CN107275554A - It is a kind of to spray polyolefin micropore film preparation composite lithium battery membrane and preparation method thereof with electrospun fibers - Google Patents
It is a kind of to spray polyolefin micropore film preparation composite lithium battery membrane and preparation method thereof with electrospun fibers Download PDFInfo
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- CN107275554A CN107275554A CN201710447448.1A CN201710447448A CN107275554A CN 107275554 A CN107275554 A CN 107275554A CN 201710447448 A CN201710447448 A CN 201710447448A CN 107275554 A CN107275554 A CN 107275554A
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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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- 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
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- 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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
- D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
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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
- D04H1/4326—Condensation or reaction polymers
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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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- 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
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- 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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Abstract
It is a kind of to spray polyolefin micropore film preparation composite lithium battery membrane and preparation method thereof with electrospun fibers, composite lithium battery membrane is a kind of in sandwich diaphragm made from polyalkene diaphragm surface coating electrospun fibers, the intermediate layer of sandwich diaphragm is made up of polyolefin micropore barrier diaphragm, outer layer is made up of high temperature resistant and the good poly (aryl ether sulfone ketone) nano fibrous membrane of electrolyte wetability, the polyalkene diaphragm in intermediate layer can make composite membrane possess higher mechanical strength, the poly (aryl ether sulfone ketone) nanofiber of outer layer is then effectively improved the heat endurance and electrolyte wetability of polyalkene diaphragm.Electro-chemical test shows that composite diaphragm shows higher ionic conductivity and less interface resistance.In addition, composite diaphragm assembling cell testing results show stable cycle performance and good big multiplying power discharging property.Therefore, polyolefin/poly (aryl ether sulfone ketone) sandwich diaphragm is expected to turn into a kind of novel high-performance lithium battery diaphragm.
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 kind
The method that polyolefin micropore film preparation composite lithium battery membrane is sprayed with electrospun fibers, belongs to lithium battery diaphragm technology neck
Domain.
Background technology
With the exhaustion increasingly of the fossil fuels such as coal, oil, energy problem increasingly causes the attention of people.Lithium battery
Due to the advantage with high-energy-density and high power density, the production of the portable electronics such as mobile phone, notebook is had been widely used for
Product, recently as the popularization of electric automobile, hybrid vehicle, lithium dynamical battery demand is more extensive, while also to lithium electricity
The security performance and charge-discharge performance in pond propose higher requirement.
Barrier film is a significant components in lithium battery, it primarily serve prevent positive and negative electrode from directly contacting and meanwhile make lithium from
The effect freely transmitted of son, traditional polyolefin micropore barrier diaphragm has a good chemical stability, thickness of thin and mechanical performance compared with
Height, but polyalkene diaphragm porosity is low, electrolyte wetability is poor, and this will be unfavorable for obtaining higher ionic conductivity, and
Lithium battery overcharge/cross put or the limiting condition of other non-normal uses under can produce substantial amounts of heat, easily make polyalkene diaphragm
Dimensional contraction or fusing are produced, the short circuit of both positive and negative polarity localized contact is in turn resulted in.Therefore, in order to improve the big multiplying power of dynamic lithium battery
Charge-discharge performance and security performance, need the lithium battery diaphragm for developing novel high-performance badly.
