CN105990039A - Wear-resistant flexible composite separator material used for supercapacitor - Google Patents
Wear-resistant flexible composite separator material used for supercapacitor Download PDFInfo
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- CN105990039A CN105990039A CN201610055339.0A CN201610055339A CN105990039A CN 105990039 A CN105990039 A CN 105990039A CN 201610055339 A CN201610055339 A CN 201610055339A CN 105990039 A CN105990039 A CN 105990039A
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- 239000000463 material Substances 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 20
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000010439 graphite Substances 0.000 claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000839 emulsion Substances 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000004744 fabric Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002121 nanofiber Substances 0.000 claims description 8
- 238000009941 weaving Methods 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- -1 polypropylene Polymers 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000005098 hot rolling Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000009987 spinning Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000002560 therapeutic procedure Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000004745 nonwoven fabric Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000006240 Fast Extruding Furnace Substances 0.000 abstract 2
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract 2
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract 2
- 239000004114 Ammonium polyphosphate Substances 0.000 abstract 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 abstract 1
- 229920001276 ammonium polyphosphate Polymers 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 7
- 238000002955 isolation Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- 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
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/43—Acrylonitrile series
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/14—Polyalkenes, e.g. polystyrene polyethylene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/16—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
- D21H15/10—Composite fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/07—Nitrogen-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/35—Polyalkenes, e.g. polystyrene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Nonwoven Fabrics (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses wear-resistant flexible composite separator material used for a supercapacitor. The wear-resistant flexible composite separator material is prepared by the raw material of the following parts by weight: 35-40 parts of polyvinyl alcohol fiber, 33-35 parts of mekralon, 10-13 parts of polyacrylonitrile powder, 30-32 parts of acetone, 72-75 parts of N,N-dimethyl formamide, 8-10 parts of water soluble PVA fiber of 70 DEG C, 2-3 parts of polymethyl methacrylate, 9-11 parts of graphite oxide, 4-5 parts of fast extruding furnace black, 3-4 parts of ptfe emulsion and 2-2.5 parts of ammonium polyphosphate. Graphite oxide, fast extruding furnace black, ptfe emulsion and other components are added in the preparation process of the basic nonwoven fabric through a series of technology processing and uniformly dispersed so that flexibility and wear resistance of the product can be enhanced, strength and toughness of the separator material can be enhanced and the prepared supercapacitor has high specific capacitance.
Description
Technical field
The present invention relates to capacitor diaphragm technical field, particularly relate to a kind of wear-resisting pliable and tough composite diaphragm material of ultracapacitor.
Background technology
Ultracapacitor is the accumulator of a kind of great market competitiveness, owing to it can realize quick charge, heavy-current discharge, and has the charge lifetimes of more than 100,000 times, needs to occupy critical role in the application of high-multiplying power discharge in short-term at some.The extensive of this Novel energy storage apparatus of ultracapacitor is paid attention in also result in worldwide by hybrid vehicle and the requirement to electrical source of power for the electric automobile.In the composition of ultracapacitor, electrode, electrolyte and the diaphragm paper performance on ultracapacitor plays conclusive impact.The electrode of current ultracapacitor and electrolyte are the focuses of research, but people are not high for research and the attention rate of barrier film.
The diaphragm paper of ultracapacitor is positioned between two porous carbon electrodes, and complete wetting is in the electrolytic solution together with electrode, plays the effect of isolation during repeated charge, stops electronics conduction, prevents from contacting the internal short-circuit causing between the two poles of the earth.This requires the insulator that diaphragm material is electronics, has good isolation performance, and its hole should be as far as possible less than the minimum grain size of electrode active surface material.The necessary aperture of the preferable diaphragm paper of isolation performance is little, the circulation of electrolyte so can be made to decline, battery charging and discharging hydraulic performance decline；And electrolyte to be impregnated with rate higher, ion is more more by the good diaphragm material often hole of property, easily causes and contacts the internal short-circuit causing between the two poles of the earth.The maximum advantage of ultracapacitor be charge/discharge rates fast, can be with high power discharge, therefore, diaphragm material will thinner towards thickness, porosity is higher, aperture is less and the contour performance trend development that is more evenly distributed.
The material being currently used for diaphragm of supercapacitor mainly has cellulosic separator paper and conventional batteries barrier film, and High-performance diaphragm paper manufactures technical difficulty, and price is high；Conventional batteries membrane thicknesses is thicker, and porosity is low, and to electrolyte compatibility difference, and electrostatic spinning nano fiber film manufacturing technology is simple, low cost, and barrier film porosity is up to 90%, good to electrolyte compatibility, but a disadvantage is that intensity is not high.If cellulosic separator paper can be combined with electrospun fibers film, learning from other's strong points to offset one's weaknesses, low cost, the composite diaphragm material that porosity is high, intensity is big can be obtained.
