CN106941145A - With high temperature resistant, the barrier film of flame-retarding characteristic and preparation method - Google Patents
With high temperature resistant, the barrier film of flame-retarding characteristic and preparation method Download PDFInfo
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- CN106941145A CN106941145A CN201710094602.1A CN201710094602A CN106941145A CN 106941145 A CN106941145 A CN 106941145A CN 201710094602 A CN201710094602 A CN 201710094602A CN 106941145 A CN106941145 A CN 106941145A
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- barrier film
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- temperature resistant
- flame
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- 230000004888 barrier function Effects 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000009987 spinning Methods 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 28
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000004642 Polyimide Substances 0.000 claims abstract description 19
- 229920001721 polyimide Polymers 0.000 claims abstract description 19
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003929 acidic solution Substances 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 8
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 abstract description 7
- 239000001913 cellulose Substances 0.000 abstract description 7
- 239000003063 flame retardant Substances 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000004804 winding Methods 0.000 abstract description 4
- 238000005213 imbibition Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 51
- 239000000463 material Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- 229920001747 Cellulose diacetate Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- -1 vinyl trimethyl silicon Alkane Chemical class 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WGRZHLPEQDVPET-UHFFFAOYSA-N 2-methoxyethoxysilane Chemical compound COCCO[SiH3] WGRZHLPEQDVPET-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/52—Separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
There is high temperature resistant, the barrier film of flame-retarding characteristic and preparation method the present invention relates to a kind of, comprise the following steps：A. skeleton of the polybenzimidazoles film as barrier film is prepared, b. by the spinning solution containing polyimides, cellulose acetate and silane coupler by the method spinning of electrostatic spinning on the both sides of skeleton, form barrier film just finished product, c. finished product at the beginning of barrier film is soaked in dilute acidic solution, unnecessary acid solution is cleaned with pure water again, through roll-in, winding obtains barrier film finished product after cutting.High temperature resistant with excellent specific property, fire-retardant barrier film can be prepared by the inventive method, while maintaining the excellent electrolyte imbibition characteristic of cellulose family barrier film again.
Description
[technical field]
The present invention relates to battery, capacitive diaphragm, more particularly to a kind of there is high temperature resistant, the barrier film of flame-retarding characteristic and preparation side
Method.
[background technology]
With advances in technology and the whole world to energy shortage, environmental pollution the problems such as concern, new energy car is increasingly
It is applied to more among real life, and barrier film is the crucial former material of the power energy storage device such as lithium ion battery, ultracapacitor
Material one of, its performance determines the micro interface structure of its electrochemical system, directly affects energy storage device capacity, circulation and
Security performance.Due to polyolefin, cellulose material relative low price, lithium ion battery, super electricity are currently widely used for
In the power energy storage device such as container, but above-mentioned commercialized polyalkene diaphragm, cellulose family overall performance still have one at present
A little not enough, on the one hand, because its fusing point is low, heat endurance is poor, once micro-short circuit occurs for inside battery, electricity is drawn in overcharge etc.
Pond superheating phenomenon, polyalkene diaphragm reaches fusing point, cannot recur to buffer action, causes both positive and negative polarity to be in contact, so as to occur
Cross the danger such as thermal explosion；Simultaneously, because polyolefin polar is small, so the wetability to highly polar electrolyte is poor, influence cell performance
The raising of energy；In addition, the poor fire of the material such as TPO, cellulose, limited oxygen index (is respectively less than 21, belonged to than relatively low
Combustible material), all it is to have naked light generation during burning, occurs in power energy storage device under extreme security incident, often aggravation peace
The generation of full accident.
The limited oxygen index (LOI) of each fibrous material of table 1
| Material type | Cotton | Acetate fiber | PAN | PP | PE | Polyester |
| LOI | 18.0 | 17 | 18.5 | 17 | 18 | 23.5 |
Based on above reason, in recent years, people are from electrokinetic cell security consideration is improved, and on conventional membrane surface, coating is firm
Property oxide membranes, such as Al2O3, although such barrier film can temporarily ensure barrier film in the case of a high temperature by the support of oxide
Do not shrink, the security of electrokinetic cell is improved to a certain extent, but during thermal runaway extreme by battery, the temperature inside battery core
Degree may be steeply risen to 400~500 DEG C, and such barrier film still melts, until burning.
