CN108281598A - A kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm and preparation method - Google Patents
A kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm and preparation method Download PDFInfo
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- CN108281598A CN108281598A CN201810093202.3A CN201810093202A CN108281598A CN 108281598 A CN108281598 A CN 108281598A CN 201810093202 A CN201810093202 A CN 201810093202A CN 108281598 A CN108281598 A CN 108281598A
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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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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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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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- 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
- H01M50/449—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
A kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm of present invention proposition and preparation method, by poly-vinyl alcohol solution electrostatic spinning, lapping forms silk screen, then film is mixed with ceramic raw material, fire the porous ceramic film for obtaining disperseing fine through hole, using the porous ceramic film as substrate, silane is immersed into duct, hydrolyze gelation, it is dry, aerosil is formed in duct, is then applied polytetrafluoroethylene (PTFE) on substrate two sides, is obtained a kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm.The present invention provides the above method and overcomes existing lithium battery membrane for polymer poor heat resistance, wettability is poor, easy thermal deformation, the defect of ionic conductance difference, diaphragm obtained has excellent ionodialysis characteristic, and diaphragm porosity is high, wellability is excellent, has good intensity and thermal dimensional stability, is particularly suitable for high power capacity, the lithium battery for automobile power of high power work uses.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of dynamic lithium battery dedicated ceramic capillary ionodialysis every
Film and preparation method.
Background technology
Coal, oil, the fossil fuel that three big main energy sources of natural gas are representative make energy resource structure unreasonable,
Environmental pollution is serious, and the global warming and the deterioration of the ecological environment that thus cause receive more and more attention, and find new
Energy storage device has become the focus of attention of new energy related field.Lithium ion battery（Li-ion, Lithium Ion
Battery）As a kind of Novel clean, reproducible secondary energy sources, there is high, big, light weight of energy density of operating voltage etc.
Advantage is obtained for extensive use in fields such as mobile phone, laptop, electric tool, digital cameras.
Lithium ion battery relies primarily on lithium ion, and movement carrys out work between a positive electrode and a negative electrode.In charge and discharge process, Li+
Round-trip insertion and deintercalation between two electrodes：When charging, Li+ is embedded in cathode from positive deintercalation, by electrolyte, and cathode is in
Rich lithium state；It is then opposite when electric discharge.There are a film material, commonly referred to as diaphragm between lithium ion cell positive and cathode, it
It is the important component of lithium ion battery.There are two types of basic functions for diaphragm tool：Positive and negative electrode is isolated, prevents battery internal short-circuit；
The channel to form Ion transfer can be soaked by electrolyte.Should also have following characteristics in practical application：(1) insulating properties of electronics；
（2）High conductivity；（3）Good mechanical performance, can carry out machine-building processing；（4）Thickness is uniform；（5）Size when heated
Steady-state deformation amount wants small.
The performance of diaphragm and voidage, pore size and distribution, air penetrability, hot property and mechanical property etc. are related.Poly- second
Alkene (PE), polypropylene (PP) microporous barrier have higher porosity, lower resistance, higher tearing toughness, preferable antiacid
Alkali ability, good elasticity and to the retention property of aprotic solvent, thus Study on Li-ion batteries initial stage of development use its as
Diaphragm material.The diaphragm of lithium battery commercialization at present is mostly polymer microporous film, and as a kind of thermoplastic material, apertured polymeric film exists
Higher than the self-closing under conditions of glass transition temperature with shrinkage porosity, explosion etc. caused by overheat can be prevented existing
As.But polyethylene, polypropylene diaphragm have the shortcomings that poor to electrolyte compatibility, can not fully meet battery and quickly fill
The requirement of electric discharge, and influence the service life cycle of battery.Especially power battery, it is desirable that high power capacity, quick charge, because
This, polymer film poor thermal shock resistance is that its use is limited with the defect of deformation.
