CN103579554A - Electrochemical power-supply composite membrane and preparation method thereof - Google Patents
Electrochemical power-supply composite membrane and preparation method thereof Download PDFInfo
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- CN103579554A CN103579554A CN201210257647.3A CN201210257647A CN103579554A CN 103579554 A CN103579554 A CN 103579554A CN 201210257647 A CN201210257647 A CN 201210257647A CN 103579554 A CN103579554 A CN 103579554A
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- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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Abstract
The invention provides an electrochemical power-supply composite membrane and a preparation method thereof. The electrochemical power-supply composite membrane comprises a non-woven fabrics membrane layer and an organic-inorganic composite layer combining with the surface of the non-woven fabrics membrane layer; the organic-inorganic composite layer comprises an organic binder, a hollow inorganic powder, inorganic nanometer fiber and an organic solvent formula component, wherein the organic binder accounts for 1%-50% by mass of the sum of the organic binder and the organic solvent; the hollow inorganic powder and the inorganic nanometer fiber respectively accounts for 0.5%-25% by mass of the sum of the organic binder the hollow inorganic powder, the inorganic nanometer fiber and the organic solvent; the sum of the hollow inorganic powder and the inorganic nanometer fiber accounts for 25.5%-50% by mass of the sum of the organic binder, the hollow inorganic powder, the inorganic nanometer fiber and the organic solvent. The composite membrane is high in membrane rupture temperature and strength, light in weight and high in safety. The preparation method of the composite membrane is simple in technology and high in production efficiency, and is suitable for industrial production.
Description
Technical field
The invention belongs to electrochemical power source technical field, be specifically related to a kind of electrochemical power source composite diaphragm and preparation method thereof.
Background technology
Along with the development of human being's production power, increasing running car is in city, streets and lanes, rural.The life of popularizing to people of automobile brings great convenience.Yet incident problem is also more and more serious.The consumption of the non-renewable energy resources such as oil is constantly accelerated, and the impact that the discharge of vehicle exhaust causes to environment also constantly expands.At present, people are in order to address these problems proposition Development of EV, to replacing orthodox car.And whether key is to have energy density, power density enough large, cycle life long enough, safe and reliable electrokinetic cell replace internal combustion engine.Wherein, the fail safe of power supply is the most important thing.For electrochemical power source (power supply lithium ion battery and ultracapacitor), thereby important potential safety hazard is exactly to put or short circuit causes the temperature of power supply inside sharply to raise causing burning or blast because overcharge or cross.If power supply itself has good thermal conductivity, can fast heat be distributed, just can effectively reduce this potential safety hazard.
At present, the barrier film generally adopting as lithium ion battery at electrochemical power source is porous polyolefin barrier film.Because porous polyolefin barrier film is polymer, its thermal conductivity is very poor, the heat producing can not be derived in time in charge and discharge process, can cause temperature in power supply sharply to raise.Again because porous polyolefin barrier film is polymer, itself poor heat resistance, when temperature approaches barrier film fusing point (130 ℃, polyethylene barrier film, 160 ℃ of polypropylene diaphragms), this barrier film will shrink even and break, thereby make power supply inside likely occur positive and negative between directly contact and short circuit, cause battery security hidden danger, as phenomenons such as burning, blasts.
Current, what for this porous polyolefin barrier film, exist has carried out some explorations and research as the deficiency of above-mentioned thermal conductivity, poor heat resistance, and has obtained certain achievement, as in porous polyolefin membrane surface compliant coat.But such coating is owing to having increased the weight of porous polyolefin barrier film, cause the energy density of power supply to reduce, reduce the specific energy of power supply, thereby limited the application of this power supply.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, provide a kind of broken film temperature and intensity high, lightweight electrochemical power source composite diaphragm.
