CN103469488A - Preparation method of reinforced electrostatic spinning nano-fiber lithium-ion battery separator - Google Patents
Preparation method of reinforced electrostatic spinning nano-fiber lithium-ion battery separator Download PDFInfo
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Abstract
The invention provides a preparation method of a reinforced electrostatic spinning nano-fiber lithium-ion battery separator. The preparation method is characterized in that the reinforced electrostatic spinning nano-fiber lithium-ion battery separator is a composite film formed by two polymers with the differences of melting temperatures being more than 30 DEG C, the composite film is a nano-fiber film which is prepared from a spinning solution system formed by two polymers with the differences of melting temperatures being more than 30 DEG C through an electrostatic spinning technique, the fiber film is stilled for 10 hours under normal temperature under the negative pressure so as to evaporate organic solvents left in the fiber film, then the fiber film is subjected to hot-pressing treatment for a certain time under a certain pressure intensity, the hot-pressing temperature is between the melting temperature of the low-melt-point polymer and the melting temperature of the high-melt-point polymer, the low-melt-point polymer is fused to enable nano-fibers in the fiber film to be mutually bonded, so that the mechanical strength of the fiber film is greatly improved. The method is easy and convenient to operate, the prepared separator reserves the advantages of high porosity and high pick-up rate of an electrostatic spinning separator, and the defects of poor dynamic performance and non-existence of effective bonding points between fibers of the electrostatic spinning separator are also overcome.
Description
Technical field
The present invention relates to field of batteries, particularly relate to that a kind of mechanical strength is good, porosity is high, the preparation method of the Static Spinning lithium ion battery separator of Heat stability is good.
Background technology
Lithium ion battery has that voltage is high, and specific energy is high, and long, memory-less effect of life-span and the low advantage of self-discharge rate, be widely used as mobile phone, notebook, small portable electrical equipment and electric car power supply.Lithium battery mainly is comprised of positive pole, negative pole, electrolyte, barrier film and shell etc.Its septation is the important component part of lithium ion battery, its Main Function: the one, and stop electronics to pass through, prevent short circuit between electrodes; The 2nd, allow ion to pass through, the passage of ion transportation is provided in charge and discharge process for battery.The performance of barrier film has important impact to charge-discharge performance, cycle performance and the security performance of lithium ion battery.Therefore, require battery diaphragm must possess the characteristics such as good insulation preformance, porosity is high, mechanical property good, chemical stability is excellent.
Application at present commercialization barrier film more widely is MIcroporous polyolefin film, and its processing mode is that polyolefin film is carried out to single shaft or biaxial stretch-formed, makes film surface form micropore and is prepared from.This barrier film has good mechanical performance, but its processing technology is loaded down with trivial details, pore-size distribution is irregular, porosity is lower, absorbent is poor, is unfavorable for the migration of lithium ion in the lithium ion battery charge and discharge process.In addition, the polyolefin battery separation film surface can be low, causes film poor to the wetting property of electrolyte, thereby limited lithium battery in numerous high-tech sectors, the particularly high-power application that discharges and recharges field.
Electrostatic spinning refers under the effect of forceful electric power field force a kind of spining technology that polymer solution or melt is drawn into to fiber.Barrier film fibre diameter prepared by the method, at nanoscale, has the characteristics such as specific area is large, porosity is high, aperture is little and even.Polymer lithium cell diaphragm prepared by method of electrostatic spinning have advantages of Material Used extensively, imbibition and guarantor's fluidity can be good, ionic conductivity is high, is generally acknowledged high performance lithium ion battery diaphragm material.But the Static Spinning barrier film is to be overlapped and form mutually by mixed and disorderly fiber, there is no effective bonding point between fiber and fiber, so the barrier film mechanical property is poor, does not many times reach the requirement to barrier film intensity of package or battery pack process of assembling.
Main by the mechanical performance of the method raising electrostatic spinning nano fiber films such as MULTILAYER COMPOSITE, inorganic nanoparticles filling and heat treatment at present.
