CN106128793A - The hybrid supercapacitor diaphragm material that a kind of isolation performance is good - Google Patents

Abstract

The invention discloses the hybrid supercapacitor diaphragm material that a kind of isolation performance is good, it is prepared by the raw materials in: vinal 35 40, polypropylene fibre 33 35, polyacrylonitrile powder 10 13, acetone 30 32, N, N dimethylformamide 72 75,70 DEG C of water-soluble PVA fibers 8 10, cationic starch 45, glass cotton 45, liquid paraffin 23, polydimethylsiloxane 1.5 2, potter's clay 9 11, Palmic acid 23, polyester powders 34.The composition such as glass cotton, potter's clay is also added in the preparation of product by the present invention by a series of modification, good permeability, improve the mechanical strength of product, and improve its heat-resisting ability, make super capacitor material the most also can keep good isolation, extend the service life of ultracapacitor.

Description

The hybrid supercapacitor diaphragm material that a kind of isolation performance is good

Technical field

The present invention relates to capacitor diaphragm technical field, particularly relate to the hybrid supercapacitor that a kind of isolation performance is good Diaphragm material.

Background technology

Ultracapacitor is the accumulator of a kind of great market competitiveness, owing to it can realize quick charge, big electric current Electric discharge, and there is the charge lifetimes of more than 100,000 times, in some need the application of high-multiplying power discharge in short-term, occupy critical role. Hybrid vehicle and electric automobile also result in the requirement of electrical source of power in worldwide that this is new to ultracapacitor The extensive attention of type energy storage device.In the composition of ultracapacitor, electrode, electrolyte and the diaphragm paper property to ultracapacitor Conclusive impact can be played.Electrode and the electrolyte of ultracapacitor is the focus studied at present, but people are for barrier film Research and attention rate the highest.

The diaphragm paper of ultracapacitor is between two porous carbon electrodes, and complete wetting is at electrolyte together with electrode In, during repeated charge, play the effect of isolation, stop electronics conduction, prevent between the two poles of the earth, contacting the inside caused short Road.This just requires that diaphragm material is the insulator of electronics, has good isolation performance, and its hole should be as far as possible less than electricity 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 to be impregnated with rate higher, ion is by the good diaphragm material often hole of property relatively The most more, easily cause and between the two poles of the earth, contact the internal short-circuit caused.The advantage of ultracapacitor maximum is charge/discharge rates Hurry up, can be 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 material being currently used for diaphragm of supercapacitor mainly has cellulosic separator paper and conventional batteries barrier film, high-performance every Film paper manufactures technical difficulty, and price is high；Conventional batteries membrane thicknesses is thicker, and porosity is low, poor to electrolyte affinity, and quiet Electro spinning nanometer fiber membrane manufacturing technology is simple, low cost, and barrier film porosity is up to 90%, good to electrolyte affinity, but lacks Point is that intensity is the highest.If cellulosic separator paper can be combined with electrospun fibers film, learning from other's strong points to offset one's weaknesses, can be become The composite diaphragm material that this is low, porosity is high, intensity is big.

Summary of the invention

The object of the invention is contemplated to make up the defect of prior art, it is provided that the compound super electricity that a kind of isolation performance is good Container diaphragm material.

The present invention is achieved by the following technical solutions:

The hybrid supercapacitor diaphragm material that a kind of isolation performance is good, is prepared by the raw materials in: polyvinyl alcohol Fiber 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, cationic starch 4-5, glass cotton 4-5, liquid paraffin 2-3, polydimethylsiloxane 1.5-2, Potter's clay 9-11, Palmic acid 2-3, polyester powder 3-4.

