CN106449161A - Electrostatic spinning supercapacitor membrane material for in-situ production of nanometer titanium dioxide - Google Patents
Electrostatic spinning supercapacitor membrane material for in-situ production of nanometer titanium dioxide Download PDFInfo
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- CN106449161A CN106449161A CN201610930066.XA CN201610930066A CN106449161A CN 106449161 A CN106449161 A CN 106449161A CN 201610930066 A CN201610930066 A CN 201610930066A CN 106449161 A CN106449161 A CN 106449161A
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- spinning
- electrostatic spinning
- supercapacitor
- boehmite
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- 239000000463 material Substances 0.000 title claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 13
- 239000012528 membrane Substances 0.000 title claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 title abstract description 4
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 14
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000009987 spinning Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- -1 silicon Alkane Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract 4
- 239000002033 PVDF binder Substances 0.000 abstract 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- 238000005299 abrasion Methods 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention discloses an electrostatic spinning supercapacitor membrane material for in-situ production of nanometer titanium dioxide. The material is prepared from, by weight, 80-83 parts of polyvinylidene fluoride, 20-22 parts of polymethyl methacrylate, a proper amount of DMF, 2-3 parts of nanometer boehmite, 0.8-1 part of silane coupling agent KH550, a proper amount of deionized water, 1-1.3 parts of nanometer barium oxide, 3-4 parts of hydrochloric acid with the concentration of 36 wt%, 5-6 parts of tetrabutyl titanate and 13-15 parts of absolute ethyl alcohol. Through hydrolysis of tetrabutyl titanate in a mixed solution of polyvinylidene fluoride and polymethyl methacrylate, titanium dioxide is produced in situ, and then electrostatic spinning is conducted. Combined with the addition of nanometer barium oxide, the tensile strength and elongation at break of a membrane are remarkably improved, and the heat resistance and abrasion resistance are also improved at the same time. The product process is simple, the prepared membrane material has good electrochemical performances, ionic conductivity at room temperature is improved and the membrane material is suitable for being used in a supercapacitor.
Description
Technical field
The present invention relates to supercapacitor technologies field, more particularly, to a kind of Static Spinning of in-situ preparation nano titanium oxide
Diaphragm of supercapacitor material.
Background technology
Ultracapacitor is a kind of accumulator of the great market competitiveness, because it can realize quick charge, high current
Electric discharge, and there are the charge lifetimes of more than 100,000 times, need to occupy critical role in the application of high-multiplying power discharge in short-term at some.
The requirement to electrical source of power of hybrid vehicle and electric automobile also result in that in worldwide, this is new to ultracapacitor
The extensive attention of type energy storage device.In the composition of ultracapacitor, electrode, the electrolyte and diaphragm paper property to ultracapacitor
Conclusive impact can be played.The electrode of ultracapacitor and electrolyte are the focuses studied at present, but people are for barrier film
Research and attention rate not high.
The diaphragm paper of ultracapacitor is located between two porous carbon electrodes, and complete wetting is in electrolyte together with electrode
In, play the effect of isolation during repeated charge, stop electronics conduction, prevent between the two poles of the earth, contacting the inside caused short
Road.This requires that diaphragm material is the insulator of electronics, has good isolation performance, and its hole should be less than electricity as far as possible
The minimum grain size of pole surfactant.The necessary aperture of the preferable diaphragm paper of isolation performance is little, so can make the circulation of electrolyte
Property decline, battery charging and discharging hydraulic performance decline;And electrolyte is impregnated with that rate is higher, ion passes through the good diaphragm material of property, and often hole is relatively
More greatly, easily cause and between the two poles of the earth, contact the internal short-circuit causing.The maximum advantage of ultracapacitor is charge/discharge rates
Hurry up, can with high power discharge, therefore, diaphragm material will thinner towards thickness, porosity is higher, aperture is less and is more evenly distributed
Contour performance trend development.
The non-woven fabrics of electrostatic spinning preparation have the advantages that three-dimensional micropore structure, specific surface area be big, porosity is high, in lithium electricity
There is preferable application prospect in pond barrier film field.《Method of electrostatic spinning preparation PAN/PVDF-HFP diaphragm of supercapacitor and its power
Learn performance evaluation》In one literary composition, PAN/PVDF-HFP composite nano-fiber membrane is prepared by electrostatic spinning technique, to PAN/
PVDF-HFP/PAN three-decker composite membrane carries out hot-pressing processing, although the diaphragm material obtaining than product film performance
Improve, but yet suffer from low intensity, short life, the shortcoming yielding poorly, need further electrostatic spinning diaphragm material to be carried out
Modification, to improve heat stability, the mechanical property of barrier film.
Content of the invention
The object of the invention is exactly the defect in order to make up prior art, provides a kind of the quiet of in-situ preparation nano titanium oxide
Electrospinning diaphragm of supercapacitor material.