Another object of the present invention is to provide the electrochemical power source composite diaphragm that a kind of technique is simple, cost is low preparation method.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A composite diaphragm, comprises nonwoven fabrics membrane layer and the organic and inorganic composite bed that is combined in described nonwoven fabrics membrane layer surface; Described organic and inorganic composite bed comprises organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent recipe ingredient; Wherein, the quality of described organic binder accounts for 1%～50% of described organic binder and organic solvent gross mass, the quality of described Hollow Inorganic powder, inorganic nano-fiber accounts for respectively described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 0.5%～25%, and the quality sum of described Hollow Inorganic powder and inorganic nano-fiber accounts for described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 25.5%～50%.
And a kind of preparation method of electrochemical power source composite diaphragm, comprises the steps:
Organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent component are mixed, be mixed with organic and inorganic suspension; Wherein, the quality of described organic binder accounts for 1%～50% of described organic binder and organic solvent gross mass, the quality of described Hollow Inorganic powder, inorganic nano-fiber accounts for respectively described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 0.5%～25%, and the quality sum of described Hollow Inorganic powder and inorganic nano-fiber accounts for described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 25.5%～50%;
Described organic and inorganic suspension is coated in to nonwoven fabrics membrane surface, and dry under the condition of anaerobic, obtain described electrochemical power source composite diaphragm.
It is matrix that above-mentioned electrochemical power source composite diaphragm adopts nonwoven fabrics membrane layer, has effectively strengthened intensity, the flexibility of this electrochemical power source composite diaphragm, has improved its thermal endurance, has effectively prevented the phenomenon generation that it shrinks because being heated or breaks.In organic and inorganic composite bed, contain the Hollow Inorganic powder with excellent heat conducting performance, the heat that power supply can be produced in charge and discharge process derives fast in time, thereby improved the heat conductivility of electrochemical power source composite diaphragm, keep power supply temperature constant in the course of the work, thereby effectively avoided existing barrier film because even broken by thermal contraction, cause power supply inside likely occur positive and negative between directly contact and short circuit causes the generation of battery security hidden danger.In addition, the inorganic particle containing due to organic and inorganic composite bed is hollow, has effectively reduced the weight of this electrochemical power source composite diaphragm, thereby effectively raises the energy density of electrochemical power source.The inorganic nano-fiber that organic and inorganic composite bed contains can effectively improve the mechanical strength of this electrochemical power source composite diaphragm.Therefore, at electrochemical power source composite diaphragm of the present invention, adopt organic and inorganic composite bed to be combined with nonwoven fabrics membrane layer, can make organic and inorganic composite bed to combine closely with nonwoven fabrics membrane layer, strengthened broken film temperature, heat dispersion and the intensity of electrochemical power source composite diaphragm and reduced its weight, its height electrochemical power source composite diaphragm fail safe and extended its useful life, thereby improved electrochemical power source security performance and extended its service life cycle and improved electrochemical power source energy density.
It is matrix surface that above-mentioned electrochemical power source composite diaphragm preparation method is directly coated in nonwoven fabrics membrane layer by organic and inorganic composite bed slurry, and dry, technique is simple, condition is easily controlled, low for equipment requirements, production efficiency, production cost is low, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is a kind of structural representation of embodiment of the present invention electrochemical power source composite diaphragm;
Fig. 2 is embodiment of the present invention electrochemical power source composite diaphragm preparation method's process chart.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Example of the present invention provides a kind of broken film temperature and high, the lightweight electrochemical power source composite diaphragm of intensity, and its structure as shown in Figure 1.In Fig. 1, this electrochemical power source composite diaphragm comprises nonwoven fabrics membrane layer 1 and is combined in the two-sided organic and inorganic composite bed 2 of nonwoven fabrics membrane layer 1.This organic and inorganic composite bed 2 comprises organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent recipe ingredient; Wherein, the quality of described organic binder accounts for 1%～50% of described organic binder and organic solvent gross mass, the quality of described Hollow Inorganic powder, inorganic nano-fiber accounts for respectively described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 0.5%～25%, and the quality sum of described Hollow Inorganic powder and inorganic nano-fiber accounts for described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 25.5%～50%.
