CN103258978A - Preparation method of P(VDF-HFP) (Poly(Vinyl Fluoride-Hexafluoropropylene)) inorganic compound porous nano fiber lithium ion battery separator - Google Patents
Preparation method of P(VDF-HFP) (Poly(Vinyl Fluoride-Hexafluoropropylene)) inorganic compound porous nano fiber lithium ion battery separator Download PDFInfo
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Abstract
The invention relates to a preparation method of a P(VDF-HFP) [Poly(Vinyl Fluoride-Hexafluoropropylene)] inorganic compound porous nano fiber lithium ion battery separator. The method comprises the following specific steps of: (1) adding P(VDF-HFP) and PEG (Polyethylene Glycol) into an organic solvent; heating and agitating to dissolve to form a transparent solution; cooling the solution to be at room temperature; and dispersing inorganic nano grains into the solution by agitation and ultrasonic treatment to obtain a spinning solution; (2) statically spinning the obtained spinning solution to obtain a primarily-formed P(VDF-HFP) inorganic compound porous nano fiber membrane; and (3) immersing the primarily-formed P(VDF-HFP) inorganic compound porous nano fiber membrane into distilled water to remove the PEG; and carrying out drying treatment to obtain the P(VDF-HFP) inorganic compound porous nano fiber lithium ion battery separator. The lithium ion battery separator prepared by using the preparation method disclosed by the invention has high liquid absorption rate and good electrochemical stability, and has a good heat-resisting shrinkage performance.
Description
Technical field
The present invention relates to the preparation method of the inorganic composite porous nanofiber lithium ion battery separator of a kind of P (VDF-HFP), belong to nano-functional material and lithium ion battery field.
Technical background
Lithium ion battery mainly contains both positive and negative polarity, barrier film, electrolyte composition.Its septation is between the positive and negative pole material, to isolate both positive and negative polarity, prevents short circuit, stops electronics to pass through, and allows ion to pass through.The performance of barrier film determines internal resistance and the internal interface structure of battery, and then influences capacity, charge-discharge performance, cycle performance and the security performance etc. of battery, so membrane properties has material impact to the combination property of lithium ion battery.
Gel polymer electrolyte refers to the polymer mesh system that swelling forms behind the membrane for polymer Electolyte-absorptive, and it has the diffusivity of liquid and the caking property of solid, is widely used in the lithium ion battery.At present, the more lithium ion battery gel polymer electrolyte material of research has polymethyl methacrylate (PMMA), poly-oxireme (PEO), polyacrylonitrile (PAN) and Kynoar (PVDF) and copolymer thereof.Wherein, Kynoar-hexafluoropropylene P (VDF-HFP) not only has the good thermal stability of PVDF, chemical resistance, oxidative resistance, weatherability, also have easy processing, flexible strong characteristics, the HFP of the amorphous state in the polymer molecule can promote the absorption of electrolyte, and the PVDF of crystalline state can provide strong backing for matrix, is the lithium ion battery gel polymer material of present better performances.Polyethylene glycol (PEG) can be dissolved in organic solvent with P (VDF-HFP) blend, can be dissolved in the water again.
Qi etc. are dissolved in PLA and dispose spinning solution in carrene/n-butanol mixed solvent, method of electrostatic spinning prepares porous nano-fibre, by regulating pore structure (the Qi Z on carrene and n-butanol proportion of composing control nanofiber surface, Yu H, Chen Y, et al.Highly porous fibers prepared by electrospinning a ternary system of nonsolvent/solv-ent/po-ly (l-lactic acid) .Materials Letters.2009,63 (3-4): 415-418.).Zhang etc. are dissolved in DMF jointly with PAN and PEO and obtain blend solution, prepare nanofiber by electrostatic spinning technique, after drying, be immersed in the deionized water, remove PEO and form PAN porous nano-fibre (ZHANG L F, HSIEH Y L.Nanoporous ultrahigh specific surf-ace polyacrylonitrile fibres.Nanotechnology, 2006,17 (17): 4416-4423.).Patent CN102268745 is dissolved in DMF and chloroform (CHCl respectively with PAN and PEO respectively
3) in, again these two kinds of solution are carried out composite acquisition spinning solution, adopt method of electrostatic spinning to prepare porous nano-fibre.The CHCl that this method is used
3Carcinogenesis is arranged, penetrate in illumination and easily decompose the phosgene that generates severe toxicity down, the harm personal safety.Patent CN102493009A adds the dispersing liquid immiscible with solvent in fibre-forming polymer solution, add surfactant again and prepare emulsion, carry out electrostatic spinning, volatilization by dispersing liquid, perhaps in spinning process and washing process afterwards with the dispersing liquid flush away, obtain porous nano-fibre.The adding of surfactant has influenced the performance of nanofiber to a certain extent in the method.In addition, though these methods have prepared porous nano-fibre, do not propose it should be used as lithium ion battery separator, its chemical property is not carried out test analysis.