The present invention is achieved by the following technical solutions:
A kind of Static Spinning diaphragm of supercapacitor material of in-situ preparation nano titanium oxide, by the raw material system of following weight portion
Become:Kynoar 80-83, polymethyl methacrylate 20-22, appropriate DMF, nm boehmite 2-3, silane coupler
KH5500.8-1, appropriate deionized water, nano oxidized barium 1-1.3, concentration are the hydrochloric acid 3-4 of 36wt%, butyl titanate 5-6, no
Water-ethanol 13-15.
A kind of Static Spinning diaphragm of supercapacitor material of described in-situ preparation nano titanium oxide, by following concrete grammar
It is prepared from:
(1)After nm boehmite is completely dried inside vacuum drying oven be dissolved in the silane coupled of 4-5 times amount deionized water
Agent KH550 mixes, and after ultrasonic disperse 30-40 minute, terminates anti-after being heated to 140-150 DEG C of backflow 90-120 minute while stirring
Should, centrifugation standing, solid deionized water is cleaned 2-3 time, is then put in vacuum drying oven solid with 60-70 DEG C of temperature
It is dried 12 hours, obtain the boehmite of modification;
(2)At normal temperatures Kynoar, polymethyl methacrylate are mixed, add the DMF of total amount 8-9 times amount, with 400-
Stir under 500 revs/min of speed to after be completely dissolved and add step(1)The product that obtains, nano oxidized barium, continue stirring 120-
Ultrasonic disperse 40-50 minute after 150 minutes;
(3)In step(2)In product add concentration be 36wt% hydrochloric acid, stand-by after stirring, then by butyl titanate with
Dehydrated alcohol mix homogeneously, adds in said mixture, under room temperature, stirs 3-4 hour with 400-500 rev/min of speed, obtains
Spinning liquid;
(4)Spinning liquid is carried out electrostatic spinning, controls and push away liquid speed degree 0.002mm/s, receiving range 18cm, the condition of voltage 22kv
Lower electrostatic spinning 2 hours, after the completion of spinning, after the fiber membrane collected is dried 12 hours in 60-70 DEG C of vacuum drying oven
Take out, push down in vacuum drying oven hot pressing 90-120 minute at 120 DEG C with clean glass is smooth, take out after natural cooling
Obtain final product.
It is an advantage of the invention that:The present invention is by carrying out to boehmite being added to Kynoar, poly- first after surface modification
Base acrylic acid methyl ester. compounds in spinning liquid, obtains composite fibre diaphragm material by electrostatic spinning technique, intensity after hot-pressing processing
Strengthened, be there is good pick up simultaneously;Cooperation boehmite interpolation, due to boehmite particles surface polar group with
Polymer polarity Interaction of substituents, on the one hand can improve the heat stability of barrier film, mechanical strength, pore-size stability,
On the other hand the compatibility to electrolyte for the barrier film can be improved;In addition boehmite has excellent heat conductivility, can improve electricity
Container barrier film Heat Conduction Problems;The diaphragm material heat stability that the present invention makes is good, mechanical strength is improved, pick up high,
Electrochemical stability is good, have preferable high magnification capacity and good cyclic reversibility, is highly suitable for ultracapacitor
In.
The present invention hydrolyzes raw in situ in Kynoar, polymethyl methacrylate mixed solution also by butyl titanate
Become electrostatic spinning after titanium dioxide, coordinate the interpolation of nano oxidized barium, the tensile strength of barrier film and elongation at break to have significantly
Raising, thermostability, wearability are also improved simultaneously;Product Process of the present invention is simple, is easy to Industry Control, is simultaneously manufactured
Diaphragm material there is good chemical property, improve conductivity at room temperature, suitable ultracapacitor uses, be suitable for big
Large-scale production.
Specific embodiment
A kind of Static Spinning diaphragm of supercapacitor material of in-situ preparation nano titanium oxide, by following weight portion(Kilogram)
Raw material make:Kynoar 80, polymethyl methacrylate 20, appropriate DMF, nm boehmite 2, silane coupler
KH5500.8, appropriate deionized water, nano oxidized barium 1, concentration are the hydrochloric acid 3 of 36wt%, butyl titanate 5, dehydrated alcohol 13.
A kind of Static Spinning diaphragm of supercapacitor material of described in-situ preparation nano titanium oxide, by following concrete grammar
It is prepared from:
(1)With the silane coupler being dissolved in 4 times amount deionized waters after nm boehmite is completely dried inside vacuum drying oven
KH550 mixes, and ultrasonic disperse, after 30 minutes, terminates reaction after being heated to 140 DEG C of backflows while stirring 90 minutes, is centrifuged standing,
Solid deionized water is cleaned 2 times, then puts into solid in vacuum drying oven and is dried 12 hours with 60 DEG C of temperature, is changed
The boehmite of property;
(2)At normal temperatures by Kynoar, polymethyl methacrylate mix, add total amount 8 times amount DMF, with 400 turns/
Stir to after be completely dissolved under the speed divided and add step(1)The product that obtains, nano oxidized barium, after continuing stirring 120 minutes
Ultrasonic disperse 40 minutes;
(3)In step(2)In product add concentration be 36wt% hydrochloric acid, stand-by after stirring, then by butyl titanate with
Dehydrated alcohol mix homogeneously, adds in said mixture, under room temperature, is stirred 3 hours with 400 revs/min of speed, obtains spinning
Liquid;
(4)Spinning liquid is carried out electrostatic spinning, controls and push away liquid speed degree 0.002mm/s, receiving range 18cm, the condition of voltage 22kv
Lower electrostatic spinning 2 hours, after the completion of spinning, takes after the fiber membrane of collection is dried 12 hours in 60 DEG C of vacuum drying ovens
Go out, push down in vacuum drying oven hot pressing 90 minutes at 120 DEG C with clean glass is smooth, take out after natural cooling and obtain final product.
