CN102587040A - Preparation method of nanofiber membrane for lithium ion battery diaphragm - Google Patents
Preparation method of nanofiber membrane for lithium ion battery diaphragm Download PDFInfo
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Abstract
The invention discloses a preparation method of a nanofiber membrane for a lithium ion battery diaphragm. The preparation method comprises the following steps: 1) dissolving a polyvinylidene fluoride (PVDF)-based polymer into an amide organic solvent, and uniformly stirring the mixture to obtain a PVDF-based polymer solution, wherein the solution has a determined viscosity of 500 to 600mPa.S; 2) performing electrostatic spinning on the prepared PVDF-based polymer solution, and forming a fiber membrane when the solution reaches a receiving device; and 3) post-treating the fiber membrane obtained after the spinning is finished, and removing the residual solvent in the fiber membrane to prepare a nanofiber membrane for the lithium ion battery diaphragm. The method is simple, high in machining efficiency and favorable for the high-current charging and discharging of a battery; and the performance of the diaphragm is improved.
Description
Technical field
The present invention relates to the lithium ion battery separator field, especially a kind of lithium ion battery separator is put into the preparation method.
Background technology
Lithium ion battery need adopt barrier film to separate both positive and negative polarity, prevents internal short-circuit of battery, thereby diaphragm material must possess excellent electric insulating, and in the temperature of broad and voltage range, can keep chemical stability.Diaphragm material mainly is the polymer film of micropore.Also need satisfy for the applicable porous septum material of reality: (1) thinner thickness is also even as far as possible, to satisfy the requirement of lithium ion battery high-energy, high power and cycle performance aspect; (2) aperture that is fit to, the particle size less than electrode material will be satisfied in the aperture of barrier film, it is generally acknowledged, and sub-micron pore can effectively stop penetrating of electrode material; (3) higher porosity, porosity are low excessively, and the liquid electrolyte that exists in the hole crosses that I haven't seen you for ages influences the chemical property of battery; (4) certain gas permeability; (5) certain mechanical strength satisfies the demand of lithium ion battery in assembling and use etc.
At present, commercial lithium ion battery separator material mainly is the polyolefin micropore polymer film that adopts the biaxial tension preparation, comprises polyethylene film (PE), polypropylene screen (PP), polyethylene-polypropylene (PP-PE-PP) biaxial stretching film etc.This method has dry method and wet method, and there are many shortcomings in this kind microporous barrier, and porosity is the highest to be merely 40%, and electrolyte absorption is lower than 150%, the porosity distribution broad, and poor stability has limited the raising of lithium ion mobility, is unfavorable for the large current density of battery.
Summary of the invention
Lower for the processed complex, the working (machining) efficiency that overcome existing lithium ion battery separator, membrane properties is relatively poor, be unfavorable for the deficiency of the large current density of battery, the present invention provides that a kind of technology is simple, working (machining) efficiency is higher, promote membrane properties, help the preparation method of the nano fibrous membrane that is used for lithium ion battery separator of the large current density of battery.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of preparation method who is used for the nano fibrous membrane of lithium ion battery separator, said preparation method may further comprise the steps:
1) the PVDF based polyalcohol is dissolved in the amide-type organic solvent; The mass and size specific concentration 10-30% of PVDF based polyalcohol wherein; Said mass volume ratio unit is g/ml, the PVDF based polyalcohol solution that stirs and form, and the mensuration viscosity of said solution is between 500～600mPa.S;
2) with the PVDF based polyalcohol solution electrostatic spinning for preparing; When arriving receiving system, said solution forms tunica fibrosa; The condition of said electrostatic spinning is: voltage 10～30KV, positive and negative electrode spacing 10～20cm, solution flow rate are 0.6～6mL/h; Rotating speed 100～the 500rpm of receiving system, the spinning time is 50-100min;
3) tunica fibrosa that obtains after the spinning completion is carried out post processing:
60 ℃ of-80 ℃ of vacuumize 12-14h put into air dry oven 100 ℃-160 ℃ heating 1-3h or 40 ℃ of-80 ℃ of hot pressing 1-3h with film then earlier;
After removing solvent residual in the said tunica fibrosa, make the nano fibrous membrane that is used for lithium ion battery separator.
Further, in the said step 1), the dissolving back adds diameter 30-100nm hydrophobic nano SiO
2Ceramic particle is 100% with amide-type organic solvent volume, and the mass and size percentage that adds ceramic particle is 0.1～10%.
In the said step 1), the dissolving back drips ethyl orthosilicate, is 100% with amide-type organic solvent volume, and the mass and size percentage that drips ethyl orthosilicate is 0.1～10%.
In the said step 1), add cosolvent again, said cosolvent is Triton-100, peregal or Tween-80, is 100% with amide-type organic solvent volume, and the mass and size percentage of said cosolvent is 0.05～0.1%.
Said PVDF based polyalcohol is following a kind of or two or more at least mixing: PVDF, PVDF-HFP and PAN.
Said amide-type organic solvent is N, the mixed solvent of dinethylformamide, DMAC N,N and acetone, and both volume ratios are 2 in the said mixed solvent: 8-8: 2.Certainly, also can adopt the amide-type organic solvent of other types.
Before dripping ethyl orthosilicate, at first adding ammoniacal liquor, is 100% with amide-type organic solvent volume, and the mass and size percentage of said ammoniacal liquor is 0.05～0.2%.
In the said step 1), temperature maintenance makes the solution homogeneous transparent at 50 ℃-85 ℃ under stirring.
Further again, in the said step 1), in whole process, to feed nitrogen.
Among the present invention, said mass volume ratio unit is g/ml.