In addition, inventor finds under study for action, and the thickness of the organic and inorganic composite bed 2 in this embodiment has significant impact to the thermal diffusivity of electrochemical power source composite diaphragm.When its thickness is too low, can cause the thermal conductivity of this composite diaphragm to decline and broken film temperature reduction, the heat producing in power work can better not derived, although the relatively existing barrier film of this electrochemical power source composite diaphragm is compared, there is good rate of heat dissipation and relatively high broken film temperature, all can not reach optimum state.If these organic and inorganic composite bed 2 thickness are excessive, although this composite diaphragm thermal conductivity is excellent and broken film temperature raises, but can increase electric charge as the prolongation of lithium ion bang path in composite diaphragm, thereby affect the performance that charges and discharge of power supply, also can reduce the energy density of electrochemical power source simultaneously.Therefore in a preferred embodiment, the thickness of this organic and inorganic composite bed 2 is 5～45 microns, more elects 5～10 microns as.This preferred thickness effectively excellent and broken film temperature and power supply of the thermal conductivity of this composite diaphragm of balance charge and discharge performance, make this electrochemical power source fail safe and charge and discharge performance better.The thickness of this electrochemical power source barrier film is preferably 10～50 microns.
Particularly, above-mentioned nonwoven fabrics membrane layer 1 is preferably PET nonwoven fabrics membrane layer or PAN nonwoven fabrics membrane layer, and its thickness is preferably 5～50 microns.This preferred nonwoven fabrics membrane layer 1 has higher intensity, flexibility and thermal endurance.
In the recipe ingredient of above-mentioned organic and inorganic composite bed 2, organic binder is preferably at least one in polyvinyl alcohol, polytetrafluoroethylene, Kynoar (PVDF), modified styrene butadiene rubber (SBR), Viton, polyurethane.This organic binder can be dispersed in the inorganic particle component in this recipe ingredient in organic solvent, and Hollow Inorganic powder and inorganic nano-fiber are firmly bonded in to the surface of nonwoven fabrics membrane layer 1, to improve the bond strength of organic and inorganic composite bed 2 and nonwoven fabrics membrane layer 1, strengthened the mechanical strength of electrochemical power source composite diaphragm, prevent coming off of organic and inorganic composite bed 2, extend the useful life of electrochemical power source composite diaphragm, thereby extended electrochemical power source security performance and service life cycle.
It is ether, pentane, carrene, carbon disulfide, acetone, chloroform, methyl alcohol, hexane, three fluoro acetic acid, 1,1 that above-mentioned organic solvent is preferably organic solvent, at least one in 1-trichloroethanes, carbon tetrachloride.This preferred organic solvent can effectively dissolve above-mentioned organic binder component.
Hollow Inorganic powder in above-mentioned recipe ingredient is preferably at least one in the hollow alumina that average grain diameter is 3～1000nm, hollow silica, hollow aluminium nitride.This preferred Hollow Inorganic powder has excellent heat conductivility, and this Hollow Inorganic powder forms skeleton in organic and inorganic composite bed 2, thereby make embodiment of the present invention electrochemical power source composite diaphragm there is excellent heat dispersion, can also improve the broken film temperature of nonwoven fabrics barrier film, improve the security performance of chemical power source barrier film.Because inorganic particle is hollow, can reduce significantly the weight of electrochemical power source composite diaphragm so again, thereby improve electrochemical power source energy density.In addition, inventor is also discovery under study for action, and the particle diameter of this Hollow Inorganic powder of suitable change, can affect this composite diaphragm pore.The Hollow Inorganic powder of this preferable particle size scope has higher specific surface and good absorption property, this higher specific surface energy effectively improves the pore of this composite diaphragm pore, be conducive to the transmission of electric charge, then with this, strengthened this composite diaphragm conductivity in conjunction with its good absorption property.
It is that 0.1～1 μ m, diameter are glass fibre and the ceramic fibre of 3～100nm that above-mentioned inorganic nano-fiber is preferably fibre length.The inorganic nano-fiber of this preferred thickness and kind is combined in nonwoven fabrics membrane layer 1 surface under the effect of binding agent, to reach the mechanical strength of further enhancing electrochemical power source composite diaphragm.
