CN107681090A - A kind of lithium ion cell nano fiber composite barrier film of high security and preparation method thereof - Google Patents
A kind of lithium ion cell nano fiber composite barrier film of high security and preparation method thereof Download PDFInfo
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- CN107681090A CN107681090A CN201710658372.7A CN201710658372A CN107681090A CN 107681090 A CN107681090 A CN 107681090A CN 201710658372 A CN201710658372 A CN 201710658372A CN 107681090 A CN107681090 A CN 107681090A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y02E60/10—Energy storage using batteries
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Abstract
A kind of lithium ion cell nano fiber composite barrier film of high security, described composite diaphragm includes the upper and lower, the lower floor is general engineering resin PVDF based polyalcohol layers of nanofibers, described upper strata is the polyethersulfone resin PPES and polyethersulfone ketone resin PPESK layers of nanofibers of high-performance polyarylether resin class, and described upper strata is covered in lower floor.And provide a kind of preparation method of the lithium ion cell nano fiber composite barrier film of high security.The present invention provides a kind of lithium ion cell nano fiber composite barrier film of high security and preparation method thereof.
Description
Technical field
The invention belongs to high-voltage electrostatic spinning field, lithium ion cell nano fibre diaphragm industry.The present invention relates to one kind
The lithium ion cell nano fiber compound barrier film extremely preparation method of high security.
Background technology
Lithium ion battery (abbreviation lithium battery) belongs to green pollution-free battery.Because the ratio apparent power of battery in itself is big,
Have extended cycle life, charge-discharge performance is stable, many merits such as memoryless efficiency.It is widely used in new-energy automobile, mobile communication, boat
Numerous technical fields such as empty space flight, defence and military.Lithium battery is by positive and negative electrode material, electrolyte, barrier film and the part group of shell four
Into wherein critical component is barrier film.Because the effect of barrier film is that battery positive and negative electrode is separated, pass through for lithium ion conveying, barrier electricity
Subflow is moved, in order to avoid cause short circuit.Thus use process of the performance to battery of barrier film, security, current density, cycle performance be all
With important influence, there is porosity high so barrier film must possess, mechanical property is good, and good insulation preformance, chemical stability is excellent,
Excellent heat conducting stability and good self-closing performance.
At present, lithium battery diaphragm largely uses polyolefine material.Such as PP films, PE films or PP and PE composite membranes.In technique
Using biaxial tension or wet production, it is not that very uniformly the span in aperture is larger to obtain membrane pore size.About 0.15-
Between 0.85nm, the safe transfer for the lithium ion being unfavorable in battery charge and discharge process.And also there is porosity mistake for barrier film
It is small, only 40% or so, cause the wellability to electrolyte poor.It is high-power in battery because the fusing point of polyolefine material is relatively low
During electric discharge, the rapid height of battery pack temperature, the easy contraction distortion of barrier film, stop the missing of the efficiency of electronics, cause inside battery
Short circuit.Battery burns, and is led to that battery pack is exploded, thus carrys out hidden danger to safety belt.
In recent years, according to the deficiency of biaxial tension barrier film, occurs the film of method of electrostatic spinning novel nano fibre diaphragm again
Technology.Polymer Solution in the technology is polarized under high voltage electric field effect, under the driving of electric field force, is overcome molten
The constraint of liquid surface tension, sprays jet from spinneret, in electric field, continuous cracking, refinement.Volatilize, receiving through solvent
Solidify in screen, form fibre diaphragm.The lithium battery diaphragm produced using electrostatic spinning technique, there is the small (50- of aperture diameter
350nm), specific surface area is big, and porosity is up to 70-80%, and liquid absorption is big, and wellability is good.The Nanowire of method of electrostatic spinning production
Barrier film is tieed up, certain performance is produced than original biaxial tension method, to use barrier film caused by dry or wet, improved very in performance
It is more.Solve the shortcomings that original barrier film porosity is low, and liquid absorption is small, and specific surface area is too small, wellability difference, be lithium battery diaphragm row
The huge advance of industry.
But with the increase of a large amount of utilizations of new-energy automobile, especially the course continuation mileage requirement to electric automobile, add
The increase of speed and vehicle every aspect requirement to new-energy automobile, the lithium battery group power of electric automobile are increased
Add, lithium battery group capacity largely extends.New-energy automobile use environment is changed, and from simple urban transit system, is changed to grow
Apart from high-speed cruising, with new-energy automobile receives the delivery condition general-utility car as, frequently accelerate, climb, braking and
The use of heavy duty, causes battery pack significantly to heat up, under extreme case, causes processing temperature in battery pack resistance to well beyond barrier film
The limiting temperature of temperature.Barrier film will be melted, and short circuit will occur for battery, cause and cause cells burst, battery pack blast serious accident
Occur.It is well known that the fusing point of polyalkene diaphragm is 130 DEG C or so, and ordinary times, battery pack normal use temperature are
80 DEG C or so, generally battery pack can keep normal use temperature, but if electric automobile accelerates frequently, to climb
Bank, hypervelocity, the mutation of excessive situations such as waiting of load promote the bearing temperature beyond barrier film.Thus, with new energy vapour
A large amount of utilizations of car, the risk of the barrier film security of lithium battery group are increasing.The nano fiber diaphragm of method of electrostatic spinning production
The membrane properties of dry or wet production in performance than the production of biaxial tension method are good.But in the security performance of barrier film not
What breaks through advantage.It is the urgent issue for currently having to solve so solving lithium battery group safety issue.Only thoroughly solve
The certainly safety problem of lithium battery, new-energy automobile ability safe operation, can just be developed on a large scale.