Poly (aryl ether sulfone ketone) (PPESK) is a kind of special engineering plastics of the structure of ketone containing diazanaphthalene biphenyl, and it has higher
Mechanical performance and excellent heat endurance, and dissolve in and common are machine solvent, thus electrostatic spinning technique can be used
It is prepared into nano-fiber film.In recent years, the tunica fibrosa that prepared by electrostatic spinning technique is widely used in grinding for lithium battery diaphragm
Study carefully, there is the connective and higher ratio table of higher porosity (general up to 80%-90%), good hole mainly due to it
Area, these advantages are all conducive to absorbing more electrolyte, promote freely transmitting for lithium ion, thus electrostatic spinning fiber film is suitable
Lithium battery for manufacturing high ionic conductivity and high power density.But the poor mechanical property limitation of electrospun fibers film
Its as lithium battery diaphragm commercial Application because barrier film can be by along along coiling direction during lithium battery assembling
Larger tensile force, and existing electrospun fibers film is difficult to reach such requirement.By conventional polyolefins barrier film and electrostatic
Spinning fibre film combination gets up to prepare three layers of composite diaphragm of polyolefin/poly (aryl ether sulfone ketone), then it is good both to have played polyalkene diaphragm
Good mechanical strength, can play the good resistance to elevated temperatures of poly (aryl ether sulfone ketone) material and higher electrolyte wetability, most again
Feature and security are prepared eventually all compares excellent novel lithium battery barrier film.
Patent of the present invention uses electrostatic spinning technique, using polyolefin micropore barrier diaphragm as substrate is received, with poly (aryl ether sulfone ketone)
(PPESK) resin solution carries out electrostatic spinning, polymer is penetrated as spinning solution under certain voltage and reception distance condition
Flow through and be sufficiently tensile, solvent volatilization and solidify, one layer of fine and close poly (aryl ether sulfone ketone) nanometer is finally formed on polyalkene diaphragm surface
Tunica fibrosa, obtains three layers of composite diaphragm of polyolefin/poly (aryl ether sulfone ketone), has given full play to polyalkene diaphragm and poly (aryl ether sulfone ketone) fiber
The premium properties of film.The composite diaphragm prepared, which not only has, maintains the higher mechanical strength of polyalkene diaphragm, thermally-stabilised
Property be also obviously improved, stable size can be kept not shrink at a temperature of 150 DEG C.While composite membrane mean porosities
There is lifting, high porosity and the good electrolyte wetabilitys of PPESK substantially increase the electrolyte absorptivity of composite diaphragm.Electrification
Learn test and show that composite diaphragm shows higher ionic conductivity and less interface resistance.In addition, composite diaphragm assembling electricity
Pond test result shows stable cycle performance and good big multiplying power discharging property.Therefore, polyolefin/poly (aryl ether sulfone ketone) three
Layer composite cellulosic membrane is expected to turn into a kind of novel high-performance lithium battery diaphragm.
Patent CN201510716512.2 proposes a kind of preparation method of sandwich lithium battery diaphragm, lithium battery diaphragm bag
Include upper strata barrier film, lower floor's barrier film and the ceramic slurry bed of material, ceramic slurry bed of material two sides is fitted upper strata barrier film and lower floor's barrier film respectively.Prepare
Method is the wherein one side brushing ceramic slurry bed of material in upper strata barrier film or lower floor's barrier film；The correspondence laminating lower floor on the ceramic slurry bed of material
Barrier film or upper strata barrier film；The ceramic slurry bed of material for being fitted with upper strata barrier film and lower floor's barrier film is dried.The invention is in the ceramic slurry bed of material
Two sides is fitted upper strata barrier film and lower floor's barrier film respectively, greatly increases the security of barrier film, lithium battery manufacturing process is greatly lowered
With the short circuit phenomenon produced during use, but the presence of middle ceramic slurry, may make above and below it is viscous between membrane layer
Tie power limited, easily occur relative slide.
Patent CN201410542516.9 proposes a kind of lithium battery ceramic coating membrane and preparation method thereof, mainly
Ceramic Composite is made in base material membrane surface in the aqueous ceramic coating slurry that will be made up of aluminum oxide, bonding agent etc., even application
Barrier film, ceramic coating membrane thermal safety prepared by this method improves, strong to electrolyte wettability, and applying can on lithium battery
To improve the cycle life of battery, but the adhesion between ceramic phase and organic phase is weaker, ceramics easily occurs and comes off (dry linting)
Phenomenon.