By testing to the present embodiment diaphragm material, porosity is 63.8%, and pick up is 586%, percentage elongation
75.8%, at 110 DEG C, percent thermal shrinkage is less than 1%, and at 150 DEG C, percent thermal shrinkage is less than 1%.
Claims (2)
1. a kind of Static Spinning diaphragm of supercapacitor material of in-situ preparation nano titanium oxide is it is characterised in that by following heavy
The raw material of amount part is made:Kynoar 80-83, polymethyl methacrylate 20-22, appropriate DMF, nm boehmite 2-3, silicon
Alkane coupling agent KH5500.8-1, appropriate deionized water, nano oxidized barium 1-1.3, concentration are the hydrochloric acid 3-4 of 36wt%, metatitanic acid four fourth
Ester 5-6, dehydrated alcohol 13-15.
2. according to claims 1 a kind of in-situ preparation nano titanium oxide Static Spinning diaphragm of supercapacitor material,
It is characterized in that, it is prepared from by following concrete grammar:
(1)After nm boehmite is completely dried inside vacuum drying oven be dissolved in the silane coupled of 4-5 times amount deionized water
Agent KH550 mixes, and after ultrasonic disperse 30-40 minute, terminates anti-after being heated to 140-150 DEG C of backflow 90-120 minute while stirring
Should, centrifugation standing, solid deionized water is cleaned 2-3 time, is then put in vacuum drying oven solid with 60-70 DEG C of temperature
It is dried 12 hours, obtain the boehmite of modification;
(2)At normal temperatures Kynoar, polymethyl methacrylate are mixed, add the DMF of total amount 8-9 times amount, with 400-
Stir under 500 revs/min of speed to after be completely dissolved and add step(1)The product that obtains, nano oxidized barium, continue stirring 120-
Ultrasonic disperse 40-50 minute after 150 minutes;
(3)In step(2)In product add concentration be 36wt% hydrochloric acid, stand-by after stirring, then by butyl titanate with
Dehydrated alcohol mix homogeneously, adds in said mixture, under room temperature, stirs 3-4 hour with 400-500 rev/min of speed, obtains
Spinning liquid;
(4)Spinning liquid is carried out electrostatic spinning, controls and push away liquid speed degree 0.002mm/s, receiving range 18cm, the condition of voltage 22kv
Lower electrostatic spinning 2 hours, after the completion of spinning, after the fiber membrane collected is dried 12 hours in 60-70 DEG C of vacuum drying oven
Take out, push down in vacuum drying oven hot pressing 90-120 minute at 120 DEG C with clean glass is smooth, take out after natural cooling
Obtain final product.
Priority Applications (1)
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CN201610930066.XA CN106449161A (en) | 2016-10-31 | 2016-10-31 | Electrostatic spinning supercapacitor membrane material for in-situ production of nanometer titanium dioxide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CN201610930066.XA CN106449161A (en) | 2016-10-31 | 2016-10-31 | Electrostatic spinning supercapacitor membrane material for in-situ production of nanometer titanium dioxide |
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CN106449161A true CN106449161A (en) | 2017-02-22 |
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CN201610930066.XA Pending CN106449161A (en) | 2016-10-31 | 2016-10-31 | Electrostatic spinning supercapacitor membrane material for in-situ production of nanometer titanium dioxide |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102516477A (en) * | 2011-11-23 | 2012-06-27 | 华南理工大学 | Nano titanium dioxide/ acrylate composite emulsion and preparation method thereof |
CN104409673A (en) * | 2014-11-06 | 2015-03-11 | 湘潭大学 | Method for repairing and modifying perforated lithium ion battery diaphragm |
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 |
-
2016
- 2016-10-31 CN CN201610930066.XA patent/CN106449161A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102516477A (en) * | 2011-11-23 | 2012-06-27 | 华南理工大学 | Nano titanium dioxide/ acrylate composite emulsion and preparation method thereof |
CN104409673A (en) * | 2014-11-06 | 2015-03-11 | 湘潭大学 | Method for repairing and modifying perforated lithium ion battery diaphragm |
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 |
Non-Patent Citations (1)
Title |
---|
胥会: "静电纺丝制备勃姆石改性 PVDF/PMMA锂电池隔膜的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Application publication date: 20170222 |