CN108842303A - Boehmite/polyacrylonitrile composite nano fiber diaphragm and the preparation method and application thereof - Google Patents
Boehmite/polyacrylonitrile composite nano fiber diaphragm and the preparation method and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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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
- D01F6/54—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 polymers of unsaturated nitriles
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/43—Acrylonitrile series
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
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- 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
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Abstract
The invention discloses boehmite/polyacrylonitrile composite nano fiber diaphragms and the preparation method and application thereof.The preparation method is that the method for forming colloidal sol with sol-gal process control aluminium alcoholates salt hydrolysis prepares boehmite sol, then it is stirred boehmite sol and polyacrylonitrile solution to obtain homogeneous spinning solution, boehmite/polyacrylonitrile composite nano fiber diaphragm of porous three-dimensional net structure is spun by the method for electrostatic spinning.The diaphragm material that boehmite/polyacrylonitrile composite nano fiber diaphragm is applied as lithium ion battery has excellent lyophily performance, heat resistance and mechanical performance, can significantly improve the chemical property of lithium ion battery.In addition, it is preparation method simple process of the invention, environmentally protective, low in cost, reproducible, it has a good application prospect.
Description
Technical field
The present invention relates to the technology of preparing neighborhoods of lithium battery diaphragm, compound more particularly to a kind of boehmite/polyacrylonitrile
The preparation method of nano fiber diaphragm.
Background technique
Lithium ion battery separator is a kind of porous film, and barrier positive and negative anodes prevent internal short-circuit of battery, but allow ion
Stream quickly through, thus complete quick transmission of the lithium ion between positive and negative anodes during charge discharge.Traditional
Lithium battery commercialization diaphragm is mainly the polyolefins diaphragm that manufacture with dry or wet, and such diaphragm is with lyophily performance and heat-resisting
The deficiencies of performance is poor, to will affect the chemical property of battery.
Boehmite is the chief component of bauxite, is a kind of important industrial chemicals, has unique crystal structure,
It is widely used in the multiple fields such as catalyst, adsorbent, inorganic fire retardants.
Chinese invention patent application 2014108301100 discloses the aqueous laminated diaphragm of lithium ion battery.The multilayer
Diaphragm is made of polymeric substrate, inorganic particulate coatings, organic granular coating, by prepare inorganic or is had using rubbing method
Machine slurry is coated on polymeric substrate, and this method improves the high temperature resistance and mechanical performance of diaphragm to a certain extent.But
It is that due to using multiple coating technique, and inorganic particle and binder are only simple physical blending, be easy to cause layer
Between conformability it is poor, there is the hidden danger of " picking " to cause whole peeling in the problem of caking property deficiency.In addition, since basement membrane is adopted
It is microporous barrier, it is the problems such as coating procedure is likely to result in the blocking microporous situation of inorganic particle, causes porosity low, unfavorable
In the safety and chemical property that improve battery.
Chinese invention patent application 201680020283 discloses secondary lithium batteries composite diaphragm and its manufacturing method.It should
Secondary lithium batteries composite diaphragm includes：Porous base, refractory layer and fused layers.The technique is utilized using cladding process simultaneously
Refractory layer slurry and fused layers slurry are coated in micropore basal membrane one or both sides simultaneously and form multilayer by multi-layer groove coating die
Composite diaphragm.The diaphragm thermal stability and service life of this method preparation increase, and still, the technique is still using poly-
Olefines microporous barrier is modified it by introducing inorganic/organic granular coating, however it remains inorganic particle as basal lamina material
Blocking microporous situation, is unfavorable for the transmission of lithium ion, to influence the electrochemistry of battery at the problem of causing porosity to reduce
Energy.
Summary of the invention
For the deficiency of existing commercial diaphragm, existing multiple coating technology appearance is overcome the present invention provides one kind and " is fallen
The problem of powder "；Nano fiber diaphragm has porous network structure, and porosity reaches 70%~85%, and ionic conductivity reaches
1.5mS cm-1~3.0mS cm-1, boehmite/polyacrylonitrile composite nano fiber diaphragm and its system that contact angle is 0 °~15 °
Preparation Method.
Another object of the present invention is to provide the boehmite/polyacrylonitrile composite nano fiber diaphragm as lithium-ion electric
The application of pond diaphragm.
