CN109346654A - It is a kind of based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material and preparation method thereof - Google Patents
It is a kind of based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material and preparation method thereof Download PDFInfo
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- CN109346654A CN109346654A CN201811049648.2A CN201811049648A CN109346654A CN 109346654 A CN109346654 A CN 109346654A CN 201811049648 A CN201811049648 A CN 201811049648A CN 109346654 A CN109346654 A CN 109346654A
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M50/411—Organic material
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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
- H01M50/431—Inorganic material
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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
- H01M50/44—Fibrous material
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- 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
Abstract
The invention discloses a kind of based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material and preparation method thereof, the diaphragm material is by two kinds of materials of zircite fiber film and aramid fiber film, the structure composition being superimposed with three layers of sandwich style, pass through sol-gal process and method of electrostatic spinning, using aramid fiber film as intermediate base bottom, two layers of covering makees adhesive by high-temp glue with Zirconium oxide fibre.By the composite cellulosic membrane diameter after high-temperature heat treatment in 200nm or less, chemical property is stablized, high temperature resistant and organic-inorganic acid corrosion, also has the function of high temperature closed pore simultaneously, electric current conduction can be cut off in battery overheat, the features such as highly-safe, fiber lightweight, fibre diameter is thin, electrolysis liquid particles transmitance is good, large specific surface area.But also having small in size, size is controllable, long service life, low to environmental requirement, is suitable for multiple battery diaphragm, and the potential using value in fields such as space flight in future, micro cell, shellproof batteries is huge.
Description
Technical field
The invention belongs to battery diaphragm technical fields, and in particular to a kind of based on zirconium oxide/aramid fiber composite nano fiber
High temperature closed pore function battery diaphragm material and preparation method thereof.
Background technique
Battery diaphragm directly influences battery into safety and use as an important component in battery structure
Service life, the main function of battery diaphragm are isolation positive and negative anodes, prevent electronics in battery from passing freely through, prevent the two poles of the earth contact and
Short circuit allows the particle in electrolyte to pass freely through between positive and negative anodes.Diaphragm material must have nonconducting special, current business
The material of upper common battery diaphragm is mainly PE(polyethylene) and PP(polypropylene).For lithium battery series, due to electrolyte
For organic solvent system, thus the diaphragm material of organic solvent-resistant is needed, and there is enough chemistry and electrochemically stable
Property.Lithium battery diaphragm requires material to have certain aperture and porosity simultaneously, guarantees low resistance and high ionic conductivity,
There is good permeability to lithium ion.
At present improve battery diaphragm performance method there are four types of: constructed in membrane surface or internal void high-temperature-resistant layer,
In membrane surface modification, using polymer or inorganic solid electrolyte.The wherein side of inorganic ceramic powder powder or addition coating
Method, preparation process is more complicated, and the prior art is immature, increases battery production cost.Its another method uses poly-
Polymer solution uses the diaphragm of method of electrostatic spinning preparation, and diaphragm material is single, and envelop of function is too narrow, and limit battery applies model
It encloses.
Zirconia ceramics has high temperature resistant, corrosion resistant feature, is insoluble in water and inorganic acid, pure zirconium oxide fusing point is reachable
2700 DEG C, and its performance with acidproof alkali liquid corrosion, meanwhile, zirconium oxide also has the spy of high resistance and low thermal coefficient of expansion
Property, the stable zirconium oxide of chemical property has been successfully applied in the fields such as high-temperaure coating and insulating materials.And it applies also for aoxidizing
In reducing atmosphere and vacuum, therefore before the fields such as space flight and aviation, atomic energy, petrochemical industry also have very extensive application
Scape.Zirconium oxide fibre can be made by dry spinning, centrifugation Static Spinning, centrifugal drying silk method, wherein oxygen made from centrifugation Static Spinning
Change zirconium fibre diameter up to Nano grade, the zirconia nanopowder fiber size of microcrystal after high-temperature calcination is small, and size distribution is equal
Even, density is small, is high-grade light fibre material.