Patent CN102790195 adopts the solution casting method to prepare the composite lithium ion cell barrier film P (VDF-HFP) and particles of inorganic material mixing.Barrier film porosity and the ionic conductivity of the preparation of this method are low, and it can increase the internal resistance of battery as lithium ion battery separator, influence the cycle performance of battery.Patent CN102820446, US2010/0316903A1 and US6432586B1 apply one deck at the microporous barrier matrix and mix the porous layer of forming by inorganic oxide particles and macromolecule organic or binding agent, prepare the lithium ion battery composite diaphragm.The composite membrane thickness of this method preparation is bigger, and pick up is not high, and the internal resistance of cell is bigger, easily layering in processing, use, and inorganic particle easily comes off and further influences battery performance.
Patent WO2012050682A2, TW201230453A and US2012082884A1 directly are deposited on P (VDF-HFP) and inorganic ceramic particle composite nano fiber on positive electrode or the negative material by method of electrostatic spinning.The barrier film of this method preparation directly is compounded on the electrode material, its membrane thicknesses and uniformity test are subjected to certain limitation, be unfavorable for the on-line debugging in the production process, the compound complexity that increases technology of barrier film and electrode material in addition, be unfavorable for production management, also be unfavorable for the preferred disposition of barrier film and electrode material.
Patent CN102779964 is with macromolecule organic and small organic molecule solution organic solvent, add inorganic nano-particle configuration mixed liquor again, by method of electrostatic spinning mixed liquor is coated in and forms composite membrane on the film matrix, again small organic molecule is extracted, and form the porous nano-fibre composite membrane.Interaction force is not strong between the composite film of this method preparation and the layer, behind the Electolyte-absorptive, easily separation takes place and influences the performance of battery.Patent CN102268783 joins Single Walled Carbon Nanotube and lithium salts and forms mixed liquor in the organic solvent, dissolve in PVDF, dissolve in polyvinylpyrrolidone again, join spinning solution, electrostatic spinning is shaped, and the gained tunica fibrosa is flooded the PVDF porous nano-fibre lithium ion battery separator that 1-2h obtains to have the macroion transport number in ethanol.The employed PVDF degree of crystallinity of this method is higher, is unfavorable for the absorption of electrolyte and the raising of ionic conductivity, and tunica fibrosa is to remove polyvinylpyrrolidone in ethanol, forms porous nano-fibre, and cost is higher to be unfavorable for large-scale production.
Summary of the invention
At the deficiencies in the prior art, the problem that quasi-solution of the present invention is determined is that a kind of P (VDF-HFP) is provided the preparation method of inorganic composite porous nanofiber lithium ion battery.This preparation method's technology is simple, and control is easy, and easy to operate, cost is low, and the products obtained therefrom good heat stability has than high-liquid absorbing rate and electrochemical stability window.
In order to solve the problems of the technologies described above, the invention provides the preparation method of the inorganic composite porous nanofiber lithium ion battery separator of a kind of preparation P (VDF-HPF), it is characterized in that this barrier film is made up of P (VDF-HFP)/compound porous nanofiber of inorganic particle, concrete making step is:
The first step: P (VDF-HFP) and PEG are joined in the organic solvent, 40～50 ℃ of heating stirring and dissolving, form clear solution, be cooled to room temperature, add inorganic nanoparticles, stirring at room, preliminary dispersing nanometer particle, ultrasonic dispersion 15～30min, further the dispersing nanometer particle obtains spinning solution;
Second step: with the spinning solution electrostatic spinning of gained, obtain nascent P (VDF-HFP) inorganic composite nanofiber film.