The diaphragm has porous three-dimensional net structure, and composite nano fiber specific surface area with higher, this has
Help improve the mechanical performance and lyophily performance of diaphragm.The good thermal conductivity of boehmite and anti-flammability also effectively improve it is compound every
The heat resistance of film.Application of the composite diaphragm on lithium ion battery, because of its good lyophily performance and thermodynamic property, very greatly
The security performance and cycle performance of battery are improved in degree.
Boehmite has the features such as heat resisting temperature is high, good with organic matter compatibility；Its hardness is low, can reduce to mechanical mill
It damages, it is advantageous in cost；Boehmite is as a kind of inorganic fire retardants simultaneously, by can be effective with the compound of high molecular material
Improve the heat resistance of material.The excellent thermal conductivity of boehmite can improve the heat conduction problem of lithium ion battery, and anti-flammability can be with
Prevent a wide range of burning and explosion of battery；Boehmite is layer structure, and when material abnormal heating, boehmite is expanded, and is closed
Conduction hole is closed, to block electric current.Material volume is shunk upon a drop in temperature, and electric current conduction hole reopens.Therefore, boehmite
The security performance of lithium ion battery can be effectively improved, provides possibility for the application of high energy battery such as power battery.
The nano fibrous membrane prepared by method of electrostatic spinning has spacial framework and higher porosity, and has good
Mechanical performance, be ideal lithium battery diaphragm material.
The present invention obtains boehmite sol by aluminium alcoholates salt water solution, and homogeneous spinning is then mixed to form with polyacrylonitrile solution
Silk liquid, prepares boehmite/polyacrylonitrile composite nano fiber diaphragm by electrospinning process.It is prepared by the present invention it is compound every
Porous three-dimensional net structure is presented in film, has excellent absorbent, heat resistance and a mechanical performance, and it is in assembling
Under lithium battery, there is good chemical property.
To realize the above-mentioned technical purpose, the present invention uses following technical scheme：
A kind of preparation method of boehmite/polyacrylonitrile composite nano fiber diaphragm, comprises the steps of：
1) alcohol aluminium salt is added in deionized water, 3~4h is stirred at 60-80 DEG C, when there is white precipitate, be added dilute
Nitric acid solution, adjusting pH value of solution is 2~5, then continues to be heated to reflux 8~12h of stirring at 90~100 DEG C, is obtained stable vigorous
Nurse stone colloidal sol；
2) by polyacrylonitrile powder be added organic solvent in, first at room temperature be swollen 8~12h, after stirred at 70~90 DEG C
5~6h is mixed, polyacrylonitrile solution is obtained；The organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- first
One of base pyrrolidones and acetone are a variety of；
3) it is cooled to room temperature to polyacrylonitrile solution, the resulting boehmite sol of step 1) is added to the polypropylene
In nitrile solution, 5~6h is mixed at 70~90 DEG C, naturally cools to room temperature, stands 1~2h, obtains boehmite/polypropylene
Nitrile spinning solution；Then boehmite/polyacrylonitrile composite diaphragm, vacuum at 80~160 DEG C are obtained by the method for electrostatic spinning
It is dry, remove organic solvent and moisture；The mass ratio for controlling boehmite sol and polyacrylonitrile powder is 1~5:10.
To further realize the purpose of the present invention, it is preferable that in step 1), the alcohol aluminium salt is aluminium isopropoxide, sec-butyl alcohol
One of aluminium and boehmite are a variety of.
Preferably, in step 3), the condition of electrostatic spinning is：15~30 DEG C of temperature；Voltage is：10~25kV；Flow velocity is：
0.05~1.5mL/h；Receiving distance is：14~18cm；Syringe needle walking speed back and forth：15~35cm/min；Spinning time 8-15h；Needle
Head diameter be：0.15~0.25mm.
Preferably, in step 1), the mass ratio of the alcohol aluminium salt and deionized water is 1~5:100, alcohol aluminium salt and dust technology
Mass ratio be 1:0.1~0.5.
Preferably, in step 1), stirring for the first time and second of stirring are mechanical stirring or magnetic agitation, stirring rate
For 400~1000r/min.
Preferably, in step 2), the mass ratio of the polyacrylonitrile powder and organic solvent is 0.5~2:10.