Aramid fiber material is a kind of insulator, and more preferable than other diaphragm material heat resistances, ensure that aramid fiber as battery every
The safety of membrane material.Aramid fiber has good mechanical performance simultaneously, and meta-aramid is resistant to the inorganic acid of most of high concentrations, often
Alkaline resistance properties under temperature is also very good.According to University of Michigan studies have shown that the nanofiber membrane product of aramid fiber material can be made
Must be very frivolous, to greatly reduce the size of battery, the storage energy of battery is improved, the application prospect of battery is extended.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of based on zirconium oxide/aramid fiber composite nano fiber
High temperature closed pore function battery diaphragm material and preparation method thereof
The purpose of the present invention is prepare it is a kind of with corrosion-and high-temp-resistant can zirconium oxide/aramid fiber composite nano fiber battery every
Membrane material.In superposition shape structure of composite membrane, zirconia nanopowder fiber and aramid fiber pass through the composite nano-fiber material fiber
High-temperature adhesives are additional together.For average diameter in 200nm or so, nanofiber mats are in tridimensional network, tortuous intercommunicating pore
Structure, permeability are good.With insulation, suitable voidage, efficient ion transmission, the long-life, it is highly-safe the advantages that, not only
Reach the requirement of the performance of common commercial battery diaphragm, the advantageous feature not having for common batteries diaphragm more.
In order to solve the above technical problems, the invention adopts the following technical scheme:
It is a kind of based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material, pass through sol-gal process
It being obtained with method of electrostatic spinning, the high temperature closed pore function battery diaphragm material is formed by inorfil and organic fiber are compound,
Middle inorfil is zirconia nanopowder fiber, and organic fiber is aramid nano-fiber, zirconia nanopowder fiber and aramid fiber
Mass ratio is 1:(0.1-10).
Zirconia nanopowder fiber and aramid fiber composite nano fiber are according to three in the high temperature closed pore function battery diaphragm material
The zircite fiber film of Mingzhi's formula/aramid fiber film/Zirconium oxide fibre form membrane is compound, i.e., using aramid fiber film as intermediate base
Bottom, in two layers of aramid fiber film covering with zircite fiber film.
Inorfil crystal (zirconia grains the are in cubic phase mono-crystalline structures) partial size is 20-50nm, diameter 100-
500nm, preferably 100-200nm.Organic fiber diameter is 30-120nm, porosity 0.20-0.85cm3/g。
The preparation side based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material
Method, it is characterised in that use following steps:
(1) by load weighted PMIA(meta-aramid) it is first impregnated and is stirred with methanol and dried after 30-60min minutes, then with third
Ketone impregnates and stirs drying after 1-3h；
(2) DMAC(N, N- dimethyl acetamide is added in PMIA dry in step (1)) in obtained PMIA/DMAC mix it is molten
Liquid；
(3) mixed solution stirs 4-10h at 60-100 DEG C, until solution obtains spinning solution in substantially uniformity state；
(4) electrostatic spinning is carried out using spinning solution obtained in step (3) and obtains aramid fiber film；
(5) methanol and glacial acetic acid are poured into beaker and is stirred evenly, CH is then added2O7Zr2With Y (NO)3•6H2O, 25 DEG C-
Magnetic agitation 12-48h under conditions of 70 DEG C；
(6) reaction product obtained by step (5) is taken out, solvent is evaporated under reduced pressure at 30 DEG C -70 DEG C with Rotary Evaporators, by solution
Being evaporated to viscosity is that 700-2500mpas obtains colloidal sol；
(7) on the receiver by the package of aramid fiber film obtained by step (4) electrostatic spinning, by colloidal sol obtained by step (6) using quiet
Electrical spinning method spinning on aramid fiber film is wrapped on aramid fiber film side so that zirconia nanopowder tunica fibrosa is compound, benefit
Aramid fiber film other side side is also covered into zircite fiber film with same method and obtains multilayer materials；
(8) multilayer materials of step (7) are carried out spraying bonding with jet high-temp glue, then carries out high-temperature heat treatment and obtains height
Warm closed pore function battery diaphragm material.