Presumable people thinks, can use high performance polyarylether resin solution and the relatively low universal engineering tree of fusing point
Lipoprotein solution, two kinds of solution are respectively charged into the different syringe pump of electrospinning device, start pump, and different solution exists in syringe pump
In the presence of high-pressure electrostatic electric field, jet is formed in respective nozzle respectively, jet is mixed in motion, enter to draw variation and
Winding, ultimately forms silk union tunica fibrosa.Somebody thinks that this existing thermal stability of film is high, there is the general of low melting point again
Property engineering resin fiber, security are very high.In fact, this mixing nano fibrous membrane be interweaved by two kinds of different nanometers and
Into both rules without intertexture, and the positioning without intertexture.Mixed and disorderly intertexture forms fiber hole (i.e. empty) one by one.Normal
At a temperature of, because hole is nano level, it is available for ion proper flow, stops electronics operation, battery can brings into normal play operation.But work as
Battery necessarily heats up in powerful use, battery.When battery temperature reaches 130 DEG C or so, versatility engineering resin fiber must
It can so be melted, the hole fiber of barrier film is melted, and the aperture of hole will expand significantly, and stopping electronic action will lose.Battery
Short circuit will occur, and accident occurs.It is simple versatility engineering resin solution and high-performance polyarylether resin solution so say
The barrier film produced using common method of electrostatic spinning blend spinning, it is not single to protect when battery temperature is more than 130 DEG C or so
Card safety, and with the continuous fusing of universal engineering resin fiber, the hole of film is increasing, and battery short circuit situation will more
Come more serious.So normal operation is infeasible in the case of blend spinning method can guarantee that barrier film overtemperature.
The content of the invention
In order to overcome the shortcomings of that the security of existing lithium ion cell nano fiber composite barrier film is poor, the present invention provides one
Lithium ion cell nano fiber composite barrier film of kind high security and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of lithium ion cell nano fiber composite barrier film of high security, described composite diaphragm include upper strata with
Layer, the lower floor is general engineering resin PVDF based polyalcohol layers of nanofibers, and described upper strata is high-performance polyarylether resin
The polyethersulfone resin PPES and polyethersulfone ketone resin PPESK layers of nanofibers of class, described upper strata is covered in lower floor.
Further, the ratio that the mass content of described the upper and lower accounts for total content is respectively：Upper strata 55%-75%,
Lower floor 25%-45%.
Further, in described PVDF based polyalcohol layers of nanofibers, the polymer quality portion rate of two components is：
PVDF50-65 parts, PAN (polyacrylonitrile) 35-50 parts；Three component solvent quality portion rates are：N.N dimethylformamides 25-
35 parts, dimethyl acetamide 35-50 parts, acetone 15-40 parts.
Further, described PVDF based polyalcohols, by quality parts ratio, after mixing, after being dissolved by the solvent, add straight
Footpath is 50-150nm hydrophobic nanos SiO2Particle 1-10 parts, 1 part -5 parts of ethyl orthosilicate, 1 part -8 of cosolvent TYitom-100
Part, 1 part -5 parts of ammoniacal liquor.
The polyethersulfone resin PPES and polyethersulfone ketone resin PPESK layers of nanofibers of the high-performance polyarylether resin class
In, two component polymer mass fractions are：Polyethersulfone resin PPES55-65 parts, polyethersulfone ketone resin PPESK35-45 parts；Three
The solvent quality portion rate of individual component is：1-METHYLPYRROLIDONE ketone (NMP) 10-20 parts, N.N- dimethyl acetamides 25-45
Part, acetone 10-30 parts.
A kind of preparation method of the lithium ion cell nano fibre diaphragm of high security, comprises the following steps：
(1) manufacturing process of PVDF based polyalcohols layers of nanofibers is：
(1.1) two component PVDF based polyalcohol quality parts ratios are：PVDF50-65 parts, PAN 35-50 parts, by two
The polymer of component is mixed by quality parts ratio, is put into mixer and is stirred, and is reached and is uniformly dispersed well；
(1.2) three component solvent quality portion rates are：N.N dimethylformamide 25-35 parts, dimethyl acetamide 35-
50 parts, acetone 15-40 parts；Three component solvents are fused by quality parts ratio, it is agitated, reach the molten of transparent and homogeneous degree
Liquid；
(1.3) solvent fused is added in the polymer composition of three components, stands 4-6 hours, it is agitated
Machine stirs, and adds SiO successively2Particle, ethyl orthosilicate, cosolvent and ammoniacal liquor, then middling speed operation 6-8 hours, reach solution and glue
600-800Pa.s is spent, 3.5-4.5 hours is stood, is put into the first liquid reserve tank of electrostatic spinning machine, waits spinning；
(1.4) electrostatic spinning machine is high to temperature requirement, the spinning fields in machine, and temperature preferably must be held in 21 DEG C ± 1 DEG C, wet
Degree is between 30% ± 2%；The outer operating temperature of machine preferably must be held in 23 DEG C ± 2 DEG C；Humidity must assure that between 40% ± 2%；
Strict Temperature and Humidity Control is to ensure that nanofiber diameter is uniform, fiber interweaving into silk screen space composite demand, fibre guide is clear
Clear basic condition；
Electrostatic spinning voltage range 10-50kv, electric field both positive and negative polarity distance 10-30cm, solution flow rate control 150- during spinning
Regulate and control between 500ml/n；Nano fiber diaphragm usual thickness 10-30um, can be regulated and controled on request；
(2) the polyethersulfone resin PPES of high-performance polyarylether resin class and polyethersulfone ketone resin PPESK layers of nanofibers
Manufacturing process is：
(2.1) the polyethersulfone resin PPES of high-performance polyarylether resin class and polyethersulfone ketone resin PPESK layers of nanofibers
In, two component polymer mass fractions are：Polyethersulfone resin PPES55-65 parts, polyethersulfone ketone resin PPESK35-45 parts；Three
The solvent quality portion rate of individual component is：1-METHYLPYRROLIDONE ketone (NMP) 10-20 parts, N.N- dimethyl acetamides 25-45
