CN106450101A - Method for preparing novel lithium battery diaphragm by coaxial electrostatic spinning - Google Patents
Method for preparing novel lithium battery diaphragm by coaxial electrostatic spinning Download PDFInfo
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- CN106450101A CN106450101A CN201610747668.1A CN201610747668A CN106450101A CN 106450101 A CN106450101 A CN 106450101A CN 201610747668 A CN201610747668 A CN 201610747668A CN 106450101 A CN106450101 A CN 106450101A
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- electrostatic spinning
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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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
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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
-
- 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
-
- 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 provides a method for preparing a novel lithium battery diaphragm by coaxial electrostatic spinning, and belongs to the technical field of the lithium battery diaphragm. The novel lithium battery diaphragm is a composite fiber membrane prepared by a coaxial electrostatic spinning technology and having a core/shell structure; the core and shell layers of the composite fiber membrane are concentric-coaxial-shaped; the core layer consists of high-melting-point polyarylether sulfone ketone nanofibers; the shell layer consists of low-melting-point polyvinylidene fluoride nanofibers; particularly, the coaxial composite diaphragm is subjected to hot-press treatment at certain temperature and pressure; and the shell layer fibers generate micro melting or melting to enhance the binding power between fibers, so that the tensile strength of the composite diaphragm in each direction is greatly improved. The porosity of the novel lithium battery diaphragm reaches greater than 75%; and the electrolyte absorption rate reaches greater than 550%; the diaphragm can withstand a temperature of 180 DEG C, so that the diaphragm prepared by the method has good electrochemical property, thermal performance and mechanical performance, which has high application value in the fields of aviation, spaceflight, electric vehicle and the like.
Description
Technical field
The present invention relates to a kind of novel lithium ion battery diaphragm and preparation method thereof, specifically, the present invention relates to one
The method preparing novel lithium battery barrier film with coaxial electrostatic spinning, belongs to lithium battery diaphragm technical field.
Background technology
Lithium ion battery, due to the advantage of high-energy-density and high power density, has been widely used for mobile phone, notebook
Deng portable type electronic product, increasingly serious with the scarcity of petroleum resources and environmental problem, it is currently also progressively extended to electricity
The new-energy automobile such as electrical automobile, hybrid vehicle field, power lithium-ion battery has very big development potentiality, also will face
Increasing challenge.
Lithium ion battery separator plays the effect of lithium ion in conducting liquid electrolyte, isolate battery plus-negative plate simultaneously in case
The two contacts with each other and is short-circuited.Lithium battery diaphragm general in the market is mainly by prepared by dry or wet gathering
Ethene (PE) and polypropylene (PP) barrier film, such barrier film has good electrochemical stability and suitable mechanical strength, simultaneously
There is certain heat and close performance.But it is high that some inferior positions of conventional polyolefins barrier film make it be difficult to meet power lithium-ion battery
Energy density and the requirement of high safety performance, porosity as relatively low in polyalkene diaphragm, poor electrolyte wetability and high temperature
Hot dimensional contraction serious down.The porosity of business polyalkene diaphragm typically about 40%, nonpolar polyolefine material with
The electrolyte wetability of carbonates is poor, so that the electrolyte pick up of barrier film is relatively low, it is impossible to obtain good ion-conductance
Conductance, has had a strong impact on big multiplying power discharging property and the cyclical stability of lithium ion battery；Polyalkene diaphragm at high temperature tight
Weight dimensional contraction can cause internal short-circuit of battery, may finally cause fire or explosion accident.New-energy electric vehicle uses into
Thousand up to ten thousand battery cores are together in series as driving force, and the fuel factor in cell operations is more significantly, so, in order to meet electricity
The requirements at the higher level that membrane properties is proposed by electrical automobile and energy storage lithium battery, need research and development to have good chemical property and Gao An
The novel lithium ion battery diaphragm of full performance.
Electrostatic spinning technique use polymer solution carry out spinning at normal temperatures, can spinning material wide material sources, technique letter
Single, and the appearance structure controllable of gained nanofiber, can be used for preparing fibre diameter little, the big polymer nano of specific surface area
Rice tunica fibrosa.The polymer solution with certain viscosity polarizes in high voltage electric field, charged polymer jet through high-speed stretch,
Solvent volatilization is finally solidificated on reception pole plate, obtains the tunica fibrosa at micro-nano-scale for the diameter.Prepared by electrostatic spinning
Tunica fibrosa typically has higher porosity, generally up to more than 70%, so Static Spinning barrier film has good gas permeability, and can
It is substantially reduced the internal resistance of cell, improve charge-discharge performance.