The mass fraction of PMIA is 2 ~ 20% in step (2) the PMIA/DMAC mixed solution.
The mass ratio of methanol and glacial acetic acid is (0.5-5.0) in the step (5): 1.0.
CH in the step (5)2O7Zr2With Y (NO)3•6H2The molar ratio of O is 1.0:(0.02-0.12),
The temperature of step (5) the high temperature heat treatment is 600-1600 DEG C.
Electrostatic spinning apparatus is mainly by hydraulic accumulator in the step (4) and (7), injector, roller reception device and one
High voltage power sending device composition,
When work, the voltage of high pressure generator is 10-30kV, and the distance of nozzle to the reception device is 10-25cm, and spray head is straight
Diameter 0.5-1.5mm, the electrostatic spinning flow quantity of ejection are 0.1-3.0mL/h, collection device revolving speed 50-1000rpm.
The organic nano fibrous membrane with inorganic compounding of zirconium oxide/aramid fiber of the invention is by zircite fiber film and aramid fiber
Two kinds of materials of film, the structure being superimposed with three layers of sandwich style is made, with PMIA, DMAC, CH2O7Zr2、Y(NO)3•6H2O, methanol and
Acetic acid is raw material, and by sol-gal process and method of electrostatic spinning, using aramid fiber film as intermediate base bottom, two sides are covered with zirconium oxide
Fiber makees adhesive by high-temp glue, by the composite cellulosic membrane diameter after high-temperature heat treatment in 200nm hereinafter, chemical property is steady
It is fixed, high temperature resistant and organic-inorganic acid corrosion, while also having the function of high temperature closed pore, electric current, which can be cut off, in battery overheat passes
It leads, highly-safe, fiber lightweight, fibre diameter is thin, is electrolysed the features such as good liquid particles transmitance, large specific surface area.But also have
Have small in size, size is controllable, long service life, and it is low to environmental requirement, it is suitable for multiple battery diaphragm, in space flight in future, micro- electricity
The potential using value in the fields such as pond, shellproof battery is huge.
Compared with existing battery diaphragm material and preparation method thereof, the invention has the following advantages that
(1) electrostatic spinning technique is utilized, the zirconia nanopowder average fibre diameter of preparation is in 150nm or so, light-weight, heat resistance
Good, good corrosion resistance.It is added to zirconium oxide/aramid fiber composite cellulosic membrane diaphragm material and not only has performance needed for common batteries,
And since zirconium oxide has excellent high temperature resistant and corrosion resistance, so that the erosion of new material more electrolyte resistance, together
When expand battery to the range of use environment, so that battery is played bigger effect in dual-use field.
(2) composite diaphragm Jing Guo high-temperature heat treatment has the function of high temperature closed pore, can cut off electric current in battery overheat
Conduction improves the safety of battery to play the role of protecting battery.