Part, acetone 10-30 parts, the solvent fused is added in the polymer composition of three components, is put into electrostatic spinning machine
In second liquid reserve tank, spinning is waited, second liquid reserve tank connects with another group of nozzle；
(2.2) by the PVDF based polyalcohol layers of nanofibers after the completion of electrostatic spinning, it is put into electrostatic spinning machine receiving screen machine
In structure, as the base material of electrostatic spinning machine receiving mechanism, in base material running, an independent nozzle, equipped with modified third
The binding agent of the concentration of olefin(e) acid 0.5%, is uniformly sprayed on base material, improves polymer fiber film and will spray the polyether sulfone spun on
The adhesive of resin fibre film；
(2.3) another group of nozzle alignment PVDF based polyalcohol layers of nanofibers on electrostatic spinning machine, the tube chamber in nozzle fill
Full polyethersulfone resin solution and high pressure nitrogen gas；Liquid pump, resin and nitrogen mixture liquid are started, on high fast direction receiving screen
PDVF nanofiber basement membranes, uniform fold one layer of high-performance polyethersulfone based nano-fiber layer on film, due to polyether sulfone based sols
Mix the nitrogen that pressure is 0.8-1.8pas pressure, and the electric field gravitation of the carrying capacity of conveying liquid pump and electrostatic field, therefore
Wire vent speed is improved a lot, and 1.5 times are improved than common electrostatic spinning wire vent speed；It is not single to accelerate due to the addition of high pressure nitrogen
Solution goes out liquid speed degree, and the nozzle of prior solution electrostatic spinning machine is more, and the high speed fluid column that each nozzle sprays is interleaved with each other,
The problem of easily causing electrostatic reaction and taylor cone whard to control.Because nitrogen gas molecule is non-conductive, and divides in the solution
Dissipate and the new electrostatic of vapour-liquid generation uniformly, has been obstructed in high voltage electric field.Due to gas in solution and solution weave in, tolerance
Stability of flow and steady controllable.The taylor cone size and shape that thus the outer solution of nozzle is formed can be controlled, so
The nanofiber diameter problem of non-uniform of electrostatic spinning is resolved.
Further, in the step (1.3), the solution prepared is loaded in the first liquid reserve tank, noted in casing in appendix
Enter 0.8-1.8pas pressure nitrogen gas, allow nitrogen fully to be rolled 2 hours in solution, allow nitrogen gas to be fully distributed in solution, gas
Body molecule merges in the solution.
In the step (2.1), the polymer of two components is mixed, it is uniformly good to reach decentralization；Again
Three component solvents are merged, after agitated, form transparent and homogeneous degree solution；The solution of three components is added to two
In the mixed liquor of polymer, stirred 1.5 hours with magnetic stirrer, stand 3-4 hours, continuous moderate-speed mixer 7-8 hours, reach
Solution viscosity 650-700pas stops.
In the step (2.1), the solution prepared is loaded the second liquid reserve tank, injects 0.8- in appendix in case
The nitrogen of 1.6pas pressure, allow nitrogen fully to roll two hours in the solution, allow nitrogen to be fully distributed in solution, gas molecule
Fusion is in the solution.
Further, the preparation method is further comprising the steps of：
(2.3) through compound nano fiber diaphragm, pressurizeed by Heating roll, increase the bonding force of composite membrane, pressure roller adds
Hot temperature is 70-100 DEG C, and roller speed is 5-10 ms/min, pressure 50-70KG.
The present invention technical concept be：The diaphragm material of the present invention, we use PVDF.PVDF extremely co-polymer chemicals
Can be stable, better mechanical property after film forming, although resistance to temperature does not have outstanding advantage with PP, PE, reaching 130 DEG C of critical-temperature
When, the self-closing performances of PVDF are fine, can complete the closing of barrier film very well.We must find a kind of high-performance, high thermoplasticity, Gao Ke
The polymer of dissolubility, and the necessary self-closing performance of the polymer is good.And the polyether sulfone (PPES) of polyarylether resin be as first choice,
The resin is not single to can dissolve multi-solvents at normal temperatures, and uniform for the nanofiber diameter that electrostatic spinning is prepared, and receives
The even aperture distribution of rice tunica fibrosa, ion pass through superior performance.The barrier film wellability energy consumption produced, voidage is high,
More valuable is polyether sulfone (PPES) resin temperature resistant grade height, and hot property is excellent, and the plexiglas temperature is 305 DEG C.In pressure
In the case of 1.8pas, thermal change temperature is up to 267 DEG C, reaches more than one times of the resistance to temperature of PVDF barrier films.
According to case above, using low-melting PVDF nano fibrous membranes and the high polyether sulfone nano fibrous membrane of fusing point, enter
Draw compound, manufactured composite nano fibre diaphragm, in new-energy automobile power battery group by heavy current impact.Battery temperature reaches
During to 130 DEG C or so, when there is thawing situation in PVDF tunica fibrosas, be compounded in polyether sulfone (PPES) nano fibrous membrane of a wheel but according to
So intact, intact performance stops the effect of electron stream, allows lithium ion to continue to flow, avoids the generation of battery accident.Due to multiple
The lithium battery nano fiber diaphragm of conjunction adds anti-satellite line together, so the safety coefficient of lithium battery is greatly improved, prevents
New-energy automobile due in the process of running, the magnitude of current substantial increase of burst cause battery high-temperature, barrier film fusing and formed
Battery short circuit, avoid the generation of serious accident.
The present invention provides a kind of lithium ion cell nano fiber composite barrier film of high security and preparation method thereof.The present invention
The composite nano fiber barrier film produced, to solve the lithium battery safety problem of new-energy automobile, make effective contribution.For
New-energy automobile largely develops, and solves the security bottleneck of maximum.