Therefore, countries in the world business men proposes respective solution one after another, du pont company announces to develop for 2010
Available for the new type polyimide barrier film of lithium ion battery, resistant to elevated temperatures polyimide material has been used.Toray (Toray)
Externally announce to develop with the co-partnership company of eastern burning (Tonen) by base material of aramid fiber resin heat-resisting " micro- porous aramid fiber is thin
Film ".Germany wins the Separion barrier films of wound Degussa exploitation, and its preparation method is using non-woven fabrics as support, in its surface recombination
One layer of Al2O3Or other inorganic ceramic oxide coverings, its security and TPO barrier film have a larger improvement, but barrier film is worn
Thorn intensity need to be improved.Chinese patent publication No. CN103579562A disclose a kind of lithium battery fire-retardant cellulose barrier film and
Preparation method, prepares fire resistance fibre barrier film, this method is only letter by the cellulose treated through fire retardant using the wet method method of manufacturing paper with pulp
It is single that fire retardant is introduced into barrier film.The diaphragm material used in the above method still exist not from it is basic solve barrier film high temperature resistant,
Fire-retardant the problem of.
[content of the invention]
It is an object of the invention to resin material polybenzimidazoles (PBI) fiber with high flame retardant is chosen for skeleton,
Polyimides and cellulose acetate are compounded on skeleton by electrospinning process, it is thermally-stabilised between membrane fibers to improve
Property and mechanical performance, especially add a certain proportion of silane coupler, can be prepared with excellent by the above method
The high temperature resistant of characteristic, fire-retardant barrier film, while maintaining the excellent electrolyte imbibition characteristic of cellulose family barrier film again.
There is high temperature resistant, the preparation method of flame-retarding characteristic barrier film there is provided a kind of to achieve these goals, it includes following
Step：
A. skeleton of the polybenzimidazoles film as barrier film is prepared,
B. it will pass through containing the spinning solution of polyimides, cellulose acetate (cellulose acetate) and silane coupler quiet
The method spinning of Electrospun forms barrier film just finished product on the both sides of skeleton,
C. finished product at the beginning of barrier film is soaked in dilute acidic solution, then unnecessary acid solution is cleaned with pure water, through roll-in, wound,
Barrier film finished product is obtained after cutting.
The preparation method also has following optimize technique：
In step a, described polybenzimidazoles film is spun by the spinning solution containing polybenzimidazoles by electrostatic spinning machine
The methods such as silk can be made.
In step a, described skeleton prepares polyphenyl and miaow by the spinning solution containing polybenzimidazoles by methods such as spinning
After azoles fiber, then polybenzimidazoles film is made.
Described spinning solution is dissolved in dimethyl sulfoxide (DMSO) or dimethylacetylamide, N, N- dimethyl pyrazoles by polybenzimidazoles
In pyrrolidone or 10%~30% sulfuric acid, obtained after being stirred at 50 DEG C~90 DEG C.
In step a, the polybenzimidazoles film porosity of preparation is 80%~90%, and thickness is 0.01~0.02mm.
In step b, described spinning solution is that polyimides and cellulose acetate are dissolved in into dimethylformamide, diformazan
In base sulfoxide, dimethylacetylamide or N, N- dimethyl pyrrolidone, stirred at 60 DEG C~80 DEG C, then add silicon
What alkane coupling agent was obtained after being sufficiently stirred for.
Polyimides, cellulose acetate account for solid masses, and (solid masses is polyimides, cellulose acetate, silane herein
Coupling agent quality summation) percentage is respectively between 40%~75% and 20%~50%.
In step b, described silane coupler includes vinyl three (methoxy ethoxy) silane, vinyl trimethyl silicon
Alkane, VTES, 3- aminopropyl triethoxysilanes, anilinomethyl triethoxysilane, silane coupler are accounted for
Solid masses (solid masses is polyimides, cellulose acetate, silane coupler quality summation herein) percentage amounts 1%~5%
Between.
In step b, just finished product porosity is 50%~70% for the barrier film being made, and thickness is between 0.02~0.04mm.
Barrier film finished product porosity is 60%~70%, and thickness is between 0.02~0.035mm.
The invention has the advantages that：
1. the PBI fiber reinforcements in the present invention have the insulating properties and heat resistance of height, decomposition temperature is up to 660 DEG C, pole
Limited oxygen index is up to 48, is that anti-flammability is especially good, can not change shape with resistance to 400 DEG C of high temperature, and it is non-ignitable, do not form molten drop,
Therefore battery security can be greatly improved.