Patent CN201410806915.1 proposes a kind of preparation method of lithium battery diaphragm, by two layers of polyethylene film layer
Non-woven substrate upper and lower surface is pressed together on, the lithium battery diaphragm of preparation has high porosity, low thickness, high liquid absorption, low resistance
Characteristic, make the advantages of lithium battery capacity is high, service life is long, but the polyethylene diagrams of composite membrane outer layer cause barrier film overall
Heat endurance it is poor, it is impossible to play a part of improve lithium battery diaphragm security performance.
Patent CN201610038212.8 proposes a kind of novel high-performance Static Spinning poly (aryl ether sulfone ketone) lithium battery diaphragm
Preparation method, the poly- of fiber height orientation is made during electrostatic spinning using the transfer roller of rotation at a high speed as reception device
Aryl ether sulfone ketone nano fibrous membrane, barrier film porosity made from this method is high, be resistant to 220 DEG C of high temperature, good to the wellability of electrolyte
It is good, but the orientation fibre diaphragm only has higher mechanical strength in a direction, another direction mechanical strength has much room for improvement.
The content of the invention
Present invention seek to address that lithium ion battery separator prior art exist more than it is not enough there is provided a kind of porosity it is high,
Chemical property is good and has the preparation method of the novel high-performance lithium battery diaphragm of higher mechanical strength.
To achieve the above object, the technical scheme that provides of the present invention is：
It is a kind of to spray polyolefin micropore film preparation composite lithium battery membrane, described composite lithium ion battery with electrospun fibers
Barrier film is a kind of in sandwich diaphragm, the thickness of composite lithium battery membrane made from polyalkene diaphragm surface coating electrospun fibers
Spend for 30-100 μm, porosity is 45%-75%.The intermediate layer of sandwich diaphragm is made up of polyolefin micropore barrier diaphragm, and outer layer is
The electrostatic spinning poly (aryl ether sulfone ketone) nano fibrous membrane prepared using electrostatic spinning technique is constituted.Described polyolefin micropore barrier diaphragm is
Polyethylene (PE) or polypropylene (PP) lithium battery diaphragm；The described resistance to height of electrostatic spinning poly (aryl ether sulfone ketone) PPESK nano fibrous membranes
Warm and electrolyte wetability is good, and poly (aryl ether sulfone ketone) PPESK refers to that the class grown up on the basis of polyarylether resin can
Dissolubility High performance plastic resin, is a kind of new PPESK of structure containing diazanaphthalene biphenyl, wherein S represents sulfone
Base (O=S=O), K represents carbonyl (C=O), and S/K ratios are adjustable.
The polyalkene diaphragm in intermediate layer can make composite membrane possess higher mechanical strength, the poly (aryl ether sulfone ketone) nanometer of outer layer
Fiber is then effectively improved the heat endurance and electrolyte wetability of polyalkene diaphragm.Electro-chemical test shows composite diaphragm exhibition
Reveal higher ionic conductivity and less interface resistance.In addition, composite diaphragm assembling cell testing results show stabilization
Cycle performance and good big multiplying power discharging property.Therefore, three layers of composite cellulosic membrane of polyolefin/poly (aryl ether sulfone ketone) have had concurrently poly-
The mechanical performance of alkene barrier film and the excellent chemical property of poly (aryl ether sulfone ketone) tunica fibrosa, are expected to turn into a kind of novel high-performance lithium
Battery diaphragm.
The above-mentioned preparation method method that polyolefin micropore film preparation composite lithium battery membrane is sprayed with electrospun fibers, tool
Body comprises the following steps：
The first step：By PPESK (PPESK) dissolving in organic solvent, stirring forms homogeneous at 20-80 DEG C
Stable spinning solution, is stored in sealed glass jars, stand-by.Described poly (aryl ether sulfone ketone) solution concentration is 10-25wt%.Institute
The organic solvent stated is N, N dimethyl acetamide (DMAc), N, N-dimethylformamide (DMF), N- methyl-pyrrolidons
(NMP), one or both of tetrahydrofuran (THF) solvent mixed above.