Content of the invention
The object of the invention is contemplated to make up the defect of prior art, provides a kind of ultracapacitor wear-resisting pliable and tough composite diaphragm material.
The present invention is achieved by the following technical solutions:
A kind of ultracapacitor is with wear-resisting pliable and tough composite diaphragm material, it is prepared by the raw materials in: vinal 35-40, polypropylene fibre 33-35, polyacrylonitrile powder 10-13, acetone 30-32, DMF 72-75,70 DEG C of water-soluble PVA fiber 8-10, polymethyl methacrylate 2-3, graphite oxide 9-11, fast extrusion carbon black 4-5, ptfe emulsion 3-4, APP 2-2.5.
According to claims 1, a kind of ultracapacitor is with wear-resisting pliable and tough composite diaphragm material, is prepared from by following concrete grammar:
(1) by acetone and N, dinethylformamide mixes at normal temperatures, add polyacrylonitrile powder, stir 3 hours with the speed of 100 revs/min at normal temperatures, form polyacrylonitrile spinning solution, receiving range be 20cm, voltage be that 25kV, feed flow speed carry out electrostatic spinning 2 hours under conditions of being 1mL/h, spin out the polyacrylonitrile nanofiber film that thickness is 10 μm stand-by；
(2) polypropylene fibre is mixed with vinal, add appropriate water, put in beater, carry out being dispersed into fibrous suspension by 2% concentration, add 70 DEG C of water-soluble PVA fibers, be heated to 70 DEG C while stirring with the speed of 1000 revs/min, until 70 DEG C of water-soluble PVA fibers to be completely dissolved formation mixing suspension stand-by；
(3) graphite oxide washing clean post-drying with water, being subsequently adding in the water of 3 times amount, the speed stirring with 300 revs/min forms suspension, centrifugal after continuing ultrasonic 60 minutes, takes supernatant rotary evaporation, obtains graphite oxide slurry；Cross 400 mesh sieves by extruding carbon black soon, mix with ptfe emulsion, put into ball milling 40 minutes in ball mill, then mix with above-mentioned graphite oxide slurry, send into granulation in comminutor, pulverize after cooling, cross 800 mesh sieves, obtain reinforcer；
(4) mixing suspension that will obtain in step (2) adds step (3) reinforcer that obtains and remaining residual components, continuously add appropriate water, stir 30 minutes with the speed of 600 revs/min, form the slurry that online concentration is 0.1wt%, use wet therapy forming process that above-mentioned slurry is sent into paper machine through wet end and press section drainage and formation, then electricity consumption hot blast is dried 10 minutes, then it is stand-by to use hot forming machine to obtain non-weaving cloth base fabric with the temperature heat pressure adhesive of 135 DEG C；
(5) the polyacrylonitrile nanofiber film obtaining step (1) covers on the non-weaving cloth base fabric that step (4) obtains, and carries out hot binding by the hot-rollings of 135 DEG C, shears, is packaged to be the present invention after cooling.
The invention have the advantage that first polyacrylonitrile is carried out electrostatic spinning and make polyacrylonitrile nanofiber film by the present invention, then vinal is utilized to mix with polypropylene fibre, wet nonwoven fabrics technique is used to make non-weaving cloth, both are well bonded together by way of hot pressing, intensity height, the performance of good permeability can be obtained, and preferably control aperture and the distribution of diaphragm material, aperture less is more evenly distributed, porosity high, it is thus possible to be preferably impregnated with electrolyte so that discharge current is evenly；70 DEG C of water-soluble PVA fibers of interpolation are as reinforcing agent simultaneously, and the composite diaphragm material made also has preferable tensile strength, chemical stability, and fluidity and isolation performance are protected in imbibition.
Graphite oxide, soon the extrusion composition such as carbon black, ptfe emulsion are added in the preparation process of non-weaving cloth base fabric by a series of PROCESS FOR TREATMENT by the present invention, it is uniformly dispersed, enhance pliability and the wearability of product, can improve intensity and the toughness of diaphragm material, the ultracapacitor made is higher than electric capacity.
Detailed description of the invention
A kind of ultracapacitor is with wear-resisting pliable and tough composite diaphragm material, it is made up of the raw material of following weight portion (kilogram): vinal the 35th, polypropylene fibre the 33rd, polyacrylonitrile powder the 10th, acetone the 30th, DMF the 72nd, 70 DEG C of water-soluble PVA fiber the 8th, polymethyl methacrylate the 2nd, graphite oxide the 9th, fast extrusion carbon black the 4th, ptfe emulsion the 3rd, APP 2.