Patent CN101787651A for strengthening matrix, receives one deck electrostatic spinning nano fiber film based on eyelet fabric thereon, preparation enhancement mode electrostatically spun composite material.Due to the existence of eyelet fabric, the composite material surface flatness of preparation is affected, and when when the lithium ion battery separator, affects the interface stability of itself and positive and negative pole material.Patent CN102299287A, at MIcroporous polyolefin film surface recombination one layer of polymeric nanofibres film, prepares composite nanometer fiber lithium ion battery diaphragm.With respect to nano fibrous membrane, because the composite membrane mechanical property that exists of body increases, still, in process, need MIcroporous polyolefin film is carried out to surface treatment, technique is loaded down with trivial details, and energy consumption is high.Patent US20120077015A1 presss from both sides one deck nanofiber film preparation MULTILAYER COMPOSITE nano composite material between two supporting layers, as lithium ion battery separator.Though this barrier film mechanical performance obviously improves, but porosity is lower, thickness is larger, increases the internal resistance of battery.
The reason that the inorganic particle filled composite nano-fiber membrane intensity to preparing by electrostatic spinning in spinning solution improves has: (1) composite diaphragm fibre diameter is less, and specific area is large, and the contact area between fiber is also larger; (2) can attract each other between the polar group on inorganic particle surface and between the atom on inorganic particle polar group and organic molecule chain, play the effect of physical crosslinking.The nano inorganic particle used at present mainly contains SiO
2, Al
2o
3, TiO
2, BaTiO
3, organo-clay and CNT.Patent CN101624757A adds multi-walled carbon nano-tubes and prepares composite nano-fiber membrane in electrostatic spinning liquid, and the multi-walled carbon nano-tubes of take increases the machinery brute force of nano fibrous membrane as strengthening body.Because these nano particles have higher specific area, easily reunite, need use equipment or the dispersant minimizing reunions such as ball mill, ultrasonic wave while directly adding, improve the uniformity of nanoparticulate dispersed with this.
The people such as Choi by the preparation Static Spinning PVDF nano fibrous membrane after 150-160 ℃ of heat treatment, it is large that fibre-forming polymer degree of crystallinity becomes, barrier film mechanical performance (the Choi S that increases, Lee Y S, Joo C W, et al.Electrospun PVDF nanofiber web as polymer electrolyte or separator[J] .Electrochimica Acta.2004,50 (2-3): 339-343).But heat-treating methods does not fundamentally solve the problem of the effective bonding point of nothing between the Static Spinning membrane fiber, and mechanical performance improves limited.
Patent CN102140734A is dissolved in the two Component Systems of fluoropolymer resin and base polyurethane prepolymer for use as in solvent and prepares the nonwoven film by the high-voltage electrostatic spinning technology, again the nonwoven film is at room temperature made in base polyurethane prepolymer for use as-NCO and water in air-react crosslinked, auto polymerization of OH generates polyurethane, make nanofiber composition fluoropolymer resin adhered to one another and polyurethane bicomponent composite membrane in the nonwoven film, improved the mechanical strength of tunica fibrosa.Though the method has improved the mechanical performance of electrostatic spinning nano fiber barrier film to a certain extent, but the existence of base polyurethane prepolymer for use as must be arranged in raw material, scope is restricted, and is subject to the impact of moisture etc. with the base polyurethane prepolymer for use as of the isocyanate group group of high reaction activity, and the storage life is shorter.
Summary of the invention
It is high that the present invention aims to provide a kind of intensity, has the preparation method of the electrostatic spinning nano fiber lithium ion battery separator of high porosity, good wetting property concurrently.This preparation method can make in barrier film between fiber and fiber bonding mutually, improves mechanical strength and does not affect the basic structure of nano fiber porous film, and the performance of lithium ion battery is improved.
For achieving the above object, technical scheme provided by the invention is: a kind of enhancement mode electrostatic spinning nano fiber barrier film, it is characterized in that, described enhancement mode electrostatic spinning nano fiber barrier film is that two kinds of melt temperatures differ the two component films of polymer more than 30 ℃, it is to differ nano fibrous membrane prepared by electrostatic spinning technique by the polymer dope system more than 30 ℃ by two kinds of melt temperatures, by this tunica fibrosa standing 10h of normal temperature under negative pressure, make organic solvent volatilization residual in tunica fibrosa, by tunica fibrosa hot-pressing processing certain hour under certain pressure intensity, hot pressing temperature is between low melting point polymer and the happy and harmonious temperature of high-melting-point polymer, nanofiber in tunica fibrosa is bondd each other, thereby prepare enhancement mode electrostatic spinning nano fiber barrier film.This barrier film porosity is up to 60-80%, and its tensile break strength is with respect to before hot-pressing processing, not improved 3-5 doubly.