The 3rd step: with nascent P (VDF-HFP) the inorganic composite fiber film immersion of gained in distilled water, remove the PEG composition, taking-up places the dry processing of drying box, removes the moisture in the tunica fibrosa, namely obtains the inorganic composite porous nanofiber lithium ion battery separator of P (VDF-HFP).
Preferably, the organic solvent in the described first step is N, dinethylformamide, N, the mixture of one or two or more kinds in N-dimethylacetylamide, acetone, N-methyl pyrrolidone, hexafluoroisopropanol, the oxolane.
Preferably, the inorganic nanoparticles in the described first step is one or two or more kinds the mixture in alundum (Al, silicon dioxide, titanium dioxide, barium titanate, magnesium oxide, zirconium dioxide, zinc oxide, the carborundum.
Preferably, P (VDF-HFP), PEG and the inorganic nanoparticles mass ratio in the described first step is: 0.7～0.9: 0.05～0.25: 0.01～0.08.
Preferably, the electrostatic spinning condition is in described second step: temperature is room temperature, and relative humidity is 20～65%, and spinning speed is 0.1～1.0mL/h, and the distance between spinning nozzle and the receiver is 10～25cm, and spinning voltage is 10～25kV.
Preferably, the electrostatic spinning receiving system in described second step is one or more in aluminium foil, iron plate, iron net, copper mesh, iron roller, aluminum drum and the non-woven material.
Preferably, the distilled water temperature in described the 3rd step is 20～55 ℃, and the time is 2～4h.
Preferably, the baking temperature in described the 3rd step is 60-120 ℃, and the time is 1～4h.
Compared with prior art, the invention has the advantages that:
1, the inorganic composite porous nanofiber lithium ion battery separator of P (VDF-HFP) of the present invention's preparation, not only has the good absorbent of PVDF-HFP material, remove the PEG composition and form porosity and the pick up that loose structure further improves barrier film at fiber, nano-inorganic substance can adsorb low amounts of water and the HF that electrolyte decomposition produces in the battery cyclic process, improve battery efficiency, prolong battery cycle life.
2, the method for the inorganic composite porous nanofiber lithium ion battery separator of the P of preparation provided by the invention (VDF-HFP) do not use the irrelevant and carcinogenicity of surfactant etc. and product material, pore forming process is carried out in water, easy to operate, technological process is short, and cost is lower.
3, the inorganic composite porous nanofiber lithium ion battery separator of P (VDF-HFP) of the present invention's preparation is made up of the nanofiber that comprises inorganic particle, and thickness is less and easy to control, layering and nano particle obscission can not occur in production, the use.
4, the inorganic composite porous nanofiber lithium ion battery separator of P (VDF-HFP) of the present invention preparation has lower percent thermal shrinkage, good electrochemical stability, higher porosity and pick up, and mechanical strength can satisfy the requirement of battery pack process of assembling simultaneously.
5, the inorganic composite porous nanofiber lithium ion battery separator of P (VDF-HFP) of the present invention's preparation has solution corrosion resistance, good interface stability.
Embodiment
Provide specific embodiments of the invention below.These specific embodiments only are used for further narration the present invention, do not limit the claim protection range of the present patent application.
Embodiment 1
At room temperature, take by weighing dried P (VDF-HFP), PEG and nanometer Al
2O
3(mass ratio is 8: 1.8: 0.2) adds P (VDF-HFP) and PEG in a certain amount of DMF/ acetone mixed solvent to earlier, carries out the magnetic agitation dissolving under 45 ℃ of conditions, to forming transparent mixed solution.The mixed solution that obtains is cooled to room temperature, again with nanometer Al
2O
3Add in the mixed solution, stir the preliminary dispersing nanometer particle of certain hour under the room temperature, ultrasonic processing 20min further is dispersed in nano particle in the solution again, makes spinning solution.
25 ℃ of room temperatures, under humidity 30% condition, above-mentioned spinning solution is carried out electrostatic spinning with the spinning speed of 0.1ml/h, the voltage that applies is 10kv; Spinning between syringe needle and receiver distance is 10cm, with spun fiber laydown to the receiver of electrospinning device; After spinning is finished P (VDF-HFP) the inorganic composite nanofiber film of preparation is taken off from receiver, be dipped in 20 ℃ of distilled water and take out behind the 4h, place drying box to dry, temperature is 60 ℃, time is 4h, obtains the inorganic composite porous nano fibrous membrane of P (VDF-HFP).