Second step：2-10ml poly (aryl ether sulfone ketone) spinning solution is extracted using injector for medical purpose, syringe is placed in quiet
On the propeller of Electrospun machine, it is connected using flat mouth stainless steel syringe needle with syringe as spinning syringe needle, and by stainless steel syringe needle
It is connected with the positive pole of high voltage power supply.Polyalkene diaphragm after cutting is pasted onto to the reception pole plate being connected with high voltage power supply negative pole
On, in order in polyalkene diaphragm surface spraying poly (aryl ether sulfone ketone) nanofiber.Spinning syringe needle and the distance received between pole plate are set
It is set to 10-25cm.Reception pole plate is rectangle.
3rd step：Before experiment, the temperature and humidity of electrostatic spinning machine is set, treats that temperature and humidity reaches predetermined value and stably
Afterwards, experiment is proceeded by.Electrostatic spinning voltage is set to 8-25kV, poly (aryl ether sulfone ketone) solution injection speed is set to 0.02-
0.2mm/min, carries out spinning 1-6h, in spinning process, the jet of polymer solution formation polarizes in the presence of high voltage electric field,
Stretching, volatilizees through solvent, solidify to form polymer nanofiber, randomly-oriented PPESK nanofibers are in polyalkene diaphragm table
Continuous stack forms multilayer complex films on face.The temperature of the electrostatic spinning machine of setting is 20-50 DEG C, and humidity is set to 20%-
50%.
4th step：Continuous spinning for a period of time after, by polyalkene diaphragm from receive pole plate remove, then barrier film is turned just
Reverse side is pasted onto on reception pole plate, repeats the spinning process of the 3rd step so that Static Spinning PPESK fibers are uniformly sprayed in polyene
The two sides of hydrocarbon barrier film.
5th step, polyalkene diaphragm is removed from reception pole plate, drying process for a period of time, is obtained in vacuum drying oven
Three layers of composite lithium battery membrane of polyolefin/poly (aryl ether sulfone ketone).Drying temperature is 40-80 DEG C, and drying time is 12-24h.
Compared with prior art, electrospun fibers spraying polyolefin micropore film preparation complex lithium provided by the present invention
The method of battery diaphragm has advantages below：
(1) the poly (aryl ether sulfone ketone) fibrous layer of composite diaphragm outer layer has excellent resistance to elevated temperatures, can substantially improve polyene
The high high-temp stability of hydrocarbon barrier film, the polyolefin prepared/poly (aryl ether sulfone ketone) sandwich diaphragm size base under 150 DEG C of high temperature
Do not shunk in sheet, be conducive to tackling hot situation complicated in electric automobile running, substantially increase dynamic lithium battery
Security performance；
(2) substantial amounts of ether, carbonyl, sulfuryl isopolarity group are contained in poly (aryl ether sulfone ketone) strand, for carbonates
Electrolyte has a good wetability, thus can effectively improve the electrolyte pick up and ionic conductivity of polyalkene diaphragm,
Compatibility preferably, can improve the charge and discharge cycles stability of lithium battery between composite diaphragm and metal lithium electrode.In addition, poly- virtue
The presence of ether sulfone ketone fibrous layer also improves the electrochemical stability window of barrier film, is conducive to applying in high-voltage lithium field.
(3) compared with conventional electrostatic spinning fibre film is as lithium battery diaphragm, polyolefin/polyether sulphone prepared by the present invention
Ketone sandwich diaphragm not only has good chemical property, while had higher mechanical strength concurrently, and polymer coating
Compared to ceramic coating, the compatibility with polyalkene diaphragm is more preferable, difficult for drop-off.
Brief description of the drawings
Fig. 1 is electrostatic spinning PPESK fiber coating polyolefin micropore barrier diaphragm schematic diagrames.
Fig. 2 is tri- layers of composite lithium battery membrane schematic diagrames of PP/PPESK.
Fig. 3 is PP and tri- layers of composite diaphragm assembling battery discharge specific capacity-cycle-index curves of PP/PPESK.