Beneficial effects of the present invention are mainly manifested in：A large amount of for the high-power lithium battery group on new-energy automobile make
With the safety problem of battery turns into issues that need special attention.Car crash accident alarm bell occurs because of cells burst both at home and abroad
Yowl.The present invention prevents because of the high-power use of battery, causes battery heating too fast, causes barrier film fusing closed pore crisis when occurring,
Establish a safety curtain.When the relatively low PVDF barrier films of heatproof go wrong, the also high PPESP barrier films of heatproof amplitude are made
For powerful backing, battery is safeguarded, makes battery that short circuit not occur, causes burning.When there is closed pore phenomenon in PVDF barrier films, battery
Interior ion flow approach will change, and be influenceed by PVDF closures, ion circulation passage is largely reduced, and electricity also largely drops
Low, automobilism speed declines therewith, and driver and conductor may know that out of joint, arrange new battery pack to be changed, and ensures
The safety of the goods of vehicle.Contributed for the safety of new-energy automobile.
Brief description of the drawings
Fig. 1 is the structural representation of lithium ion cell nano fiber composite barrier film.
Embodiment
The invention will be further described below in conjunction with the accompanying drawings.
Reference picture 1, a kind of lithium ion cell nano fiber composite barrier film of high security, described composite diaphragm include upper
Layer 1 and lower floor 2, the lower floor 2 are general engineering resin PVDF based polyalcohol layers of nanofibers, and described upper strata 1 is high-performance
The polyethersulfone resin PPES of polyarylether resin class and polyethersulfone ketone resin PPESK layers of nanofibers, described upper strata 1 are covered in down
On layer 2.
Further, the ratio that 2 mass contents of described upper strata 1 and lower floor account for total content is respectively：Upper strata 55%-
75%, lower floor 25%-45%.
Further, in described PVDF based polyalcohol layers of nanofibers, the polymer quality portion rate of two components is：
PVDF50-65 parts, PAN (polyacrylonitrile) 35-50 parts；Three component solvent quality portion rates are：N.N dimethylformamides 25-
35 parts, dimethyl acetamide 35-50 parts, acetone 15-40 parts.
Further, described PVDF based polyalcohols, by quality parts ratio, after mixing, after being dissolved by the solvent, add straight
Footpath is 50-150nm hydrophobic nanos SiO2Particle 1-10 parts, 1 part -5 parts of ethyl orthosilicate, 1 part -8 of cosolvent TYitom-100
Part, 1 part -5 parts of ammoniacal liquor.
The polyethersulfone resin PPES and polyethersulfone ketone resin PPESK layers of nanofibers of the high-performance polyarylether resin class
In, two component polymer mass fractions are：Polyethersulfone resin PPES55-65 parts, polyethersulfone ketone resin PPESK35-45 parts；Three
The solvent quality portion rate of individual component is：1-METHYLPYRROLIDONE ketone (NMP) 10-20 parts, N.N- dimethyl acetamides 25-45
Part, acetone 10-30 parts.
A kind of preparation method of the lithium ion cell nano fiber composite barrier film of high security, comprises the following steps：
(1) manufacturing process of PVDF based polyalcohols layers of nanofibers is：
(1.1) two component PVDF based polyalcohol quality parts ratios are：PVDF50-65 parts, PAN 35-50 parts, by two
The polymer of component is mixed by quality parts ratio, is put into mixer and is stirred, and is reached and is uniformly dispersed well；
(1.2) three component solvent quality portion rates are：N.N dimethylformamide 25-35 parts, dimethyl acetamide 35-
50 parts, acetone 15-40 parts；Three component solvents are merged by quality parts ratio, it is agitated, reach the molten of transparent and homogeneous degree
Liquid；
(1.3) solvent fused is added in the polymer composition of three components, stands 4-6 hours, it is agitated
Machine stirs, and adds SiO successively2Particle, ethyl orthosilicate, cosolvent and ammoniacal liquor, then middling speed operation 6-8 hours, reach solution and glue
600-800Pa.s is spent, 3.5-4.5 hours is stood, is put into the first liquid reserve tank of electrostatic spinning machine, waits spinning；
(1.4) electrostatic spinning machine is high to temperature requirement, the spinning fields in machine, and temperature preferably must be held in 21 DEG C ± 1 DEG C, wet
Degree is between 30% ± 2%；The outer operating temperature of machine preferably must be held in 23 DEG C ± 2 DEG C；Humidity must assure that between 40% ± 2%；
Strict Temperature and Humidity Control is to ensure that nanofiber diameter is uniform, fiber interweaving into silk screen space composite demand, fibre guide is clear
Clear basic condition；
Electrostatic spinning voltage range 5-50kv, electric field both positive and negative polarity distance 10-30cm, solution flow rate control 150- during spinning
Regulate and control between 500ml/n；Nano fiber diaphragm usual thickness 10-30um, can be regulated and controled on request；
(2) the polyethersulfone resin PPES of high-performance polyarylether resin class and polyethersulfone ketone resin PPESK layers of nanofibers
Manufacturing process is：
(2.1) the polyethersulfone resin PPES of high-performance polyarylether resin class and polyethersulfone ketone resin PPESK layers of nanofibers
In, two component polymer mass fractions are：Polyethersulfone resin PPES55-65 parts, polyethersulfone ketone resin PPESK35-45 parts；Three
The solvent quality portion rate of individual component is：1-METHYLPYRROLIDONE (NMP) 10-20 parts, N.N- dimethyl acetamide 25-45 parts,
Acetone 10-30 parts, the solvent fused are added in the polymer composition of three components, are put into the second of electrostatic spinning machine
In liquid reserve tank, spinning is waited, second liquid reserve tank connects with another group of nozzle；
(2.2) by the PVDF based polyalcohol layers of nanofibers after the completion of electrostatic spinning, it is put into electrostatic spinning machine receiving screen machine
