CN103474610A - Method for preparing composite lithium-ion battery separator through electrostatic spinning/electrostatic spraying - Google Patents
Method for preparing composite lithium-ion battery separator through electrostatic spinning/electrostatic spraying Download PDFInfo
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- CN103474610A CN103474610A CN2013104544645A CN201310454464A CN103474610A CN 103474610 A CN103474610 A CN 103474610A CN 2013104544645 A CN2013104544645 A CN 2013104544645A CN 201310454464 A CN201310454464 A CN 201310454464A CN 103474610 A CN103474610 A CN 103474610A
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Abstract
The invention relates to the field of lithium-ion batteries, in particular to a method for preparing a composite lithium-ion battery separator through electrostatic spinning/electrostatic spraying. The method specifically includes the steps of firstly, adding high molecular polymer into an organic solvent, dissolving the high molecular polymer through mechanical stirring to form a transparent solution, and obtaining an electrostatic spinning solution; secondly, mixing inorganic nanometer particles with the high molecular polymer and adding the mixture into the organic solvent, and conducting mechanical stirring to obtain inorganic nanometer particle suspension liquid; thirdly, conducting electrostatic spinning on the spinning solution prepared in the first step to prepare a lower layer nanometer fiber film, and enabling the inorganic nanometer particle suspension liquid prepared in the second step to be deposited on the lower layer nanometer fiber film through electrostatic spraying to obtain an interlayer; finally, receiving an electrostatic spun nanometer fiber layer on an inorganic particle layer to obtain the composite lithium-ion battery separator. The composite lithium-ion battery separator has the high imbibing rate and good electrochemical stability under the room temperature and has good heat shrinkage resistance performance at the same time.
Description
Technical field
The present invention relates to the lithium ion battery field, particularly relate to a kind of method that adopts electrostatic spinning/electrostatic spray to prepare the MULTILAYER COMPOSITE lithium ion battery separator.
Technical background
Lithium ion battery mainly contains both positive and negative polarity, barrier film, electrolyte and utmost point shell and forms.Its septation is between positive and negative pole material, plays the isolation both positive and negative polarity, prevents short circuit, stops electronics to pass through, the effect that allows ion to pass through.The performance of barrier film determines internal resistance and the internal interface structure of battery, and then affects capacity, charge-discharge performance, cycle performance and the security performance of battery.
Gel polymer electrolyte refers to the polymer mesh system that swelling forms after the membrane for polymer Electolyte-absorptive, and it has the diffusivity of liquid and the caking property of solid, is widely used in lithium ion battery.At present, study more lithium ion battery gel polymer electrolyte material polymethyl methacrylate (PMMA), polyethylene glycol oxide (PEO), polyacrylonitrile (PAN) and Kynoar (PVDF) and copolymer thereof etc. are arranged.
Patent CN102790195A adds the inorganic ceramic particle in organic polymer soln and has prepared the composite lithium ion cell barrier film through casting, and this barrier film pick up and porosity are lower; Patent WO2012077015A1 is filled into electrostatic spinning in polymer dope by inorganic nanoparticles and prepares organic/inorganic composite nanofiber lithium ion battery separator; But all there will be the problem of inorganic particle in being difficult to be dispersed in organic solution in above provided two kinds of barrier film preparation methods, need to use the equipment such as dispersant or ball mill, and inorganic particle disperses inhomogeneous meeting to have a strong impact on mechanical performance and the chemical property of barrier film.
Patent WO2012050682A2, TW201230453A and US2012082884A1 by method of electrostatic spinning by P (VDF-HFP) and inorganic ceramic particle composite nano fiber Direct precipitation on positive electrode or negative material.The standby barrier film direct combination of this legal system is on electrode material, its membrane thicknesses and uniformity test are subject to certain limitation, be unfavorable for the on-line debugging in production process, the compound complexity that increases technique of barrier film and electrode material in addition, be unfavorable for production and processing, also be unfavorable for the preferred disposition of barrier film and electrode material.
Patent CN102820446, US2010/0316903A1 and US6432586B1 apply one deck and mix by inorganic oxide particles and macromolecule organic or binding agent the porous layer formed on the microporous barrier matrix, prepare the lithium ion battery composite diaphragm.The standby composite membrane thickness of this legal system is larger, and pick up is not high, and the internal resistance of cell is larger, and in processing, use procedure, inorganic particle easily comes off and affects battery performance.Propose in patent CN102407623A to adopt magnetron sputtering method at organic barrier film both sides sputter inorganic oxide, prepare the method for composite lithium ion cell barrier film.Need in the method organic barrier film is placed in the magnetron sputtering cavity, at twice to barrier film two sides sputter inorganic matter, production can not be carried out in serialization, and efficiency is low.