According to the hybrid supercapacitor diaphragm material that a kind of isolation performance described in claims 1 is good, by following tool Body method is prepared from:

(1) acetone is mixed homogeneously at normal temperatures with DMF, add polyacrylonitrile powder, with 100 revs/min Speed stirs 3 hours at normal temperatures, formed polyacrylonitrile spinning solution, receiving range be 20cm, voltage be 25kV, feed flow speed Rate is to carry out electrostatic spinning 2 hours under conditions of 1mL/h, spins 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 by 2% concentration It is dispersed into fibrous suspension, adds 70 DEG C of water-soluble PVA fibers, be heated to 70 DEG C while stirring with the speed of 1000 revs/min, until It is stand-by that 70 DEG C of water-soluble PVA fibers are completely dissolved formation mixing suspension；

(3) glass cotton is pulverized, cross 200 mesh sieves, mix in polydimethylsiloxane, put into ball milling in ball mill and add after 40 minutes Enter potter's clay, continue ball milling 1 hour, pour out rear direct sintering, roasting 2 hours under conditions of 650 DEG C, take out stand-by after cooling； To add the water of 10 times amount in polyester powder, stirring, to being uniformly dispersed, is subsequently adding the product after above-mentioned sintering, with 300 revs/min Speed stir and be spray-dried after 50 minutes, obtain reinforcer；

(4) mixing suspension that will obtain in step (2) adds reinforcer, the polyacrylamide emulsion that step (3) obtains And remaining residual components, continuously add appropriate water, stir 30 minutes with the speed of 600 revs/min, forming online concentration is The slurry of 0.1wt%, uses wet therapy forming process by above-mentioned slurry feeding paper machine through wet end and press section drainage and formation, then Electricity consumption hot blast is dried 10 minutes, then uses hot forming machine to obtain non-weaving cloth base fabric with the temperature heat pressure adhesive of 135 DEG C to treat With；

(5) polyacrylonitrile nanofiber film step (1) obtained covers on the non-weaving cloth base fabric that step (4) obtains, Carry out hot binding by the hot-rollings of 135 DEG C, shear after cooling, be packaged to be the present invention.

The invention have the advantage that first polyacrylonitrile is carried out electrostatic spinning and make polyacrylonitrile nanofiber by the present invention Film, then utilizes vinal to mix with polypropylene fibre, uses wet nonwoven fabrics technique to make non-weaving cloth, incite somebody to action both Well it is bonded together by the way of hot pressing, intensity height, the performance of good permeability can be obtained, and preferably control The aperture of diaphragm material and distribution so that aperture is less to be more evenly distributed, porosity is high such that it is able to be preferably impregnated with electrolysis Liquid 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 is also Having preferable tensile strength, chemical stability, fluidity and isolation performance are protected in imbibition.

The composition such as glass cotton, potter's clay is also added in the preparation of product by the present invention by a series of modification, breathability Good, improve the mechanical strength of product, and improve its heat-resisting ability so that super capacitor material the most also can be protected Hold good isolation, extend the service life of ultracapacitor.

Detailed description of the invention

The hybrid supercapacitor diaphragm material that a kind of isolation performance is good, by the raw material system of following weight portion (kilogram) Become: vinal 35, polypropylene fibre 33, polyacrylonitrile powder 10, acetone 30,72,70 DEG C of water of DMF Molten PVA fiber 8, cationic starch 4, glass cotton 4, liquid paraffin 2, polydimethylsiloxane 1.5, potter's clay 9, Palmic acid 2, polyester Rubber powder 3.

According to the hybrid supercapacitor diaphragm material that a kind of isolation performance described in claims 1 is good, by following tool Body method is prepared from:

(1) acetone is mixed homogeneously at normal temperatures with DMF, add polyacrylonitrile powder, with 100 revs/min Speed stirs 3 hours at normal temperatures, formed polyacrylonitrile spinning solution, receiving range be 20cm, voltage be 25kV, feed flow speed Rate is to carry out electrostatic spinning 2 hours under conditions of 1mL/h, spins 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 by 2% concentration It is dispersed into fibrous suspension, adds 70 DEG C of water-soluble PVA fibers, be heated to 70 DEG C while stirring with the speed of 1000 revs/min, until It is stand-by that 70 DEG C of water-soluble PVA fibers are completely dissolved formation mixing suspension；