Detailed description of the invention
Fig. 1 is the organic structural simulation figure with the nanofiber of inorganic compounding of zirconium oxide/aramid fiber prepared by the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of the zirconia nanopowder fiber of sol-gal process combination method of electrostatic spinning of the present invention preparation.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment 1
The preparation side based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material of the present embodiment
Method, steps are as follows:
1) by load weighted PMIA(meta-aramid) it is first impregnated with methanol and is dried after stirring 30min minutes, then soaked with acetone
It steeps and stirs drying after 1h；
2) a certain amount of DMAC(N, N- dimethyl acetamide is added in the PMIA dried in step 1)) solvent, take mass ratio PMIA:
DMAC=0.1:1 is dissolved into the PMIA/DMAC spinning solution that mass fraction is 10%；
3) step 2 acquired solution stirs 8h at 60 DEG C in wide-mouth bottle, until solution is in substantially uniformity state；
4) spinning solution carries out electrostatic spinning and obtains aramid fiber in step 3), and gained aramid fiber average diameter is 40nm, distribution
Wider range, fiber is less, and diameter is meticulous, and fiber hole is larger, than more loose；Electrospinning device mainly by hydraulic accumulator, pushes away
Infuse device, roller reception device and a high voltage power sending device composition；When electrostatic spinning apparatus works, the electricity of high pressure generator
Pressure is 20kV, and the distance of nozzle to the reception device is 13cm, and the electrostatic spinning flow quantity of jet diameters 0.7mm, ejection are
0.2mL/h, collection device revolving speed 70rpm；
5) load weighted methanol and glacial acetic acid are poured into beaker and are stirred evenly, the mass ratio of methanol and glacial acetic acid is 0.9:
1.0；Then CH is added2O7Zr2With Y (NO)3•6H2O, CH2 O7 Zr2With Y (NO)3•6H2The molar ratio of O is 1.0:0.04, magnetic
30 DEG C of stirring 20h on power blender；
6) reaction product obtained by step 5) is taken out, solvent is evaporated under reduced pressure at 35 DEG C with Rotary Evaporators, solution is evaporated to
Viscosity is the colloidal sol of 800mpas；
7) on the receiver, colloidal sol obtained by step 6) will be aoxidized using method of electrostatic spinning for the package of aramid fiber film obtained by step 4)
Zirconium nanofiber is compound to be wrapped on aramid fiber film, and aramid fiber two sides are all covered zircite fiber film using same method and are obtained
To multilayer materials；When electrostatic spinning apparatus works, the voltage of high pressure generator is 20kV, nozzle to the reception device
Distance is 13cm, and jet diameters 0.7mm, the electrostatic spinning flow quantity of ejection is 0.2mL/h, collection device revolving speed 70rpm；
8) multilayer materials of step 7) are carried out spraying bonding with jet high-temp glue, then carries out high-temperature heat treatment, temperature is
800 DEG C, obtain high temperature closed pore function battery diaphragm material；Gained zirconia nanopowder average fibre diameter is 300nm, size of microcrystal
For 10nm, hole is less.
Embodiment 2
The preparation side based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material of the present embodiment
Method, steps are as follows:
1) by load weighted PMIA(meta-aramid) it is first impregnated with methanol and is dried after stirring 40min minutes, then soaked with acetone
It steeps and stirs drying after 1.5h；
2) a certain amount of DMAC(N, N- dimethyl acetamide is added in the PMIA dried in step 1)) solvent, take mass ratio PMIA:
DMAC=0.12:1 is dissolved into the PMIA/DMAC spinning solution that mass fraction is 12%；
3) step 2 acquired solution stirs 7h at 70 DEG C in wide-mouth bottle, until solution is in substantially uniformity state；
4) spinning solution carries out electrostatic spinning in step 3), and electrospinning device is mainly by hydraulic accumulator, injector, roller reception device
It is formed with a high voltage power sending device；Gained aramid fiber average diameter is 93nm, and distribution is wider, and fiber has in cluster
Shape；When electrostatic spinning apparatus works, the voltage of high pressure generator is 22kV, and the distance of nozzle to the reception device is 15cm,
Jet diameters 0.7mm, the electrostatic spinning flow quantity of ejection are 0.3mL/h, collection device revolving speed 90rpm；
5) load weighted methanol and glacial acetic acid are poured into beaker and are stirred evenly, the mass ratio of methanol and glacial acetic acid is 1.0:
1.0；Then CH is added2 O7 Zr2With Y (NO)3•6H2O, CH2 O7 Zr2With Y (NO)3•6H2The molar ratio of O is 1.0:0.06,
40 DEG C of stirring 22h on magnetic stirring apparatus；
6) reaction product obtained by step 5) is taken out, solvent is evaporated under reduced pressure at 30 DEG C -70 DEG C with Rotary Evaporators, solution is steamed
It is sent to the colloidal sol that viscosity is 1000mpas；
7) on the receiver, colloidal sol obtained by step 6) will be aoxidized using method of electrostatic spinning for the package of aramid fiber film obtained by step 4)
Zirconium nanofiber is compound to be wrapped on aramid fiber film, and aramid fiber two sides are all covered zircite fiber film using same method and are obtained
To multilayer materials；Gained zirconia nanopowder average fibre diameter is 400nm, and size of microcrystal 8nm, hole is less, crystal grain
Partial size is smaller；When electrostatic spinning apparatus works, the voltage of high pressure generator is 22kV, and the distance of nozzle to the reception device is
15cm, jet diameters 0.7mm, the electrostatic spinning flow quantity of ejection are 0.3mL/h, collection device revolving speed 90rpm；
8) multilayer materials of step 8) are carried out spraying bonding with jet high-temp glue, then carries out high-temperature heat treatment, temperature is