Embodiment
Below by the Examples detail present invention, it is necessary to which explanation is that these instantiations are only used for being further discussed below this hair
It is bright, it is not intended to limit the claims of the present patent application.
Embodiment 1
A certain amount of N is taken, N dimethyl acetamide (DMAc) solvent dissolves a certain amount of PPESK powders in round-bottomed flask,
Prepare the PPESK polymer solutions for obtaining mass fraction 25%；PPESK solution is placed in 60 DEG C of constant temperature magnetic force in magnetic stirring apparatus
8h is stirred, spinning solution is made, is then stored in stand-by in Brown Glass Brown glass bottles and jars only.5ml polyether sulphones are taken using disposable syringe
Ketone spinning solution, from a diameter of 0.6mm flat mouth stainless steel syringe needle as spinning syringe needle, syringe is fixed on spinning machine support
On, smooth being pasted onto of polypropylene PP barrier films is received on pole plate, adjustment spinning needle position makes syringe needle be in PP diaphragm centers
Position.The temperature inside electrostatic spinning machine is set as 25 DEG C, humidity is 25%, regulation flat mouth stainless steel syringe needle is with receiving pole plate
The distance between be 20cm, regulation voltage be 20kV, poly (aryl ether sulfone ketone) solution injection speed be 0.08mm/min, the spinning time
2.5h, after treating that spinning terminates, removes barrier film from reception pole plate, then barrier film is turned positive and negative and pasted on receiver board,
Spray fiber is carried out to another side, technological parameter is as before, removes composite diaphragm after spinning 2.5h, is placed in vacuum drying oven
100 DEG C of processing 12h.
Tri- layers of composite diaphragms of the PP/PPESK prepared under the conditions of this, thickness is 40 μm, porosity 65%, in LiFePO4 electricity
Solve liquid (EC:DEC=1：1 volume ratio) in pick up reach 580%, diaphragm electrolyte system ionic electrical conductivity reaches 2.38mS
cm-1。
Embodiment 2
It is 6 to take a certain amount of volume ratio:4 tetrahydrofuran and DMF (DMF) mixed solvent, dissolving is certain
The PPESK powders of amount prepare the PPESK polymer solutions for obtaining mass fraction 20%, solution are placed in magnetic in round-bottomed flask
60 DEG C of temperature constant magnetic stirring 12h in power agitator, are made spinning solution, are then stored in stand-by in Brown Glass Brown glass bottles and jars only.By poly- third
Alkene PP barrier films are smooth to be pasted onto on reception pole plate, adjusts the position that spinning needle position makes syringe needle be in PP diaphragm centers.If
It is 30 DEG C to determine temperature inside electrostatic spinning machine, and humidity is 20%, regulation flat mouth stainless steel syringe needle and receive between pole plate away from
From for 25cm, regulation voltage is 25kV, and poly (aryl ether sulfone ketone) solution injection speed is 0.12mm/min, spinning time 1.5h, waits to spin
After silk terminates, barrier film is removed from reception pole plate, barrier film then is turned into positive and negative pastes on receiver board, to another side
Spray fiber is carried out, technological parameter is as before, remove composite diaphragm after spinning 1.5h, be placed in vacuum drying oven 80 DEG C and do
Dry 12h, it is stand-by.