Technical conceive of the present invention is: electrostatic spinning is a kind of nano material preparation technology with broad prospect of application; This technology is mainly used in the preparation high polymer nanometer fiber membrane; In the electrostatic spinning process process, polymer solution is placed between the high-voltage electrostatic field of several thousand to several ten thousand volts, the surface tension of utilizing electric field force to overcome Polymer Solution forms charged jet; When concentrated polymer solution flows out the directive receiving system from capillary end; Acceleration, stretching phenomenon can occur, follow solvent evaporates, finally on receiving system, form the nano-scale fiber film; The present invention is applied to electrostatic spinning technique the preparation technology of nano fibrous membrane.
Stronger in Kynoar (PVDF) and the copolymer (PVDF-HFP) thereof owing to carbon-fluorine bond (C-F) bond energy; And per two fluorine atoms surround a carbon atom; Make carbon atom be not easy and other atomic reaction; Chemical property is more stable, and the better mechanical property after the film forming is considered to desirable membrane material.Blend PAN helps the complexing lithium ion owing to have strong polarity-CN base, and because nano ceramics particle SiO
2Be adsorbed in the fiber, can (interaction O-) improves the adsorptivity of electrolyte and the intensity of itself with some group of polymer dielectric.Therefore adopting PVDF based polyalcohol electrostatic spinning to prepare nano fibrous membrane is to be well suited for being used for lithium ion battery separator.
Beneficial effect of the present invention mainly shows: technology is simple, operating efficiency is higher, promotes membrane properties, helps the large current density of battery; Prepared nanofiber film thickness, aperture, porosity and fibre diameter etc. are all controlled.
Description of drawings
Fig. 1 will be for utilizing charging and discharging curve figure behind the nano fiber diaphragm assembling button cell that the present invention prepares.
The specific embodiment
Below in conjunction with accompanying drawing the present invention is further described.
With reference to Fig. 1, a kind of preparation method who is used for the nano fibrous membrane of lithium ion battery separator, said preparation method may further comprise the steps:
1) the PVDF based polyalcohol is dissolved in the amide-type organic solvent; The mass and size specific concentration 10-30% of PVDF based polyalcohol wherein; Said mass volume ratio unit is g/ml, the PVDF based polyalcohol solution that stirs and form, and the mensuration viscosity of said solution is between 500～600mPa.S;
2) with the PVDF based polyalcohol solution electrostatic spinning for preparing; When arriving receiving system, said solution forms tunica fibrosa; The condition of said electrostatic spinning does; Voltage 10～30KV, positive and negative electrode spacing 10～20cm, solution flow rate are 0.6～6mL/h, the rotating speed 100～500rpm of receiving system, and the spinning time is 50-100min;
3) tunica fibrosa that obtains after the spinning completion is carried out post processing:
60 ℃ of-80 ℃ of vacuumize 12-14h put into air dry oven 100 ℃-160 ℃ heating 1-3h or 40 ℃ of-80 ℃ of hot pressing 1-3h with film then earlier;
After removing solvent residual in the said tunica fibrosa, make the nano fibrous membrane that is used for lithium ion battery separator.
Embodiment one: 12gPVDF is dissolved in N, and dinethylformamide and acetone volume ratio are among 7: 3 the mixed solvent 100ml, and temperature maintenance is at 60-80 ℃, and dissolving forms transparent and homogeneous solution under electronic stirring, and the mensuration viscosity of said solution is 500mPa.S.Preset spinning condition as requested: voltage 18KV; Positive and negative electrode spacing 13cm; Solution flow rate is 2.48ml/h, the rotating speed 100rpm of receiving system, behind the spinning time 100min to tunica fibrosa; Tunica fibrosa is put into about the dry 12h of 60-70 ℃ of vacuum drying chamber, then put into air dry oven and heat 2h for about 100 ℃.Thickness through the test tunica fibrosa is 30-40 μ m, and the average diameter of fiber is 700-900nm, and the aperture is that 0.09-0.12 μ m TENSILE STRENGTH is that 3-4MPa, porosity are 43-50%, and electrolytical adsorption rate is 300-400%.
In the present embodiment, PVDF, model is FR-904, manufacturer is that Shanghai three is liked rich; DMAC N,N, manufacturer is: Chemical Reagent Co., Ltd., Sinopharm Group, acetone, manufacturer is: Hangzhou chemical reagent Co., Ltd.
The porosity of present embodiment tunica fibrosa can be tested through following method: the polymer fiber film is soaked 60min in methyl alcohol; Take out the film surface adsorption is blotted in the back with filter paper methyl alcohol; Soak (the Δ m) of poor quality of methyl alcohol front and back with electronic balance weighing polymer fiber film, use Δ m again divided by the density (ρ) of methyl alcohol and the volume (V) of polymer fiber film film.Obtain the porosity ε (ε=Δ m/ ρ V * %) of polymer fiber film.
According to the thickness of SJ/T 10171.1-91 method of testing measurement tunica fibrosa, be 23 ± 2 ℃ with tunica fibrosa in temperature, humidity is handled in the environment of (50 ± 2) %.Make the moisture between the temperature and humidity atmosphere of sample and regulation reach balance.When being separated by about 1-1.5h, twice weighing result of sample differed 0.25% o'clock that is no more than gross mass, just calculated to reach balance.Under above-mentioned standard conditions, the thickness with thickness meter (or micrometer) measurement any two diagonal angles of sample and a middle part reads reading.The arithmetic mean of instantaneous value of getting 15 thickness measurements of gained is as test result.