1000 DEG C, obtain high temperature closed pore function battery diaphragm material.
Embodiment 3
The preparation side based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material of the present embodiment
Method, steps are as follows:
1) by load weighted PMIA(meta-aramid) it is first impregnated with methanol and is dried after stirring 50min minutes, then soaked with acetone
It steeps and stirs drying after 2h；
2) a certain amount of DMAC(N, N- dimethyl acetamide is added in the PMIA dried in step 1)) solvent, take mass ratio PMIA:
DMAC=0.14:1 is dissolved into the PMIA/DMAC spinning solution that mass fraction is 14%；
3) step 2 acquired solution stirs 6h at 80 DEG C in wide-mouth bottle, until solution is in substantially uniformity state；
4) spinning solution carries out electrostatic spinning and obtains aramid fiber in step 3), and gained aramid fiber average diameter is 47nm, diameter
It is evenly distributed, porosity and pore size are moderate, and fiber distribution is close, and electrospinning device is mainly by hydraulic accumulator, injector, rolling
Cylinder reception device and a high voltage power sending device composition；When electrostatic spinning apparatus works, the voltage of high pressure generator is 24
KV, the distance of nozzle to the reception device are 17cm, and jet diameters 0.7mm, the electrostatic spinning flow quantity of ejection is 0.4mL/
H, collection device revolving speed 110rpm；
5) load weighted methanol and glacial acetic acid are poured into beaker and are stirred evenly, the mass ratio of methanol and glacial acetic acid is 1.1:
1.0；Then CH is added2 O7 Zr2With Y (NO)3•6H2O, CH2 O7 Zr2With Y (NO)3•6H2The molar ratio of O is 1.0:0.08,
It is stirred for 24 hours for 45 DEG C on magnetic stirring apparatus；
6) reaction product obtained by step 5) is taken out, solvent is evaporated under reduced pressure at 30 DEG C -70 DEG C with Rotary Evaporators, solution is steamed
It is sent to the colloidal sol that viscosity is 1200mpas；
7) on the receiver, colloidal sol obtained by step 6) will be aoxidized using method of electrostatic spinning for the package of aramid fiber film obtained by step 4)
Zirconium nanofiber is compound to be wrapped on aramid fiber film, and aramid fiber two sides are all covered to zircite fiber film using same method；
Gained zirconia nanopowder average fibre diameter is 200nm, size of microcrystal 6nm, and fiber surface is smoothly fine and close；Electrostatic spinning apparatus
When work, the voltage of high pressure generator is 24 kV, and the distance of nozzle to the reception device is 17cm, jet diameters 0.7mm,
The electrostatic spinning flow quantity of ejection is 0.4mL/h, collection device revolving speed 110rpm；
8) multilayer materials of step 8) are carried out spraying bonding with jet high-temp glue, then carries out high-temperature heat treatment, temperature is