Cho etc. are by SiO
2or Al
2o
3particle coating is on the polyolefine fiber non-woven material, receiving afterwards one deck Static Spinning PAN nanofiber processes and has prepared three layers of composite lithium ion cell barrier film (Cho T through hot rolling again, Tanaka M, Ohnishi H, et al.Composite nonwoven separator for lithium-ion battery:Development and characterization[J] .Journal ofPower Sources.2010,195 (13): 4272-4277.).The standby composite diaphragm thickness of this legal system is large, porosity and air penetrability lower.A kind of preparation method of composite diaphragm is provided in patent CN102751462A, and this composite diaphragm comprises supporting layer, inorganic particulate granulosa and polytetrafluoroethylene floor, and wherein the inorganic particulate granulosa is between supporting layer and polytetrafluoroethylene floor.The polytetrafluoroethylmaterial material surface of using can be lower, wettability is poor, with compatibility and the bad adhesion of other materials, need carry out surface modification to it, also use bonding agent and a small amount of acid in the course of processing, complex process, processing cost is high.
Summary of the invention
For the deficiencies in the prior art, the problem that quasi-solution of the present invention is determined is that a kind of method for preparing the composite lithium ion cell barrier film by electrostatic spinning/electrostatic spray is provided.This preparation process can complete on same electrostatic spinning apparatus, realizes composite diaphragm serialization production, and technique is simple, controls easily, and easy to operate, cost is low.
The prepared composite diaphragm of the inventive method is three-decker: upper and lower two-layer is the electrostatic spinning nano fiber film, the nano-particle layer that internal layer is the electrostatic spray deposition, and the heat-resisting shrinkage of products obtained therefrom is good, has than high-liquid absorbing rate and electrochemical stability window.
Concrete making step is:
The first step: high molecular polymer is joined in organic solvent, and mechanical agitation is dissolved, and forms clear solution, makes electrostatic spinning liquid.
Second step: the mixture of inorganic nanoparticles and high molecular polymer is joined in organic solvent, and mechanical agitation, make inorganic nanoparticles suspension.
The 3rd step: the spinning solution electrostatic spinning prepared in the first step is prepared to lower floor's nano fibrous membrane; The inorganic nanoparticles suspension prepared in second step being deposited on lower floor's nano fibrous membrane through electrostatic spray, is intermediate layer again; Finally, receive one deck electrostatic spinning nano fiber film on the inorganic particulate granulosa, make the composite lithium ion cell barrier film.
Preferably, one or more the mixture that the high molecular polymer in the described first step and second step is PMMA, PAN, PEO, PVDF and P (VDF-HFP).
Preferably, the organic solvent in the described first step and second step is one or two or more kinds the mixture in DMF, DMA, acetone, 1-METHYLPYRROLIDONE, hexafluoroisopropanol, oxolane.
Preferably, the inorganic nanoparticles in described second step is Al
2o
3, SiO
2, TiO
2, BaTiO
3, MgO, ZrO
2, one or two or more kinds the mixture in ZnO, SiC.
Preferably, the electrostatic spinning receiving system in described the 3rd step is one or more in aluminium foil, iron plate, iron net, copper mesh, iron roller, aluminum drum and non-woven material.
Preferably, in described second step, the mass ratio of inorganic nanoparticles and high molecular polymer is: 0.9～0.95: 0.1～0.05.
Preferably, in described the 3rd step, the thickness of prepared composite diaphragm is 20～40 μ m, and wherein the thickness of inorganic nanoparticles layer is 5～10 μ m.
Compared with prior art, the invention has the advantages that:
1, the electrostatic spinning that prepared by the present invention/electrostatic spray composite lithium ion cell barrier film, upper and lower two-layer is the reticular membrane structure with nanofiber composition of specific area, centre is the inorganic particle accumulation horizon of microcellular structure, can store a large amount of electrolyte.This composite membrane is Electolyte-absorptive rapidly, and outer field nanofiber layer is gel state and pins the electrolyte that the inorganic particulate granulosa absorbs, and has higher guarantor's liquid rate.
2, the method for preparing electrostatic spinning/electrostatic spray lithium ion battery separator provided by the invention do not use affect the diaphragm electrochemical performance without related substance, whole processing preparation process completes on same electrospinning device, can realize serialization production, easy to operate, technological process is short, and cost is low.
3, the electrostatic spinning that prepared by the present invention/electrostatic spray composite lithium ion cell barrier film, inorganic particle is between two-layer nano fibrous membrane, in production, use procedure, not there will be obscission.
4, the electrostatic spinning that prepared by the present invention/electrostatic spray composite lithium ion cell barrier film has lower percent thermal shrinkage, good electrochemical stability and higher porosity, and mechanical strength can meet the requirement of battery pack process of assembling simultaneously.