Tri- layers of composite diaphragms of the PP/PPESK prepared under the conditions of this, thickness is 35 μm, porosity 56%, in LiFePO4 electricity
Solve liquid (EC:DEC=1：1 volume ratio) in pick up reach 530%, diaphragm electrolyte system ionic electrical conductivity reaches 2.2mS
cm-1。
Embodiment 3
It is 4 to take a certain amount of volume ratio:6 tetrahydrofuran and N, N dimethyl acetamide (DMAc) mixed solvent, dissolving is certain
The PPESK powders of amount prepare the PPESK polymer solutions for obtaining mass fraction 15% in round-bottomed flask；Solution is placed in magnetic
60 DEG C of temperature constant magnetic stirring 12h in power agitator, are made spinning solution, are then stored in stand-by in Brown Glass Brown glass bottles and jars only.By poly- second
Alkene PE barrier films are smooth to be pasted onto on reception pole plate, adjusts the position that spinning needle position makes syringe needle be in PE diaphragm centers.If
It is 35 DEG C to determine temperature inside electrostatic spinning machine, and humidity is 20%, regulation flat mouth stainless steel syringe needle and receive between pole plate away from
From for 10cm, regulation voltage is 15kV, and poly (aryl ether sulfone ketone) solution injection speed is 0.08mm/min, spinning time 2.5h, waits to spin
After silk terminates, barrier film is removed from reception pole plate, barrier film then is turned into positive and negative pastes on receiver board, to another side
Spray fiber is carried out, technological parameter is as before, remove composite diaphragm after spinning 2.5h, be placed in vacuum drying oven 60 DEG C and do
Dry 12h, it is stand-by.
After tested, the tri- layers of composite diaphragms of PE/PPESK prepared under the conditions of being somebody's turn to do, thickness is 40 μm, porosity 53%, in phosphorus
Sour iron lithium electrolyte (EC:DEC=1：1 volume ratio) in pick up reach 475%, diaphragm electrolyte system ionic electrical conductivity reaches
To 1.98mS cm-1。
Embodiment 4
It is 3 to take a certain amount of volume ratio:7 tetrahydrofuran and 1-METHYLPYRROLIDONE mixed solvent, dissolves a certain amount of
PPESK powders prepare the PPESK polymer solutions for obtaining mass fraction 10% in round-bottomed flask；Solution is placed in into magnetic force to stir
60 DEG C of temperature constant magnetic stirring 12h in device are mixed, spinning solution is made, is then stored in stand-by in Brown Glass Brown glass bottles and jars only.By polythene PE
Barrier film is smooth to be pasted onto on reception pole plate, adjusts the position that spinning needle position makes syringe needle be in PE diaphragm centers.Setting is quiet
Temperature inside Electrospun machine is 30 DEG C, and humidity is 20%, and the distance between regulation flat mouth stainless steel syringe needle and receiving roll are
15cm, regulation voltage is 8kV, and poly (aryl ether sulfone ketone) solution injection speed is 0.02mm/min, spinning time 6h, treats that spinning terminates it
Afterwards, barrier film is removed from reception pole plate, barrier film then is turned into positive and negative is pasted on receiver board, and another side is sprayed
Fiber, technological parameter is as before, removes composite diaphragm after spinning 6h, is placed in drying at room temperature 24h in vacuum drying oven, treats
With.
After tested, the tri- layers of composite nano-fiber membranes of PE/PPESK prepared under the conditions of being somebody's turn to do, thickness is 58 μm, porosity
75%, in LiFePO4 electrolyte (EC:DEC=1：1 volume ratio) in pick up reach 612%, diaphragm electrolysis liquid system from
Electron conductivity reaches 3.5mS cm-1。
Claims (8)
1. a kind of composite lithium battery membrane that polyolefin micropore film preparation is sprayed with electrospun fibers, it is characterised in that described
Composite lithium battery membrane be a kind of in sandwich diaphragm made from polyalkene diaphragm surface coating electrospun fibers, this is combined
The thickness of lithium battery diaphragm is 30-100 μm, and porosity is 45%-75%；The intermediate layer of sandwich diaphragm by polyolefin micropore every
Film is constituted, and outer layer is that the electrostatic spinning poly (aryl ether sulfone ketone) PPESK nano fibrous membranes prepared using electrostatic spinning technique are constituted.
2. it is according to claim 1 it is a kind of with electrospun fibers spray polyolefin micropore film preparation composite lithium ion battery every
Film, it is characterised in that described polyolefin micropore barrier diaphragm is polythene PE or polypropylene PP lithium battery diaphragms.
