CN1851957A - Polymer composite diaphragm and its preparing method - Google Patents
Polymer composite diaphragm and its preparing method Download PDFInfo
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- CN1851957A CN1851957A CNA2006100781270A CN200610078127A CN1851957A CN 1851957 A CN1851957 A CN 1851957A CN A2006100781270 A CNA2006100781270 A CN A2006100781270A CN 200610078127 A CN200610078127 A CN 200610078127A CN 1851957 A CN1851957 A CN 1851957A
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Abstract
This invention discloses a polymer compound membrane and its preparation method, in which, the method includes: mixing strengthening bodies of a matrix film and inorganic nm materials in an organic solvent to get a uniform slurry to be coated on both sides of a non-woven cloth to get a polymer compound membrane, in which, said strengthening bodies are selected from the following three: 1, an organic monomer and its related initiator, 2, two or more than two polymers, 3, organic monomers and their related initiators and two or more than two polymers, 4, organic monomers and two or more than two polymers.
Description
Technical field
The present invention relates to a kind of polymer composite diaphragm and preparation method thereof.
Background technology
Liquid lithium ionic cell is a kind of novel secondary cell that occurs after Ni-H, Ni-Cd and plumbic acid secondary cell, evolution in nearly two more than ten years, because its some intrinsic advantages such as monomer battery voltage platform height, environmentally friendly, gravimetric specific energy height and memory-less effect etc. make liquid lithium ionic cell obtain development at full speed.Polymer Li-ion battery is a battery product of new generation after liquid lithium ionic cell, in the polymer Li-ion battery composition material, except packaged type, polymer dielectric film is the most tangible difference in polymer battery and the liquid lithium ionic cell material, so also be the most important thing of research.Polymer dielectric film separates positive/negative plate and provides the lithium ion passage except playing at lithium ion battery, also plays the effect that keeps electrolyte, owing to have good compatibility between itself and the pole piece, for battery later stage cycle performance considerable influence is arranged simultaneously.
Membrane for polymer can be divided into straight polymer barrier film and polymer composite diaphragm on structure is formed.Straight polymer barrier film multiselect makes in its solvent that is dissolved in certain proportioning with the good polymer of a certain chemical property, adds pore creating material and other auxiliary agent simultaneously, and back system film stirs.With Bellcore house journal is representative (U.S.patent5,540,741), this straight polymer barrier film preparation method, the pore-creating process generally adopts extraction, promptly adopts extractant that homodisperse pore creating material in the film is extracted, and has equally distributed microporous barrier thereby make.But this method must adopt a large amount of extractants, reclaims to be difficult for, and increase cost, and environmental pollution is more serious.
The preparation of composite diaphragm generally selects for use the higher film of mechanical property as base film earlier, on its surface or the inner coating of extended structure or crosslinked other functional polymer, make that performance replenishes mutually laminated film, its pore-creating principle is identical with the straight polymer barrier film.This method makes the power-type lithium ion battery of making large tracts of land, ultrathin type, high-energy-density become possibility.
Summary of the invention
The purpose of this invention is to provide a kind of porosity height, mechanical strength is good, absorbency is excellent polymer Li-ion battery with polymer composite diaphragm and preparation method thereof.
Polymer composite diaphragm provided by the present invention prepares according to following method: base film is strengthened body and inorganic nano material mixing in organic solvent obtains uniform sizing material, this slurry coating in nonwoven fabrics matrix film two sides, is after heat treatment obtained polymer composite diaphragm;
Described base film strengthens body and is selected from following 1) to 4) in any one: 1) organic monomer and its corresponding initator; 2) two or more polymer; 3) organic monomer and its corresponding initator and two or more polymer; 4) organic monomer and two or more polymer.
Heat treatment process in this method has comprised that the polymerization process of organic monomer promptly forms the crossings on different level network configuration, also comprises the volatilization process of solvent component and the forming process of diaphragm material pore structure.
Described nonwoven fabrics matrix film is PP nonwoven fabrics or PE nonwoven fabrics or PP/PE compound nonwoven cloth or PP/PE/PP compound nonwoven cloth to be carried out densification to handle the thickness of making be the film of 10-50 μ m.