In order to improve the thermal stability of existing lithium battery membrane for polymer, enhance the security performance of battery, ceramic diaphragm its
As one of the main selection of substitution conventional polyolefins diaphragm.Ceramic Composite diaphragm be on the basis of MIcroporous polyolefin film, with
Grow up based on the demand of high performance lithium ion battery, organic material assigns composite diaphragm enough flexibilities, meets
The requirement of lithium ion battery assembly technology, at the same it is similar to polyolefins diaphragm, and under the high temperature conditions, organic component is melted and is blocked up
Diaphragm duct is filled in, composite diaphragm closed pore function is assigned, prevents battery short circuit to a certain extent；Inorganic material be distributed in it is compound every
In the three-dimensional structure of film, specific rigid backbone is formed, diaphragm can be effectively prevent in thermal runaway item by high thermal stability
It shrinks, melt under part；Storeroom is realized by the good fit composite diaphragm being prepared by organic and inorganic material
Performance complement disclosure satisfy that the demand of new type lithium ion battery high security and high-power quick impulse electricity.
Chinese invention patent application number 201310139677.9 discloses a kind of ceramic diaphragm, will be with certain draw ratio
The inorganic matters such as nanostructure nano wire, nanotube, nanometer rods, nanofiber are coated on diaphragm material as ceramic powder body and make
Standby obtained ceramic diaphragm has good tensile strength and thermal stability, but diaphragm matrix prepared by the program is porous
Polymeric material is reduction of ionic conductivity although the coating of nano ceramics can improve film mechanical performance.
Chinese invention patent application number 201410821301.0 discloses a kind of high inorganic solid phase content ceramic diaphragm, including inorganic nano
Fiber and binder, quality shared by inorganic nano-fiber are the 45%-80% of the diaphragm gross mass, and the hole of ceramic diaphragm is by inorganic
Nanofiber randomly stacks to be formed, which is increased to 300 DEG C or more by diaphragm part heat resisting temperature, while percent thermal shrinkage is substantially
Decline, puncture resistance greatly improves, and still, the wellability between inorganic nano-fiber and electrolyte is poor, ionic conductivity
Difference causes the rush of current reduced performance of lithium ion battery, stability test poor.
In consideration of it, it is necessary to be improved to existing diaphragm, exploitation is a kind of to have excellent ionodialysis characteristic, wellability
Diaphragm material excellent, with good intensity and thermal dimensional stability, to meet the power lithium battery pool technology continued to develop
Demand.
Invention content
For existing lithium battery membrane for polymer poor heat resistance, wettability is poor, easy thermal deformation, the defect of ionic conductance difference,
A kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm of present invention proposition and preparation method, manufactured diaphragm have excellent
Ionodialysis characteristic, and diaphragm porosity is high, wellability is excellent, has good intensity and thermal dimensional stability, especially
It is suitble to the lithium battery for automobile power of high power capacity, high power work to use.
To solve the above problems, the present invention uses following technical scheme：A kind of dynamic lithium battery dedicated ceramic capillary ion
Dialysis diaphragm uses porous ceramic film for baseplate material, and the pore on porous ceramic film and aerosil are compound, shape
At three-dimensional ion channel, outer layer covers polytetrafluoroethylene material enhances the wellability of diaphragm.
Preferably, the porous ceramic film be Woelm Alumina, silicon oxide ceramics film, film thickness be 5-80 microns, described two
The aperture of silica aerogel is 40-80nm.
Preferably, the thickness of the polytetrafluoroethylene film is 5-80 microns.
On the other hand, the present invention provides a kind of preparation method of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm,
Specific preparation method is as follows：
（1）9-14 parts of polyvinyl alcohol, 0-3 parts of surfactant, 86-91 parts of deionized water are weighed by mass fraction, at 90-96 DEG C
Lower heating stirring 2-3 hours controls spinning condition, obtains polyvinyl alcohol silk until forming the poly-vinyl alcohol solution of homogeneous viscous
Net；
（2）The polyvinyl alcohol silk screen is mixed with sodium metasilicate or sodium aluminate solution, the sodium metasilicate or sodium aluminate solution it is dense
Degree is 1.2-1.9mol/L, and after adsorbing 10-20 hours, naturally dry obtains disperseing fine by 400-600 DEG C of high temperature sintering
The porous ceramic film of through hole；
（3）The porous ceramic film is put into closed container, silane is re-filled with, after adsorbing 5-10 hours, is filled with deionized water,
Silane hydrolyzate forms aerosil after drying full of Silica hydrogel in fine duct in duct, obtains dialysis
Diaphragm active layer；
（4）Polytetrafluoroethylene material is applied on dialysis diaphragm active layer two sides, obtains ceramic capillary ionodialysis diaphragm.