The electrolyte adsorption rate of tunica fibrosa can be used following method test: the polymer fiber film is immersed in 60min in the electrolyte; The electrolyte on film surface is blotted in taking-up with filter paper; Soak (the Δ m) of poor quality of electrolyte solution with the electronic balance weighing tunica fibrosa; With the quality (m) of Δ m, obtain electrolyte adsorption rate K=Δ m/m * 100% of tunica fibrosa again divided by tunica fibrosa before soaking.
The ionic conductivity of tunica fibrosa can be used following test:
With tunica fibrosa at concentration 1mol/L liquid electrolyte LiPF6/DMC/EMC/EC (1M; DMC/EMC/EC:1/1/1; V/v/v) soak in about 30min, take out the back and blot the raffinate on film surface, this fiber dielectric film is sandwiched between the two stainless steel electrode rods with filter paper; Be assembled into the simulation button cell, chemical property all carries out on the EG&GM273 electrochemical analysis system.Adopt AC impedence method to record the electrolytical body resistance R of fiber
b, then according to formula σ=d/ (S * R
b) calculate ionic conductivity, wherein d, S represent the thickness and the effective area of tunica fibrosa respectively.
Embodiment two: 10gPAN is dissolved in N, and among the dinethylformamide 100ml, temperature maintenance is at 70-85 ℃, and dissolving forms uniform solution under electronic stirring, and the mensuration viscosity of said solution is 520mPa.S.Set spinning condition: applying fixed voltage is 20KV; The distance of spinning head and receiving system is 20cm, and the fixed solution flow velocity is 2.48ml/h, the rotating speed 100rpm of receiving system; Spinning time 90min; Barrier film is put into about 75-80 ℃ of vacuum drying chamber 14h, and then putting into air dry oven 155-160 ℃ of heating 1h is 35-40 μ m through the thickness of testing (method is with example one) tunica fibrosa, and the average diameter of fiber is 700-813nm; The aperture is that 0.07-0.09 μ m TENSILE STRENGTH is that 3-4.5MPa, porosity are 50-67%, and electrolytical adsorption rate is 400-520%.Polyacrylonitrile (PAN) nano fibrous membrane is also owing to have strong polarity-CN base to the Li in the electrolyte
+Ion plays complexing, and is very favourable to electrolytical absorption.
In the present embodiment, said PAN, manufacturer is a Shanghai Petrochemical Co. Ltd., said N, dinethylformamide, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group.
Other schemes of present embodiment are all identical with embodiment one with the course of work.
Embodiment three: it is among 3: 7 the mixed solvent 100ml that 14g PVDF-HFP is dissolved in DMAC N,N and acetone volume ratio, and dissolving forms that to add quality 6g diameter behind the clear solution be the hydrophobic type SiO about 60nm
2Nano particle, temperature maintenance stir 6h and form transparent and homogeneous or pale yellow solution at 70-75 ℃, and the mensuration viscosity of said solution is 550mPa.S.Preset spinning condition: fixed voltage 22kV, constant spacing 16cm, fixed solution flow 6mL/h, the rotating speed 220rpm of receiving system, about spinning time 50min after, obtain tunica fibrosa.Tunica fibrosa is put into about the dry 12.5h of 65-70 ℃ of vacuum drying chamber, then put into air dry oven and heat 3h for about 135 ℃.Thickness through test (method of testing is with example one) tunica fibrosa is 30-40 μ m, and the average diameter of fiber is 650-800nm, and the aperture is that 0.08-0.11 μ m TENSILE STRENGTH is that 3-5MPa, porosity are 40-60%, and electrolytical adsorption rate is 350-400%.
In the present embodiment, PVDF-HFP, model is 2801, manufacturer is: French A Kema, DMAC N,N, manufacturer is: Chemical Reagent Co., Ltd., Sinopharm Group, acetone, manufacturer is: Hangzhou chemical reagent Co., Ltd.
Other schemes of present embodiment are all identical with embodiment one with the course of work.
Embodiment four: it is among 3: 7 the mixed solvent 100ml that 24g PVDF-HFP is dissolved in DMAC N,N and acetone volume ratio, and dissolving forms that to add quality 0.1g diameter behind the clear solution be the hydrophobic type SiO about 30nm
2Nano particle, temperature maintenance, stir about 6h under the nitrogen protection at 70-75 ℃, form transparent and homogeneous or pale yellow solution, and the mensuration viscosity of said solution is 580mPa.S.Preset spinning condition: fixed voltage 24kV, constant spacing 10cm, fixed solution flow 0.6mL/h, the rotating speed 300rpm of receiving system, about spinning time 60min after, obtain tunica fibrosa.Tunica fibrosa is put into the dry 14h of 75-80 ℃ of vacuum drying chamber, then put into about air dry oven 150-155 ℃ of heating 2.5h.Thickness through test (method of testing is with example one) tunica fibrosa is 30-40 μ m, and the average diameter of fiber is 650-800nm, and the aperture is that 0.08-0.11 μ m TENSILE STRENGTH is that 3-5MPa, porosity are 40-65%, and electrolytical adsorption rate is 350-410%.
In the present embodiment, PVDF-HFP, model is 2801, manufacturer is: French A Kema, DMAC N,N, manufacturer is: Chemical Reagent Co., Ltd., Sinopharm Group, acetone, manufacturer is: Hangzhou chemical reagent Co., Ltd.
Other schemes of present embodiment are all identical with embodiment one with the course of work.