In structure, as the base material of electrostatic spinning machine receiving mechanism, in base material running, an independent nozzle, equipped with modified third
The binding agent of the concentration of olefin(e) acid 0.5%, is uniformly sprayed on base material, improves polymer fiber film and will spray the polyether sulfone spun on
The adhesive of resin fibre film；
(2.3) another group of nozzle alignment PVDF based polyalcohol layers of nanofibers on electrostatic spinning machine, the tube chamber in nozzle fill
Full polyethersulfone resin solution and high pressure nitrogen gas；Liquid pump, resin and nitrogen mixture liquid are started, on high fast direction receiving screen
PDVF nanofiber basement membranes, uniform fold one layer of high-performance polyethersulfone based nano-fiber layer on film, due to polyether sulfone based sols
Mix the nitrogen that pressure is 0.8-1.8pas pressure, and the electric field gravitation of the carrying capacity of conveying liquid pump and electrostatic field, therefore
Wire vent speed is improved a lot, and 1.5 times are improved than common electrostatic spinning wire vent speed；It is not single to accelerate due to the addition of high pressure nitrogen
Solution goes out liquid speed degree, and the nozzle of prior solution electrostatic spinning machine is more, and the high speed fluid column that each nozzle sprays is interleaved with each other,
The problem of easily causing electrostatic reaction and taylor cone whard to control.Because nitrogen gas molecule is non-conductive, and divides in the solution
Dissipate and the new electrostatic of vapour-liquid generation uniformly, has been obstructed in high voltage electric field.Due to gas in solution and solution weave in, gas
Stability of flow and steady controllable.The taylor cone size and shape that thus the outer solution of nozzle is formed can be controlled, so
The nanofiber diameter problem of non-uniform of electrostatic spinning is resolved.
Further, in the step (1.3), the solution prepared is loaded in the first liquid reserve tank, noted in casing in appendix
Enter 0.8-1.8pas pressure nitrogen gas, allow nitrogen fully to be rolled 2 hours in solution, allow nitrogen gas to be fully distributed in solution, gas
Body molecule merges in the solution.
In the step (2.1), the polymer of two components is mixed, it is uniformly good to reach decentralization；Again
Three component solvents are merged, after agitated, form transparent and homogeneous degree solution；The solution of three components is added to two
In the mixed liquor of polymer, stirred 1.5 hours with magnetic stirrer, stand 3-4 hours, continuous moderate-speed mixer 7-8 hours, reach
Solution viscosity 650-700Pa.s stops.
In the step (2.1), the solution prepared is loaded the second liquid reserve tank, injects 0.8- in appendix in case
The nitrogen of 1.8pas pressure, allow nitrogen fully to roll two hours in the solution, allow nitrogen to be fully distributed in solution, gas molecule
Fusion is in the solution.
Further, the preparation method is further comprising the steps of：
(2.3) through compound nano fiber diaphragm, pressurizeed by Heating roll, increase the bonding force of composite membrane, pressure roller adds
Hot temperature is 70-100 DEG C, and roller speed is 5-10 ms/min, pressure 50-70KG.
Embodiment 1
In the present embodiment, the ratio that the mass contents of described the upper and lower accounts for total content is respectively：Upper strata 55%, under
Layer 45%.
Described lower floor PVDF is polymeric nanofiber layer.The polymer quality portion rate of two components is：PVDF50
Part, 50 parts of PAN.Three component solvent quality portion rates are：25 parts of N.N dimethylformamides, 35 parts of dimethyl acetamide, third
15 parts of ketone.
Described upper strata is high-performance polyethersulfone resin (PPES) layers of nanofibers, two component polymer mass fractions
For：55 parts of PPES (polyether sulfone), PPESK45 parts.The quality parts ratio of three solvents is：20 parts of 1-METHYLPYRROLIDONE (NMP),
30 parts of N.N- dimethyl acetamides (CDMAC), 15 parts of acetone.
The preparation method of the present embodiment is identical with preparation method above.
Lithium ion cell nano fiber composite barrier film prepared by the embodiment, is assembled into battery, and according to power requirement,
Battery pack is assembled into, is tested.The output quantity of high current, until reaching the maximum of electric current.The temperature of battery is also progressively
Rising, when battery temperature reaches 130 DEG C, there is closed pore in PVDF polymeric nanofiber layers, due to closed pore, what ion passed through
Passage largely blocks, and only fraction ion is still through polyether sulfone layers of nanofibers interstitial flow, therefore the magnitude of current is a large amount of
Lower, the temperature of battery is also gradually reduced from high point.In this temperature-rise period, although have there is closed pore fusing in PVDF barrier films, resistance
Electric function is blocked to have lost, but because with the presence of this barrier of high-performance polyethersulfone layers of nanofibers composite membrane, battery does not occur
Combustion incident caused by short circuit, reach the requirement of composite diaphragm security.
Embodiment 2
In the present embodiment, the ratio that the mass contents of described the upper and lower accounts for total content is respectively：Upper strata 58%, under
Layer 42%.
Described lower floor PVDF is polymeric nanofiber layer.The polymer quality portion rate of two components is：PVDF52
Part, 48 parts of PAN.Three component solvent quality portion rates are：27 parts of N.N dimethylformamides, 40 parts of dimethyl acetamide, third
19 parts of ketone.
Described upper strata is high-performance polyethersulfone resin (PPES) layers of nanofibers, two component polymer mass fractions
For：57 parts of PPES (polyether sulfone), PPESK43 parts.The quality parts ratio of three solvents is：10 parts of 1-METHYLPYRROLIDONE (NMP),
32 parts of N.N- dimethyl acetamides (CDMAC), 19 parts of acetone.