Preferably, shown surfactant be rhamnolipid, seaweed glycolipid, sophorolipid, sorbitan, ethylene glycol and
One kind in glyceryl monoacetate.
Preferably, the spinning condition is flow 0.1-0.3ml/h；25 DEG C of temperature in chassis；Humidity 45%-55%, aluminium foil
As material is received, voltage is set as 12-20kV, receives distance 15cm.
Preferably, the high temperature sintering time is 3-8 hours.
Preferably, the volume ratio of the silane and deionized water is 1:5-8.
Preferably, it after coating polytetrafluoroethylene (PTFE), is formed in ptfe surface by mechanical stretching compact arranged micro-
The aperture in hole, the micropore is 100-500nm.
Preferably, it is 1.2-3.5% that control machinery, which stretches the polytetrafluoroethylene (PTFE) deformation quantity,.
For existing lithium battery membrane for polymer poor heat resistance, wettability is poor, easy thermal deformation, the defect of ionic conductance difference,
A kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm of present invention proposition and preparation method.By poly-vinyl alcohol solution electrostatic
Spinning, lapping form silk screen, and film is then mixed with ceramic raw material, fire the porous ceramic film for obtaining disperseing fine through hole,
Using the porous ceramic film as substrate, silane is immersed into duct, hydrolyzes gelation, it is dry, silica airsetting is formed in duct
Then glue applies polytetrafluoroethylene (PTFE) on substrate two sides, obtains a kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm.This
Invention significant advantage is the pore by forming perforation in ceramic membrane, and silica gas is further formed in pore
Gel, and applying polytetrafluoroethylene (PTFE) on substrate two sides so that diaphragm has excellent ionodialysis characteristic, and diaphragm hole
Rate is high, wellability is excellent, has good intensity and thermal dimensional stability, is particularly suitable for the automobile of high power capacity, high power work
Dynamic lithium battery uses.
By a kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm of the present invention compared with commercially available polyalkene diaphragm, such as
Shown in table 1.
Table 1：
| Thickness（μm） | Porosity (%) | 120 DEG C of percent thermal shrinkage（%） | Tensile strength（KN/m） | |
| The present invention | 35 | 74-80 | 0.48-0.52 | 2.1-2.4 |
| Polyolefin | 35 | 73 | 2.5 | 1.9 |
A kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm of the present invention and preparation method, compared with prior art,
Prominent feature and excellent effect are：
1, the present invention combines electrostatic spinning technique, and it is baseplate material to be made with the porous ceramic film of fine through hole is disperseed, more
Pore and aerosil on the ceramic membrane of hole is compound, forms three-dimensional ion channel, diaphragm outer layer covers polytetrafluoroethyl-ne
Alkene material so that diaphragm has excellent ionodialysis characteristic, and diaphragm porosity is high, wellability is excellent, diaphragm is not fragile
It is broken, not easy to break, there is good intensity and thermal dimensional stability.