Preferably, in step 2), the stirring be mechanical stirring or magnetic agitation, stirring rate be 600~
1000r/min。
Preferably, in step 3), the vacuum drying absolute vacuum degree is -0.1~-0.05MPa, when vacuum drying
Between be 8~15h.
A kind of boehmite/polyacrylonitrile composite nano fiber diaphragm, is made by above-mentioned preparation method, the boehmite/poly-
Propylene nitrile nanofibre composite diaphragm has porous three-dimensional net structure, and porosity is 70%~85%, avarage fiber diameter
For 250nm~400nm, with a thickness of 40 μm~70 μm, contact angle is that shrinking percentage is 0%~10% at 0 °~15 °, 135 DEG C, ion
Conductivity is 1.5mScm-1~3.0mS cm-1。
The boehmite/application of the polyacrylonitrile composite nano fiber diaphragm as lithium ion battery separator.
Compared with the existing technology, the present invention has the following advantages that：
1) present invention it is compound with polyacrylonitrile solution with boehmite sol, by method of electrostatic spinning be prepared into boehmite/gather
Acrylonitrile composite nano fiber diaphragm.The diaphragm has porous three-dimensional net structure, and composite nano fiber is with higher
Specific surface area, this helps to improve the mechanical performance of diaphragm and lyophily performance.The good thermal conductivity of boehmite and anti-flammability
The effective heat resistance for improving composite diaphragm.Application of the composite diaphragm on lithium ion battery, because of its good lyophily performance
And thermodynamic property, largely improve the security performance and cycle performance of battery.
2) preparation process of the present invention is simple, mild condition, boehmite/polypropylene easy to operate, low in cost, and preparing
The excellent combination properties such as nitrile nanofibre composite diaphragm heat resistance, chemical property.
3) present invention uses aluminium alcoholates salt hydrolysis, and sol-gal process prepares boehmite sol, then multiple with polyacrylonitrile solution
Conjunction obtains homogeneous spinning solution, prepares porous nanofiber composite diaphragm by electrostatic spinning technique.Wherein, compound obtained by spinning
Diaphragm can be firmly built on polyacrylonitrile fibre with straight forming, boehmite particle, overcome existing multiple coating technology
The problem of caking property is insufficient, " picking ".
4) present invention has porous network structure using nano fiber diaphragm prepared by method of electrostatic spinning, significantly
The porosity for improving diaphragm, much higher than the diaphragm of prior art preparation；And composite diaphragm straight forming, it is reproducible.
Detailed description of the invention
Fig. 1 is boehmite/polyacrylonitrile composite nano fiber diaphragm SEM figure prepared by embodiment 1, wherein Fig. 1 a) and
Fig. 1 b) be respectively under 5000 times and 50000 times SEM figure；
Fig. 2 is 2400 type single layer of boehmite/polyacrylonitrile composite nano fiber diaphragm and Celgard prepared by embodiment 1
The contact angle test figure of PP diaphragm；Wherein Fig. 2 a) and Fig. 2 b) be respectively boehmite/polyacrylonitrile composite nano fiber diaphragm from
0s to 2s contact angle test figure；Fig. 2 c) and Fig. 2 d) it is respectively the contact angle survey from 0s to 2s of 2400 type single layer PP diaphragm of Celgard
Attempt.
Fig. 3 is that boehmite/polyacrylonitrile composite nano fiber diaphragm prepared by embodiment 1 is schemed with PP diaphragm DSC；
Fig. 4 is what boehmite/polyacrylonitrile composite nano fiber diaphragm prepared by embodiment 1 assembled respectively with PP diaphragm
The cycle performance figure of button cell.
Specific embodiment
In order to better understand the present invention, the present invention is described further with reference to the accompanying drawings and examples, but sends out
Bright embodiment is without being limited thereto.