In the present invention program, described polymer is that in polymethyl methacrylate (PMMA), Kynoar (PVDF), Kynoar-hexachloropropylene copolymer (PVDF-HFP), polyacrylonitrile (PAN), polyethylene glycol oxide (PEO), melt temperature differs any two kinds more than 30 ℃.
In the present invention program, the organic solvent that described spinning solution system is used is one or two or more kinds the mixture in DMF, DMA, acetone, 1-METHYLPYRROLIDONE, hexafluoroisopropanol, oxolane.
In the present invention program, described hot pressing time is 10-300s, and pressure is 3-10MPa.
In the present invention program, described hot pressing temperature is between two kinds of used happy and harmonious temperature of polymer.
In the present invention program, described enhancement mode electrostatic spinning nano fiber membrane preparation method, comprise the following steps:
1) high and low fusing point polymer is dissolved in organic solvent by certain mass ratio, forms uniform and stable spinning solution, concentration of dope is 10-18wt%;
2) by step 1) the gained spinning solution injects the syringe pump of electrospinning device, and the syringe needle of syringe pump is connected with high voltage source by wire; Place the metal of a ground connection by receiving apparatus at the opposite side of distance syringe needle 10-25cm; Cover one deck aluminium-foil paper on the metal receiving system;
3) rising supply voltage, and the flow velocity of adjusting syringe pump, solution, under the effect of high voltage electric field, penetrates from the flat mouth syringe needle nozzle of syringe, whip occurs in motion process and move and tangle, and finally is collected on aluminium-foil paper and forms tunica fibrosa; The gained tunica fibrosa is placed in to vacuum drying chamber, and normal temperature decompression operation 10h, after noresidue solvent in film, take out;
4) by step 3) nano fibrous membrane for preparing is placed on hot press and carries out hot-pressing processing, and pressure is 3-10MPa, and the time is 20-300s, and temperature, between two kinds of polymer melting temperatures, obtains enhancement mode electrostatic spinning nano fiber film;
Wherein said polymer be in polymethyl methacrylate (PMMA), Kynoar (PVDF), Kynoar-hexachloropropylene copolymer (PVDF-HFP), polypropylene fine (PAN), polyethylene glycol oxide (PEO) melt temperature differ more than 30 ℃ any two kinds;
In the present invention program, described organic solvent is one or two or more kinds the mixture in DMF, DMA, acetone, 1-METHYLPYRROLIDONE, hexafluoroisopropanol, oxolane.
Compared with prior art, preparation enhancement mode electrostatic spinning nano fiber barrier film provided by the present invention (as lithium ion battery separator) method has the following advantages:
1. the enhancement mode electrostatic spinning nano fiber film surfacing of preparation, even thickness, as lithium ion battery separator, have good contact with electrode, and thickness is little, and can control flexibly according to the flow velocity of spinning time and syringe, can reduce lithium ion battery internal resistance.
2. the nanofiber clothes that prepared through electrostatic spinning by spinning solution, without through preliminary treatment, directly carry out hot pressing and obtain enhancement mode electrostatic spinning nano fiber film, and process operation is easy, flow process is short, energy consumption is low.
3. add under thermal agitation and just polymer can be dissolved in to organic solvent and form transparent uniform spinning solution, without using ball mill, ultrasonic equipment, technique is simple.
4. the electrostatic spinning nano fiber film is through hot-pressing processing, and the melting of low melting point polymer composition, bond the nanofiber in tunica fibrosa each other, forms inierpeneirating network structure, thereby improves the mechanical strength of tunica fibrosa.
Test shows, the enhancement mode electrostatic spinning nano fiber film that adopts the present invention to prepare has improved 3-5 doubly than the tensile break strength of routine intravenous electrospun fiber membrane.
The accompanying drawing explanation
Fig. 1 Static Spinning P (VDF-HFP)/PEO tunica fibrosa and P (VDF-HFP)/PEO enhancement mode electrostatic fibre film SEM figure: (1) is Static Spinning P (VDF-HFP)/PEO tunica fibrosa, and (2) are P (VDF-HFP)/PEO enhancement mode electrostatic fibre film.
Fig. 2 Static Spinning P (VDF-HFP)/PEO tunica fibrosa and P (VDF-HFP)/PEO enhancement mode electrostatic fibre membrane stress strain curve figure: a is Static Spinning P (VDF-HFP)/PEO tunica fibrosa, and b is P (VDF-HFP)/PEO enhancement mode electrostatic fibre film.