Certainly, should be appreciated that, in above-described embodiment the two-sided combination of nonwoven fabrics membrane layer 1 organic-inorganic compounding layer 2, at nonwoven fabrics membrane layer 1 wherein within the scope of one side in conjunction with organic-inorganic compounding layer 2 also and protection open in the present invention.
From the above mentioned, it is matrix that above-mentioned electrochemical power source composite diaphragm adopts nonwoven fabrics membrane layer 1, has effectively strengthened intensity, the flexibility of this electrochemical power source composite diaphragm, has improved its thermal endurance, has effectively prevented the phenomenon generation that it shrinks because being heated or breaks.In organic and inorganic composite bed 2, contain the Hollow Inorganic powder with excellent heat conducting performance, the heat that power supply can be produced in charge and discharge process derives fast in time, thereby improved the heat dispersion of electrochemical power source composite diaphragm, keep power supply temperature constant in the course of the work, thereby effectively avoided existing barrier film because even broken by thermal contraction, cause power supply inside likely occur positive and negative between directly contact and short circuit causes the generation of battery security hidden danger.In addition, the inorganic particle containing due to organic and inorganic composite bed 2 is hollow, has effectively reduced the weight of this electrochemical power source composite diaphragm, thereby effectively raises the energy density of electrochemical power source.The inorganic nano-fiber that organic and inorganic composite bed 2 contains can effectively improve the mechanical strength of this electrochemical power source composite diaphragm.Hence one can see that, in embodiment of the present invention electrochemical power source composite diaphragm, organic and inorganic composite bed 2 by between its recipe ingredient and and nonwoven fabrics membrane layer 1 between synergy, can make organic and inorganic composite bed 2 to combine closely with nonwoven fabrics membrane layer 1, strengthened the broken film temperature of electrochemical power source composite diaphragm, heat dispersion, fail safe and the mechanical strength of composite diaphragm have been strengthened, reduced its weight, extended the useful life of electrochemical power source composite diaphragm, thereby extend electrochemical power source security performance and service life cycle and improved electrochemical power source energy density.
The embodiment of the present invention also provides a kind of method of preparing above-mentioned electrochemical power source composite diaphragm, and the method process chart as shown in Figure 2, refers to Fig. 1 simultaneously, comprises the steps:
The preparation of step S01. organic and inorganic suspension: organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent component are mixed, be mixed with organic and inorganic suspension; Wherein, the quality of described organic binder accounts for 1%～50% of described organic binder and organic solvent gross mass, the quality of described Hollow Inorganic powder, inorganic nano-fiber accounts for respectively described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 0.5%～25%, and the quality sum of described Hollow Inorganic powder and inorganic nano-fiber accounts for described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 25.5%～50%;
Step S02. applies organic-inorganic suspension and drying is processed: the organic and inorganic suspension of step S01 preparation is coated in to nonwoven fabrics barrier film 1 two-sided, and dry under the condition of anaerobic, obtain described electrochemical power source composite diaphragm.
Particularly, in step S01, organic binder, Hollow Inorganic powder, inorganic nano-fiber and the preferred kind of organic solvent and content as described above, in order to save length, do not repeat them here.In the process of preparation of preparing organic and inorganic suspension, preferably first organic binder is joined in organic solvent, after organic binder is dissolved completely, adding Hollow Inorganic powder and inorganic nano-fiber, each component is uniformly dispersed.In order to accelerate the rate of dissolution of organic binder and inorganic particle to be uniformly dispersed, in preparation, also follow the operation of stirring.
In step S02, organic and inorganic suspension is coated in the combination that the two-sided mode of nonwoven fabrics barrier film 1 is preferably one or more modes in dip coated, scraper for coating, scraper coating, spraying.This preferred coating method can be dispersed in organic and inorganic suspension nonwoven fabrics barrier film 1 surface uniformly, thereby makes to form on nonwoven fabrics barrier film 1 surface the organic and inorganic composite bed 2 of even thickness.In order to make final organic and inorganic composite bed 2 have suitable thickness, this organic and inorganic suspension is coated in nonwoven fabrics barrier film 1 dose,surface, and to be preferably the organic and inorganic coat thickness forming after organic and inorganic suspension is dry be 5～45 microns.Certainly, this organic and inorganic suspension also can apply on a surface of nonwoven fabrics barrier film 1, makes the electrochemical power source composite diaphragm in conjunction with organic-inorganic compounding layer 2 at nonwoven fabrics barrier film 1 one side.