5, in electrostatic spinning provided by the invention/electrostatic spray composite lithium ion cell barrier film preparation method, the preparation technology of inorganic nanoparticles suspension is simple, and whether less to the composite diaphragm Effect on Mechanical Properties nano granule suspension is evenly.
The accompanying drawing explanation
Fig. 1 is electrostatic spinning/electrostatic spray composite diaphragm preparation process figure, and wherein (1) is the preparation of first floor static spinning membrane, and (2) are the preparation of second layer electrostatic spray deposition inorganic particulate granulosa, and (3) are the 3rd layer of electrostatic spinning nano fiber layer preparation.
The morphosis figure that Fig. 2 is electrostatic spinning/electrostatic spray composite diaphragm, wherein, a is the composite diaphragm cross section structure, and b is outer nano fibrous membrane, and c is middle inorganic particulate granulosa
Embodiment
Below provide specific embodiments of the invention.These specific embodiments, only for further narration the present invention, do not limit the claim protection range of the present patent application.
At room temperature, take dried PVDF and add in a certain amount of DMF/ acetone mixed solvent, stirring and dissolving prepares polymer dope.Take again nanometer Al
2o
3with PVDF (mass ratio 0.8: 0.2) joins in the DMF solvent, prepare nano granule suspension.
Polymer dope prepares the PVDF nano fibrous membrane through electrostatic spinning and is deposited on receiving system, again nano granule suspension is deposited on nano fibrous membrane through electrostatic spray, receive again afterwards one deck Static Spinning PVDF nano fibrous membrane on the inorganic particulate granulosa, obtained electrostatic spinning/electrostatic spray composite lithium ion cell barrier film.
The electrostatic spinning of preparation/electrostatic spray composite lithium ion cell barrier film is placed in to 150 ℃ of hot casees and processes 1h, shrinkage is 1.25%, this tunica fibrosa is immersed in the electrolyte of the ethylene carbonate/dimethyl carbonate of 1mol lithium hexafluoro phosphate/diethyl carbonate (mass ratio is 1: 1: 1), the pick up of acquisition is 496%, ionic conductivity is that 1.83mS/cm, electrochemical stability window are 5.27V.
Embodiment 2
At room temperature, take dried P (VDF-HFP) and add in a certain amount of DMF solvent, stirring and dissolving prepares polymer dope.Take again nanometer SiO
2with P (VDF-HFP) (mass ratio 0.9: 0.1) joins in the DMF solvent, prepare nano granule suspension.
Polymer dope prepares P (VDF-HFP) nano fibrous membrane through electrostatic spinning and is deposited on receiving system, again nano granule suspension is deposited on nano fibrous membrane through electrostatic spray, receive again afterwards one deck Static Spinning P (VDF-HFP) nano fibrous membrane on the inorganic particulate granulosa, obtained electrostatic spinning/electrostatic spray composite lithium ion cell barrier film.
[0025] electrostatic spinning of preparation/electrostatic spray composite lithium ion cell barrier film is placed in to 150 ℃ of hot casees and processes 1h, shrinkage is 1.36%, this tunica fibrosa is immersed in the electrolyte of the ethylene carbonate/dimethyl carbonate of 1mol lithium hexafluoro phosphate/diethyl carbonate (mass ratio is 1: 1: 1), the pick up of acquisition is 542%, ionic conductivity is that 2.24mS/cm, electrochemical stability window are 5.32V.
At room temperature, take dried PMMA and add in a certain amount of DMAc/ acetone mixed solvent, stirring and dissolving prepares polymer dope.Take again nanometer ZrO
2with PMMA (mass ratio 0.98: 0.02) joins in the DMAc solvent, prepare nano granule suspension.
Polymer dope prepares the PMMA nano fibrous membrane through electrostatic spinning and is deposited on receiving system, again nano granule suspension is deposited on nano fibrous membrane through electrostatic spray, receive again afterwards one deck Static Spinning PMMA nano fibrous membrane on the inorganic particulate granulosa, obtained electrostatic spinning/electrostatic spray composite lithium ion cell barrier film.
The electrostatic spinning of preparation/electrostatic spray composite lithium ion cell barrier film is placed in to 150 ℃ of hot casees and processes 1h, shrinkage is 0.94%, this tunica fibrosa is immersed in the electrolyte of the ethylene carbonate/dimethyl carbonate of 1mol lithium hexafluoro phosphate/diethyl carbonate (mass ratio is 1: 1: 1), the pick up of acquisition is 478%, ionic conductivity is that 1.62mS/cm, electrochemical stability window are 5.41V.
Embodiment 4
At room temperature, take dried PAN and add in a certain amount of DMF/NMP bonding solvent, stirring and dissolving prepares polymer dope.Take again nano-TiO
2with PAN (mass ratio 0.95: 0.05) joins in the DMAc solvent, prepare nano granule suspension.