The specific embodiment
Below provide specific embodiments of the invention.These specific embodiments, only for further narration the present invention, do not limit the claim protection domain of the present patent application.
By PVDF and P (VDF-HFP), being dissolved in mass ratio with the N.N-dimethyl formamide at 0.95: 0.05 is 7 with the acetone quality ratio; In 3 mixed solvent, be configured to the solution that mass fraction is 16%, under 40-50 ℃, heating is stirred to polymer and fully dissolves, and makes spinning solution.The spinning solution obtained is injected in the syringe with the flat mouth syringe needle, and syringe needle connects high voltage source, the metal receiving system that is a ground connection at the other end of distance syringe 20cm.The injection speed of regulating syringe pump is 0.1ml/h, and slowly boosted voltage is to 15kv.Syringe needle ejection rice solution drawing-off under the high voltage electric field effect from syringe, form with tunica fibrosa is collected on the aluminium-foil paper of metal receiving system, gained nonwoven film is placed in to vacuum drying chamber, normal temperature decompression operation 10h, after noresidue solvent in film, take out, obtain PVDF/P (VDF-HFP) composite nano fiber clothes.
By the preparation PVDF/P (VDF-HFP) composite nano-fiber membrane be placed in light and hot press on carry out hot-pressing processing, wherein temperature is: 145 ℃ of patrixes, 135 ℃ of counterdies; Pressure is 3MPa, and the time is 100s, takes out, and obtains the fine tunica fibrosa of enhancement mode PVDF/P (VDF-HFP) Static Spinning nanometer.
Table with test results and P (VDF-HFP) melting of low happy and harmonious temperature after hot pressing bonds the nanofiber in tunica fibrosa each other, form inierpeneirating network structure, and the tensile break strength of tunica fibrosa, with respect to before hot-pressing processing not, is increased to by 3.52MPa
16.64MPa, improved approximately 3.73 times.
By PAN and P (VDF-HFP) be dissolved at 0.7: 0.3 in mass ratio with the DMF solvent in, be configured to the solution that mass fraction is 18%, under 40-50 ℃, heating is stirred to polymer and fully dissolves, and makes spinning solution.The spinning solution obtained is injected in the syringe with the flat mouth syringe needle, and syringe needle connects by high voltage source, the metal receiving system that is a ground connection at the other end of distance syringe 15cm.The injection speed of regulating syringe pump is 0.8ml/h, and slowly boosted voltage is to 18kv.From the solution drawing-off under the high voltage electric field effect of gushing out of the syringe needle of syringe, form with tunica fibrosa is collected on the aluminium-foil paper of metal receiving system, gained nonwoven film is placed in to vacuum drying chamber, normal temperature decompression operation 10h, after noresidue solvent in film, take out, obtain PAN/P (VDF-HFP) composite nano-fiber membrane
PAN/P (VDF-HFP) composite nano-fiber membrane of preparation is placed on the hot press of light face and carries out hot-pressing processing, and wherein temperature is: 145 ℃ of patrixes, 135 ℃ of counterdies; Pressure is 10MPa, and the time is 10s, takes out, and obtains enhancement mode PAN/P (VDF-HFP) electrostatic spinning nano fiber film.
P (VDF-HFP) melting of low happy and harmonious temperature after test result surface hot pressing, nanofiber in tunica fibrosa is bondd each other, form inierpeneirating network structure, the tensile break strength of tunica fibrosa is with respect to before hot-pressing processing not, be increased to 9.78MPa by 1.72MPa, improved approximately 4.69 times.
Embodiment 3
By in PMMA and the PVDF mixed solvent that to be dissolved in mass ratio with DMA and acetone quality ratio at 0.5: 0.5 be 7: 3, be configured to the solution that mass fraction is 10%, under 40-50 ℃, heating is stirred to polymer and fully dissolves, and makes spinning solution.The spinning solution obtained is injected in the syringe with the flat mouth syringe needle, and syringe needle connects high voltage source, the metal receiving system that is a ground connection at the other end of distance syringe 25cm.The injection speed of regulating syringe pump is 1.0ml/h, and slowly boosted voltage is to 20kv.From the solution drawing-off under the high voltage electric field effect of gushing out of the syringe needle of syringe, form with tunica fibrosa is collected on the aluminium-foil paper of metal receiving system, gained nonwoven film is placed in to vacuum drying chamber, normal temperature decompression operation 10h, after noresidue solvent in film, take out, obtain the PMMA/PVDF composite nano-fiber membrane.