In this step S02, in order to be coated in the organic and inorganic suspension on nonwoven fabrics barrier film 1 surface, in dry run, do not change, dry should being dried under the condition of anaerobic in this step, remove organic solvent, make organic and inorganic suspension dry, be both and effectively avoid Hollow Inorganic powder oxidized, form organic-inorganic compounding layer 2.Preferably, the condition of this anaerobic is at least one dry gas or the vacuum in hydrogen, nitrogen, inert gas.Dry temperature is preferably 40 ℃～200 ℃, and the time is changeable, as long as make organic and inorganic composite bed 2 bone dries.
From the above mentioned, it is matrix surface that the preparation method of above-described embodiment electrochemical power source composite diaphragm is directly coated in nonwoven fabrics barrier film by organic and inorganic composite mortar, dry, technique is simple, and condition is easily controlled, low for equipment requirements, production efficiency, production cost is low, is suitable for suitability for industrialized production.
By a plurality of embodiment, illustrate above-mentioned electrochemical power source composite diaphragm and preparation method thereof below, with and the aspect such as performance.
Embodiment 1
A kind of electrochemical power source composite diaphragm and preparation method thereof:
As shown in Figure 1, it comprises PET nonwoven fabrics membrane layer 1 and in conjunction with the two-sided organic and inorganic composite bed 2 of nonwoven fabrics membrane layer 1 to this electrochemical power source composite diaphragm structure.Wherein, the thickness of PET nonwoven fabrics barrier film is 30 microns, and the thickness of organic and inorganic composite bed 2 is 5 microns.The recipe ingredient that this organic and inorganic composite bed 2 comprises following mass fraction:
Wherein, the average grain diameter of hollow alumina is 500nm, and the average length of glass fibre is 1 μ m, and diameter is 50nm.
This electrochemical power source composite diaphragm preparation method:
The preparation of step S11. organic and inorganic suspension: according to the recipe ingredient of organic and inorganic composite bed 2 in the present embodiment 1, first polytetrafluoroethylene is dissolved in acetone, the process of dissolving is followed the operation of stirring, to accelerate dissolving and the dispersion of polytetrafluoroethylene, after polytetrafluoroethylene dissolves, then hollow alumina, glass fibre are added in solvent, stir, make hollow alumina, glass fibre dispersed in this solvent, obtain homodisperse organic and inorganic suspension;
Step S12. applies organic-inorganic suspension and drying is processed: PET nonwoven fabrics barrier film be immersed in the organic and inorganic suspension of step S11 preparation and retain after 30min, in the flowing nitrogen environment of 80 ℃, be dried 12 hours, obtain described electrochemical power source composite diaphragm.
The electrochemical power source composite diaphragm of the present embodiment 1 preparation carries out porosity, aperture, thickness, air penetrability and broken film temperature and measures, wherein, porosity and aperture adopt porosity instrument to measure, thickness is measured by amesdial, air penetrability is measured by air penetrability measuring instrument, and the thermal endurance of barrier film is that barrier film is placed in and at 200 ℃, is incubated the variation of measuring its size after 30 minutes.Learn after measured, the electrochemical power source composite diaphragm porosity of the present embodiment 1 preparation is 40%, and aperture is 100 nanometers, thickness is 35 microns, air penetrability is 200s/100cc, and after 200 ℃ of insulation 30min, significant change does not occur size, illustrates that the thermal endurance of this barrier film is higher than 200 ℃.
Embodiment 2
A kind of electrochemical power source composite diaphragm and preparation method thereof:
This electrochemical power source composite diaphragm structure is as the electrochemical power source composite diaphragm structure in embodiment 1.Wherein, the thickness of PET nonwoven fabrics barrier film is 26 microns, and the thickness of organic and inorganic composite bed is 8 microns.The recipe ingredient that this organic and inorganic composite bed comprises following mass fraction:
Wherein, the average grain diameter of hollow silica is 200nm, and the average length of glass fibre is 1 μ m, and diameter is 50nm.
