CN103579551A - Electrochemical power-supply composite membrane and preparation method thereof - Google Patents
Electrochemical power-supply composite membrane and preparation method thereof Download PDFInfo
- Publication number
- CN103579551A CN103579551A CN201210257525.4A CN201210257525A CN103579551A CN 103579551 A CN103579551 A CN 103579551A CN 201210257525 A CN201210257525 A CN 201210257525A CN 103579551 A CN103579551 A CN 103579551A
- Authority
- CN
- China
- Prior art keywords
- organic
- inorganic
- power source
- electrochemical power
- aluminium nitride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
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, aluminium nitride, 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; aluminium nitride and the inorganic nanometer fiber respectively accounts for 1%-49% by mass of the sum of the organic binder, aluminium nitride, the inorganic nanometer fiber and the organic solvent; and the sum of aluminium nitride and the inorganic nanometer fiber accounts for 30%-50% of the sum of the organic binder, aluminium nitride, the inorganic nanometer fiber and the organic solvent. The electrochemical power-supply composite membrane is good in heat dissipation performance and mechanical strength, and the safety performance of the composite membrane is improved. 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.
Therefore, for improving the security performance of power supply, make it meet the requirement as electrical source of power, how to develop a kind of good heat conductivity, the barrier film that thermal stability is high is the technical barrier that urgent need overcomes.
Summary of the invention
The above-mentioned deficiency that the object of the invention is to overcome prior art, provides a kind of good heat conductivity, the electrochemical power source composite diaphragm that thermal stability is high.
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, aluminium nitride, 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 aluminium nitride, inorganic nano-fiber accounts for respectively described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 1%～49%, and the quality sum of described aluminium nitride and inorganic nano-fiber accounts for described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 30%～50%.
And a kind of preparation method of electrochemical power source composite diaphragm, comprises the steps:
Organic binder, aluminium nitride, 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 aluminium nitride, inorganic nano-fiber accounts for respectively described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 1%～49%, and the quality sum of described aluminium nitride and inorganic nano-fiber accounts for described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 30%～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.Organic and inorganic composite bed contains the aluminium nitride 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, make this electrochemical power source composite diaphragm there is high thermal stability, 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.The inorganic nano-fiber that organic and inorganic composite bed contains can effectively improve the mechanical strength of this electrochemical power source composite diaphragm.In addition, organic and inorganic composite bed by between its recipe ingredient and and nonwoven fabrics membrane layer between synergy, can make organic and inorganic composite bed to combine closely with nonwoven fabrics membrane layer, heat conductivility and the mechanical strength of electrochemical power source composite diaphragm have been strengthened, prevent coming off of organic and inorganic composite bed, improve the fail safe of composite diaphragm, extended the useful life of electrochemical power source composite diaphragm.
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, aluminium nitride, inorganic nano-fiber and organic solvent recipe ingredient; Wherein, the quality of organic binder accounts for 1%～50% of described organic binder and organic solvent gross mass, the quality of aluminium nitride, inorganic nano-fiber accounts for respectively described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 1%～49%, and the quality sum of aluminium nitride and inorganic nano-fiber accounts for described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 30%～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 aluminium nitride component in this recipe ingredient in organic solvent, and aluminium nitride 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, extended the useful life of electrochemical power source composite diaphragm.
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.
In above-mentioned recipe ingredient, aluminium nitride has excellent heat conductivility, thereby give embodiment of the present invention electrochemical power source composite diaphragm, has excellent heat dispersion.Meanwhile, under the synergy of this aluminium nitride, electrodeless nanofiber and nonwoven fabrics membrane layer 1, strengthen thermal endurance and the intensity of nonwoven fabrics membrane layer 1, thereby improved the security performance of electrochemical power source composite diaphragm.In addition, inventor is also discovery under study for action, and the particle diameter of suitable this aluminium nitride of change, can affect this composite diaphragm pore.In a preferred embodiment, the particle diameter of this aluminium nitride is preferably 3～1000nm.The aluminium nitride of this particle size range has higher specific surface and good absorption property, this higher specific surface energy effectively improves the pore of this composite diaphragm, 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 the glass fibres of 3～100nm, one or both in ceramic fibre that above-mentioned inorganic nano-fiber is preferably fibre length.The inorganic nano-fiber of this preferred size 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.Organic and inorganic composite bed 2 contains the aluminium nitride 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, make this electrochemical power source composite diaphragm there is high thermal stability, 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.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.In addition, 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, the intensity that has strengthened electrochemical power source composite diaphragm, prevents coming off of organic and inorganic composite bed.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, electrochemical power source composite diaphragm heat conductivility and mechanical strength have been strengthened, improved the fail safe of above-mentioned composite diaphragm, extended the useful life of electrochemical power source composite diaphragm, thereby improved electrochemical power source security performance and extended its service life cycle.