Embodiment 1
A kind of preparation method of boehmite/polyacrylonitrile composite nano fiber diaphragm, comprises the steps of：
(1) in terms of mass fraction, 1 part of aluminium secondary butylate is slowly added in 100 parts of deionized waters, stirs 4h at 80 DEG C,
When there is white precipitate, be added 0.1 part of dilute nitric acid solution, adjust pH value of solution=3, then continue 90 DEG C, 800r/min next time
Magnetic agitation 12h is flowed, stable boehmite sol is obtained；
(2) in terms of mass fraction, 1 part of polyacrylonitrile powder is added in 10 parts of n,N-Dimethylformamide, first in room temperature
Lower swelling 12h, after at 80 DEG C, 800r/min magnetic agitation 6h, obtain polyacrylonitrile solution；
(3) in terms of mass fraction, it is cooled to room temperature to polyacrylonitrile solution, 1 part of boehmite sol is added to 10 parts and is gathered
In acrylonitrile solution, at 80 DEG C, magnetic agitation 6h under 1000r/min, it is uniformly mixed, naturally cools to room temperature, stand 2h, obtain
Then boehmite/polyacrylonitrile spinning solution passes through the method (temperature of electrostatic spinning：25 DEG C, voltage：16kV receives distance：
16cm, flow velocity：0.64mL/h, syringe needle size：0.21mm, syringe needle walking speed back and forth：20cm/min, time 8h) obtain boehmite/poly-
Acrylonitrile composite diaphragm, 80 DEG C, vacuum drying 12h removes extra solvent under -0.01MPa absolute vacuum degree.
2400 type single layer PP diaphragm (Celgard company of the U.S.) of Celgard is used as comparative example, with a thickness of 25 μm, hole
Rate is 41%.
Fig. 1 is boehmite/polyacrylonitrile composite nano fiber diaphragm SEM figure prepared by embodiment 1, wherein Fig. 1 a) and figure
1b) be respectively under 5000 times and 50000 times SEM figure.As can be seen from Figure 1, boehmite/polyacrylonitrile nanofiber composite diaphragm
With porous three-dimensional net structure, porosity reaches 85%, and avarage fiber diameter is 390 ± 50nm, measures it by micrometer
With a thickness of 45 μm.
Contact angle test is carried out to diaphragm using OCA40Micro type Surface Tension Surface contact angle tester.In Fig. 2, figure
2a) and Fig. 2 b) be respectively boehmite/polyacrylonitrile composite nano fiber diaphragm from 0s to 2s contact angle, contact angle from 70.1 °,
Variation is 6 ° after 2s；In Fig. 2, Fig. 2 c) and Fig. 2 d) it is respectively that 2400 type single layer PP diaphragm of Celgard is contacted from 0s to 2s
Angle, contact angle from 103.1 °, after 2s variation be 101.5 °, illustrate boehmite/polyacrylonitrile nanofiber composite diaphragm ratio PP every
Film has more excellent wettability.1247% (Celgard is up to by the imbibition rate that weight in wet base method can obtain composite diaphragm
169%) 2400 type single layer PP diaphragms are only.
Using differential scanning calorimetry (DSC) test diaphragm thermal stability, 100~250 DEG C of temperature range, heating rate
For 10 DEG C/min.From figure 3, it can be seen that PP diaphragm has a biggish endothermic peak, and boehmite/poly- third when temperature is 167 DEG C
Alkene nitrile nanofibre composite diaphragm does not have apparent peak, shows that composite diaphragm has more excellent thermal stability.
The PP diaphragm of boehmite/polyacrylonitrile nanofiber composite diaphragm and comparison is assembled into CR2016 in glove box
Button cell, charge and discharge cycles 100 times under 0.5C multiplying power, as can be seen from Figure 4, using boehmite/polyacrylonitrile nanofiber
The battery ratio PP diaphragm of composite diaphragm shows better cycle performance, and capacity retention ratio reaches 87.68%, and PP diaphragm is only
It is 55.73%.
The prior art there are diaphragm caking property it is insufficient, porosity is lower the problems such as, there is also the hidden danger of " picking ", are unfavorable for
Improve the safety and chemical property of battery.The present embodiment uses aluminium alcoholates salt hydrolysis, and sol-gal process prepares boehmite sol, so
Homogeneous spinning solution is compounded to form with polyacrylonitrile solution afterwards, porous nano-fibre composite diaphragm is obtained by electrostatic spinning.Wherein,
Composite diaphragm is by electrostatic spinning straight forming, and the coating being not required to by multilayer is modified, and boehmite particle is embedded in strongerly
Onto polyacrylonitrile fibre, existing paint-on technique is overcome because of caking property deficiency, causes the problem of " losing powder "；Electrostatic spinning simultaneously
Nano fiber diaphragm prepared by method has porous network structure, more significantly improves the porosity of diaphragm.Therefore this reality
Original technology can effectively be overcome the shortcomings of by applying composite diaphragm prepared by example, be had to security performance and the chemical property of battery aobvious
The improvement of work.