Place 150 ℃ of hot casees to handle 1.5h the inorganic composite porous nano fibrous membrane of P (VDF-HFP), shrinkage is 2.5%, this tunica fibrosa is immersed in the electrolyte of ethylene carbonate/dimethyl carbonate/diethyl carbonate (mass ratio is 1: 1: 1) of 1mol lithium hexafluoro phosphate, the pick up of acquisition is 573.6%, ionic conductivity is that 1.16mS/cm, electrochemical stability window are 5.2V.
Embodiment 2
At room temperature, take by weighing dried P (VDF-HFP), PEG and nanometer ZrO
2(mass ratio is 9: 0.5: 0.5) adds P (VDF-HFP) and PEG in a certain amount of DMAc/ acetone mixed solvent to earlier, carries out the magnetic agitation dissolving under 50 ℃ of conditions, to forming transparent mixed solution.The mixed solution that obtains is cooled to room temperature, again with nanometer ZrO
2Add in the mixed solution, stir the preliminary dispersing nanometer particle of certain hour under the room temperature, ultrasonic processing 15min further is dispersed in nano particle in the solution again, makes spinning solution.
25 ℃ of room temperatures, under humidity 40% condition, above-mentioned spinning solution is carried out electrostatic spinning with the spinning speed of 0.4ml/h, the voltage that applies is 15kv; Spinning between syringe needle and receiver distance is 15cm, with spun fiber laydown to the receiver of electrospinning device; After spinning is finished P (VDF-HFP) the inorganic composite nanofiber film of preparation is taken off from receiver, be dipped in 40 ℃ of distilled water and take out behind the 3h, place drying box to dry, temperature is 80 ℃, time is 3.5h,, obtain the inorganic composite porous nano fibrous membrane of P (VDF-HFP).
Place 150 ℃ of hot casees to handle 1.5h the inorganic composite porous nano fibrous membrane of P (VDF-HFP), shrinkage is 1.7%, this tunica fibrosa is immersed in the electrolyte of ethylene carbonate/dimethyl carbonate/diethyl carbonate (mass ratio is 1: 1: 1) of 1mol lithium hexafluoro phosphate, the pick up of acquisition is 484.3%, ionic conductivity is that 1.58mS/cm, electrochemical stability window are 5.0V.
Embodiment 3
At room temperature, take by weighing dried P (VDF-HFP), PEG and nano-TiO
2(mass ratio is 8.5: 1: 0.5) adds P (VDF-HFP) and PEG in a certain amount of DMF/ acetone mixed solvent to earlier, carries out the magnetic agitation dissolving under 50 ℃ of conditions, to forming transparent mixed solution.The mixed solution that obtains is cooled to room temperature, again with nano-TiO
2Add in the mixed solution, stir the preliminary dispersing nanometer particle of certain hour under the room temperature, ultrasonic processing 30min further is dispersed in nano particle in the solution again, makes spinning solution.
25 ℃ of room temperatures, under humidity 30% condition, above-mentioned spinning solution is carried out electrostatic spinning with the spinning speed of 0.6ml/h, the voltage that applies is 20kv; Spinning between syringe needle and receiver distance is 20cm, with spun fiber laydown to the aluminium foil receiver of electrospinning device; After spinning is finished P (VDF-HFP) the inorganic composite nanofiber film of preparation is taken off from receiver, be dipped in 55 ℃ of distilled water and take out behind the 2h, place drying box to dry, temperature is 90 ℃, time is 3h, obtains the inorganic composite porous nano fibrous membrane of P (VDF-HFP).
Place 150 ℃ of hot casees to handle 1.5h the inorganic composite porous nano fibrous membrane of P (VDF-HFP), shrinkage is 2.0%, this tunica fibrosa is immersed in the electrolyte of ethylene carbonate/dimethyl carbonate/diethyl carbonate (mass ratio is 1: 1: 1) of 1mol lithium hexafluoro phosphate, the pick up of acquisition is 461.4%, ionic conductivity is that 2.29mS/cm, electrochemical stability window are 5.1V.