Embodiment five: with the 14g mass ratio is that to be dissolved in DMAC N,N and acetone volume ratio be that adding quality 10g diameter is the hydrophobic type SiO about 100nm among 8: 2 the mixed solution 100ml for 2: 1 PVDF and PAN blend
2Nano particle, temperature maintenance stir about 4h at 75-80 ℃, form transparent and homogeneous or pale yellow solution, and the mensuration viscosity of said solution is 600mPa.S.The condition that said static is put spinning is: spinning voltage is fixed as 14,16,18,20kV, constant spacing 16cm, fixed solution flow 6mL/h, the rotating speed 500rpm of receiving system, about spinning time 70min after, obtain nano fibrous membrane.This film is put into about the dry 12h of 60-65 ℃ of vacuum drying chamber, then put into 135 ℃ of heating of air dry oven 1.5-2h.Thickness through test (method is with example one) tunica fibrosa is 35-40 μ m, and the average diameter of fiber is 600-800nm, and the aperture is that 0.05-0.08 μ m TENSILE STRENGTH is that 4-7MPa, porosity are 45-70%, and electrolytical adsorption rate is 400-500%.
In the present embodiment, PVDF, model is FR-904, manufacturer is that Shanghai three is liked rich; PAN, manufacturer are Shanghai Petrochemical Co. Ltd.; DMAC N,N, manufacturer is: Chemical Reagent Co., Ltd., Sinopharm Group, acetone, manufacturer is: Hangzhou chemical reagent Co., Ltd.
Other schemes of present embodiment are all identical with embodiment one with the course of work.
Embodiment six: it is that adding quality 8g diameter is the hydrophobic type SiO about 60nm among 2: 8 the mixed solution 100ml that 30gPVDF-HFP is dissolved in DMAC N,N and acetone volume ratio
2Nano particle, temperature maintenance, stir about 5h under the nitrogen protection at 65-70 ℃, form transparent and homogeneous or pale yellow solution, and the mensuration viscosity of said solution is 500mPa.S.Spinning voltage is fixed as 22kV; Constant spacing is respectively 14,15,17cm; Fixed solution flow 6mL/h, the rotating speed 400rpm of receiving system is about spinning time 50min; Tunica fibrosa is put into about the dry 12h of 60-70 ℃ of vacuum drying chamber, then put into about 135 ℃ of heating of air dry oven 1.5-2h.Thickness through test (method is with example one) tunica fibrosa is 35-40 μ m, and the average diameter of fiber is 500-600nm, and the aperture is that 0.04-0.07 μ m TENSILE STRENGTH is that 5-7MPa, porosity are 50-75%, and electrolytical adsorption rate is 419-500%.
In the present embodiment, PVDF-HFP, model is 2801, manufacturer is French A Kema, DMAC N,N, manufacturer is: Chemical Reagent Co., Ltd., Sinopharm Group, acetone, manufacturer is: Hangzhou chemical reagent Co., Ltd.
Other schemes of present embodiment are all identical with embodiment one with the course of work.
Embodiment seven: 16g, 25g and 30gPVDF-HFP are dissolved in N; N-dimethylacetylamide and acetone volume ratio are that temperature maintenance is at 50-60 ℃, under the nitrogen protection among 3: 7 the mixed solution 100ml; Stir and form transparent and homogeneous solution about 2h, the mensuration viscosity of said solution is 450mPa.S.Spinning fixed voltage 30kV, constant spacing 15cm, fixed solution flow 6mL/h; The rotating speed 400rpm of receiving system; Spinning time 50min puts into tunica fibrosa about the dry 12h of 60-65 ℃ of vacuum drying chamber, then puts into about air dry oven 75-80 ℃ of hot pressing 3h; Thickness through test (method is with example one) tunica fibrosa is 35-40 μ m; The average diameter of fiber is 600-800nm, and the aperture is that 0.03-0.06 μ m TENSILE STRENGTH is that 5.8-7.4MPa, porosity are 61-80%, and electrolytical adsorption rate is 427-580%.
In the present embodiment, PVDF-HFP, model is 2801, manufacturer is French A Kema, DMAC N,N, manufacturer is: Chemical Reagent Co., Ltd., Sinopharm Group, acetone, manufacturer is: Hangzhou chemical reagent Co., Ltd.
Other schemes of present embodiment are all identical with embodiment one with the course of work.
Embodiment eight: 16g, 25g and 30gPVDF-HFP are dissolved in N; N-dimethylacetylamide and acetone volume ratio are among 7: 3 the mixed solution 100ml; Temperature maintenance, stirs about 3h under the nitrogen protection at 70-75 ℃; Form transparent and homogeneous or pale yellow solution, the mensuration viscosity of said solution is 450mPa.S.Fixing spinning voltage 22kV, constant spacing 15cm, fixed solution flow 6mL/h; The rotating speed 400rpm of receiving system; About spinning time 50min, tunica fibrosa is put into about the dry 12h of 60-70 ℃ of vacuum drying chamber, then put into about air dry oven 40-50 ℃ of hot pressing 2h; Thickness through test (method is with example one) tunica fibrosa is 35-40 μ m; The average diameter of fiber is 600-800nm, and the aperture is that 0.03-0.06 μ m TENSILE STRENGTH is that 5.8-7.4MPa, porosity are 61-80%, and electrolytical adsorption rate is 427-580%.
In the present embodiment, PVDF-HFP, model is 2801, manufacturer is French A Kema, DMAC N,N, manufacturer is: Chemical Reagent Co., Ltd., Sinopharm Group, acetone, manufacturer is: Hangzhou chemical reagent Co., Ltd.
Other schemes of present embodiment are all identical with embodiment one with the course of work.