2, present invention process controllability is good, environmental-friendly, simple for process, the lithium battery dedicated ceramic capillary ion being prepared into
Dialysis diaphragm by good fit, realizes the performance complement of storeroom by organic and inorganic material, be particularly suitable for high power capacity,
The lithium battery for automobile power of high power work uses.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）9 parts of polyvinyl alcohol, 0.2 part of rhamnolipid, 91 parts of deionized water, the heating stirring 3 at 90 DEG C are weighed by mass fraction
Hour, until forming the poly-vinyl alcohol solution of homogeneous viscous, control spinning flow 0.1ml/h, 25 DEG C of temperature in chassis, humidity
55%, aluminium foil is set as 12kV as material, voltage is received, and receives distance 15cm, obtains polyvinyl alcohol silk screen；
（2）The polyvinyl alcohol silk screen is mixed, a concentration of 1.2mol/L of the sodium silicate solution with sodium silicate solution, is adsorbed
After 20 hours, naturally dry, by 400 DEG C of high temperature sinterings, the high temperature sintering time is 8 hours, obtains disperseing fine through hole
Porous ceramic film；
（3）It is put into the silica porous ceramic film for being 5 microns for film thickness in closed container, is re-filled with silane, adsorbs 10 hours
Afterwards, it is filled with deionized water, the volume ratio of silane and deionized water is 1:5, silane hydrolyzate is full of Silica hydrogel, warp in fine duct
It crosses after drying, forms the aerosil that aperture is 40nm in duct, obtain dialysis diaphragm active layer；
（4）Polytetrafluoroethylene material, the polytetrafluoroethylene (PTFE) that coating thickness is 5-80 microns are applied on dialysis diaphragm active layer two sides
Film, after coating polytetrafluoroethylene (PTFE), control machinery is by mechanical stretching, and tensile deformation amount is 1.2%, in ptfe surface shape
At compact arranged micropore, the grain size of the micropore is 200nm, obtains ceramic capillary ionodialysis diaphragm.It will be in the present embodiment
The ceramic capillary ionodialysis diaphragm of preparation is tested, and test result is as shown in table 2.
Embodiment 2
（1）13 parts of polyvinyl alcohol, 3 parts of sophorolipid, 88 parts of deionized water, the heating stirring 2.5 at 92 DEG C are weighed by mass fraction
Hour, until forming the poly-vinyl alcohol solution of homogeneous viscous, control spinning flow 0.15ml/h, 25 DEG C of temperature in chassis, humidity
46%, aluminium foil is set as 20kV as material, voltage is received, and receives distance 15cm.Obtain polyvinyl alcohol silk screen；
（2）The polyvinyl alcohol silk screen is mixed, a concentration of 1.85mol/L of the sodium aluminate solution with sodium aluminate solution, is inhaled
After attached 16 hours, naturally dry, by 480 DEG C of high temperature sinterings, the high temperature sintering time is 6 hours, obtains disperseing fine through hole
Porous ceramic film；
（3）It is put into the porous alumina ceramic film for being 35 microns for film thickness in closed container, is re-filled with silane, adsorbs 6 hours
Afterwards, it is filled with deionized water, the volume ratio of silane and deionized water is 1:8, silane hydrolyzate is full of Silica hydrogel in fine duct,
After drying, the aerosil that aperture is 80nm is formed in duct, obtains dialysis diaphragm active layer；
（4）Polytetrafluoroethylene material, the polytetrafluoroethylene (PTFE) that coating thickness is 5-80 microns are applied on dialysis diaphragm active layer two sides
Film, after coating polytetrafluoroethylene (PTFE), control machinery is by mechanical stretching, and tensile deformation amount is 1.2%, in ptfe surface shape
At compact arranged micropore, the grain size of the micropore is 100nm, obtains ceramic capillary ionodialysis diaphragm.It will be in the present embodiment
The ceramic capillary ionodialysis diaphragm of preparation is tested, and test result is as shown in table 2.
Embodiment 3
（1）14 parts of polyvinyl alcohol, 86 parts of deionized water, heating stirring 3 hours at 96 DEG C are weighed by mass fraction, until being formed
The poly-vinyl alcohol solution of homogeneous viscous, control spinning flow 0.3ml/h, 25 DEG C of temperature in chassis, humidity 47%, aluminium foil are used as and connect
Material is received, voltage is set as 18kV, receives distance 15cm, obtains polyvinyl alcohol silk screen；
（2）The polyvinyl alcohol silk screen is mixed, a concentration of 1.4mol/L of the sodium silicate solution with sodium silicate solution, is adsorbed
After 14 hours, naturally dry, by 430 DEG C of high temperature sinterings, the high temperature sintering time is 7 hours, obtains disperseing fine through hole
Porous ceramic film；
（3）It is put into the porous silica ceramic membrane for being 5 microns for film thickness in closed container, is re-filled with silane, adsorbs 9 hours
Afterwards, it is filled with deionized water, the volume ratio of silane and deionized water is 1:8, silane hydrolyzate is full of Silica hydrogel, warp in fine duct
It crosses after drying, forms the aerosil that aperture is 60nm in duct, obtain dialysis diaphragm active layer；
（4）Polytetrafluoroethylene material is applied on dialysis diaphragm active layer two sides, coating thickness is 65 microns of polytetrafluoroethylene film,
After coating polytetrafluoroethylene (PTFE), control machinery is 2.5% by mechanical stretching, tensile deformation amount, is formed tightly in ptfe surface
The grain size of the micropore of solid matter row, the micropore is 350 microns, obtains ceramic capillary ionodialysis diaphragm.It will be made in the present embodiment
Standby ceramic capillary ionodialysis diaphragm is tested, and test result is as shown in table 2.