Embodiment 4
At room temperature, take by weighing dried P (VDF-HFP), PEG and nanometer Al
2O
3(mass ratio is 7: 2.5: 0.5) adds P (VDF-HFP) and PEG in a certain amount of DMF/ acetone mixed solvent to earlier, carries out the magnetic agitation dissolving under 50 ℃ of conditions, to forming transparent mixed solution.The mixed solution that obtains is cooled to room temperature, again with nanometer Al
2O
3Add in the mixed solution, stir the preliminary dispersing nanometer particle of certain hour under the room temperature, ultrasonic processing 20min further is dispersed in nano particle in the solution again, makes spinning solution.
25 ℃ of room temperatures, under humidity 42% condition, above-mentioned spinning solution is carried out electrostatic spinning with the spinning speed of 0.8ml/h, the voltage that applies is 25kv; Spinning between syringe needle and receiver distance is 25cm, with spun fiber laydown to the receiver of electrospinning device; After spinning is finished P (VDF-HFP) the inorganic composite nanofiber film of preparation is taken off from receiver, be dipped in 50 ℃ of distilled water and take out behind the 2.4h, place drying box to dry, temperature is 100 ℃, time is 2h, obtains the inorganic composite porous nano fibrous membrane of P (VDF-HFP).
Place 150 ℃ of hot casees to handle 1.5h the inorganic composite porous nano fibrous membrane of P (VDF-HFP), shrinkage is 2.4%, this tunica fibrosa is immersed in the electrolyte of ethylene carbonate/dimethyl carbonate/diethyl carbonate (mass ratio is 1: 1: 1) of 1mol lithium hexafluoro phosphate, the pick up of acquisition is 464.3%, ionic conductivity is that 1.52mS/cm, electrochemical stability window are 5.3V.
Embodiment 5
At room temperature, take by weighing dried P (VDF-HFP), PEG and nano-ZnO (mass ratio is 7.4: 2.5: 0.5), earlier P (VDF-HFP) and PEG are added in a certain amount of DMF solvent, under 50 ℃ of conditions, carry out the magnetic agitation dissolving, to forming transparent mixed solution.The mixed solution that obtains is cooled to room temperature, nano-ZnO is added in the mixed solution again, stir the preliminary dispersing nanometer particle of certain hour under the room temperature, ultrasonic processing 20min further is dispersed in nano particle in the solution again, makes spinning solution.
25 ℃ of room temperatures, under humidity 35% condition, above-mentioned spinning solution is carried out electrostatic spinning with the spinning speed of 1.0ml/h, the voltage that applies is 15kv; Spinning between syringe needle and receiver distance is 20cm, with spun fiber laydown to the receiver of electrospinning device; After spinning is finished P (VDF-HFP) the inorganic composite nanofiber film of preparation is taken off from receiver, be dipped in 30 ℃ of distilled water and take out behind the 3.5h, place drying box to dry, temperature is 110 ℃, time is 1.5h, obtains the inorganic composite porous nano fibrous membrane of P (VDF-HFP).
Place 150 ℃ of hot casees to handle 1.5h the inorganic composite porous nano fibrous membrane of P (VDF-HFP), shrinkage is 2.0%, this tunica fibrosa is immersed in the electrolyte of ethylene carbonate/dimethyl carbonate/diethyl carbonate (mass ratio is 1: 1: 1) of 1mol lithium hexafluoro phosphate, the pick up of acquisition is 393.4%, ionic conductivity is that 1.39mS/cm, electrochemical stability window are 5.0V.
Embodiment 6
At room temperature, take by weighing dried P (VDF-HFP), PEG and nano-ZnO (mass ratio is 7.7: 1.5: 0.8), earlier P (VDF-HFP) and PEG are added in a certain amount of DMF solvent, under 50 ℃ of conditions, carry out the magnetic agitation dissolving, to forming transparent mixed solution.The mixed solution that obtains is cooled to room temperature, nano-ZnO is added in the mixed solution again, stir the preliminary dispersing nanometer particle of certain hour under the room temperature, ultrasonic processing 30min further is dispersed in nano particle in the solution again, makes spinning solution.