This electrochemical power source composite diaphragm preparation method:
The preparation of step S21. organic and inorganic suspension: according to the recipe ingredient of organic and inorganic composite bed in the present embodiment 2, first polyvinyl alcohol is dissolved in carrene, the process of dissolving is followed the operation of stirring, to accelerate dissolving and the dispersion of polyvinyl alcohol, after polyvinyl alcohol dissolves, more hollow silica, ceramic fibre are added in solvent, stir, make hollow silica, ceramic fibre dispersed in this solvent, obtain homodisperse organic and inorganic suspension;
Step S22. applies organic-inorganic suspension and drying is processed: PET nonwoven fabrics barrier film be immersed in the organic and inorganic suspension of step S21 preparation and retain after 30min, in the flowing nitrogen environment of 60 ℃, be dried 6 hours, obtain described electrochemical power source composite diaphragm.
The electrochemical power source composite diaphragm of the present embodiment 2 preparations carries out porosity, aperture, thickness, air penetrability and broken film temperature and measures, wherein, porosity and aperture adopt porosity instrument to measure, thickness is measured by amesdial, air penetrability is measured by air penetrability measuring instrument, and the thermal endurance of barrier film is that barrier film is placed in and at 200 ℃, is incubated the variation of measuring its size after 30 minutes.Learn after measured, the electrochemical power source composite diaphragm porosity of the present embodiment 2 preparations is 45%, and aperture is 200 nanometers, thickness is 34 microns, air penetrability is 100s/100cc, and after 200 ℃ of insulation 30min, significant change does not occur size, illustrates that the thermal endurance of this barrier film is higher than 200 ℃.
Embodiment 3
A kind of electrochemical power source composite diaphragm and preparation method thereof:
This electrochemical power source composite diaphragm structure is as the electrochemical power source composite diaphragm structure in embodiment 1, wherein, nonwoven fabrics is PAN nonwoven fabrics barrier film, and thickness is 40 microns, the thickness of organic and inorganic composite bed is 15 microns, the recipe ingredient that this organic and inorganic composite bed comprises following mass fraction:
Wherein, the average grain diameter of hollow silica is 200nm, and the average length of glass fibre is 100nm, and diameter is 50nm.
This electrochemical power source composite diaphragm preparation method:
The preparation of step S31. organic and inorganic suspension: according to the recipe ingredient of organic and inorganic composite bed in the present embodiment 3, first modified styrene butadiene rubber is dissolved in carbon tetrachloride, the process of dissolving is followed the operation of stirring, to accelerate dissolving and the dispersion of modified styrene butadiene rubber, after modified styrene butadiene rubber dissolves, then hollow alumina, glass fibre are added in solvent, stir, make hollow alumina, glass fibre dispersed in this solvent, obtain homodisperse organic and inorganic suspension;
Step S32. applies organic-inorganic suspension and drying is processed: PAN nonwoven fabrics barrier film be immersed in the organic and inorganic suspension of step S21 preparation and retain after 30min, in the flowing nitrogen environment of 40 ℃, be dried 15 hours, obtain described electrochemical power source composite diaphragm.
The electrochemical power source composite diaphragm of the present embodiment 3 preparations carries out porosity, aperture, thickness, air penetrability and broken film temperature and measures, wherein, porosity and aperture adopt porosity instrument to measure, thickness is measured by amesdial, air penetrability is measured by air penetrability measuring instrument, and the thermal endurance of barrier film is that barrier film is placed in and at 200 ℃, is incubated the variation of measuring its size after 30 minutes.Learn after measured, the electrochemical power source composite diaphragm porosity of the present embodiment 3 preparations is 50%, and aperture is 500 nanometers, thickness is 55 microns, air penetrability is 100s/100cc, and after 200 ℃ of insulation 30min, significant change does not occur size, illustrates that the thermal endurance of this barrier film is higher than 200 ℃.