Embodiment 4
（1）12 parts of polyvinyl alcohol, 1 part of glyceryl monoacetate, 90 parts of deionized water, the heating stirring at 92 DEG C are weighed by mass fraction
2 hours, until forming the poly-vinyl alcohol solution of homogeneous viscous, control spinning flow 0.18ml/h, 25 DEG C of temperature in chassis, humidity
52%, aluminium foil is set as 17kV as material, voltage is received, and receives distance 15cm, obtains polyvinyl alcohol silk screen；
（2）The polyvinyl alcohol silk screen is mixed, a concentration of 1.75mol/L of the sodium aluminate solution with sodium aluminate solution, is inhaled
After attached 14 hours, naturally dry, by 580 DEG C of high temperature sinterings, the high temperature sintering time is 5.4 hours, obtains disperseing fine perforation
The porous ceramic film in hole；
（3）It is put into the porous alumina ceramic film for being 5 microns for film thickness in closed container, is re-filled with silane, absorption 9.5 is small
Shi Hou, is filled with deionized water, and the volume ratio of silane and deionized water is 1:6.5, silane hydrolyzate is solidifying full of silicon in fine duct
Glue forms the aerosil that aperture is 75nm in duct, obtains dialysis diaphragm active layer after drying；
（4）Polytetrafluoroethylene material is applied on dialysis diaphragm active layer two sides, coating thickness is 80 microns of polytetrafluoroethylene film,
After coating polytetrafluoroethylene (PTFE), control machinery is 3.5% by mechanical stretching, tensile deformation amount, is formed tightly in ptfe surface
The grain size of the micropore of solid matter row, the micropore is 340nm, obtains ceramic capillary ionodialysis diaphragm.It will be prepared in the present embodiment
Ceramic capillary ionodialysis diaphragm tested, test result is as shown in table 2.
Embodiment 5
（1）12 parts of polyvinyl alcohol, 1 part of ethylene glycol, 89 parts of deionized water, the heating stirring at 92 DEG C are weighed by mass fraction
2.4 hours, until forming the poly-vinyl alcohol solution of homogeneous viscous, spinning flow 0.15ml/h is controlled, 25 DEG C of temperature in chassis is wet
Degree 52%, aluminium foil are set as 16kV as material, voltage is received, receive distance 15cm, obtain polyvinyl alcohol silk screen；
（2）The polyvinyl alcohol silk screen is mixed, a concentration of 1.3mol/L of the sodium silicate solution with sodium silicate solution, is adsorbed
After 11 hours, naturally dry, by 430 DEG C of high temperature sinterings, the high temperature sintering time is 4 hours, obtains disperseing fine through hole
Porous ceramic film；
（3）It is put into the porous silica ceramic membrane for being 32 microns for film thickness in closed container, is re-filled with silane, absorption 8.5 is small
Shi Hou, is filled with deionized water, and the volume ratio of silane and deionized water is 1:7, silane hydrolyzate is full of Silica hydrogel in fine duct,
After drying, the aerosil that aperture is 65nm is formed in duct, obtains dialysis diaphragm active layer；
（4）Polytetrafluoroethylene material is applied on dialysis diaphragm active layer two sides, coating thickness is 13 microns of polytetrafluoroethylene film,
After coating polytetrafluoroethylene (PTFE), control machinery is 1.8% by mechanical stretching, tensile deformation amount, is formed tightly in ptfe surface
The grain size of the micropore of solid matter row, the micropore is 200nm, obtains ceramic capillary ionodialysis diaphragm.It will be prepared in the present embodiment
Ceramic capillary ionodialysis diaphragm tested, test result is as shown in table 2.