The PMMA/PVDF composite nano-fiber membrane of preparation is placed on the hot press of light face and carries out hot-pressing processing, wherein temperature is: 185 ℃ of patrixes, 175 ℃ of counterdies; Pressure is to be 50s the 8MPa time, takes out, and obtains enhancement mode PMMA/PVDF electrostatic spinning nano fiber film.
The PVDF melting of low happy and harmonious temperature after test result surface hot pressing, nanofiber in tunica fibrosa is bondd each other, form inierpeneirating network structure, the tensile break strength of tunica fibrosa is with respect to before hot-pressing processing not, be increased to 11.83MPa by 2.24MPa, improved approximately 4.28 times.
P (VDF-HFP) and PEO are dissolved in and N in mass ratio at 0.8: 0.2, in the mixed solvent that dinethylformamide and acetone quality ratio are 7: 3, be configured to the solution that mass fraction is 18%, under 40-50 ℃, heating is stirred to polymer and fully dissolves, and makes spinning solution.The spinning solution obtained is injected in the syringe with the flat mouth syringe needle, and syringe needle connects high voltage source, the metal receiving system that is a ground connection at the other end of distance syringe 20cm.The injection speed of regulating syringe pump is 0.3ml/h, and slowly boosted voltage is to 18kv.From the solution drawing-off under the high voltage electric field effect of gushing out of the syringe needle of syringe, form with tunica fibrosa is collected on the aluminium-foil paper of metal receiving system, gained nonwoven film is placed in to vacuum drying chamber, normal temperature decompression operation 10h, after noresidue solvent in film, take out, obtain P (VDF-HFP)/PEO composite nano-fiber membrane.
The P (VDF-HFP)/PEO composite nano-fiber membrane of preparation is placed on the hot press of light face and carries out hot-pressing processing, wherein temperature is 110 ℃ of patrixes, 100 ℃ of counterdies; Pressure is 3MPa, and the time is 300s, takes out, and obtains enhancement mode P (VDF-HFP)/PEO electrostatic spinning nano fiber film.
Table with test results and the PEO melting of low happy and harmonious temperature after hot pressing, nanofiber in tunica fibrosa is bondd each other, form inierpeneirating network structure, the tensile break strength of tunica fibrosa is with respect to before hot-pressing processing not, be increased to 11.24MPa by 2.47MPa, improved approximately 3.55 times.
Embodiment 5
By in PVDF and the PAN mixed solvent that to be dissolved in mass ratio with DMA and acetone quality ratio at 0.15: 0.85 be 8: 2, be configured to the solution that mass fraction is 15%, under 40-50 ℃, heating is stirred to polymer and fully dissolves, and makes spinning solution.The spinning solution obtained is injected in the syringe with the flat mouth syringe needle, and syringe needle connects high voltage source, the metal receiving system that is a ground connection at the other end of distance syringe 20cm.The injection speed of regulating syringe pump is 0.5ml/h, and slowly boosted voltage is to 20kv.From the solution drawing-off under the high voltage electric field effect of gushing out of the syringe needle of syringe, form with tunica fibrosa is collected on the aluminium-foil paper of metal receiving system, gained nonwoven film is placed in to vacuum drying chamber, normal temperature decompression operation 10h, after noresidue solvent in film, take out, obtain the PVDF/PAN composite nano-fiber membrane.
The PVDF/PAN composite nano-fiber membrane of preparation is placed on the hot press of light face and carries out hot-pressing processing, wherein temperature is: 195 ℃ of patrixes, 180 ℃ of counterdies; Pressure is 10MPa, and the time is 90s, takes out, and obtains enhancement mode PVDF/PAN electrostatic spinning nano fiber film.
Table with test results and the PVDF melting of low happy and harmonious temperature after hot pressing, nanofiber in tunica fibrosa is bondd each other, form inierpeneirating network structure, the tensile break strength of tunica fibrosa is with respect to before hot-pressing processing not, be increased to 8.24MPa by 1.87MPa, improved approximately 3.41 times.