Embodiment 2
A kind of preparation method of boehmite/polyacrylonitrile composite nano fiber diaphragm, comprises the steps of：
(1) in terms of mass fraction, 2 parts of different aluminium alcoholates is slowly added in 100 parts of deionized waters, stir 4h at 80 DEG C,
When there is white precipitate, be added 0.2 part of dilute nitric acid solution, adjust pH value of solution=3.5, then continue 90 DEG C, 900r/min next time
Magnetic agitation 12h is flowed, stable boehmite sol is obtained；
(2) in terms of mass fraction, 8 parts of n,N-Dimethylformamide and 2 parts of acetone are added in 0.5 part of polyacrylonitrile powder
In, first be swollen 12h at room temperature, after at 80 DEG C, 800r/min magnetic agitation 6h, obtain polyacrylonitrile solution；
(3) in terms of mass fraction, it is cooled to room temperature to polyacrylonitrile solution, 2 parts of boehmite sols are added to 10 parts and are gathered
In acrylonitrile solution, at 80 DEG C, magnetic agitation 6h under 1000r/min, it is uniformly mixed, naturally cools to room temperature, stand 2h, obtain
Then boehmite/polyacrylonitrile spinning solution passes through the method (temperature of electrostatic spinning：25 DEG C, voltage：15kV receives distance：
15cm, flow velocity：0.58mL/h, syringe needle size：0.21mm, syringe needle walking speed back and forth：25cm/min, time 8h) obtain boehmite/poly-
Acrylonitrile composite diaphragm, 80 DEG C, vacuum drying 12h removes extra solvent under -0.01MPa absolute vacuum degree.
Embodiment 3
A kind of preparation method of boehmite/polyacrylonitrile composite nano fiber diaphragm, comprises the steps of：
(1) in terms of mass fraction, 1 part of aluminium secondary butylate and 2 parts of aluminium isopropoxides are added in 100 parts of deionized waters, at 80 DEG C
0.3 part of dilute nitric acid solution is added when there is white precipitate in lower stirring 4h, adjusts pH value of solution=3, then continue 90 DEG C,
Flow back magnetic agitation 12h under 800r/min, obtains stable boehmite sol；
(2) in terms of mass fraction, 1.5 parts of polyacrylonitrile powders are added in 10 parts of n,N-dimethylacetamide, first in room
Temperature is lower to be swollen 12h, after at 80 DEG C, 900r/min magnetic agitation 6h, obtain polyacrylonitrile solution；
(3) in terms of mass fraction, it is cooled to room temperature to polyacrylonitrile solution, 3 parts of boehmite sols are added to 10 parts and are gathered
In acrylonitrile solution, at 80 DEG C, magnetic agitation 6h under 1000r/min, it is uniformly mixed, naturally cools to room temperature, stand 2h, obtain
Then boehmite/polyacrylonitrile spinning solution passes through the method (temperature of electrostatic spinning：25 DEG C, voltage：16.8kV, receive away from
From：16cm, flow velocity：0.73mL/h, syringe needle size：0.23mm, syringe needle walking speed back and forth：25cm/min, time 12h) obtain Bo Mu
Stone/polyacrylonitrile composite diaphragm, 80 DEG C, vacuum drying 12h removes extra solvent under -0.01MPa absolute vacuum degree.