(3) glass cotton is pulverized, cross 200 mesh sieves, mix in polydimethylsiloxane, put into ball milling in ball mill and add after 40 minutes Enter potter's clay, continue ball milling 1 hour, pour out rear direct sintering, roasting 2 hours under conditions of 650 DEG C, take out stand-by after cooling； To add the water of 10 times amount in polyester powder, stirring, to being uniformly dispersed, is subsequently adding the product after above-mentioned sintering, with 300 revs/min Speed stir and be spray-dried after 50 minutes, obtain reinforcer；

(4) mixing suspension that will obtain in step (2) adds reinforcer, the polyacrylamide emulsion that step (3) obtains And remaining residual components, continuously add appropriate water, stir 30 minutes with the speed of 600 revs/min, forming online concentration is The slurry of 0.1wt%, uses wet therapy forming process by above-mentioned slurry feeding paper machine through wet end and press section drainage and formation, then Electricity consumption hot blast is dried 10 minutes, then uses hot forming machine to obtain non-weaving cloth base fabric with the temperature heat pressure adhesive of 135 DEG C to treat With；

(5) polyacrylonitrile nanofiber film step (1) obtained covers on the non-weaving cloth base fabric that step (4) obtains, Carry out hot binding by the hot-rollings of 135 DEG C, shear after cooling, be packaged to be the present invention.

By testing the present embodiment diaphragm material, thickness is 78 μm, and average pore size is 0.27 μm, and porosity is 66%, pick up is 598%, 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. the hybrid supercapacitor diaphragm material that an isolation performance is good, it is characterised in that by the raw material of following weight portion Make: vinal 35-40, polypropylene fibre 33-35, polyacrylonitrile powder 10-13, acetone 30-32, N, N-dimethyl Methanamide 72-75,70 DEG C of water-soluble PVA fiber 8-10, cationic starch 4-5, glass cotton 4-5, liquid paraffin 2-3, poly dimethyls Siloxanes 1.5-2, potter's clay 9-11, Palmic acid 2-3, polyester powder 3-4.

2. according to the hybrid supercapacitor diaphragm material that a kind of isolation performance described in claims 1 is good, it is characterised in that It is prepared from by following concrete grammar:

(1) acetone is mixed homogeneously at normal temperatures with DMF, add polyacrylonitrile powder, with 100 revs/min Speed stirs 3 hours at normal temperatures, formed polyacrylonitrile spinning solution, receiving range be 20cm, voltage be 25kV, feed flow speed Rate is to carry out electrostatic spinning 2 hours under conditions of 1mL/h, spins 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 by 2% concentration It is dispersed into fibrous suspension, adds 70 DEG C of water-soluble PVA fibers, be heated to 70 DEG C while stirring with the speed of 1000 revs/min, until It is stand-by that 70 DEG C of water-soluble PVA fibers are completely dissolved formation mixing suspension；

(3) glass cotton is pulverized, cross 200 mesh sieves, mix in polydimethylsiloxane, put into ball milling in ball mill and add after 40 minutes Enter potter's clay, continue ball milling 1 hour, pour out rear direct sintering, roasting 2 hours under conditions of 650 DEG C, take out stand-by after cooling； To add the water of 10 times amount in polyester powder, stirring, to being uniformly dispersed, is subsequently adding the product after above-mentioned sintering, with 300 revs/min Speed stir and be spray-dried after 50 minutes, obtain reinforcer；

(4) mixing suspension that will obtain in step (2) adds reinforcer, the polyacrylamide emulsion that step (3) obtains And remaining residual components, continuously add appropriate water, stir 30 minutes with the speed of 600 revs/min, forming online concentration is The slurry of 0.1wt%, uses wet therapy forming process by above-mentioned slurry feeding paper machine through wet end and press section drainage and formation, then Electricity consumption hot blast is dried 10 minutes, then uses hot forming machine to obtain non-weaving cloth base fabric with the temperature heat pressure adhesive of 135 DEG C to treat With；

(5) polyacrylonitrile nanofiber film step (1) obtained covers on the non-weaving cloth base fabric that step (4) obtains, Carry out hot binding by the hot-rollings of 135 DEG C, shear after cooling, be packaged to be the present invention.