Embodiment nine: with the 14g mass ratio is that 3: 1 PVDF and PVDF-HFP blend is dissolved in N; N-dimethylacetylamide and acetone volume ratio are among 3: 7 the mixed solution 100ml; Temperature maintenance is at 55-60 ℃; Under the nitrogen protection, stir 1-1.5h and form transparent and homogeneous or pale yellow solution, the mensuration viscosity of said solution is 400mPa.S.Spinning voltage is fixed as 22kV, constant spacing 16cm, and fixed solution flow 6mL/h, the rotating speed 400rpm of receiving system about spinning time 50min, at room temperature places a period of time with tunica fibrosa and makes residual Si-(OC
2H
5)
4All be hydrolyzed into SiO
2, tunica fibrosa is put into about the dry 12h of 60-70 ℃ of vacuum drying chamber, then put into about air dry oven 70-80 ℃ of hot pressing 1h.Thickness through test (method is with example one) tunica fibrosa is 35-40 μ m, and the average diameter of fiber is 419-500nm, and the aperture is that 0.08-0.10 μ m TENSILE STRENGTH is that 3.0-4.0MPa, porosity are 50-70%, and electrolytical adsorption rate is 390-480%.
In the present embodiment, PVDF, model is D-691, manufacturer is a Dupont; PVDF-HFP, model is 2801, manufacturer is French A Kema, DMAC N,N, manufacturer is: Chemical Reagent Co., Ltd., Sinopharm Group, acetone, manufacturer is: Hangzhou chemical reagent Co., Ltd.
Other schemes of present embodiment are all identical with embodiment one with the course of work.
Embodiment ten: it is that the mensuration viscosity of said solution is 400mPa.S among 7: 3 the mixed solution 100ml that 14gPVDF-HFP is dissolved in DMAC N,N and acetone volume ratio.Spinning voltage is fixed as 22kV, constant spacing 16cm, and fixed solution flow 6mL/h, the rotating speed 400rpm of receiving system about spinning time 50min, at room temperature places a period of time with tunica fibrosa and makes residual Si-(OC
2H
5)
4All be hydrolyzed into SiO
2, put into then about the dry 12h of 60-65 ℃ of vacuum drying chamber, then put into air dry oven and heat 2h for about 135 ℃.Thickness through test (method is with example one) tunica fibrosa is 35-40 μ m, and the average diameter of fiber is 419-500nm, and the aperture is that 0.08-0.10 μ m TENSILE STRENGTH is that 3.5-5.4MPa, porosity are 40-63%, and electrolytical adsorption rate is 350-400%.Show and generate nanometer SiO
2Important effect is played in modification to tunica fibrosa.
In the present embodiment, PVDF-HFP, model is 2801, manufacturer is French A Kema, DMAC N,N, manufacturer is: Chemical Reagent Co., Ltd., Sinopharm Group, acetone, manufacturer is: Hangzhou chemical reagent Co., Ltd.
Other schemes of present embodiment are all identical with embodiment one with the course of work.
Embodiment 11: the mixture of 14gPVDF, PVDF-HFP and PAN is dissolved in N; N-dimethylacetylamide and acetone volume ratio are among 7: 3 the mixed solution 100ml; Wherein, The mass ratio of PVDF, PVDF-HFP and PAN is 1: 1: 1 in the mixture, and the mensuration viscosity of said solution is 420mPa.S.Spinning voltage is fixed as 22kV, constant spacing 16cm, and the rotating speed 400rpm of receiving system, fixed solution flow 6mL/h about spinning time 50min, at room temperature places a period of time with tunica fibrosa and makes residual Si-(OC
2H
5)
4All be hydrolyzed into SiO
2, put into then about the dry 14h of 80-85 ℃ of vacuum drying chamber, then put into air dry oven and heat 1-2h for about 160 ℃.Thickness through test (method is with example one) tunica fibrosa is 35-40 μ m, and the average diameter of fiber is 419-500nm, and the aperture is that 0.08-0.10 μ m TENSILE STRENGTH is that 3.5-5.4MPa, porosity are 45-60%, and electrolytical adsorption rate is 350-400%.
In the present embodiment, PVDF, model is FR-904, manufacturer is that Shanghai three is liked rich; PVDF-HFP, model is 2801, manufacturer is French A Kema; PAN, manufacturer are Shanghai Petrochemical Co. Ltd.; DMAC N,N, manufacturer is: Chemical Reagent Co., Ltd., Sinopharm Group, acetone, manufacturer is a Hangzhou chemical reagent Co., Ltd.
Other schemes of present embodiment are identical with embodiment one.
Embodiment 12: with mass ratio is that 4: 1 PVDF-HFP and PAN blend 15g is dissolved among the mixed solvent 100ml of DMAC N,N and acetone, and the DMAC N,N in the mixed solvent and the volume ratio of acetone are for being 2: 8.Adding above-mentioned blend quality 6g diameter behind the dissolving formation clear solution is the hydrophobic type SiO about 60nm
2Nano particle, and add 0.05g cosolvent Triton-100, temperature maintenance, stirs about 6h under the nitrogen protection at 80-85 ℃, forms transparent and homogeneous or pale yellow solution.The mensuration viscosity of said solution is 400mPa.S.Preset spinning condition: fixed voltage 14kV, constant spacing 16cm, fixed solution flow 2.48mL/h; The rotating speed 420rpm of receiving system, about spinning time 100min, the barrier film aftertreatment technology is with embodiment one; Thickness through test (method is with example one) tunica fibrosa is 25-30 μ m; The average diameter of fiber is 500-600nm, and the aperture is that 0.05-0.08 μ m TENSILE STRENGTH is that 3.0-4.5MPa, porosity are 70-80%, and electrolytical adsorption rate is 500-600%.