Electrostatic spinning Kynoar (PVDF) barrier film has that porosity is high, electrolyte wetability is good and electrode compatibility
Wait well outstanding advantages, have very big development potentiality in field of lithium ion battery, but PVDF fusing point is at about 175 DEG C, with polypropylene
(PP) melt temperature is suitable, is at high temperature easy to dimensional contraction, it is difficult to improve the heat-resistant stable of lithium battery diaphragm.
Poly (aryl ether sulfone ketone) (PPESK) resin of structure containing diazanaphthalene biphenyl has higher heat resistance, and vitrification point is at 250-
Between 370 DEG C.Containing substantial amounts of ehter bond (-O-), carbonyl (C=O) and sulfuryl (O=S=O) isopolarity group in its molecule, have
It is beneficial to improve the wellability to carbonates electrolyte for the diaphragm material.Electrostatic spinning poly (aryl ether sulfone ketone) random orientation nanofiber every
Film not only has good gas permeability and ionic conductivity, and can keep its normal morphology under 220 DEG C of high temperature, is greatly improved
The chemical property of lithium battery diaphragm and high temperature dimensional stability, be the novel lithium battery separator product of a kind of great potential.
The moulding process feature of electrostatic spinning technique itself determine fiber be simply piled into have certain thickness thin
Film, is only combined together by overlap joint between nanofiber, so adhesive property is poor, in drawing process fibrage and layer it
Between be susceptible to Relative sliding, mechanical strength is generally relatively low, limits its actual application.Receive therefore, it is necessary to solve electrostatic spinning
The problem of the poor mechanical property of rice tunica fibrosa, just can prepare excellent electrochemical performance and have the comprehensive high of suitable mechanical intensity concurrently
Performance lithium ion battery separator.
The present invention uses coaxial electrostatic spinning technology, using Kynoar (PVDF) polymer solution as spinning stratum nucleare,
Poly (aryl ether sulfone ketone) (PPESK) resin solution, as spinning shell, carries out Static Spinning under the conditions of identical voltage and receiving range
Silk, two kinds of polymer solutions polarize after the match at high-pressure electrostatic simultaneously and produce jet, polymer jet through being sufficiently tensile, solvent waves
Send out and solidification, finally prepared the concentric shafts fiber non-woven cloth diaphragm of fiber random arrangement, given full play to the excellent of bi-material
Optimum energy.The composite diaphragm preparing carries out hot pressing post processing at a certain temperature, and the shell fiber of low melting point produces micro-molten
Melting or melting and make the cohesive force between fiber strengthen, stratum nucleare fiber remains to keep former due to its good resistance to elevated temperatures simultaneously
Carrying out form, the tensile strength of composite membrane all directions is all greatly improved.
Patent CN103474600A proposes the preparation method of a kind of polyimide nanofiber membrane with cross-linked structure.
Realize crosslinked knot by performing etching process in the ammonia spirit of Ph=8-10 to presoma polyamic acid nano fibrous membrane
The nanofiber of loose overlap joint is formed network structure by crosslinking points by structure, then carries out ladder in electric drying oven with forced convection
Degree intensification hot imidization prepares the polyimide nanofiber membrane with cross-linked structure.This kind of barrier film hole up to about 80%,
Greatly reducing battery impedance, improve big multiplying power discharging property, the mechanical strength of barrier film increases substantially simultaneously, but crosslinked
The more difficult control of condition of reaction, is unfavorable for obtaining the homogeneous High-performance diaphragm of performance.
Patent CN101562243A proposes the electrostatic spinning preparation method of high-performance polyarylether resin lithium battery diaphragm.Should
Method is to be respectively placed in the different syringe pumps of spinning-drawing machine high-performance polyarylether resin solution from general engineering resin solution, with
When carry out to two resinoid solution mixing Electrospun, utilize in spinning process mutually tangle between various fibers, braiding, finally with
The form of fabric nonwoven cloth is collected on the reception device, and prepares high-performance lithium battery diaphragm.This composite diaphragm has well
Ion permeable performance and the wetting property excellent to electrolyte, but the interfacial adhesion point mechanical property between two kinds of different fibers
Poor, and two kinds of polymer fiber diameter differences are relatively big, easily cause the chemical property causing owing to membrane thicknesses is uneven
Unstable.