Embodiment 4
A kind of preparation method of boehmite/polyacrylonitrile composite nano fiber diaphragm, comprises the steps of：
(1) in terms of mass fraction, 3 parts of boehmites is added in 100 parts of deionized waters, stir 4h at 80 DEG C, gone out
When existing white precipitate, 0.3 part of dilute nitric acid solution is added, adjusts pH value of solution=3, then continue the magnetic that flows back at 90 DEG C, 800r/min
Power stirs 12h, obtains stable boehmite sol；
(2) in terms of mass fraction, 1 part of polyacrylonitrile powder is added in 10 parts of N methyl pyrrolidones, it is first molten at room temperature
Swollen 12h, after at 80 DEG C, 800r/min magnetic agitation 6h, obtain polyacrylonitrile solution；
(3) in terms of mass fraction, it is cooled to room temperature to polyacrylonitrile solution, 4 parts of boehmite sols are added to 10 parts and are gathered
In acrylonitrile solution, at 80 DEG C, magnetic agitation 6h under 1000r/min, it is uniformly mixed, naturally cools to room temperature, stand 2h, obtain
Then boehmite/polyacrylonitrile spinning solution passes through the method (temperature of electrostatic spinning：30 DEG C, voltage：17.5kV, receive away from
From：17cm, flow velocity：0.58mL/h, syringe needle size：0.22mm, syringe needle walking speed back and forth：30cm/min, time 10h) obtain Bo Mu
Stone/polyacrylonitrile composite diaphragm, 80 DEG C, vacuum drying 12h removes extra solvent under -0.01MPa absolute vacuum degree.
To above embodiments and PP diaphragm, every physics and electrochemical property test are as shown in table 1 below.Wherein, PP diaphragm
For Celgard2400 type single-layer septum.
Composite diaphragm thickness is by miking；
Porosity is measured and is calculated using n-butanol method, and different diaphragms are separately immersed in n-butanol after 1h,
The weight before and after diaphragm imbibition is weighed, equation is：
Porosity (%)=(weight before weight-imbibition after imbibition) × 100%/(density × diaphragm of n-butanol
Volume)；
The measurement of imbibition rate is to weigh diaphragm imbibition front and back respectively after diaphragm is impregnated 1h in the electrolytic solution in glove box
Weight, and be calculated, equation is：
Imbibition rate (%)=(weight before weight-imbibition after imbibition) × 100%/(weight before imbibition)；
The shrinking percentage of diaphragm is tested, and diaphragm is cut into the disk that diameter is 19mm using sheet-punching machine, and by different diaphragms
It is placed in air dry oven, 1h is heated at 135 DEG C, the area of measurement heating front and back diaphragm is calculated, equation is by equation：
Shrinking percentage (%)=(diaphragm area-heating metacneme area before heating) × 100%/(diaphragm area before heating)；
Ionic conductivity is that different diaphragms are assembled into stainless steel substrates | diaphragm | 2016 type occluded corrosion cell of stainless steel substrates CR,
The impedance for measuring different diaphragms respectively by Gamry electrochemical workstation, is calculated by equation, and equation is：
Ionic conductivity=membrane thicknesses/(diaphragm volume resistance × diaphragm area)；
Different diaphragms are assembled into 2016 type battery of CR in glove box, are tested by new prestige battery general performance test
The chemical properties such as specific discharge capacity, efficiency for charge-discharge, the circulating ratio of battery.
Table 1
It can be seen that from 1 test result of table, Examples 1 to 4 not only has more excellent porosity, imbibition compared to PP diaphragm
Rate and ionic conductivity, and shrinking percentage is low, and heat-resistant stability is good, while having excellent chemical property.
The present invention uses aluminium alcoholates salt hydrolysis, and sol-gal process prepares boehmite sol, then compound with polyacrylonitrile solution
Homogeneous spinning solution is obtained, porous nanofiber composite diaphragm is prepared by electrostatic spinning technique.Wherein, obtained by spinning it is compound every
Film can be firmly built on polyacrylonitrile fibre with straight forming, boehmite particle, and it is viscous to overcome existing multiple coating technology
The problem of knot property is insufficient, " picking "；Nano fiber diaphragm prepared by method of electrostatic spinning has porous network structure simultaneously, more
Add and significantly improve the porosity of diaphragm, much higher than the diaphragm of prior art preparation；And composite diaphragm straight forming, prepare work
Skill is relatively simple, reproducible.Therefore nanofiber composite diaphragm prepared by the present invention can effectively overcome original technology not
Foot, and the security performance and chemical property of battery can be significantly improved.
Can to sum up obtain, the present invention prepared by boehmite/polyacrylonitrile composite nano fiber diaphragm can not only meet lithium from
The basic demand of sub- battery diaphragm, and can effectively improve mechanical performance, lyophily performance, heat resistance and the electrochemistry of diaphragm
Performance.Preparation process of the invention is simple, mild condition, boehmite/polypropylene easy to operate, low in cost, and preparing
The excellent combination properties such as nitrile nanofibre composite diaphragm heat resistance, chemical property, have a good application prospect.