Embodiment 6
By PEO and PVDF be dissolved at 0.2: 0.8 in mass ratio with the DMF solvent in, be configured to the solution that mass fraction is 18%, under 40-50 ℃, heating is stirred to polymer and fully dissolves, and makes spinning solution.The spinning solution obtained is injected in the syringe with the flat mouth syringe needle, and syringe needle connects high voltage source, the metal receiving system that is a ground connection at the other end of distance syringe 20cm.The injection speed of regulating syringe pump is 1.0ml/h, and slowly boosted voltage is to 15kv.From the solution drawing-off under the high voltage electric field effect of gushing out of the syringe needle of syringe, form with tunica fibrosa is collected on the aluminium-foil paper of metal receiving system, gained nonwoven film is placed in to vacuum drying chamber, normal temperature decompression operation 10h, after noresidue solvent in film, take out, obtain the PEO/PVDF composite nano-fiber membrane.
The PEO/PVDF composite nano-fiber membrane of preparation is placed on the hot press of light face and carries out hot-pressing processing, wherein temperature is: 115 ℃ of patrixes, 105 ℃ of counterdies; Pressure is 5MPa, and the time is 150s, takes out, and obtains enhancement mode PEO/PVDF electrostatic spinning nano fiber film.
The PEO melting of low happy and harmonious temperature after test result surface hot pressing, nanofiber in tunica fibrosa is bondd each other, forms inierpeneirating network structure, the tensile break strength of tunica fibrosa with respect to last hot-pressing processing before, be increased to 9.91MPa by 2.28MPa, improved approximately 3.37 times.
Claims (7)
1. the preparation method of an enhancement mode electrostatic spinning nano fiber lithium ion battery separator, is characterized in that, concrete steps are:
The first step: high and low melt temperature polymer is dissolved in organic solvent by certain mass ratio, forms uniform and stable spinning solution, concentration of dope is 10-18wt%;
Second step: first step gained spinning solution is injected to the syringe pump of electrospinning device, the syringe needle of syringe pump is connected with high voltage source by wire; Place the metal receiving system of a ground connection at the opposite side of distance syringe needle 10-25cm; Cover one deck aluminium-foil paper on the metal receiving system;
The 3rd step: rising high power supply voltage, and the flow velocity of adjusting syringe pump, under the effect of high voltage electric field, from the flat mouth syringe needle nozzle of syringe pump, penetrate, whip occurs in motion process to be moved and tangle, finally be collected on aluminium-foil paper and form tunica fibrosa; The gained tunica fibrosa is placed in to vacuum drying chamber, and normal temperature decompression operation 10h, after noresidue solvent in film, take out;
The 4th step: nano fibrous membrane prepared by the 3rd step is placed on hot press and carries out hot-pressing processing, and pressure is 3-10MPa, and the time is 20-300s, and temperature, between two kinds of polymer melting temperatures, obtains enhancement mode electrostatic spinning nano fiber film.
2. a kind of enhancement mode electrostatic spinning nano fiber membrane preparation method as claimed in claim 1, it is characterized in that, the polymer in the described first step be in polymethyl methacrylate (PMMA), Kynoar (PVDF), Kynoar-hexachloropropylene (PVDF-HFP), polypropylene fine (PAN), polyethylene glycol oxide (PEO) melt temperature differ more than 30 ℃ any two kinds.
3. a kind of enhancement mode electrostatic spinning nano fiber membrane preparation method as claimed in claim 1, it is characterized in that, organic solvent in the described first step is N, the mixture of one or two or more kinds in dinethylformamide, DMA, acetone, 1-METHYLPYRROLIDONE, hexafluoroisopropanol, oxolane.
4. a kind of enhancement mode electrostatic spinning nano fiber membrane preparation method as claimed in claim 1, is characterized in that, the high melting temperature polymer in the described first step is 0.5-0.95: 0.5-0.05 with low melting glass polymer quality ratio.
5. a kind of enhancement mode electrostatic spinning nano fiber membrane preparation method as claimed in claim 1, is characterized in that, the high-voltage power voltage in described second step is 15-25KV, and the syringe flow velocity is 0.1-1.0ml.
6. a kind of enhancement mode electrostatic spinning nano fiber membrane preparation method as claimed in claim 1, is characterized in that, the hot pressing temperature in described the 4th step is between two kinds of polymer melting temperatures.
7. a kind of enhancement mode electrostatic spinning nano fiber membrane preparation method as claimed in claim 1, is characterized in that, low melting glass polymer melting in described the 4th step, bond the fiber in tunica fibrosa each other, thereby improve the tensile break strength of tunica fibrosa.
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