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, aluminium nitride, 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 aluminium nitride, inorganic nano-fiber accounts for respectively described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 1%～49%, and the quality sum of described aluminium nitride and inorganic nano-fiber accounts for described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 30%～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, the preferred kind of organic binder, aluminium nitride, inorganic nano-fiber and 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 aluminium nitride and inorganic nano-fiber, each component is uniformly dispersed.In order to accelerate the rate of dissolution of organic binder and aluminium nitride 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, effectively avoid aluminium nitride oxidized, form organic-inorganic compounding layer 2 simultaneously.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 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, nonwoven fabrics membrane layer 1 is the PET nonwoven fabrics of 30 micron thick, and the thickness of organic and inorganic composite bed 2 is 10 microns, the recipe ingredient that this organic and inorganic composite bed 2 comprises following mass fraction:
Wherein, the average grain diameter of aluminium nitride is 500nm, and the average length of glass fibre is 1 μ m, and diameter is 20nm.
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 aluminium nitride, glass fibre are added in solvent, stir, make aluminium nitride, 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 100 ℃, 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 40 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, nonwoven fabrics membrane layer 1 is the PET nonwoven fabrics of 26 micron thick, 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 aluminium nitride is 200nm, and the average length of glass fibre is 1 μ m, and diameter is 20nm.
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, then aluminium nitride, ceramic fibre are added in solvent, stir, make aluminium nitride, 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 membrane layer 1 is the PAN nonwoven fabrics of 40 micron thick, and 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 aluminium nitride 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 aluminium nitride, glass fibre are added in solvent, stir, make aluminium nitride, 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, wherein, nonwoven fabrics membrane layer 1 is the PAN nonwoven fabrics of 20 micron thick, 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 aluminium nitride of mass ratio 1:8 and 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 aluminium nitride 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, then aluminium nitride, glass fibre are added in solvent, stir, make aluminium nitride, 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 180 ℃, 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, aluminium nitride, 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 aluminium nitride, inorganic nano-fiber accounts for respectively described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 1%～49%, and the quality sum of described aluminium nitride and inorganic nano-fiber accounts for described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 30%～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 aluminium nitride is that average grain diameter is 3～1000nm.
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, aluminium nitride, 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 aluminium nitride, inorganic nano-fiber accounts for respectively described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 1%～49%, and the quality sum of described aluminium nitride and inorganic nano-fiber accounts for described organic binder, aluminium nitride, inorganic nano-fiber and organic solvent gross mass 30%～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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210257525.4A CN103579551A (en) | 2012-07-24 | 2012-07-24 | Electrochemical power-supply composite membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210257525.4A CN103579551A (en) | 2012-07-24 | 2012-07-24 | Electrochemical power-supply composite membrane and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103579551A true CN103579551A (en) | 2014-02-12 |
Family
ID=50050874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210257525.4A Pending CN103579551A (en) | 2012-07-24 | 2012-07-24 | Electrochemical power-supply composite membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103579551A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810548A (en) * | 2014-07-15 | 2015-07-29 | 万向A一二三系统有限公司 | High-performance lithium titanate power battery |
| CN105047847A (en) * | 2015-09-11 | 2015-11-11 | 江西师范大学 | PI-AlN-PTFE ternary nano-composite multi-curve pore membrane material and preparing method and application thereof |