Comparative example 1
Commercial polyethylene porous membrane is diaphragm, and diaphragm test data is as shown in table 2, and diaphragm material is same as Example 5
Scheme is prepared into battery, carries out the test with embodiment 5, the results are shown in Table 3.
Comparative example 2
（1）9-14 parts of polyvinyl alcohol, 86-91 parts of deionized water are weighed by mass fraction, heating stirring 2-3 is small at 90-96 DEG C
When, until forming the poly-vinyl alcohol solution of homogeneous viscous, control spinning flow 0.1-0.3ml/h, 25 DEG C of temperature in chassis, humidity
45%-55%, aluminium foil are set as 12-20kV as material, voltage is received, receive distance 15cm.Obtain polyvinyl alcohol silk screen；
（2）The polyvinyl alcohol silk screen is mixed with sodium metasilicate or sodium aluminate solution, the sodium aluminate or sodium silicate solution it is dense
Degree is 1.2-1.9mol/L, after adsorbing 10-20 hours, naturally dry, by 400-600 DEG C of high temperature sintering, high temperature sintering time
It is 3-8 hours, obtains the porous ceramic film for disperseing fine through hole；
（3）Polytetrafluoroethylene material is applied on porous ceramic film two sides, the polytetrafluoroethylene film that coating thickness is 5-80 microns applies
After covering polytetrafluoroethylene (PTFE), control machinery is 1.2-3.5% by mechanical stretching, tensile deformation amount, is formed in ptfe surface
The grain size of compact arranged micropore, the micropore is 100-1500 microns, obtains ceramic capillary ionodialysis diaphragm.This is implemented
The ceramic capillary ionodialysis diaphragm prepared in example is tested, and test result is as shown in table 2.
Table 2
| Thickness（μm） | Angle of wetting（°） | Average pore size（nm） | Porosity (%) | 120 DEG C of percent thermal shrinkage（%） | Heat resisting temperature（℃） | Tensile strength（KN/m） | Impedance（Ω） | |
| Embodiment 1 | 20 | 18 | 130 | 74 | 0.48 | ＞ 190 | 2.1 | 1.3 |
| Embodiment 2 | 22 | 17 | 150 | 81 | 0.52 | ＞ 190 | 2.3 | 1.3 |
| Embodiment 3 | 28 | 18 | 180 | 78 | 0.50 | ＞ 190 | 2.2 | 1.5 |
| Embodiment 4 | 30 | 16 | 230 | 80 | 0.49 | ＞ 190 | 2.3 | 1.6 |
| Embodiment 5 | 35 | 19 | 260 | 79 | 0.51 | ＞ 190 | 2.4 | 1.8 |
| Comparative example 1 | 35 | 32 | 1200 | 73 | 2.5 | ＞ 130 | 1.9 | 2.2 |
| Comparative example 2 | 35 | 20 | 800 | 79 | 0.62 | ＞ 170 | 2.1 | 1.9 |
Ceramic capillary ionodialysis diaphragm material using the offer prepared in embodiment 5 and the polyethylene porous in comparative example 1
Film preparation is at battery, nickle cobalt lithium manganate（NCM）, conductive agent（VCX）And bonding agent（PVDF）By 94.5：2.4：3.1 ratio
It is anode pole piece to be coated to aluminium foil and be used as, using graphite as cathode, 1M LiPF6 solution（Solvent is volume ratio 1:1 EC/EMC）For
Electrolyte is assembled into button cell (CR2025) in argon gas atmosphere glove box.It is carried out more than the test of LAND battery charging and dischargings
Charge-discharge test, work system are：Constant current charge and discharge, charging and discharging currents 1C, charging/discharging voltage be 1.5V~4.8V (vs.Li+/
Li).Under conditions of 20 DEG C ± 5 DEG C of environment temperature, humidity 45%-75%, cycle life test is carried out to battery, tests battery
Capacity attenuation rate variable quantity data are as shown in table 3.