Patent CN103469488A proposes the preparation side of a kind of enhancement mode electrostatic spinning nano fiber lithium ion battery separator
Method.The polymer dope system that two kinds of melt temperatures differ more than 30 DEG C is mixed by the method by electrostatic spinning technique
Spinning, then certain temperature between low melting point polymer and high-melting-point polymer fusing point carries out hot-pressing processing, makes tunica fibrosa
Between bonding, improve the mechanical strength of tunica fibrosa, but higher heat treatment temperature will make low melting point polymer melt, right
The bigger negative effect that barrier film porosity causes, thus obtain higher ionic conductivity and chemical property by being unfavorable for.
Content of the invention
Present invention seek to address that the above deficiency that lithium ion battery separator prior art exists, offer a kind of porosity height,
Chemical property is good and the preparation method of novel high-performance lithium battery diaphragm with higher mechanical strength.Above-mentioned for realizing
Purpose, the technical scheme that the present invention provides is：A kind of coaxial electrostatic spinning prepares the method for novel lithium battery barrier film, its feature
It is：Described novel lithium battery barrier film is the composite cellulosic membrane of core/shell structure prepared by a kind of coaxial electrostatic spinning technology, its
It is characterised by：The nucleocapsid two-layer of composite cellulosic membrane is concentric shaft-like, and stratum nucleare is made up of dystectic poly (aryl ether sulfone ketone) nanofiber,
Shell is made up of the polyvinylidene fluoride nanometer fiber of low melting point, and particularly this coaxial composite membrane is carried out under uniform temperature and pressure
Hot-pressing processing, shell fiber produces micro-melted or fusing and makes the cohesive force between fiber strengthen, drawing of composite membrane all directions
Stretch intensity to be all greatly improved.This novel lithium battery barrier film porosity reaches more than 75%, and electrolyte pick up is up to 550%
Above, it is resistant to 180 DEG C of high temperature, thus barrier film prepared by the method has good chemical property and heat, mechanical property concurrently, in boat
The fields such as sky, space flight and electric automobile have very high using value.
Novel lithium battery barrier film of the present invention is a kind of core/shell structure compound co-axial tunica fibrosa through hot-pressing processing,
Wherein stratum nucleare fiber is poly (aryl ether sulfone ketone) (PPESK) material, and shell fiber is Kynoar (PVDF) material.Nuclear fibre leads to
Cross coaxial electrostatic spinning silk device to prepare, during coaxial electrostatic spinning, stratum nucleare and sheath polymers solution are attached separately to two not
With syringe in, spinneret system is coaxial but the capillary of different inner diameters forms by two, under high voltage electric field effect, outer liquid
With stratum nucleare liquid joint after body outflow, solidification first two liquid will not be admixed together, and shell liquid stretches through high frequency, high velocity spray
When penetrating, ectonexine solution interface will produce powerful shear stress, and stratum nucleare solution is under shear stress, same along shell
Axle moves, and bending whip dynamic deformation is simultaneously solidified into ultra-fine coaxial composite nano fiber.Solvent fully volatilize after composite cellulosic membrane
By the Kynoar glass transition temperature hot-pressing processing carried out above in low melting point, the polyvinylidene fluoride of shell will
Produce micro-melted or partial melting and mutually bond between nanofiber, add the effective bonding point in tunica fibrosa, thus
The tensile strength making core shell composite cellulosic membrane go up in all directions is all greatly improved, and can resist lithium battery and assemble
The power being subject on journey septation coiling direction, in hot pressing, the poly (aryl ether sulfone ketone) fiber of shell is due to its higher fusing point
Remain to keep its original form with heat resistance, thus through the coaxial tunica fibrosa of hot-pressing processing remain to keep higher porosity and
Pick up, this is significant advantage compared with common heat treatment barrier film, thus potential becomes a kind of preferable Novel lithium
Battery diaphragm product.