Polymer dope prepares the PAN nano fibrous membrane through electrostatic spinning and is deposited on receiving system, again nano granule suspension is deposited on nano fibrous membrane through electrostatic spray, receive again afterwards one deck Static Spinning PAN nano fibrous membrane on the inorganic particulate granulosa, obtained electrostatic spinning/electrostatic spray composite lithium ion cell barrier film.
The electrostatic spinning of preparation/electrostatic spray composite lithium ion cell barrier film is placed in to 150 ℃ of hot casees and processes 1h, shrinkage is 1.13%, this tunica fibrosa is immersed in the electrolyte of the ethylene carbonate/dimethyl carbonate of 1mol lithium hexafluoro phosphate/diethyl carbonate (mass ratio is 1: 1: 1), the pick up of acquisition is 452%, ionic conductivity is that 1.46mS/cm, electrochemical stability window are 5.14V.
Embodiment 5
At room temperature, take dried PVDF and PAN and add in a certain amount of DMF/ acetone mixed solvent, stirring and dissolving prepares polymer dope.Take again nano SiC and PVDF (mass ratio 0.85: 0.15) and join in the DMAc solvent, prepare nano granule suspension.
Polymer dope prepares the PVDF/PAN nano fibrous membrane through electrostatic spinning and is deposited on receiving system, again nano granule suspension is deposited on nano fibrous membrane through electrostatic spray, receive again afterwards one deck Static Spinning PVDF/PAN nano fibrous membrane on the inorganic particulate granulosa, obtained electrostatic spinning/electrostatic spray composite lithium ion cell barrier film.
The electrostatic spinning of preparation/electrostatic spray composite lithium ion cell barrier film is placed in to 150 ℃ of hot casees and processes 1h, shrinkage is 1.04%, this tunica fibrosa is immersed in the electrolyte of the ethylene carbonate/dimethyl carbonate of 1mol lithium hexafluoro phosphate/diethyl carbonate (mass ratio is 1: 1: 1), the pick up of acquisition is 489%, ionic conductivity is that 1.78mS/cm, electrochemical stability window are 5.23V.
Claims (7)
1. prepare the method for composite lithium ion cell barrier film by electrostatic spinning/electrostatic spray, it is characterized in that, concrete steps are:
The first step: high molecular polymer is joined in organic solvent, and mechanical agitation is dissolved, and forms clear solution, makes electrostatic spinning liquid;
Second step: inorganic nanoparticles and high polymer mixtures are joined in organic solvent, and mechanical agitation, make inorganic nanoparticles suspension;
The 3rd step: the spinning solution electrostatic spinning prepared in the first step is prepared to lower floor's nano fibrous membrane; The inorganic nanoparticles suspension prepared in second step being deposited on lower floor's nano fibrous membrane through electrostatic spray, is intermediate layer again; Finally, receive one deck electrostatic spinning nano fiber film on the inorganic particulate granulosa, make the composite lithium ion cell barrier film.
2. the method for preparing the composite lithium ion cell barrier film by electrostatic spinning/electrostatic spray as claimed in claim 1, it is characterized in that one or more the mixture that the high molecular polymer in the described first step and second step is PMMA, PAN, PVDF and P (VDF-HFP).
3. the method for preparing the composite lithium ion cell barrier film by electrostatic spinning/electrostatic spray as claimed in claim 1, it is characterized in that, organic solvent in the described first step and second step is N, the mixture of one or two or more kinds in dinethylformamide (DMF), DMA (DMAc), acetone, 1-METHYLPYRROLIDONE (NMP), hexafluoroisopropanol (HFIP), oxolane.
4. the method for preparing the composite lithium ion cell barrier film by electrostatic spinning/electrostatic spray as claimed in claim 1, is characterized in that, the inorganic nanoparticles in described second step is Al
2o
3, SiO
2, TiO
2, BaTiO
3, MgO, ZrO
2, one or two or more kinds the mixture in ZnO, SiC.
5. the method for preparing the composite lithium ion cell barrier film by electrostatic spinning/electrostatic spray as claimed in claim 1, is characterized in that, in described second step, the mass ratio of inorganic nanoparticles and high molecular polymer is: 0.8～0.98: 0.2～0.02.
6. the method for preparing the composite lithium ion cell barrier film by electrostatic spinning/electrostatic spray as claimed in claim 1, it is characterized in that, the electrostatic spinning receiving system in described the 3rd step is one or more in aluminium foil, iron plate, iron net, copper mesh, iron roller, aluminum drum and non-woven material.
7. the method for preparing the composite lithium ion cell barrier film by electrostatic spinning/electrostatic spray as claimed in claim 1, it is characterized in that, in described the 3rd step, the thickness of prepared composite diaphragm is 20～100 μ m, and wherein the thickness of inorganic nanoparticles layer is 5～20 μ n.
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