According to claims 1, a kind of ultracapacitor is with wear-resisting pliable and tough composite diaphragm material, is prepared from by following concrete grammar:
(1) by acetone and N, N-dimethylformamide mixes at normal temperatures, add polyacrylonitrile powder, stir 3 hours with the speed of 100 revs/min at normal temperatures, form polyacrylonitrile spinning solution, receiving range be 20cm, voltage be that 25kV, feed flow speed carry out electrostatic spinning 2 hours under conditions of being 1mL/h, spin out the polyacrylonitrile nanofiber film that thickness is 10 μm stand-by；
(2) polypropylene fibre is mixed with vinal, add appropriate water, put in beater, carry out being dispersed into fibrous suspension by 2% concentration, add 70 DEG C of water-soluble PVA fibers, be heated to 70 DEG C while stirring with the speed of 1000 revs/min, until 70 DEG C of water-soluble PVA fibers to be completely dissolved formation mixing suspension stand-by；
(3) graphite oxide washing clean post-drying with water, being subsequently adding in the water of 3 times amount, the speed stirring with 300 revs/min forms suspension, centrifugal after continuing ultrasonic 60 minutes, takes supernatant rotary evaporation, obtains graphite oxide slurry；Cross 400 mesh sieves by extruding carbon black soon, mix with ptfe emulsion, put into ball milling 40 minutes in ball mill, then mix with above-mentioned graphite oxide slurry, send into granulation in comminutor, pulverize after cooling, cross 800 mesh sieves, obtain reinforcer；
(4) mixing suspension that will obtain in step (2) adds step (3) reinforcer that obtains and remaining residual components, continuously add appropriate water, stir 30 minutes with the speed of 600 revs/min, form the slurry that online concentration is 0.1wt%, use wet therapy forming process that above-mentioned slurry is sent into paper machine through wet end and press section drainage and formation, then electricity consumption hot blast is dried 10 minutes, then it is stand-by to use hot forming machine to obtain non-weaving cloth base fabric with the temperature heat pressure adhesive of 135 DEG C；
(5) the polyacrylonitrile nanofiber film obtaining step (1) covers on the non-weaving cloth base fabric that step (4) obtains, and carries out hot binding by the hot-rollings of 135 DEG C, shears, is packaged to be the present invention after cooling.
By testing the present embodiment diaphragm material, thickness is 70 μm, and average pore size is 0.24 μm, and porosity is 63%, and pick up is 603%, and 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 ultracapacitor is with wear-resisting pliable and tough composite diaphragm material, it is characterized in that, it is prepared by the raw materials in: vinal 35-40, polypropylene fibre 33-35, polyacrylonitrile powder 10-13, acetone 30-32, DMF 72-75,70 DEG C of water-soluble PVA fiber 8-10, polymethyl methacrylate 2-3, graphite oxide 9-11, fast extrusion carbon black 4-5, ptfe emulsion 3-4, APP 2-2.5.
2. according to claims 1 a kind of ultracapacitor with wear-resisting pliable and tough composite diaphragm material, it is characterised in that be prepared from by following concrete grammar:
(1) by acetone and N, dinethylformamide mixes at normal temperatures, add polyacrylonitrile powder, stir 3 hours with the speed of 100 revs/min at normal temperatures, form polyacrylonitrile spinning solution, receiving range be 20cm, voltage be that 25kV, feed flow speed carry out electrostatic spinning 2 hours under conditions of being 1mL/h, spin out the polyacrylonitrile nanofiber film that thickness is 10 μm stand-by；
(2) polypropylene fibre is mixed with vinal, add appropriate water, put in beater, carry out being dispersed into fibrous suspension by 2% concentration, add 70 DEG C of water-soluble PVA fibers, be heated to 70 DEG C while stirring with the speed of 1000 revs/min, until 70 DEG C of water-soluble PVA fibers to be completely dissolved formation mixing suspension stand-by；
(3) graphite oxide washing clean post-drying with water, being subsequently adding in the water of 3 times amount, the speed stirring with 300 revs/min forms suspension, centrifugal after continuing ultrasonic 60 minutes, takes supernatant rotary evaporation, obtains graphite oxide slurry；Cross 400 mesh sieves by extruding carbon black soon, mix with ptfe emulsion, put into ball milling 40 minutes in ball mill, then mix with above-mentioned graphite oxide slurry, send into granulation in comminutor, pulverize after cooling, cross 800 mesh sieves, obtain reinforcer；
(4) mixing suspension that will obtain in step (2) adds step (3) reinforcer that obtains and remaining residual components, continuously add appropriate water, stir 30 minutes with the speed of 600 revs/min, form the slurry that online concentration is 0.1wt%, use wet therapy forming process that above-mentioned slurry is sent into paper machine through wet end and press section drainage and formation, then electricity consumption hot blast is dried 10 minutes, then it is stand-by to use hot forming machine to obtain non-weaving cloth base fabric with the temperature heat pressure adhesive of 135 DEG C；
(5) the polyacrylonitrile nanofiber film obtaining step (1) covers on the non-weaving cloth base fabric that step (4) obtains, and carries out hot binding by the hot-rollings of 135 DEG C, shears, is packaged to be the present invention after cooling.
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