Technical scheme：
A kind of coaxial electrostatic spinning prepares the method for novel lithium battery barrier film, and step is as follows：
The first step：It is dissolved separately in PPESK and polyvinylidene fluoride resin in organic solvent, formed homogeneous
Stable spinning solution A and spinning solution B, wherein, the concentration of PPESK solution is 10-25wt%, polyvinylidene fluoride
The concentration of olefine resin solution is 8%-20wt%；
Described organic solvent is N, N dimethyl acetamide (DMAc), N, N-dimethylformamide (DMF), N-methyl-pyrrole
One or more mixing in pyrrolidone (NMP), oxolane (THF), acetone.
Second step：Two syringes take spinning solution A and spinning solution B respectively, and are fixed on the support of electrostatic spinning machine,
Syringe is connected with coaxial electrostatic spinning equipment, and syringe and coaxial electrostatic spinning equipment master equipped with PPESK solution lead to
Road is connected；Paste one layer of aluminium foil in receiving roll, receive device as fiber, arrange end, coaxial electrostatic spinning equipment main channel with
Distance between receiving roll is 10-25cm, and end, coaxial electrostatic spinning equipment main channel is connected with high-voltage power cathode by wire,
Receiving roll is connected with high voltage power supply negative pole；
3rd step：Arranging electrostatic spinning machine temperature and humidity is predetermined value, and adjusting voltage is 8-25kV, poly (aryl ether sulfone ketone) tree
Lipoprotein solution injection speed is 0.02mm/min-0.2mm/min, and polyvinylidene fluoride resin solution injection speed is 0.04-0.2mm/
Min, remains that polyvinylidene fluoride resin solution injection speed is more than PPESK solution injection speed, starts to spin
Silk；In spinning process, two kinds of spinning solutions do not mix before curing, and internal outer layer liquid applies high voltage electric field, at spinning nozzle
Forming compound taylor cone, compound taylor cone is further drawn into core/shell structure injection thread, through too strong during stretching
Strong whip is dynamic, flexural deformation, with the gradually refinement of solvent quick volatilization and injection stream in jet drafting process, finally at fibre
Dimension receives the electrostatic spinning poly (aryl ether sulfone ketone) core-Kynoar shell composite nano-fiber membrane collecting coaxial configuration on device；
It is placed in electrostatic spinning poly (aryl ether sulfone ketone) core-Kynoar shell composite nano-fiber membrane under vacuum condition, be dried
Fully volatilize to solvent, obtain dried electrostatic spinning poly (aryl ether sulfone ketone) core-Kynoar shell composite nano-fiber membrane；
4th step：By dried electrostatic spinning poly (aryl ether sulfone ketone) core-Kynoar shell composite nano-fiber membrane from aluminium
Take off on foil paper, be cut into required form, be placed on the stainless steel mould of hot press, hot pressing temperature 150-250 DEG C is set, protect
Temperature 0.5-2h, hot pressing pressure 1-5MPa, carry out hot pressing, and hot pressing is carried out under vacuum；Obtain hot pressing is coaxial fine
Dimension composite membrane is placed under vacuum condition and is dried, and i.e. obtains novel lithium battery barrier film, and described novel lithium battery barrier film porosity is
70%-90%, electrolyte pick up is up to more than 550%, is resistant to 180 DEG C of high temperature, and thickness is 30-80 μm.
In 3rd step, the time of spinning is 1-8h；The temperature of described electrostatic spinning machine is 20-50 DEG C, and humidity is 20%-
50%.
In 3rd step, baking temperature is 40-120 DEG C, and drying time is 12-24h.
Described PPESK refers to the class solubility height growing up on the basis of polyarylether resin
Energy thermoplastic resin, is the novel PPESK of a kind of structure containing diazanaphthalene biphenyl, is called for short PPESK, and wherein S represents
Sulfuryl (O=S=O), K represents carbonyl (C=O), and S/K ratio is adjustable.Described polyvinylidene fluoride resin refers to that vinylidene is equal
Polymers or the copolymer of vinylidene and other a small amount of fluorine-containing vinyl monomers, PVDF resin has good resistance to chemical attack
Property, heat-resisting quantity, oxidative resistance etc., its glass transition temperature-39 DEG C, fusing point 170 DEG C, heat decomposition temperature about 350 DEG C, long
Phase uses temperature at-40～150 DEG C.