In the present embodiment, PVDF-HFP, model is 2801, manufacturer is French A Kema; PAN, manufacturer are Shanghai Petrochemical Co. Ltd.; DMAC N,N, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group; Acetone, manufacturer is a Hangzhou chemical reagent Co., Ltd;
Other schemes of present embodiment are identical with embodiment one.
Embodiment 13: with mass ratio be 4: 1 PVDF-HFP and PAN blend 18 be dissolved in DMAC N,N and acetone mixed solvent 100g in, the DMAC N,N in the mixed solvent and the volume ratio of acetone are 8: 2.Adding above-mentioned blend quality 6g diameter behind the dissolving formation clear solution is the hydrophobic type SiO about 60nm
2Nano particle, and add 0.1g cosolvent peregal, temperature maintenance, stirs about 6h under the nitrogen protection at 60-65 ℃, forms transparent and homogeneous or pale yellow solution, and the mensuration viscosity of said solution is 400mPa.S.Preset spinning condition: fixed voltage 14kV, constant spacing 16cm, fixed solution flow 2.48mL/h; The rotating speed 450rpm of receiving system; Spinning time 100min puts into tunica fibrosa about the dry 12h of 60-65 ℃ of vacuum drying chamber, then puts into air dry oven and heats 1.5-2h for about 135 ℃.Thickness through test (method is with example one) tunica fibrosa is 25-30 μ m, and the average diameter of fiber is 350-400nm, and the aperture is that 0.03-0.05 μ m TENSILE STRENGTH is that 6.1-8MPa, porosity are 70-80%, and electrolytical adsorption rate is 450-578%.
In the present embodiment, PVDF-HFP, model is 2801, manufacturer is French A Kema; PAN, manufacturer are Shanghai Petrochemical Co. Ltd.; DMAC N,N, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group; Acetone, manufacturer is a Hangzhou chemical reagent Co., Ltd;
Other schemes of present embodiment are identical with embodiment one.
Embodiment 14: with mass ratio is that 4: 1 PVDF-HFP and PAN blend 20g is dissolved among the mixed solvent 100ml of DMAC N,N and acetone, and the DMAC N,N in the mixed solvent and the volume ratio of acetone are 8: 2.Adding above-mentioned blend quality 6g diameter behind the dissolving formation clear solution is the hydrophobic type SiO about 60nm
2Nano particle, and add 0.08g cosolvent tween-8, temperature maintenance, stirs about 6h under the nitrogen protection at 50-60 ℃, forms transparent and homogeneous or pale yellow solution, and the mensuration viscosity of said solution is 420mPa.S.Preset spinning condition: fixed voltage 14kV, constant spacing 16cm, fixed solution flow 2.48mL/h; The rotating speed 450rpm of receiving system, about spinning time 100min, the post-processing approach of barrier film is with example two; Thickness through test (method is with example one) tunica fibrosa is 25-30 μ m; The average diameter of fiber is 350-400nm, and the aperture is that 0.03-0.05 μ m TENSILE STRENGTH is that 6.1-8MPa, porosity are 70-80%, and electrolytical adsorption rate is 450-578%.
In the present embodiment, PVDF-HFP, model is 2801, manufacturer is French A Kema; PAN, manufacturer are Shanghai Petrochemical Co. Ltd.; DMAC N,N, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group; Acetone, manufacturer is a Hangzhou chemical reagent Co., Ltd;
Other schemes of present embodiment are identical with embodiment one.
Embodiment 15: with mass ratio is that 8: 1: 1 PVDF, PVDF-HFP and PAN blend 30g is dissolved in N, and among the mixed solvent 100ml of dinethylformamide and acetone, the DMAC N,N in the mixed solvent and the volume ratio of acetone are 7: 3.Adding above-mentioned blend quality 6g diameter behind the dissolving formation clear solution is the hydrophobic type SiO about 60nm
2Nano particle, and add 0.06g cosolvent Tween-80, temperature maintenance, stirs about 6h under the nitrogen protection at 65-70 ℃, forms transparent and homogeneous or pale yellow solution, and the mensuration viscosity of said solution is 430mPa.S.Preset spinning condition: fixed voltage 14kV, constant spacing 16cm, fixed solution flow 2.48mL/h; The rotating speed 480rpm of receiving system, about spinning time 100min, the barrier film aftertreatment technology is with embodiment one; Thickness through test (method is with example one) tunica fibrosa is 20-30 μ m; The average diameter of fiber is 314-400nm, and the aperture is that 0.02-0.04 μ m TENSILE STRENGTH is that 8-9MPa, porosity are 80-90%, and electrolytical adsorption rate is 477-600%.
In the present embodiment, PVDF, model is FR-904, manufacturer is that Shanghai three is liked rich; PVDF-HFP, model is 2801, manufacturer is French A Kema; PAN, manufacturer are Shanghai Petrochemical Co. Ltd.; DMAC N,N, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group; Acetone, manufacturer is a Hangzhou chemical reagent Co., Ltd;
Other schemes of present embodiment are identical with embodiment one.
Embodiment 16: with mass ratio is that 8: 1: 1 PVDF, PVDF-HFP and PAN blend 20g is dissolved in N, and among the mixed solvent 100ml of dinethylformamide and acetone, the DMAC N,N in the mixed solvent and the volume ratio of acetone are 7: 3.After dissolving forms clear solution, add 0.05g ammoniacal liquor, add the 0.1g ethyl orthosilicate again; And add 0.1g cosolvent Tween-80, holding temperature 60-70 ℃, under the nitrogen protection; Stir about 6h, form transparent and homogeneous or pale yellow solution, the mensuration viscosity of said solution is 430mPa.S.Preset spinning condition: fixed voltage 14kV, constant spacing 16cm, fixed solution flow 2.48mL/h; The rotating speed 450rpm of receiving system, about spinning time 100min, the barrier film aftertreatment technology is with embodiment two; Thickness through test (method is with example one) tunica fibrosa is 20-30 μ m; The average diameter of fiber is 314-400nm, and the aperture is that 0.02-0.04 μ m TENSILE STRENGTH is that 8-9.5MPa, porosity are 80-90%, and electrolytical adsorption rate is 477-600%.