The preparation method of the present embodiment is same as Example 1.
Lithium ion cell nano fiber composite barrier film prepared by the embodiment, is assembled into battery, and according to power requirement,
Battery pack is assembled into, is tested.The output quantity of high current, until reaching the maximum of electric current.The temperature of battery is also progressively
Rise, when battery temperature reaches 135 DEG C, PVDF polymeric nanofiber layers early occur as soon as closed pore, due to closed pore, ion
The passage that passes through largely blocks, and only fraction ion is still through polyether sulfone layers of nanofibers interstitial flow, therefore electric current
Amount is a large amount of to be lowered, and the temperature of battery is also gradually reduced from high point.In this temperature-rise period, melted although closed pore have occurred in PVDF barrier films
Change, stop electric function and lost, but because with the presence of this barrier of high-performance polyethersulfone layers of nanofibers composite membrane, not occurring
Combustion incident caused by battery short circuit, reach the requirement of composite diaphragm security.
Embodiment 3
In the present embodiment, the ratio that the mass contents of described the upper and lower accounts for total content is respectively：Upper strata 59%, under
Layer 41%.
Described lower floor PVDF is polymeric nanofiber layer.The polymer quality portion rate of two components is：PVDF55
Part, 45 parts of PAN.Three component solvent quality portion rates are：29 parts of N.N dimethylformamides, 40 parts of dimethyl acetamide, third
24 parts of ketone.
Described upper strata is high-performance polyethersulfone resin (PPES) layers of nanofibers, two component polymer mass fractions
For：59 parts of PPES (polyether sulfone), PPESK41 parts.The quality parts ratio of three solvents is：15 parts of 1-METHYLPYRROLIDONE (NMP),
35 parts of N.N- dimethyl acetamides (CDMAC), 25 parts of acetone.
The preparation method of the present embodiment is same as Example 1.
Lithium ion cell nano fiber composite barrier film prepared by the embodiment, is assembled into battery, and according to power requirement,
Battery pack is assembled into, is tested.The output quantity of high current, until reaching the maximum of electric current.The temperature of battery is also progressively
Rise, when battery temperature reaches 140 DEG C, PVDF polymeric nanofiber layers early occur as soon as closed pore, due to closed pore, ion
The passage that passes through largely blocks, and only fraction ion is still through polyether sulfone layers of nanofibers interstitial flow, therefore electric current
Amount is a large amount of to be lowered, and the temperature of battery is also gradually reduced from high point.In this temperature-rise period, melted although closed pore have occurred in PVDF barrier films
Change, stop electric function and lost, but because with the presence of this barrier of high-performance polyethersulfone layers of nanofibers composite membrane, not occurring
Combustion incident caused by battery short circuit, reach the requirement of composite diaphragm security.
Embodiment 4
In the present embodiment, the ratio that the mass contents of described the upper and lower accounts for total content is respectively：Upper strata 61%, under
Layer 39%.
Described lower floor PVDF is polymeric nanofiber layer.The polymer quality portion rate of two components is：PVDF57
Part, 43 parts of PAN.Three component solvent quality portion rates are：30 parts of N.N dimethylformamides, 43 parts of dimethyl acetamide, third
29 parts of ketone.
Described upper strata is high-performance polyethersulfone resin (PPES) layers of nanofibers, two component polymer mass fractions
For：58 parts of PPES (polyether sulfone), PPESK42 parts.The quality parts ratio of three solvents is：18 parts of 1-METHYLPYRROLIDONE (NMP),
38 parts of N.N- dimethyl acetamides (CDMAC), 30 parts of acetone.
The preparation method of the present embodiment is same as Example 1.
Lithium ion cell nano fiber composite barrier film prepared by the embodiment, is assembled into battery, and according to power requirement,
Battery pack is assembled into, is tested.The output quantity of high current, until reaching the maximum of electric current.The temperature of battery is also progressively
Rise, when battery temperature reaches 145 DEG C, PVDF polymeric nanofiber layers early occur as soon as closed pore, due to closed pore, ion
The passage that passes through largely blocks, and only fraction ion is still through polyether sulfone layers of nanofibers interstitial flow, therefore electric current
Amount is a large amount of to be lowered, and the temperature of battery is also gradually reduced from high point.In this temperature-rise period, melted although closed pore have occurred in PVDF barrier films
Change, stop electric function and lost, but because with the presence of this barrier of high-performance polyethersulfone layers of nanofibers composite membrane, not occurring
Combustion incident caused by battery short circuit, reach the requirement of composite diaphragm security.
Embodiment 5
In the present embodiment, the ratio that the mass contents of described the upper and lower accounts for total content is respectively：Upper strata 65%, under
Layer 35%.
Described lower floor PVDF is polymeric nanofiber layer.The polymer quality portion rate of two components is：PVDF60
Part, 40 parts of PAN.Three component solvent quality portion rates are：31 parts of N.N dimethylformamides, 43 parts of dimethyl acetamide, third
32 parts of ketone.
Described upper strata is high-performance polyethersulfone resin (PPES) layers of nanofibers, two component polymer mass fractions
For：61 parts of PPES (polyether sulfone), PPESK39 parts.The quality parts ratio of three solvents is：20 parts of 1-METHYLPYRROLIDONE (NMP),
40 parts of N.N- dimethyl acetamides (CDMAC), 30 parts of acetone.
The preparation method of the present embodiment is same as Example 1.