The present invention has beneficial effect：(1) the novel PPESK of structure containing diazanaphthalene biphenyl has excellent
Resistance to elevated temperatures, carry out the coaxial compound high high-temp stability that can be substantially improved barrier film with Kynoar, prepare
Electrostatic spinning poly (aryl ether sulfone ketone)/coaxial the composite cellulosic membrane of Kynoar size under 180 DEG C of high temperature does not substantially shrink,
Be conducive to hot situation complicated in reply electric automobile running, substantially increase the security performance of dynamic lithium battery；(2) make
The coaxial composite cellulosic membrane of random orientation got ready is at Kynoar vitrification point hot-pressing processing carried out above, Kynoar
Fiber produces micro-melted or partial melting, thus adds the effective bonding point in composite cellulosic membrane, hinders in drawing process
The deformation of network of fibers, substantially increases coaxial composite membrane tensile strength in all directions, and extension test shows, uses this
The tensile strength of the novel high-performance Static Spinning poly (aryl ether sulfone ketone) lithium battery diaphragm of invention preparation is than random orientation poly (aryl ether sulfone ketone)
Nano fibrous membrane improves 4-15 times, disclosure satisfy that the mechanical performance needed for lithium battery diaphragm assembling, and owing to using Gao Rong
The poly (aryl ether sulfone ketone) fiber of point, as stratum nucleare, remains to keep original form, the porosity of coaxial composite membrane in hot pressing
Lose less, while ensureing good mechanical properties, also maintain higher porosity.(3) containing greatly in poly (aryl ether sulfone ketone) molecule
Ehter bond (-O-), carbonyl (C=O) and sulfuryl (O=S=O) the isopolarity group of amount, contains (C-F) in Kynoar molecule
Polar group, thus Static Spinning poly (aryl ether sulfone ketone)/Kynoar coaxial compound nanometre fibre film is to carbonates electrolyte
Wellability is good, and pick up may be up to more than 550%, effectively reduces the body internal resistance of lithium battery, substantially increases barrier film electricity
Solve the ionic conductivity of liquid system, while extending lithium battery cycle life, also improve the ability of big multiplying power discharging.
Brief description
Fig. 1 is Static Spinning 20%PPESK/15%PVDF nucleocapsid composite cellulosic membrane stereoscan photograph, wherein solution injection
Speed is respectively 0.08mm/min and 0.12mm/min.
Fig. 2 is the stress-strain diagram of the Static Spinning 20%PPESK/12%PVDF nucleocapsid composite cellulosic membrane through hot-pressing processing
Figure.
Fig. 3 is the coaxial electrostatic spinning 15%PPESK/12%PVDF nucleocapsid composite fibre lithium battery diaphragm Buddhist nun through hot-pressing processing
Qwest's curve map.
Fig. 4 is the method equipment therefor schematic diagram that a kind of coaxial electrostatic spinning prepares novel lithium battery barrier film.
Detailed description of the invention
Below in conjunction with accompanying drawing and technical scheme, further illustrate the detailed description of the invention of the present invention.
Embodiment 1
Taking a certain amount of volume ratio is 3:The oxolane of 7 and 1-METHYLPYRROLIDONE mixed solvent, dissolve a certain amount of
PPESK powder is in round-bottomed flask, and preparation obtains the PPESK polymer solution of mass fraction 10%；Taking a certain amount of volume ratio is
4:The N of 6, N dimethyl acetamide (DMAc) and acetone mixed solvent, dissolve a certain amount of PVDF powder in round-bottomed flask, join
Prepare the PVDF solution that mass fraction is 8%, two kinds of solution are respectively placed in 60 DEG C of temperature constant magnetic stirrings in magnetic stirring apparatus
12h, prepares spinning solution, is then saved in Brown Glass Brown glass bottles and jars only stand-by.The disposable syringe using capacity 10ml takes respectively
4ml poly (aryl ether sulfone ketone) spinning solution and 10ml Kynoar spinning solution, select the flat mouth stainless steel syringe needle of a diameter of 0.3mm
It as the stratum nucleare solution syringe needle of coaxial spinning, is separately fixed at two syringes on spinning-drawing machine support, adjust coaxial spinning pin
Head position makes syringe needle be in the position at receiving roll center, is wound around one layer of aluminium foil and is easy to receive fiber in receiving roll.Set quiet
Temperature within Electrospun machine is 30 DEG C, and humidity is 20%, and the distance between regulation flat mouth stainless steel syringe needle and receiving roll is
15cm, regulation voltage is 8kV, and poly (aryl ether sulfone ketone) stratum nucleare solution injection speed is 0.02mm/min, Kynoar shell solution
Injection speed is 0.04mm/min, and receiving roll rotating speed is 100r/min, spinning time 6h, after treating that spinning terminates, by barrier film from
Take off in receiving roll, be placed in 60 DEG C of process 12h in vacuum drying oven.Dried barrier film is cut into regular rectangular shape, is placed in
On the used stainless steel mould of hot press, arranging hot pressing temperature is 150 DEG C, and temperature retention time is 1h, and pressure is 1MPa.At hot pressing
Barrier film after reason is placed in drying at room temperature 12h in vacuum drying oven, stand-by.