In the present embodiment, PVDF, model is FR-904, manufacturer is that Shanghai three is liked rich; PVDF-HFP, model is 2801, manufacturer is French A Kema; PAN, manufacturer are Shanghai Petrochemical Co. Ltd.; DMAC N,N, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group; Acetone, manufacturer is a Hangzhou chemical reagent Co., Ltd;
Other schemes of present embodiment are identical with embodiment one.
Embodiment 17: with mass ratio is that 8: 1: 1 PVDF, PVDF-HFP and PAN blend 20g is dissolved in N, and among the mixed solvent 100ml of dinethylformamide and acetone, the DMAC N,N in the mixed solvent and the volume ratio of acetone are 7: 3.After dissolving forms clear solution, add 0.1g ammoniacal liquor, add the 5g ethyl orthosilicate again; And adding 0.06g cosolvent Tween-80, temperature maintenance is at 60-65 ℃, under the nitrogen protection; Stir about 5h, form transparent and homogeneous or pale yellow solution, the mensuration viscosity of said solution is 425mPa.S.Preset spinning condition: fixed voltage 14kV, constant spacing 16cm, fixed solution flow 2.48mL/h; The rotating speed 450rpm of receiving system, about spinning time 100min, the barrier film aftertreatment technology is with embodiment two; Thickness through test (method is with example one) tunica fibrosa is 20-30 μ m; The average diameter of fiber is 314-400nm, and the aperture is that 0.02-0.04 μ m TENSILE STRENGTH is that 8-9.5MPa, porosity are 80-90%, and electrolytical adsorption rate is 477-600%.
In the present embodiment, PVDF, model is FR-904, manufacturer is that Shanghai three is liked rich; PVDF-HFP, model is 2801, manufacturer is French A Kema; PAN, manufacturer are Shanghai Petrochemical Co. Ltd.; DMAC N,N, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group; Acetone, manufacturer is a Hangzhou chemical reagent Co., Ltd;
Other schemes of present embodiment are identical with embodiment one.
Embodiment 18: with mass ratio is that 8: 1: 1 PVDF, PVDF-HFP and PAN blend 20g is dissolved in N, and among the mixed solvent 100ml of dinethylformamide and acetone, the DMAC N,N in the mixed solvent and the volume ratio of acetone are 7: 3.After dissolving forms clear solution, add 0.15g ammoniacal liquor, add the 8g ethyl orthosilicate again; And add 0.1g cosolvent Tween-80, solution temperature 60-65 ℃, under the nitrogen protection; Stir about 3h, form transparent and homogeneous or pale yellow solution, the mensuration viscosity of said solution is 420mPa.S.Preset spinning condition: fixed voltage 14kV, constant spacing 16cm, fixed solution flow 2.48mL/h; The rotating speed 450rpm of receiving system, spinning time 100min, the barrier film aftertreatment technology is with embodiment two; Thickness through test (method is with example one) tunica fibrosa is 20-30 μ m; The average diameter of fiber is 314-400nm, and the aperture is that 0.02-0.04 μ m TENSILE STRENGTH is that 8-9.5MPa, porosity are 80-90%, and electrolytical adsorption rate is 477-600%.
In the present embodiment, PVDF, model is FR-904, manufacturer is that Shanghai three is liked rich; PVDF-HFP, model is 2801, manufacturer is French A Kema; PAN, manufacturer are Shanghai Petrochemical Co. Ltd.; DMAC N,N, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group; Acetone, manufacturer is a Hangzhou chemical reagent Co., Ltd;
Other schemes of present embodiment are identical with embodiment one.
Embodiment 19: with mass ratio is that 8: 1: 1 PVDF, PVDF-HFP and PAN blend 20g is dissolved in N, and among the mixed solvent 100ml of dinethylformamide and acetone, the DMAC N,N in the mixed solvent and the volume ratio of acetone are 7: 3.Solution temperature is kept 60-65 ℃, under the nitrogen protection, after dissolving forms clear solution; Add 0.2g ammoniacal liquor, add the 10g ethyl orthosilicate again, and add 0.1g cosolvent Tween-80; Stir about 8h, form transparent and homogeneous or pale yellow solution, the mensuration viscosity of said solution is 420mPa.S.Preset spinning condition: fixed voltage 14kV, constant spacing 16cm, fixed solution flow 2.48mL/h; The rotating speed 450rpm of receiving system, about spinning time 100min, the barrier film aftertreatment technology is with embodiment two; Thickness through test (method is with example one) tunica fibrosa is 20-30 μ m; The average diameter of fiber is 314-400nm, and the aperture is that 0.02-0.04 μ m TENSILE STRENGTH is that 8-9.5MPa, porosity are 80-90%, and electrolytical adsorption rate is 477-600%.
In the present embodiment, PVDF, model is FR-904, manufacturer is that Shanghai three is liked rich; PVDF-HFP, model is 2801, manufacturer is French A Kema; PAN, manufacturer are Shanghai Petrochemical Co. Ltd.; DMAC N,N, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group; Acetone, manufacturer is a Hangzhou chemical reagent Co., Ltd;
Other schemes of present embodiment are identical with embodiment one.