2. using polyimides and cellulose acetate mixing co-spun yarn, and a certain amount of silane coupler is added, on the one hand
It can reduce barrier film cost, barrier film be kept to the good wellability of electrolyte, while the silicon formed after silane coupler hydrolysis
Oxygen key can make inter-adhesive, the mechanical strength and heat resistance of the further barrier film of raising between fiber.
3. high the present invention relates to method feasibility, step is simple, and production can be prepared on a large scale.
[embodiment]
Hereinafter, it is described further in conjunction with the embodiments for the present invention, embodiment is only used for illustrating rather than limited
Determine protection scope of the present invention.
Embodiment 1
1. a certain amount of polybenzimidazoles is dissolved in dimethyl sulfoxide (DMSO) (DMSO), it is stirred continuously and is obtained at 50 DEG C
Even solution, be made 15%~30% spinning solution, porosity 80%~90% is made in electrostatic spinning machine, thickness is
0.015mm polybenzimidazoles film skeleton.
2. a certain amount of polyimides and cellulose diacetate are dissolved in dimethylacetylamide (DMAc) by a certain percentage
In organic solvent, stirring obtains uniform spinning solution at 60 DEG C, then adds a certain amount of 3- aminopropyl-triethoxies silicon
Alkane, is sufficiently stirred for 24 hours.
Polyimides 57% (solid masses percentage)
Cellulose diacetate 40%
3- aminopropyl triethoxysilanes 3%
The amount of dimethylacetylamide presses liquid：Gu 10：1 is prepared.
It is made as stated above after spinning solution, then electrostatic spinning film forming, 25~30kV of spinning voltage, spinning spacing 15cm
~20cm.Spinning completes one side, and film thickness is 0.018~0.019mm, careful separation film, then complete the spinning of another side
Work.Just finished product porosity is 75% for the barrier film being finally made, and thickness is between 0.025~0.027mm.
3. barrier film prepared by the above method soaks some time in 10% spirit of vinegar solution, then is cleaned with pure water
Unnecessary acid solution, after drying,
4. finished product at the beginning of film prepared by the above method collects coiled, the then roll-in on hydraulic pressure roller, during roll-in before roller temperature
70 degree of degree, winding, cutting obtains desired size.Specific performance index is shown in Table 1.
Embodiment 2
1. a certain amount of polybenzimidazoles is dissolved in N, N- dimethyl pyrrolidones (NMP) solvent, at 50 DEG C not
Disconnected stirring obtains homogeneous solution, and 15%~30% spinning solution is made, porosity 80%~90% is made in electrostatic spinning machine,
Thickness is 0.012mm polybenzimidazoles film skeleton.
2. a certain amount of polyimides and cellulose acetate are dissolved in into dimethylformamide (DMF) by a certain percentage has
In machine solvent, stirring obtains uniform spinning solution at 60 DEG C, then adds a certain amount of VTES, fully
Stirring 36 hours.
Polyimides 65% (mass percent)
Cellulose acetate 35%
VTES 5%
The amount of dimethylformamide presses liquid：Gu 8：1 is prepared.
It is made as stated above after spinning solution, then electrostatic spinning film forming, spinning voltage 30kV, spinning spacing 15cm.Spin
Silk complete one side, film thickness be 0.018~0.019mm, careful separation film, then complete another side spinning work.Finally
Just finished product porosity is 75% for the barrier film being made, and thickness is between 0.025~0.027mm.
4. finished product at the beginning of film prepared by the above method collects coiled, the then roll-in on hydraulic pressure roller, during roll-in before roller temperature
70 degree of degree, winding, cutting obtains desired size.Specific performance index is shown in Table 1.
Embodiment 3
1. a certain amount of polybenzimidazoles is added in dimethylacetylamide (DMAc), 250 when being heated to while stirring
DEG C or so, and 1.5% lithium chloride is added, after after all dissolvings, 20%~30% spinning solution is made, spinning solution is adjusted
To mass concentration about 25%, at room temperature viscosity about 1500Pas.PBI fibre is prepared by dry spinning method, then led to
0.017mm polybenzimidazoles film skeleton is made in wet nonwoven fabrics method.