After tested, the PPESK/PVDF core shell composite nano-fiber membrane of preparation under the conditions of being somebody's turn to do, thickness is 53 μm, porosity
85%, at LiFePO4 electrolyte (EC:DEC=1：1 volume ratio) in pick up reach 750%, diaphragm electrolysis liquid system from
Electron conductivity reaches 3.5mS cm-1, tensile strength is 8.6MPa, improves than the 0.95MPa of random orientation PPESK barrier film
910%.
Embodiment 2
Taking a certain amount of volume ratio is 4:The oxolane of 6 and N, N dimethyl acetamide (DMAc) mixed solvent, dissolves certain
The PPESK powder of amount is in round-bottomed flask, and preparation obtains the PPESK polymer solution of mass fraction 15%；Remove a certain amount of volume
Ratio is 3:The N of 7, N dimethyl acetamide (DMAc) and acetone mixed solvent, dissolve a certain amount of PVDF powder in round-bottomed flask
In, preparation obtains the PVDF solution that mass fraction is 12%, and two kinds of solution are respectively placed in 60 DEG C of constant temperature magnetic in magnetic stirring apparatus
Power stirs 12h, prepares spinning solution, is then saved in Brown Glass Brown glass bottles and jars only stand-by.Use the disposable syringe of capacity 10ml
Taking 4ml poly (aryl ether sulfone ketone) spinning solution and 10ml Kynoar spinning solution respectively, the flat mouth selecting a diameter of 0.3mm is stainless
Draw point head, as the stratum nucleare solution syringe needle of coaxial spinning, is separately fixed at two syringes on spinning-drawing machine support, adjusts coaxial
Spinning needle position makes syringe needle be in the position at receiving roll center, is wound around one layer of aluminium foil and is easy to receive fiber in receiving roll.
Setting the temperature within electrostatic spinning machine as 35 DEG C, humidity is 20%, between regulation flat mouth stainless steel syringe needle and receiving roll away from
From for 10cm, regulation voltage is 15kV, and poly (aryl ether sulfone ketone) stratum nucleare solution injection speed is 0.08mm/min, Kynoar shell
Solution injection speed is 0.2mm/min, and receiving roll rotating speed is 100r/min, spinning time 2.5h, after treating that spinning terminates, and will be every
Film takes off from receiving roll, is placed in 80 DEG C of process 12h in vacuum drying oven.Dried barrier film is cut into regular rectangular shape,
Being placed on the used stainless steel mould of hot press, arranging hot pressing temperature is 200 DEG C, and temperature retention time is 2h, and pressure is 3MPa.By heat
Barrier film after pressure is processed is placed in drying at room temperature 12h in vacuum drying oven, stand-by.
After tested, the 15%PPESK/12%PVDF core shell composite nano-fiber membrane of preparation under the conditions of being somebody's turn to do, thickness is 40 μ
M, porosity 81%, at LiFePO4 electrolyte (EC:DEC=1：1 volume ratio) in pick up reach 735%, diaphragm electrolysis
Liquid system ionic conductivity reaches 2.8mS cm-1, tensile strength is 26MPa, improves than the 1.8MPa of random orientation PPESK barrier film
1444%.