Embodiment 20: 14gPVDF-HFP is dissolved in N, and among the dinethylformamide 100ml, the diameter that adds 0g, 3g, 5g, 7g respectively is the hydrophobic type SiO about 60nm
2Nano particle,, the mensuration viscosity of said solution is 400mPa.S.Solution temperature is kept 60-65 ℃, under the nitrogen protection, makes solution even.Spinning voltage is fixed as 22kV, constant spacing 16cm, fixed solution flow 6mL/h, the rotating speed 500rpm of receiving system;, spinning time 50min puts into 60-65 ℃ with tunica fibrosa; About the dry 12h of vacuum drying chamber, then put into about 135 ℃ of air dry ovens, heating 1.5-2h.
In the present embodiment, PVDF-HFP, model is 2801, manufacturer is French A Kema; N, dinethylformamide, manufacturer is a Chemical Reagent Co., Ltd., Sinopharm Group;
Test (method of testing is with example one) result such as following table 1, table 1 is the nanometer SiO of different content
2To the nano fibrous membrane Effect on Performance:
Table 1
Can be found out by table 1: the thickness of nano fibrous membrane, average diameter change little, and this is owing to receiving SiO but its porosity, TENSILE STRENGTH and electrolyte adsorption rate are much improved
2The adding of rice, fortifying fibre intensity not only, SiO
2Also play electrolytical suction-operated on the surface.
The lithium battery diaphragm that utilizes the present invention to produce is used for the button electricity and carries out performance test.Its test result is following:
Thickness of sample: 25-30 μ m;
Porosity: 80-90%;
Average pore size: 0.02-0.03 μ m;
The electrolyte that uses is LB315:LiPF
6/ DMC/EMC/EC (1M, DMC/EMC/EC:1/1/1);
Ionic conductivity: 1.64 * 10-3
-3.1 * 10
-3S/cm;
The button cell initial discharge capacity 1.61-1.85mAh of this film assembling, after 100 circulations, discharge capacity is 1.39-1.48mAh, conservation rate is 79.4-84.3%.Coulombic efficiency is 87-90%.
Claims (9)
1. preparation method who is used for the nano fibrous membrane of lithium ion battery separator is characterized in that:
Said preparation method may further comprise the steps:
1) the PVDF based polyalcohol is dissolved in the amide-type organic solvent; The mass and size specific concentration 10-30% of PVDF based polyalcohol wherein; With said amide-type volume of organic solvent is 100%; Said mass volume ratio unit is g/ml, the PVDF based polyalcohol solution that stirs and form, and the mensuration viscosity of said solution is between 500～600mPa.S;
2) with the PVDF based polyalcohol solution electrostatic spinning for preparing; When arriving receiving system, said solution forms tunica fibrosa; The condition of said electrostatic spinning is: voltage 10～30KV, positive and negative electrode spacing 10～20cm, solution flow rate are 0.6～6mL/h; Rotating speed 100～the 500rpm of receiving system, the spinning time is 50-100min;
3) tunica fibrosa that obtains after the spinning completion is carried out post processing:
60 ℃ of-80 ℃ of vacuumize 12-14h put into air dry oven 100 ℃-160 ℃ heating 1-3h or 40 ℃ of-80 ℃ of hot pressing 1-3h with film then earlier;
After removing solvent residual in the said tunica fibrosa, make the nano fibrous membrane that is used for lithium ion battery separator.
2. the preparation method who is used for the nano fibrous membrane of lithium ion battery separator as claimed in claim 1 is characterized in that: in the said step 1), the dissolving back adds diameter 30-100nm hydrophobic nano SiO
2Ceramic particle is 100% with amide-type organic solvent volume, and the mass and size percentage that adds ceramic particle is 0.1～10%.
3. the preparation method who is used for the nano fibrous membrane of lithium ion battery separator as claimed in claim 1; It is characterized in that: in the said step 1); The dissolving back drips ethyl orthosilicate, is 100% with amide-type organic solvent volume, and the mass and size percentage that drips ethyl orthosilicate is 0.1～10%.
4. like claim 2 or the 3 described preparation methods that are used for the nano fibrous membrane of lithium ion battery separator; It is characterized in that: in the said step 1); Add cosolvent again; Said cosolvent is Triton-100, peregal or Tween-80, is 100% with amide-type organic solvent volume, and the mass and size percentage of said cosolvent is 0.05～0.1%.
5. like the described preparation method who is used for the nano fibrous membrane of lithium ion battery separator of one of claim 1～3, it is characterized in that: said PVDF based polyalcohol is following a kind of or two or more at least mixing: 1. PVDF, 2. PVDF-HFP, 3. PAN.
6. like the described preparation method who is used for the nano fibrous membrane of lithium ion battery separator of one of claim 1～3; It is characterized in that: said amide-type organic solvent is N; Dinethylformamide, N; The mixed solvent of N-dimethylacetylamide and acetone, both volume ratios are 2 in the said mixed solvent: 8-8: 2.
7. the preparation method who is used for the nano fibrous membrane of lithium ion battery separator as claimed in claim 3; It is characterized in that: before dripping ethyl orthosilicate, at first add ammoniacal liquor; With amide-type organic solvent volume is 100%, and the mass and size percentage of said ammoniacal liquor is 0.05～0.2%.
8. the preparation method who is used for the nano fibrous membrane of lithium ion battery separator as claimed in claim 7 is characterized in that: in the said step 1), temperature maintenance makes the solution homogeneous transparent at 50 ℃-85 ℃ under stirring.
9. the preparation method who is used for the nano fibrous membrane of lithium ion battery separator as claimed in claim 7 is characterized in that: in the said step 1), in whole process, will feed nitrogen.
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Application publication date: 20120718 |