1200 DEG C, obtain high temperature closed pore function battery diaphragm material.
Embodiment 4
The preparation side based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material of the present embodiment
Method, steps are as follows:
1) by load weighted PMIA(meta-aramid) it is first impregnated with methanol and is dried after stirring 60min minutes, then soaked with acetone
It steeps and stirs drying after 2.5h；
2) a certain amount of DMAC(N, N- dimethyl acetamide is added in the PMIA dried in step 1)) solvent, take mass ratio PMIA:
DMAC=0.16:1 is dissolved into the PMIA/DMAC spinning solution that mass fraction is 16%；
3) step 2 acquired solution stirs 5h at 90 DEG C in wide-mouth bottle, until solution is in substantially uniformity state.
4) spinning solution carries out electrostatic spinning and obtains aramid fiber in step 3), and gained aramid fiber average diameter is 86nm,
Diameter distribution broadens electrospinning device mainly by hydraulic accumulator, injector, roller reception device and a high voltage power transmission dress
Composition is set, when electrostatic spinning apparatus works, the voltage of high pressure generator is 26 kV, and the distance of nozzle to the reception device is
19cm, jet diameters 0.7mm, the electrostatic spinning flow quantity of ejection are 0.5L/h, collection device revolving speed 130rpm；
5) load weighted methanol and glacial acetic acid are poured into beaker and are stirred evenly, the mass ratio of methanol and glacial acetic acid is 1.2:
1.0, CH is then added2 O7 Zr2With Y (NO)3•6H2O, CH2 O7 Zr2With Y (NO)3•6H2The molar ratio of O is 1.0:0.1, magnetic
50 DEG C of stirring 26h on power blender；
6) reaction product obtained by step 5) is taken out, solvent is evaporated under reduced pressure at 30 DEG C -70 DEG C with Rotary Evaporators, solution is steamed
It is sent to the colloidal sol that viscosity is 1400mpas.
7) package of aramid fiber film obtained by step (4) is on the receiver, quiet that colloidal sol obtained by step 6) is utilized electrostatic spinning
Zirconia nanopowder fiber composite is wrapped on aramid fiber film by method, and aramid fiber two sides are all covered to zirconium oxide using same method
Tunica fibrosa；Gained zirconia nanopowder average fibre diameter is 400nm, size of microcrystal 11nm, and hole becomes larger, and fiber surface occurs
Relatively large crystal grain；When electrostatic spinning apparatus works, the voltage of high pressure generator is 26 kV, nozzle to the reception device
Distance be 19cm, jet diameters 0.7mm, the electrostatic spinning flow quantity of ejection is 0.5L/h, collection device revolving speed 130rpm；
8) multilayer materials of step 8) are carried out spraying bonding with jet high-temp glue, then carries out high-temperature heat treatment, temperature is
1400 DEG C, obtain high temperature closed pore function battery diaphragm material.
The present invention utilize inorfil high temperature resistant, corrosion resistant characteristic, the zirconium oxide obtained by electrospinning process/
Aramid fiber composite nano fiber battery diaphragm material, has the function of high temperature closed pore, can cut off electric current conduction, peace in battery overheat
The features such as Quan Xinggao, fiber lightweight, fibre diameter is thin, electrolysis liquid particles transmitance is good, large specific surface area, but also there is volume
Small, size is controllable, and long service life is low to environmental requirement, is suitable for multiple battery diaphragm, in space flight in future, micro cell, shellproof
The potential using value in the fields such as battery is huge.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (9)
1. a kind of based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material, it is characterised in that: institute
It states high temperature closed pore function battery diaphragm material to be formed by inorfil and organic fiber are compound, wherein inorfil is received for zirconium oxide
Rice fiber, organic fiber is aramid nano-fiber, and the mass ratio of zirconia nanopowder fiber and aramid fiber is 1:(0.1-10).