Embodiment 3
Taking a certain amount of volume ratio is 6:The oxolane of 4 and DMF (DMF) mixed solvent, dissolve certain
The PPESK powder of amount is in round-bottomed flask, and preparation obtains the PPESK polymer solution of mass fraction 20%；Remove a certain amount of volume
Ratio is 5:The N of 5, N dimethyl acetamide (DMAc) and acetone mixed solvent, dissolve a certain amount of PVDF powder in round-bottomed flask
In, preparation obtains the PVDF solution that mass fraction is 16%, and two kinds of solution are respectively placed in 60 DEG C of constant temperature magnetic in magnetic stirring apparatus
Power stirs 12h, prepares spinning solution, is then saved in Brown Glass Brown glass bottles and jars only stand-by.Use the disposable syringe of capacity 10ml
Taking 6ml poly (aryl ether sulfone ketone) spinning solution and 8ml Kynoar spinning solution respectively, the flat mouth selecting a diameter of 0.3mm is stainless
Draw point head, as the stratum nucleare solution syringe needle of coaxial spinning, is separately fixed at two syringes on spinning-drawing machine support, adjusts coaxial
Spinning needle position makes syringe needle be in the position at receiving roll center, is wound around one layer of aluminium foil and is easy to receive fiber in receiving roll.
Setting the temperature within electrostatic spinning machine as 30 DEG C, humidity is 20%, between regulation flat mouth stainless steel syringe needle and receiving roll away from
From for 25cm, regulation voltage is 25kV, and poly (aryl ether sulfone ketone) stratum nucleare solution injection speed is 0.12mm/min, Kynoar shell
Solution injection speed is 0.16mm/min, and receiving roll rotating speed is 100r/min, spinning time 1.5h, after treating that spinning terminates, and will
Barrier film takes off from receiving roll, is placed in 120 DEG C of process 12h in vacuum drying oven.Dried barrier film is cut into regular rectangular shape shape
Shape, is placed on the used stainless steel mould of hot press, and arranging hot pressing temperature is 250 DEG C, and temperature retention time is 1h, and pressure is 5MPa.
Barrier film after hot-pressing processing is placed in drying at room temperature 12h in vacuum drying oven, stand-by.
The 20%PPESK/16%PVDF core shell composite nano-fiber membrane of preparation under the conditions of Gai, thickness is 35 μm, porosity
78%, at LiFePO4 electrolyte (EC:DEC=1：1 volume ratio) in pick up reach 720%, diaphragm electrolysis liquid system from
Electron conductivity reaches 3.2mS cm-1, tensile strength is 28MPa, improves than the 3.2MPa of random orientation 20%PPESK barrier film
875%.
Embodiment 4
Take a certain amount of N, N dimethyl acetamide (DMAc) solvent, dissolve a certain amount of PPESK powder in round-bottomed flask,
Preparation obtains the PPESK polymer solution of mass fraction 25%；A certain amount of volume ratio is gone to be 7:The N of 3, N dimethyl acetamide
(DMAc) and acetone mixed solvent, dissolving a certain amount of PVDF powder in round-bottomed flask, it is 20% that preparation obtains mass fraction
PVDF solution, two kinds of solution are respectively placed in 60 DEG C of temperature constant magnetic stirring 12h in magnetic stirring apparatus, prepare spinning solution, so
After be saved in Brown Glass Brown glass bottles and jars only stand-by.It is molten that the disposable syringe using capacity 10ml takes 5ml poly (aryl ether sulfone ketone) spinning respectively
Liquid and 8ml Kynoar spinning solution, the flat mouth stainless steel syringe needle selecting a diameter of 0.3mm is molten as the stratum nucleare of coaxial spinning
Liquid syringe needle, is separately fixed at two syringes on spinning-drawing machine support, and adjusting coaxial spinning needle position makes syringe needle be in reception
The position at roller center, is wound around one layer of aluminium foil in receiving roll and is easy to receive fiber.Set temperature within electrostatic spinning machine as
25 DEG C, humidity is 25%, and the distance between regulation flat mouth stainless steel syringe needle and receiving roll is 20cm, and regulation voltage is 20kV, poly-
Aryl ether sulfone ketone stratum nucleare solution injection speed is 0.08mm/min, and Kynoar shell solution injection speed is 0.12mm/min,
Receiving roll rotating speed is 100r/min, spinning time 2.5h, after treating that spinning terminates, takes off barrier film from receiving roll, is placed in true
In empty baking oven, 100 DEG C process 12h.Dried barrier film is cut into regular rectangular shape, is placed in the used stainless steel of hot press
On mould, arranging hot pressing temperature is 300 DEG C, and temperature retention time is 0.5h, and pressure is 2MPa.Barrier film after hot-pressing processing is placed in very
Drying at room temperature 12h in empty baking oven, stand-by.