Table 3
| Diaphragm material | First discharge specific capacity mAhg-1 | Discharge capacity mAhg after cycle-1 | Recycle 100 capacity retention ratio % | Capacity attenuation rate % |
| Embodiment 5 | 215 | 208 | 99.5 | 4.7 |
| Polyolefin | 120 | 105 | 75.2 | 9.5 |
Claims (10)
1. a kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm, which is characterized in that use porous ceramic film for substrate
Material, the pore and aerosil on porous ceramic film are compound, form three-dimensional ion channel, outer layer covers polytetrafluoro
Vinyl material enhances the wellability of diaphragm.
2. a kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm according to claim 1, which is characterized in that institute
It is Woelm Alumina, silicon oxide ceramics film to state porous ceramic film, and film thickness is 5-80 microns, the aperture of the aerosil
For 40-80nm.
3. a kind of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm according to claim 1, which is characterized in that institute
The thickness for stating polytetrafluoroethylene film is 5-80 microns.
4. a kind of preparation method of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm, which is characterized in that specific preparation side
Method is as follows：
（1）9-14 parts of polyvinyl alcohol, 0-3 parts of surfactant, 86-91 parts of deionized water are weighed by mass fraction, at 90-96 DEG C
Lower heating stirring 2-3 hours controls spinning condition, obtains polyvinyl alcohol silk until forming the poly-vinyl alcohol solution of homogeneous viscous
Net；
（2）The polyvinyl alcohol silk screen is mixed with sodium metasilicate or sodium aluminate solution, the sodium metasilicate or sodium aluminate solution it is dense
Degree is 1.2-1.9mol/L, and after adsorbing 10-20 hours, naturally dry obtains disperseing fine by 400-600 DEG C of high temperature sintering
The porous ceramic film of through hole；
（3）The porous ceramic film is put into closed container, silane is re-filled with, after adsorbing 5-10 hours, is filled with deionized water,
Silane hydrolyzate forms aerosil after drying full of Silica hydrogel in fine duct in duct, obtains dialysis
Diaphragm active layer；
（4）Polytetrafluoroethylene material is applied on dialysis diaphragm active layer two sides, obtains ceramic capillary ionodialysis diaphragm.
5. a kind of preparation method of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm according to claim 4,
It is characterized in that, shown surfactant is rhamnolipid, seaweed glycolipid, sophorolipid, sorbitan, ethylene glycol and glycerine list
One kind in acid esters.
6. a kind of preparation method of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm according to claim 4,
It is characterized in that, the spinning condition is flow 0.1-0.3ml/h；25 DEG C of temperature in chassis；Humidity 45%-55%, aluminium foil are used as and connect
Material is received, voltage is set as 12-20kV, receives distance 15cm.
7. a kind of preparation method of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm according to claim 4,
It is characterized in that, the high temperature sintering time is 3-8 hours.
8. a kind of preparation method of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm according to claim 4,
It is characterized in that, the volume ratio of the silane and deionized water is 1:5-8.
9. a kind of preparation method of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm according to claim 4,
It is characterized in that, after coating polytetrafluoroethylene (PTFE), compact arranged micropore is formed in ptfe surface by mechanical stretching, it is described
The aperture of micropore is 100-500nm.
10. a kind of preparation method of dynamic lithium battery dedicated ceramic capillary ionodialysis diaphragm according to claim 9,
It is characterized in that, it is 1.2-3.5% that control machinery, which stretches the polytetrafluoroethylene (PTFE) deformation quantity,.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109004158A (en) * | 2018-09-03 | 2018-12-14 | 河南克莱威纳米碳材料有限公司 | A kind of high-temperature corrosion-resistance non-woven fabrics lithium ion battery separator and preparation method thereof |
| CN110197883A (en) * | 2019-05-09 | 2019-09-03 | 湖南文理学院 | A kind of lithium ion battery anodic aluminium oxide membrane and preparation method |
-
2018
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109004158A (en) * | 2018-09-03 | 2018-12-14 | 河南克莱威纳米碳材料有限公司 | A kind of high-temperature corrosion-resistance non-woven fabrics lithium ion battery separator and preparation method thereof |
| CN110197883A (en) * | 2019-05-09 | 2019-09-03 | 湖南文理学院 | A kind of lithium ion battery anodic aluminium oxide membrane and preparation method |
| CN110197883B (en) * | 2019-05-09 | 2022-02-18 | 湖南文理学院 | Inorganic diaphragm for lithium ion battery and preparation method |
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