Lithium ion cell nano fiber composite barrier film prepared by the embodiment, is assembled into battery, and according to power requirement,
Battery pack is assembled into, is tested.The output quantity of high current, until reaching the maximum of electric current.The temperature of battery is also progressively
Rise, when battery temperature reaches 150 DEG C, PVDF polymeric nanofiber layers early occur as soon as closed pore, due to closed pore, ion
The passage that passes through largely blocks, and only fraction ion is still through polyether sulfone layers of nanofibers interstitial flow, therefore electric current
Amount is a large amount of to be lowered, and the temperature of battery is also gradually reduced from high point.In this temperature-rise period, melted although closed pore have occurred in PVDF barrier films
Change, stop electric function and lost, but because with the presence of this barrier of high-performance polyethersulfone layers of nanofibers composite membrane, not occurring
Combustion incident caused by battery short circuit, reach the requirement of composite diaphragm security
Embodiment 6
In the present embodiment, the ratio that the mass contents of described the upper and lower accounts for total content is respectively：Upper strata 70%, under
Layer 30%.
Described lower floor PVDF is polymeric nanofiber layer.The polymer quality portion rate of two components is：PVDF62
Part, 38 parts of PAN.Three component solvent quality portion rates are：33 parts of N.N dimethylformamides, 47 parts of dimethyl acetamide, third
20 parts of ketone.
Described upper strata is high-performance polyethersulfone resin (PPES) layers of nanofibers, two component polymer mass fractions
For：63 parts of PPES (polyether sulfone), PPESK37 parts.The quality parts ratio of three solvents is：20 parts of 1-METHYLPYRROLIDONE (NMP),
43 parts of N.N- dimethyl acetamides (CDMAC), 25 parts of of acetone
The preparation method of the present embodiment is same as Example 1.
Lithium ion cell nano fiber composite barrier film prepared by the embodiment, is assembled into battery, and according to power requirement,
Battery pack is assembled into, is tested.The output quantity of high current, until reaching the maximum of electric current.The temperature of battery is also progressively
Rise, when battery temperature reaches 155 DEG C, PVDF polymeric nanofiber layers early occur as soon as closed pore, due to closed pore, ion
The passage that passes through largely blocks, and only fraction ion is still through polyether sulfone layers of nanofibers interstitial flow, therefore electric current
Amount is a large amount of to be lowered, and the temperature of battery is also gradually reduced from high point.In this temperature-rise period, melted although closed pore have occurred in PVDF barrier films
Change, stop electric function and lost, but because with the presence of this barrier of high-performance polyethersulfone layers of nanofibers composite membrane, not occurring
Combustion incident caused by battery short circuit, reach the requirement of composite diaphragm security.
Embodiment 7
In the present embodiment, the ratio that the mass contents of described the upper and lower accounts for total content is respectively：Upper strata 75%, under
Layer 25%.
Described lower floor PVDF is polymeric nanofiber layer.The polymer quality portion rate of two components is：PVDF65
Part, 35 parts of PAN.Three component solvent quality portion rates are：35 parts of N.N dimethylformamides, 50 parts of dimethyl acetamide, third
40 parts of ketone.
Described upper strata is high-performance polyethersulfone resin (PPES) layers of nanofibers, two component polymer mass fractions
For：65 parts of PPES (polyether sulfone), PPESK35 parts.The quality parts ratio of three solvents is：18 parts of 1-METHYLPYRROLIDONE (NMP),
45 parts of N.N- dimethyl acetamides (CDMAC), 30 parts of acetone.
The preparation method of the present embodiment is same as Example 1.
Lithium ion cell nano fiber composite barrier film prepared by the embodiment, is assembled into battery, and according to power requirement,
Battery pack is assembled into, is tested.The output quantity of high current, until reaching the maximum of electric current.The temperature of battery is also progressively
Rise, when battery temperature reaches 160 DEG C, PVDF polymeric nanofiber layers early occur as soon as closed pore, due to closed pore, ion
The passage that passes through largely blocks, and only fraction ion is still through polyether sulfone layers of nanofibers interstitial flow, therefore electric current
Amount is a large amount of to be lowered, and the temperature of battery is also gradually reduced from high point.In this temperature-rise period, melted although closed pore have occurred in PVDF barrier films
Change, stop electric function and lost, but because with the presence of this barrier of high-performance polyethersulfone layers of nanofibers composite membrane, not occurring
Combustion incident caused by battery short circuit, reach the requirement of composite diaphragm security.
In summary embodiment situation confirms, lithium ion cell nano fiber compound barrier film be a kind of high security it is good every
Film.Embodiment can also continue to down, because high-performance polyethersulfone resin closed pore or fusion temperature are premature.Further confirm compound
The broadness of barrier film safe range, safety coefficient amplitude are big.
Claims (10)
- A kind of 1. lithium ion cell nano fiber composite barrier film of high security, it is characterised in that：Described composite diaphragm includes The upper and lower, the lower floor are general engineering resin PVDF based polyalcohol layers of nanofibers, and described upper strata is gathered for high-performance The polyethersulfone resin PPES and polyethersulfone ketone resin PPESK layers of nanofibers of aryl ether resin class, described upper strata is covered in lower floor On.
- A kind of 2. lithium ion cell nano fiber composite barrier film of high security as claimed in claim 1, it is characterised in that：Institute The ratio that the mass content for the upper and lower stated accounts for total content is respectively：Upper strata 55%-75%, lower floor 25%-45%.
- 3. a kind of lithium ion cell nano fiber composite barrier film of high security as claimed in claim 1 or 2, its feature exist In：In described PVDF based polyalcohol layers of nanofibers, the polymer quality portion rate of two components is：PVDF50-65 parts, gather Acrylonitrile PAN 35-50 parts；Three component solvent quality portion rates are：N.N dimethylformamide 25-35 parts, dimethylacetamide Amine 35-50 parts, acetone 15-40 parts.