Embodiment 4
A kind of electrochemical power source composite diaphragm and preparation method thereof:
This electrochemical power source composite diaphragm structure is as the electrochemical power source composite diaphragm structure in embodiment 1, and wherein, nonwoven fabrics is PAN nonwoven fabrics barrier film, and thickness is 20 microns, and the thickness of organic and inorganic composite bed is 5 microns.The recipe ingredient that this organic and inorganic composite bed comprises following mass fraction:
The polyvinyl alcohol of mass ratio 1:1 and 2 parts of polytetrafluoroethylene mixing organic binders;
40 parts of the hollow alumina of mass ratio 1:8 and hollow aluminium nitride mixed powders;
25 parts, glass fibre;
Volume ratio is 100 parts of the polytetrafluoroethylene of 1:3 and Kynoar mixed organic solvents.
Wherein, the average grain diameter of hollow silica is 200nm, and the average length of glass fibre is 500nm, and diameter is 100nm.
This electrochemical power source composite diaphragm preparation method:
The preparation of step S41. organic and inorganic suspension: according to the recipe ingredient of organic and inorganic composite bed in the present embodiment 4, first will mix organic binder dissolves in mixed organic solvents, the process of dissolving is followed the operation of stirring, to accelerate to mix dissolving and the dispersion of organic binder, after organic binder to be mixed dissolves, again hollow mixed powder, glass fibre are added in solvent, stir, make hollow mixed powder, glass fibre dispersed in this solvent, obtain homodisperse organic and inorganic suspension;
Step S42. applies organic-inorganic suspension and drying is processed: PAN nonwoven fabrics barrier film be immersed in the organic and inorganic suspension of step S41 preparation and retain after 40min, in the flowing nitrogen environment of 80 ℃, be dried 3 hours, obtain described electrochemical power source composite diaphragm.
The electrochemical power source composite diaphragm of the present embodiment 4 preparations carries out porosity, aperture, thickness, air penetrability and broken film temperature and measures, wherein, porosity and aperture adopt porosity instrument to measure, thickness is measured by amesdial, air penetrability is measured by air penetrability measuring instrument, and the thermal endurance of barrier film is that barrier film is placed in and at 200 ℃, is incubated the variation of measuring its size after 30 minutes.Learn after measured, the electrochemical power source composite diaphragm porosity of the present embodiment 4 preparations is 45%, and aperture is 100 nanometers, thickness is 25 microns, air penetrability is 100s/100cc, and after 200 ℃ of insulation 30min, significant change does not occur size, illustrates that the thermal endurance of this barrier film is higher than 200 ℃.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. an electrochemical power source composite diaphragm, is characterized in that: comprise nonwoven fabrics membrane layer and the organic and inorganic composite bed that is combined in described nonwoven fabrics membrane layer surface; Described organic and inorganic composite bed comprises organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent recipe ingredient; Wherein, the quality of described organic binder accounts for 1%～50% of described organic binder and organic solvent gross mass, the quality of described Hollow Inorganic powder, inorganic nano-fiber accounts for respectively described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 0.5%～25%, and the quality sum of described Hollow Inorganic powder and inorganic nano-fiber accounts for described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 25.5%～50%.
2. electrochemical power source composite diaphragm as claimed in claim 1, is characterized in that: the thickness of described organic and inorganic composite bed is 5～45 microns.
3. electrochemical power source composite diaphragm as claimed in claim 1 or 2, is characterized in that: described Hollow Inorganic powder is that average grain diameter is at least one in 3～1000nm hollow alumina, hollow silica, hollow aluminium nitride.
4. electrochemical power source composite diaphragm as claimed in claim 1 or 2, is characterized in that: described inorganic nano-fiber is that fibre length is that 0.1～1 μ m, diameter are the glass fibres of 3～100nm, one or both in ceramic fibre.
5. electrochemical power source composite diaphragm as claimed in claim 1 or 2, is characterized in that: described organic binder is at least one in polyvinyl alcohol, polytetrafluoroethylene, Kynoar, modified styrene butadiene rubber, Viton, polyurethane.