| CN105304846A (en) * | 2015-11-10 | 2016-02-03 | 天能电池集团有限公司 | Composite non-woven fabric ceramic diaphragm for lithium ion battery and preparation method thereof |
| CN105470433A (en) * | 2014-09-29 | 2016-04-06 | 株式会社杰士汤浅国际 | Energy storage device and method of producing energy storage device |
| CN106684292A (en) * | 2017-01-18 | 2017-05-17 | 清陶（昆山）能源发展有限公司 | Ionic conductor ceramic fiber composite diaphragm and preparation method and application thereof |
| CN109216630A (en) * | 2018-08-28 | 2019-01-15 | 合肥国轩高科动力能源有限公司 | Method for manufacturing high-performance lithium ion battery composite diaphragm |
-
2012
- 2012-07-24 CN CN201210257525.4A patent/CN103579551A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104810548A (en) * | 2014-07-15 | 2015-07-29 | 万向A一二三系统有限公司 | High-performance lithium titanate power battery |
| CN105470433A (en) * | 2014-09-29 | 2016-04-06 | 株式会社杰士汤浅国际 | Energy storage device and method of producing energy storage device |
| US11283136B2 (en) | 2014-09-29 | 2022-03-22 | Gs Yuasa International Ltd. | Energy storage device and method of producing energy storage device |
| CN105047847A (en) * | 2015-09-11 | 2015-11-11 | 江西师范大学 | PI-AlN-PTFE ternary nano-composite multi-curve pore membrane material and preparing method and application thereof |
| CN105047847B (en) * | 2015-09-11 | 2017-04-05 | 江西师范大学 | PI AlN PTFE ternary nanos are combined many curved hole membrane materials and its preparation method and application |
| CN105304846A (en) * | 2015-11-10 | 2016-02-03 | 天能电池集团有限公司 | Composite non-woven fabric ceramic diaphragm for lithium ion battery and preparation method thereof |
| CN106684292A (en) * | 2017-01-18 | 2017-05-17 | 清陶（昆山）能源发展有限公司 | Ionic conductor ceramic fiber composite diaphragm and preparation method and application thereof |
| CN109216630A (en) * | 2018-08-28 | 2019-01-15 | 合肥国轩高科动力能源有限公司 | Method for manufacturing high-performance lithium ion battery composite diaphragm |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107799699B (en) | Clay mineral composite lithium battery diaphragm and preparation method thereof | |
| Liao et al. | Novel cellulose aerogel coated on polypropylene separators as gel polymer electrolyte with high ionic conductivity for lithium-ion batteries | |
| CN103579551A (en) | Electrochemical power-supply composite membrane and preparation method thereof | |
| CN103515564B (en) | A kind of composite diaphragm and preparation method thereof | |
| CN103746085B (en) | A kind of coating composite diaphragm and preparation method thereof | |
| CN106784552B (en) | Lithium ion battery coating diaphragm and preparation method thereof | |
| CN102354619B (en) | A kind of flexible solid-state supercapacitor | |
| CN104157818A (en) | Lithium battery diaphragm compounded from aqueous polymer and inorganic nanoparticles and preparation method thereof | |
| CN109980162B (en) | Polyphosphazene coated ceramic particles and application thereof in lithium ion battery diaphragm | |
| CN105470515B (en) | A kind of safe lithium ion power battery anode and the lithium ion battery containing the positive pole | |
| CN103682217B (en) | High-temperature resistant non-woven composite membrane for power lithium-ion battery and preparation method for high-temperature resistant non-woven composite membrane | |
| CN104157819A (en) | Ceramic-gel polymer multilayer composite lithium battery diaphragm and preparation method thereof | |
| CN103579554A (en) | Electrochemical power-supply composite membrane and preparation method thereof | |
| CN105633326A (en) | Aromatic polyamide composite membrane | |
| Liu et al. | A hard-template process to prepare three-dimensionally macroporous polymer electrolyte for lithium-ion batteries | |
| Cevik et al. | A comparative study of various polyelectrolyte/nanocomposite electrode combinations in symmetric supercapacitors | |
| CN103579552A (en) | Electrochemical power-supply composite membrane and preparation method thereof | |
| CN104466096A (en) | Silicon negative electrode plate of lithium ion battery and preparation method of silicon negative electrode plate | |
| CN103603178B (en) | Coating for flexible lithium-ion battery membrane, membrane containing same and preparation method thereof | |
| CN104993088A (en) | Non-woven type lithium battery diaphragm realizing hole closing at low temperature and being stable at high temperature and preparation method | |
| CN104993084A (en) | Biomass nanocrystal coated polyolefin lithium ion battery diaphragm and production method thereof | |
| WO2017084252A1 (en) | Abuse capacitor having wide temperature range, and manufacturing method therefor | |
| CN103545475A (en) | Barium sulfate diaphragm of lithium ion battery and preparation method thereof | |
| CN103579559A (en) | Diaphragm of electrochemical power supply and preparation method thereof | |
| CN112635916A (en) | Ceramic composite diaphragm, preparation method thereof and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140212 |