3. it is according to claim 1 or 2 a kind of with electrospun fibers spraying polyolefin micropore film preparation composite lithium ion battery
Barrier film, it is characterised in that in poly (aryl ether sulfone ketone) PPESK, S represents sulfuryl, and K represents carbonyl, and S/K ratios are adjustable.
4. the preparation method of any described composite lithium battery membrane of claims 1 to 3, it is characterised in that following steps：
The first step：PPESK is dissolved in organic solvent, wherein, poly (aryl ether sulfone ketone) solution concentration is 10-
Stirring forms the spinning solution of stable homogeneous at 25wt%, 20-80 DEG C, is stored in sealed glass jars, stand-by；
Second step：2-10ml poly (aryl ether sulfone ketone) spinning solution is extracted using injector for medical purpose, syringe is placed in Static Spinning
Silk machine propeller on, be connected using flat mouth stainless steel syringe needle with syringe as spinning syringe needle, and by stainless steel syringe needle and height
The positive pole of voltage source is connected；Polyalkene diaphragm after cutting is pasted onto on the reception pole plate being connected with high voltage power supply negative pole, used
In in polyalkene diaphragm surface spraying poly (aryl ether sulfone ketone) nanofiber；Spinning syringe needle and the distance received between pole plate are set to 10-
25cm；
3rd step：Before experiment, the temperature and humidity of electrostatic spinning machine is set, after temperature and humidity reaches predetermined value and stabilization,
Proceed by experiment；Electrostatic spinning voltage is set to 8-25kV, poly (aryl ether sulfone ketone) solution injection speed is set to 0.02-
0.2mm/min, carries out spinning 1-6h, in spinning process, the jet of polymer solution formation polarizes in the presence of high voltage electric field,
Stretching, volatilizees through solvent, solidify to form polymer nanofiber, randomly-oriented PPESK nanofibers are in polyalkene diaphragm table
Continuous stack forms multilayer complex films on face；
4th step：After continuous spinning terminates, polyalkene diaphragm is removed on pole plate from receiving, and barrier film is turned into positive and negative be pasted onto
Receive on pole plate, repeat the spinning process of the 3rd step so that Static Spinning PPESK fibers are uniformly sprayed the two of polyalkene diaphragm
Face；
5th step, by polyalkene diaphragm from receive pole plate on remove, be positioned in vacuum drying oven after drying process obtain polyolefin/
Three layers of composite lithium battery membrane of poly (aryl ether sulfone ketone).
5. the preparation method of composite lithium battery membrane according to claim 4, it is characterised in that having described in the first step
Machine solvent is N, N dimethyl acetamide, N, N-dimethylformamide, N- methyl-pyrrolidons, one kind in tetrahydrofuran or two
Plant solvent mixed above.
6. the preparation method of the composite lithium battery membrane according to claim 4 or 5, it is characterised in that set in the 3rd step
Electrostatic spinning machine temperature be 20-50 DEG C, humidity is set to 20%-50%.
7. the preparation method of the composite lithium battery membrane according to claim 4 or 5, it is characterised in that described in the 5th step
Drying temperature be 40-80 DEG C, drying time is 12-24h.