Described organic monomer is to contain any one monomer of esters of acrylic acid of unsaturated bond or the combination of multiple monomer, and described acrylic ester monomer is one or more combination in any in the following substances group preferably: neopentylglycol diacrylate (NPGDA), polyethylene glycol dimethacrylate (PEGDMA), diethylene glycol diacrylate (DEGDA) and methyl methacrylate.
When selecting for use organic monomer and its corresponding initator to strengthen body as matrix, two kinds of system film modes are arranged: A) described organic monomer and its corresponding initator and inorganic nano material in organic solvent copolyreaction 2-4 hour must uniform sizing material, this slurry coating is obtained composite membrane of polymer after the drying of nonwoven fabrics matrix film two sides.For example select methyl methacrylate (MMA) for use, with thermal initiator (BPO) under heated condition with inorganic nanoparticles such as nanometer SiO
2Stir copolymerization and got uniform sizing material in 2-4 hour, coat nonwoven fabrics matrix film two sides certain thickness, get composite membrane of polymer after the oven dry.
After described organic monomer and its corresponding initator and inorganic nano material mixing in organic solvent are coated on nonwoven fabrics matrix film two sides,, reach the effect that structure strengthens again by heating or illumination polymerization film formation.For example can select for use MMA polyaddition initator (BPO or azodiisobutyronitrile ALBN) and inorganic nano-particle (as SiO
2) after stirring and evenly mixing is coated on the base film two sides in organic solvent, again by heated polymerizable thing or illumination polymerization film formation.Because organic monomer can mix with molecular level in system, after the thermal polymerization, form the crossings on different level inierpeneirating network structure, the composite membrane of polymer that makes, its intensity, electrochemical stability and other performance all make moderate progress.Organic monomer also can be selected the combination of other any one monomer of esters of acrylic acid that contains unsaturated bond or multiple monomer for use, as neopentylglycol diacrylate (NPGDA), polyethylene glycol dimethacrylate (PEGDMA), diethylene glycol diacrylate (DEGDA).
Described polymer comprises: Kynoar (PVDF), polyacrylonitrile (PAN), polyoxyethylene (PEO), polyethylene glycol (PEG), polyethylene glycol dimethyl ether (PEGDME), polyacrylate (as polymetylmethacrylate), copolymerization class fluorine compounds (as poly-(biasfluoroethylene-hexafluoropropylene) (PVDF-HFP)) or the like.Above-mentioned these polymer molecular weights do not have concrete qualification, and any molecular weight all can use in acetone, N-methyl pyrrolidone (NMP) or the butanone as long as can be dissolved in.
When described two or more polymer strengthened body as base film, polymer and inorganic nano-particle were as nanometer SiO
2, after stirring is mixed and spares in mixed organic solvents (solvent and pore creating material), being coated on the base film skin drying and making polymer composite diaphragm, polymer composite diaphragm thickness is between 20-100 μ m.For example can select PVDF-HFP and PMMA for use, PVDF-HFP this moment (a) is that the part by weight of 3: 7～7: 3 (wt%) mixes with PMMA (b) by a: b, with nanometer SiO
2Particle is coated on the base film two sides behind the stirring and evenly mixing in organic solvent, oven dry makes the nonwoven fabrics polymer composite diaphragm.
It can be the co-mixing system of multiple organic polymer and organic monomer that base film strengthens body, can select for use two or more polymeric components and organic crosslinking agent blend to strengthen body as base film, for example select PVDF-HFP (a) and PEG (b) and PEGDMA (c for use, polyethylene glycol dimethacrylate), (a: b: c=5: 4: 1 or 5: 3: 2 or 5: 2: 3) evenly is coated on nonwoven fabrics matrix film two sides with inorganic nano material blended under agitation in organic mixed solvent by a certain percentage, and oven dry makes polymer composite diaphragm.Though PEGDMA contains unsaturated double-bond, but under the situation that does not add thermal initiator, polymerization reaction take place hardly in the time of≤70 ℃ utilizes with this understanding PVDF-HFP/PEG/PEGDMA/ inorganic nano material blend to be coated on nonwoven surface and makes film, its ionic conductivity＞10
-3Scm
-1, other physical and chemical performance is all good.Can utilize simultaneously the PEGDMA characteristics of (＞130 ℃) energy rapid polymerization at high temperature, can make film micropore sealing automatically at high temperature, produce the heat-seal blocking effect, prevent the battery combustion explosion, improve the security performance of polymer Li-ion battery.The dual-use function that this polymer composite diaphragm had is better than the PE micro-pore septum.