2. a certain amount of polyimides and cellulose acetate are dissolved in into dimethylacetylamide (DMAc) by a certain percentage has
In machine solvent, stirring obtains uniform spinning solution at 60 DEG C, then adds a certain amount of vinyl trimethylsilane, fully stirs
Mix 36 hours.
Polyimides 65% (mass percent)
Cellulose triacetate 32%
Vinyl trimethylsilane 3%
The amount of dimethylformamide presses liquid：Gu 8：1 is prepared.
It is made as stated above after spinning solution, then electrostatic spinning film forming, spinning voltage 30kV, spinning spacing 15cm.Spin
Silk complete one side, film thickness be 0.018~0.019mm, careful separation film, then complete another side spinning work.Finally
Just finished product porosity is 72% for the barrier film being made, and thickness is between 0.025~0.027mm.
4. finished product at the beginning of film prepared by the above method collects coiled, the then roll-in on hydraulic pressure roller, during roll-in before roller temperature
70 degree of degree, winding, cutting obtains desired size.Specific performance index is shown in Table 1.
The embodiment barrier film properties of sample index of table 1 is contrasted
Each embodiment of table 2 and the pin prick test Comparative result of the lithium ion super capacitor of commercial barrier film sample preparation
Claims (10)
1. a kind of have high temperature resistant, the preparation method of flame-retarding characteristic barrier film, it is characterised in that comprises the following steps：
A. skeleton of the polybenzimidazoles film as barrier film is prepared,
B. the method spinning for the spinning solution containing polyimides, cellulose acetate and silane coupler being passed through into electrostatic spinning
On the both sides of skeleton, barrier film just finished product is formed,
C. finished product at the beginning of barrier film is soaked in dilute acidic solution, then unnecessary acid solution is cleaned with pure water, through roll-in, wound, cutting
After obtain barrier film finished product.
2. there is high temperature resistant, the preparation method of flame-retarding characteristic barrier film as claimed in claim 1, it is characterised in that in step a, institute
The polybenzimidazoles film stated can be by being made by the spinning solution containing polybenzimidazoles after electrostatic spinning machine spinning.
3. there is high temperature resistant, the preparation method of flame-retarding characteristic barrier film as claimed in claim 1, it is characterised in that in step a, institute
By the spinning solution containing polybenzimidazoles after spinning prepares PBI fibre, then polybenzimidazoles is made in the skeleton stated
Film.
4. there is high temperature resistant, the preparation method of flame-retarding characteristic barrier film as claimed in claim 2 or claim 3, it is characterised in that described
Spinning solution is dissolved in dimethyl sulfoxide (DMSO) or dimethylacetylamide, N by polybenzimidazoles, and N- dimethyl pyrrolidones or 10%~
In 30% sulfuric acid, obtained after being stirred at 50 DEG C.
5. there is high temperature resistant, the preparation method of flame-retarding characteristic barrier film as claimed in claim 1, it is characterised in that in step a, system
Standby polybenzimidazoles film porosity is 80%~90%, and thickness is 0.01~0.02mm.
6. there is high temperature resistant, the preparation method of flame-retarding characteristic barrier film as claimed in claim 1, it is characterised in that in step b, institute
The spinning solution stated is that polyimides and cellulose acetate are dissolved in into dimethylformamide, dimethyl sulfoxide (DMSO), dimethylacetamide
In amine or N, N- dimethyl pyrrolidone, stirred at 60 DEG C, then add after silane coupler is sufficiently stirred for and obtain
's.
7. there is high temperature resistant, the preparation method of flame-retarding characteristic barrier film as claimed in claim 6, it is characterised in that polyimides,
It is respectively that between 40%~75% and 20%~50%, silane coupler accounts for solid matter that cellulose acetate, which accounts for solid masses percentage,
Between amount percentage amounts 1%~5%.
8. there is high temperature resistant, the preparation method of flame-retarding characteristic barrier film as claimed in claim 1, it is characterised in that in step b, system
Into barrier film at the beginning of finished product porosity 50%~70%, thickness is between 0.02~0.04mm.
9. there is high temperature resistant, the preparation method of flame-retarding characteristic barrier film as claimed in claim 1, it is characterised in that barrier film finished hole
Gap rate is 60%~70%, and thickness is between 0.02~0.035mm.
10. barrier film prepared by a kind of any described preparation method of use claim 1~9.
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