Above embodiments are not intended to limit the invention, done within the spirit and principles of the present invention any to repair
Change, equivalent replacement and improvement etc., should all be included in the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of boehmite/polyacrylonitrile composite nano fiber diaphragm preparation method, it is characterised in that comprise the steps of：
1) alcohol aluminium salt is added in deionized water, 3~4h is stirred at 60-80 DEG C, when there is white precipitate, dust technology is added
Solution, adjusting pH value of solution is 2~5, then continues to be heated to reflux 8~12h of stirring at 90~100 DEG C, obtains stable boehmite
Colloidal sol；
2) by polyacrylonitrile powder be added organic solvent in, first at room temperature be swollen 8~12h, after at 70~90 DEG C stirring 5~
6h obtains polyacrylonitrile solution；The organic solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl pyrrole
One of pyrrolidone and acetone are a variety of；
3) it is cooled to room temperature to polyacrylonitrile solution, it is molten that the resulting boehmite sol of step 1) is added to the polyacrylonitrile
In liquid, 5~6h is mixed at 70~90 DEG C, naturally cools to room temperature, stands 1~2h, obtains boehmite/polyacrylonitrile and spins
Silk solution；Then boehmite/polyacrylonitrile composite diaphragm is obtained by the method for electrostatic spinning, is dried in vacuo at 80~160 DEG C,
Remove organic solvent and moisture；The mass ratio for controlling boehmite sol and polyacrylonitrile powder is 1~5:10.
2. boehmite according to claim 1/polyacrylonitrile composite nano fiber diaphragm preparation method, feature exist
In in step 3), the condition of electrostatic spinning is：15~30 DEG C of temperature；Voltage is：10~25kV；Flow velocity is：0.05~1.5mL/
h；Receiving distance is：14~18cm；Syringe needle walking speed back and forth：15~35cm/min；Spinning time 8-15h；Needle diameter size is：
0.15~0.25mm.
3. boehmite according to claim 1/polyacrylonitrile composite nano fiber diaphragm preparation method, feature exist
In in step 1), the alcohol aluminium salt is one of aluminium isopropoxide, aluminium secondary butylate and boehmite or a variety of.
4. boehmite according to claim 1/polyacrylonitrile composite nano fiber diaphragm preparation method, feature exist
In in step 1), the mass ratio of the alcohol aluminium salt and deionized water is 1~5:100, the mass ratio of alcohol aluminium salt and dust technology is 1:
0.1~0.5.
5. boehmite according to claim 1/polyacrylonitrile composite nano fiber diaphragm preparation method, feature exist
In, in step 1), stirring for the first time and second stirring are mechanical stirring or magnetic agitation, stirring rate is 400~
1000r/min。
6. boehmite according to claim 1/polyacrylonitrile composite nano fiber diaphragm preparation method, feature exist
In in step 2), the mass ratio of the polyacrylonitrile powder and organic solvent is 0.5~2:10.
7. boehmite according to claim 1/polyacrylonitrile composite nano fiber diaphragm preparation method, feature exist
In in step 2), the stirring is mechanical stirring or magnetic agitation, and stirring rate is 600~1000r/min.
8. boehmite according to claim 1/polyacrylonitrile composite nano fiber diaphragm preparation method, feature exist
In in step 3), the vacuum drying absolute vacuum degree is -0.1~-0.05MPa, and the vacuum drying time is 8~15h.
9. a kind of boehmite/polyacrylonitrile composite nano fiber diaphragm, which is characterized in that it is by any one of claim 1-8 institute
It states preparation method to be made, the boehmite/polyacrylonitrile nanofiber composite diaphragm has porous three-dimensional net structure, hole
Rate is 70%~85%, and avarage fiber diameter is 250nm~400nm, and with a thickness of 40 μm~70 μm, contact angle is 0 °~15 °,
Shrinking percentage is 0%~10% at 135 DEG C, and ionic conductivity is 1.5mS cm-1~3.0mS cm-1。
10. boehmite described in claim 9/application of the polyacrylonitrile composite nano fiber diaphragm as lithium ion battery separator.
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