene lithium battery diaphragm and preparation method thereof | |
| CN108807818B (en) | Aromatic polyamide composite diaphragm and preparation method thereof | |
| CN110600662A (en) | Polyvinylidene fluoride-hexafluoropropylene/titanium dioxide composite membrane and preparation method and application thereof | |
| KR20130073182A (en) | A separator and electrochemical device having the same | |
| CN114583384A (en) | Porous fiber composite diaphragm and preparation method thereof | |
| CN108428843A (en) | A kind of high safety nonwoven fabric base composite diaphragm and preparation method thereof | |
| CN106099013B (en) | A kind of preparation method of polyimide foraminous diaphragm | |
| CN103187550A (en) | Separator and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 313100, No. 18, Qiao Qiao Road, Changxing County painting industrial park, Zhejiang, Huzhou Applicant after: Tianneng Shuai Fude Energy Co.,Ltd. Address before: 313100, No. 18, Qiao Qiao Road, Changxing County painting industrial park, Zhejiang, Huzhou Applicant before: ZHEJIANG TIANNENG ENERGY TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180821 |
|
| RJ01 | Rejection of invention patent application after publication |