25 ℃ of room temperatures, under humidity 42% condition, above-mentioned spinning solution is carried out electrostatic spinning with the spinning speed of 0.6ml/h, the voltage that applies is 18kv; Spinning between syringe needle and receiver distance is 15cm, with spun fiber laydown to the electrospinning device receiver; After spinning is finished P (VDF-HFP) the inorganic composite nanofiber film of preparation is taken off from receiver, be dipped in 45 ℃ of distilled water and take out behind the 2.8h, place drying box to dry, temperature is 120 ℃, time is 1h, obtains the inorganic composite porous nano fibrous membrane of P (VDF-HFP).
Place 150 ℃ of hot casees to handle 1.5h the inorganic composite porous nano fibrous membrane of P (VDF-HFP), shrinkage is 2.1%, this tunica fibrosa is immersed in the electrolyte of ethylene carbonate/dimethyl carbonate/diethyl carbonate (mass ratio is 1: 1: 1) of 1mol lithium hexafluoro phosphate, the pick up of acquisition is 413.6%, ionic conductivity is that 1.42mS/cm, electrochemical stability window are 5.4V.
Claims (8)
1. the preparation method of the inorganic composite porous nanofiber lithium ion battery separator of Kynoar-hexafluoropropylene is characterized in that, concrete steps are:
The first step: Kynoar-hexafluoropropylene and PEG are joined in the organic solvent, 40～50 ℃ of heating stirring and dissolving, form clear solution, be cooled to room temperature, add inorganic nanoparticles, stirring at room, preliminary dispersing nanometer particle, ultrasonic dispersion 15～30min, further the dispersing nanometer particle obtains spinning solution;
Second step: with the spinning solution electrostatic spinning of gained, obtain nascent Kynoar-hexafluoropropylene inorganic composite nanofiber film.
The 3rd step: the nascent Kynoar-hexafluoropropylene inorganic composite fiber film of gained is flooded 2～4h remove the PEG composition in distilled water, take out then and place the dry processing of drying box, remove the moisture in the tunica fibrosa, namely obtain the inorganic composite porous nanofiber lithium ion battery separator of Kynoar-hexafluoropropylene.
2. the preparation method of the inorganic composite porous nanofiber lithium ion battery separator of Kynoar-hexafluoropropylene as claimed in claim 1, it is characterized in that, organic solvent in the described first step is N, dinethylformamide, N, the mixture of one or two or more kinds in N-dimethylacetylamide, acetone, N-methyl pyrrolidone, hexafluoroisopropanol, the oxolane.
3. the preparation method of the inorganic composite porous nanofiber lithium ion battery separator of Kynoar-hexafluoropropylene as claimed in claim 1, it is characterized in that the inorganic nanoparticles in the described first step is one or two or more kinds the mixture in alundum (Al, silicon dioxide, titanium dioxide, barium titanate, magnesium oxide, zirconium dioxide, zinc oxide, the carborundum.
4. the preparation method of the inorganic composite porous nanofiber lithium ion battery separator of Kynoar-hexafluoropropylene as claimed in claim 1, it is characterized in that the Kynoar-hexafluoropropylene in the described first step, PEG and inorganic nanoparticles mass ratio are: 0.7～0.9: 0.05～0.25: 0.01～0.08.
5. the preparation method of the inorganic composite porous nanofiber lithium ion battery separator of Kynoar-hexafluoropropylene as claimed in claim 1, it is characterized in that, the electrostatic spinning condition is in described second step: temperature is room temperature, relative humidity is 20～65%, spinning speed is 0.1～1.0mL/h, distance between spinning nozzle and the receiver is 10～25cm, and spinning voltage is 10～25kV.
6. the preparation method of the inorganic composite porous nanofiber lithium ion battery separator of Kynoar-hexafluoropropylene as claimed in claim 1, it is characterized in that the electrostatic spinning receiving system in described second step is one or more in aluminium foil, iron plate, iron net, copper mesh, iron roller, aluminum drum and the non-woven material.
7. the preparation method of the inorganic composite porous nanofiber lithium ion battery separator of Kynoar-hexafluoropropylene as claimed in claim 1 is characterized in that, the distilled water temperature in described the 3rd step is 20～55 ℃, and the time is 2～4h.
8. the preparation method of the inorganic composite porous nanofiber lithium ion battery separator of Kynoar-hexafluoropropylene as claimed in claim 1 is characterized in that, the vacuum drying chamber temperature in described the 3rd step is 60-120 ℃, and be 1-4h drying time.
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