8. the preparation method of composite lithium battery membrane according to claim 6, it is characterised in that dry described in the 5th step
Dry temperature is 40-80 DEG C, and drying time is 12-24h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950703A (en) * | 2018-09-18 | 2018-12-07 | 西安交通大学 | The device and method of piezopolymer MEMS structure is prepared based on one step chemical industry skill of near field electrostatic spinning |
| CN110565269A (en) * | 2019-09-10 | 2019-12-13 | 西京学院 | Method for preparing lithium battery diaphragm through coaxial electrostatic spinning |
| CN111117039A (en) * | 2019-12-31 | 2020-05-08 | 苏州度辰新材料有限公司 | Reinforced toughened heat-conducting polyolefin composition |
| CN111916621A (en) * | 2020-08-19 | 2020-11-10 | 北京宇程科技有限公司 | High-temperature-resistant composite diaphragm for lithium ion battery and preparation method thereof |
| CN113278152A (en) * | 2021-06-07 | 2021-08-20 | 吉林大学 | Sulfonated polyarylether compound and preparation method thereof, ion selective composite porous membrane and preparation method and application thereof |
| CN113839143A (en) * | 2021-08-02 | 2021-12-24 | 兰溪聪普新材料有限公司 | Polyarylethersulfone lithium ion battery diaphragm and preparation method thereof |
| CN114243209A (en) * | 2021-12-15 | 2022-03-25 | 浙江恒威电池股份有限公司 | Composite diaphragm material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101562243A (en) * | 2009-05-20 | 2009-10-21 | 沈阳航空工业学院 | Method for manufacturing electrospinning of high-performance polyarylether resin lithium battery diaphragm |
| CN102629679A (en) * | 2012-04-28 | 2012-08-08 | 中国科学院理化技术研究所 | Nanofiber lithium ion battery diaphragm material with composite structure and preparation method thereof |
| CN102969471A (en) * | 2012-10-24 | 2013-03-13 | 中国科学院青岛生物能源与过程研究所 | High-temperature resistant aromatic polysulfonamide base lithium ion battery diaphragm |
| CN104241574A (en) * | 2013-06-21 | 2014-12-24 | 住友化学株式会社 | Laminated porous film, separator for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondart battery |
-
2017
- 2017-06-15 CN CN201710447448.1A patent/CN107275554A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101562243A (en) * | 2009-05-20 | 2009-10-21 | 沈阳航空工业学院 | Method for manufacturing electrospinning of high-performance polyarylether resin lithium battery diaphragm |
| CN102629679A (en) * | 2012-04-28 | 2012-08-08 | 中国科学院理化技术研究所 | Nanofiber lithium ion battery diaphragm material with composite structure and preparation method thereof |
| CN102969471A (en) * | 2012-10-24 | 2013-03-13 | 中国科学院青岛生物能源与过程研究所 | High-temperature resistant aromatic polysulfonamide base lithium ion battery diaphragm |
| CN104241574A (en) * | 2013-06-21 | 2014-12-24 | 住友化学株式会社 | Laminated porous film, separator for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondart battery |
Non-Patent Citations (1)
| Title |
|---|
| 齐文: "聚芳醚锂离子电池隔膜的电纺丝制备技术研究", 《中国博士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950703A (en) * | 2018-09-18 | 2018-12-07 | 西安交通大学 | The device and method of piezopolymer MEMS structure is prepared based on one step chemical industry skill of near field electrostatic spinning |
| CN110565269A (en) * | 2019-09-10 | 2019-12-13 | 西京学院 | Method for preparing lithium battery diaphragm through coaxial electrostatic spinning |
| CN111117039A (en) * | 2019-12-31 | 2020-05-08 | 苏州度辰新材料有限公司 | Reinforced toughened heat-conducting polyolefin composition |
| CN111916621A (en) * | 2020-08-19 | 2020-11-10 | 北京宇程科技有限公司 | High-temperature-resistant composite diaphragm for lithium ion battery and preparation method thereof |
| CN113278152A (en) * | 2021-06-07 | 2021-08-20 | 吉林大学 | Sulfonated polyarylether compound and preparation method thereof, ion selective composite porous membrane and preparation method and application thereof |
| CN113278152B (en) * | 2021-06-07 | 2022-06-21 | 吉林大学 | Sulfonated polyarylether compound and preparation method thereof, ion selective composite porous membrane and preparation method and application thereof |
| CN113839143A (en) * | 2021-08-02 | 2021-12-24 | 兰溪聪普新材料有限公司 | Polyarylethersulfone lithium ion battery diaphragm and preparation method thereof |
| CN114243209A (en) * | 2021-12-15 | 2022-03-25 | 浙江恒威电池股份有限公司 | Composite diaphragm material and preparation method and application thereof |
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