2. high temperature closed pore function battery diaphragm material according to claim 1, it is characterised in that: the high temperature closed pore function
Zirconia nanopowder fiber is with aramid fiber composite nano fiber according to zircite fiber film/aramid fiber of sandwich style in battery diaphragm material
Tunica fibrosa/Zirconium oxide fibre form membrane is compound, i.e., using aramid fiber film as intermediate base bottom, in two layers of aramid fiber film covering with oxygen
Change zirconium tunica fibrosa.
3. high temperature closed pore function battery diaphragm material according to claim 1, it is characterised in that: the inorfil is brilliant
Body partial size is 20-50nm, and diameter 100-500nm, organic fiber diameter is 30-120nm, porosity 0.20-0.85cm3/
g。
4. according to claim 1 to 3 based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery
The preparation method of diaphragm material, it is characterised in that use following steps:
(1) load weighted PMIA is first impregnated with methanol and is dried after stirring 30-60min minutes, then with acetone soak and stirred
1-3h is mixed to dry later；
(2) PMIA dried in step (1), which is added in DMAC, is made PMIA/DMAC mixed solution；
(3) mixed solution stirs 4-10h at 60-100 DEG C, until solution obtains spinning solution in substantially uniformity state；
(4) electrostatic spinning is carried out using spinning solution obtained in step (3) and obtains aramid fiber film；
(5) methanol and glacial acetic acid are poured into beaker and is stirred evenly, CH is then added2O7Zr2With Y (NO)3•6H2O, at 25 DEG C -70
Magnetic agitation 12-48h under conditions of DEG C；
(6) reaction product obtained by step (5) is taken out, solvent is evaporated under reduced pressure at 30 DEG C -70 DEG C with Rotary Evaporators, by solution
Being evaporated to viscosity is that 700-2500mpas obtains colloidal sol；
(7) on the receiver by the package of aramid fiber film obtained by step (4) electrostatic spinning, by colloidal sol obtained by step (6) using quiet
Electrical spinning method spinning on aramid fiber film is wrapped on aramid fiber film side so that zirconia nanopowder tunica fibrosa is compound, benefit
Aramid fiber film other side side is also covered into zircite fiber film with same method and obtains multilayer materials；
(8) multilayer materials of step (7) are carried out spraying bonding with jet high-temp glue, then carries out high-temperature heat treatment and obtains height
Warm closed pore function battery diaphragm material.
5. according to claim 4 based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material
The preparation method of material, it is characterised in that: the mass fraction of PMIA is 2 ~ 20% in step (2) the PMIA/DMAC mixed solution.
6. according to claim 4 based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material
The preparation method of material, it is characterised in that: the mass ratio of methanol and glacial acetic acid is (0.5-5.0) in the step (5): 1.0.
7. according to claim 4 based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material
The preparation method of material, it is characterised in that: CH in the step (5)2O7Zr2With Y (NO)3•6H2The molar ratio of O is 1.0:(0.02-
0.12).
8. according to claim 4 based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material
The preparation method of material, it is characterised in that: the temperature of step (5) the high temperature heat treatment is 600-1600 DEG C.
9. according to claim 4 based on zirconium oxide/aramid fiber composite nano fiber high temperature closed pore function battery diaphragm material
The preparation method of material, it is characterised in that: electrostatic spinning apparatus is mainly by hydraulic accumulator, injector, rolling in the step (4) and (7)
Cylinder reception device and high voltage power sending device composition, when work, the voltage of high pressure generator is 10-30kV, and nozzle arrives
The distance of the reception device is 10-25cm, and jet diameters 0.5-1.5mm, the electrostatic spinning flow quantity of ejection is 0.1-
3.0mL/h, collection device revolving speed 50-1000rpm.
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Cited By (1)
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| CN111668426A (en) * | 2020-06-22 | 2020-09-15 | 欣旺达电动汽车电池有限公司 | Diaphragm and preparation method thereof, lithium ion battery and electric automobile |
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Application publication date: 20190215 |