6. electrochemical power source composite diaphragm as claimed in claim 1 or 2, it is characterized in that: described organic solvent is ether, pentane, carrene, carbon disulfide, acetone, chloroform, methyl alcohol, hexane, three fluoro acetic acid, 1, at least one in 1,1-trichloroethanes, carbon tetrachloride.
7. a preparation method for electrochemical power source composite diaphragm, comprises the steps:
Organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent component are mixed, be mixed with organic and inorganic suspension; Wherein, the quality of described organic binder accounts for 1%～50% of described organic binder and organic solvent gross mass, the quality of described Hollow Inorganic powder, inorganic nano-fiber accounts for respectively described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 0.5%～25%, and the quality sum of described Hollow Inorganic powder and inorganic nano-fiber accounts for described organic binder, Hollow Inorganic powder, inorganic nano-fiber and organic solvent gross mass 25.5%～50%;
Described organic and inorganic suspension is coated in to nonwoven fabrics membrane surface, and dry under the condition of anaerobic, obtain described electrochemical power source composite diaphragm.
8. the preparation method of electrochemical power source composite diaphragm as claimed in claim 7, is characterized in that: the amount that described organic and inorganic suspension is coated in described nonwoven fabrics membrane surface is that the organic and inorganic coat thickness forming after organic and inorganic suspension is dry is 5～45 microns.
9. the preparation method of electrochemical power source composite diaphragm as claimed in claim 7 or 8, is characterized in that: described coating method is the combination of one or more modes in dip coated, scraper for coating, scraper coating, spraying.
10. the preparation method of electrochemical power source composite diaphragm as claimed in claim 7 or 8, is characterized in that: the condition of described anaerobic is at least one dry gas or the vacuum in hydrogen, nitrogen, inert gas.
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| CN201210257647.3A CN103579554A (en) | 2012-07-24 | 2012-07-24 | Electrochemical power-supply composite membrane and preparation method thereof |
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| CN104409674A (en) * | 2014-12-08 | 2015-03-11 | 清华大学 | Composite diaphragm material and preparation method and application thereof |
| CN108598342A (en) * | 2018-03-28 | 2018-09-28 | 上海恩捷新材料科技股份有限公司 | A kind of battery diaphragm, lithium ion battery and preparation method thereof |
| CN112467308A (en) * | 2020-10-27 | 2021-03-09 | 惠州锂威新能源科技有限公司 | Diaphragm, preparation method thereof and lithium ion battery |
| JP2021053856A (en) * | 2019-09-27 | 2021-04-08 | 三菱製紙株式会社 | Thermal runaway suppression fireproof sheet |
| CN113823879A (en) * | 2020-06-12 | 2021-12-21 | 厦门大学 | Fiber-reinforced ceramic diaphragm, preparation method and application |
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- 2012-07-24 CN CN201210257647.3A patent/CN103579554A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104409674A (en) * | 2014-12-08 | 2015-03-11 | 清华大学 | Composite diaphragm material and preparation method and application thereof |
| CN108598342A (en) * | 2018-03-28 | 2018-09-28 | 上海恩捷新材料科技股份有限公司 | A kind of battery diaphragm, lithium ion battery and preparation method thereof |
| JP2021053856A (en) * | 2019-09-27 | 2021-04-08 | 三菱製紙株式会社 | Thermal runaway suppression fireproof sheet |
| JP7163262B2 (en) | 2019-09-27 | 2022-10-31 | 三菱製紙株式会社 | Thermal runaway suppression refractory sheet |
| CN113823879A (en) * | 2020-06-12 | 2021-12-21 | 厦门大学 | Fiber-reinforced ceramic diaphragm, preparation method and application |
| CN112467308A (en) * | 2020-10-27 | 2021-03-09 | 惠州锂威新能源科技有限公司 | Diaphragm, preparation method thereof and lithium ion battery |
| CN112467308B (en) * | 2020-10-27 | 2023-09-05 | 惠州锂威新能源科技有限公司 | Diaphragm, preparation method thereof and lithium ion battery |
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