- A kind of 4. lithium ion cell nano fiber composite barrier film of high security as claimed in claim 3, it is characterised in that：Institute The PVDF based polyalcohols stated, by quality parts ratio, after mixing, after being dissolved by the solvent, add a diameter of 50-150nm hydrophobic types Nano-meter SiO_22Particle 1-10 parts, 1 part -5 parts of ethyl orthosilicate, 1 part -8 parts of cosolvent TYitom-100,1 part -5 parts of ammoniacal liquor.
- 5. a kind of lithium ion cell nano fiber composite barrier film of high security as claimed in claim 1 or 2, its feature exist In：In the polyethersulfone resin PPES and polyethersulfone ketone resin PPESK layers of nanofibers of the high-performance polyarylether resin class, two Component polymer mass fraction is：Polyethersulfone resin PPES55-65 parts, polyethersulfone ketone resin PPESK35-45 parts；Three components Solvent quality portion rate be：1-METHYLPYRROLIDONE (NMP) 10-20 parts, N.N- dimethyl acetamide 25-45 parts, acetone 10- 30 parts.
- 6. a kind of preparation method of the lithium ion cell nano fiber composite barrier film of high security as claimed in claim 1, bag Include following steps：(1) manufacturing process of PVDF based polyalcohols layers of nanofibers is：(1.1) two component PVDF based polyalcohol quality parts ratios are：PVDF50-65 parts, PAN 35-50 parts, by two components Polymer mixed by quality parts ratio, be put into mixer and be stirred, reach be uniformly dispersed it is good；(1.2) three component solvent quality portion rates are：N.N dimethylformamide 25-35 parts, dimethyl acetamide 35-50 parts, Acetone 15-40 parts；Three component solvents are fused by quality parts ratio, it is agitated, reach the solution of transparent and homogeneous degree；(1.3) solvent fused is added in the polymer composition of three components, stands 4-6 hours, agitated machine stirs Mix, add SiO successively2Particle, ethyl orthosilicate, cosolvent and ammoniacal liquor, then middling speed operation 6-8 hours, reach solution viscosity 600-800Pa.s, 3.5-4.5 hours are stood, are put into the first liquid reserve tank of electrostatic spinning machine, wait spinning；(1.4) electrostatic spinning machine is high to temperature requirement, and the spinning fields in machine, temperature preferably must be held in 21 DEG C ± 1 DEG C, and humidity exists Between 30% ± 2%；The outer operating temperature of machine preferably must be held in 23 DEG C ± 2 DEG C；Electrostatic spinning voltage range 10-50kv, electric field both positive and negative polarity distance 10-30cm, solution flow rate control 150- during spinning Regulate and control between 500ml/n；(2) making of the polyethersulfone resin PPES of high-performance polyarylether resin class and polyethersulfone ketone resin PPESK layers of nanofibers Process is：(2.1) in the polyethersulfone resin PPES of high-performance polyarylether resin class and polyethersulfone ketone resin PPESK layers of nanofibers, two Individual component polymer mass fraction is：Polyethersulfone resin PPES55-65 parts, polyethersulfone ketone resin PPESK35-45 parts；Three groups Part solvent quality portion rate be：1-METHYLPYRROLIDONE (NMP) 10-20 parts, N.N- dimethyl acetamide 25-45 parts, acetone 10-30 parts, the solvent fused is added in the polymer composition of three components, is put into the second liquid storage of electrostatic spinning machine In case, spinning is waited, second liquid reserve tank connects with another group of nozzle；(2.2) by the PVDF based polyalcohol layers of nanofibers after the completion of electrostatic spinning, it is put into electrostatic spinning machine receiving screen mechanism, As the base material of electrostatic spinning machine receiving mechanism, in base material running, an independent nozzle, being equipped with modified acroleic acid The binding agent of 0.5% concentration, is uniformly sprayed on base material, improves polymer fiber film and will spray the polyethersulfone resin spun on The adhesive of tunica fibrosa；(2.3) another group of nozzle alignment PVDF based polyalcohol layers of nanofibers on electrostatic spinning machine, the tube chamber in nozzle is full of poly- Ether sulfone resin solution and high pressure nitrogen gas；Start liquid pump, resin and nitrogen mixture liquid, the PDVF on high fast direction receiving screen Nanofiber basement membrane, uniform fold one layer of high-performance polyethersulfone based nano-fiber layer on film.
- 7. preparation method as claimed in claim 6, it is characterised in that：In the step (1.3), the solution for preparing is loaded the In one liquid reserve tank, injection 0.8-1.8pas pressure nitrogen gas in appendix, allows nitrogen fully to be rolled 2 hours in solution, allows in casing Nitrogen gas are fully distributed in solution, and gas molecule merges in the solution.
- 8. preparation method as claimed in claims 6 or 7, it is characterised in that：In the step (2.1), the poly- of two components Compound is mixed, and it is uniformly good to reach decentralization；Three component solvents are fused again, after agitated, formed equal One transparency solution；The solution of three components is added in the mixed liquor of two polymer, it is small with magnetic stirrer stirring 1.5 When, 3-4 hours are stood, continuous moderate-speed mixer 7-8 hours, reach solution viscosity 650-700Pa.s stoppings.
- 9. preparation method as claimed in claim 8, it is characterised in that：In the step (2.1), the solution for preparing is loaded the Two liquid reserve tanks, the nitrogen of 0.8-1.8pas pressure is injected in appendix in case, allows nitrogen fully to roll two hours in the solution, Nitrogen is allowed fully to be distributed in solution, gas molecule merges in the solution.
- 10. preparation method as claimed in claims 6 or 7, it is characterised in that：The preparation method is further comprising the steps of：(2.3) through compound nano fiber diaphragm, pressurizeed by Heating roll, increase the bonding force of composite membrane, pressure roller heating temperature Spend for 70-100 DEG C, roller speed is 5-10 ms/min, pressure 50-70KG.
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