The 25%PPESK/20%PVDF core shell composite nano-fiber membrane of preparation under the conditions of Gai, thickness is 42 μm, porosity
72%, at LiFePO4 electrolyte (EC:DEC=1：1 volume ratio) in pick up reach 650%, diaphragm electrolysis liquid system from
Electron conductivity reaches 2.5mS cm-1, tensile strength is 18MPa, improves than the 3.5MPa of random orientation 25%PPESK barrier film
514%.
Claims (5)
1. the preparation method of a novel lithium battery barrier film and coaxial electrostatic spinning thereof, it is characterised in that step is as follows：
The first step：It is dissolved separately in PPESK and polyvinylidene fluoride resin in organic solvent, form stable homogeneous
Spinning solution A and spinning solution B, wherein, the concentration of PPESK solution is 10-25wt%, Kynoar tree
The concentration of lipoprotein solution is 8%-20wt%；
Second step：Two syringes take spinning solution A and spinning solution B respectively, and are fixed on the support of electrostatic spinning machine, injection
Device is connected with coaxial electrostatic spinning equipment, equipped with syringe and the coaxial electrostatic spinning equipment main channel phase of PPESK solution
Even；Paste one layer of aluminium foil in receiving roll, receive device as fiber, end, coaxial electrostatic spinning equipment main channel and reception are set
Distance between roller is 10-25cm, and end, coaxial electrostatic spinning equipment main channel is connected with high-voltage power cathode by wire, receives
Roller is connected with high voltage power supply negative pole；
3rd step：Arranging electrostatic spinning machine temperature and humidity is predetermined value, and adjusting voltage is 8-25kV, and PPESK is molten
Liquid injection speed is 0.02mm/min-0.2mm/min, and polyvinylidene fluoride resin solution injection speed is 0.04-0.2mm/min,
Remain that polyvinylidene fluoride resin solution injection speed is more than PPESK solution injection speed, start spinning；
It is placed in electrostatic spinning poly (aryl ether sulfone ketone) core-Kynoar shell composite nano-fiber membrane under vacuum condition, be dried extremely molten
Agent is fully volatilized, and obtains dried electrostatic spinning poly (aryl ether sulfone ketone) core-Kynoar shell composite nano-fiber membrane；
4th step：By dried electrostatic spinning poly (aryl ether sulfone ketone) core-Kynoar shell composite nano-fiber membrane from aluminium-foil paper
On take off, be cut into required form, be placed on the stainless steel mould of hot press, hot pressing temperature 150-250 DEG C is set, insulation
0.5-2h, hot pressing pressure 1-5MPa, carry out hot pressing, and hot pressing is carried out under vacuum；The coaxial fiber that hot pressing is obtained
Composite membrane is placed under vacuum condition and is dried, and i.e. obtains novel lithium battery barrier film, and described novel lithium battery barrier film porosity is
70%-90%, electrolyte pick up is up to more than 550%, and being resistant to 180 DEG C of high temperature thicknesses is 30-80 μm.
2. preparation method according to claim 1, it is characterised in that described organic solvent is N, N dimethyl acetamide,
N, one or more mixing in N-dimethylformamide, N-methyl-pyrrolidon, oxolane, acetone.
3. preparation method according to claim 1 and 2, it is characterised in that in the 3rd step, the time of spinning is 1-8h；Described
The temperature of electrostatic spinning machine be 20-50 DEG C, humidity is 20%-50%.
4. preparation method according to claim 1 and 2, it is characterised in that in the 3rd step, baking temperature is 40-120 DEG C, dry
The dry time is 12-24h.
5. preparation method according to claim 3, it is characterised in that in the 3rd step, baking temperature is 40-120 DEG C, is dried
Time is 12-24h.
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