Described thermal initiator can be any peroxide thermal initiator that can be dissolved in acetone, N-methyl pyrrolidone (NMP) or butanone, as the hydroperoxides of benzoyl peroxide (BPO), azodiisobutyronitrile (AIBN), cumenyl, t-butyl perbenzoate etc.Wherein, preferred BPO or ALBN.
Described organic solvent is divided into solvent composition and pore creating material component; Described solvent composition can be acetone, N-methyl pyrrolidone (NMP) or butanone; Described pore creating material component is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or butanols; Described inorganic nano material is nanometer SiO
2, nanometer Al
2O
3, nano-TiO
2, nanometer BaTiO
3With a kind of or its combination in any among the nanometer CuO, the particle size range of described nano particle is 5-100nm.
Simultaneously, for increasing inorganic nano material dispersion effect in organic solvent, the nano grain surface of selecting for use also can have the surface group of some, as-CH
2-,-CH
3, etc. other non-polar group.
Wherein, in the porosity of resulting polymers composite membrane and porosity and the mixed solvent solvent component and pore creating material component content than relevant.
In the said method, the addition that described base film strengthens body is the 2.5-16 weight portion, and the addition of inorganic nano material is the 1-8 weight portion; Described solvent composition addition be the 40-70 weight portion, the addition of described pore creating material is the 10-30 weight portion.
If adopt organic monomer and initator, its both addition is the 2.5-16 weight portion, and the monomer wherein and the mass ratio of initator can be 95: 5-80: 20.And the various combination of two kinds of polymer or two or more polymer only influences to some extent to polymer composite diaphragm pore structure and the porosity that finally obtains, and its proportioning can arbitrarily be chosen under the homodisperse prerequisite at slurry.At this moment, the addition of all polymer is in the 2.5-16 weight portion; If adopt polymeric components and organic monomer mixed system, then both total addition levels are in the 2.5-16 weight portion.
The method that in the described method uniform sizing material is coated on nonwoven fabrics matrix film two sides can be infusion process, dip coating, knife coating or spraying process.
The polymer composite diaphragm of method for preparing also belongs to protection scope of the present invention.
The thickness of described polymer composite diaphragm is 20-100 μ m.
The present invention selects for use PP, PE, PP/PE or the PP/PE/PP nonwoven fabrics of mechanics and stable electrochemical property to make base film, utilize high molecular polymer or organic monomer and the thermal initiator etc. that two or more chemical property is good and film forming is good to strengthen body, with the common constructing polymer barrier film of inorganic nanoparticles as base film.Under high-speed stirred, base film strengthened body and inorganic nanoparticles and be scattered in and be made into component in the solvent component and make the film slurry uniformly, be coated in the base film surface uniformly and make polymer composite diaphragm.Experiment shows, adopt this method can make the polymer composite diaphragm with interpenetrating networks pore structure, porosity is 30%-60%, and air penetrability is 20 ± 5Sec/100CC, the self closing performance 130 ℃-160 ℃ adjustable, absorption electrolyte property reach 100-200%, the about 500kg/cm of mechanical strength
2, ionic conductivity can reach 1.5Scm
-1Adjust each component proportion in the slurry, obtain a series of polymer composite diaphragms with even pore size distribution.Low with this polymer composite diaphragm assembling polymer Li-ion battery short circuit ratio, the electrical property excellence.It is simple that this method prepares the polymer composite diaphragm technical process, with low cost, has bigger industrial application value.
Embodiment
Method therefor is conventional method if no special instructions among the following embodiment.
Embodiment 1, be that base film strengthens system and is equipped with polymer composite diaphragm with PVDF and PEG
With polymer P VDF and PEG is that base film strengthens body, with nanometer SiO
2Be the ionic conduction reinforcing agent, prepare the polymer dielectric composite membrane according to following method:
Thickness is that the PP nonwoven fabrics of 90-150 μ m cleans after densification (but concora crush or roll-in) obtains 30 μ m films is base film; The polyethylene glycol (PEG) of 3 weight portion Kynoar (PVDF) and 1 weight portion at room temperature is dissolved in wiring solution-forming in the 35 weight portion butanone, in this solution, adds 5 weight portion diethyl carbonates (DEC) the wiring solution-forming A that stirs then; In addition, with 1 weight portion nanometer SiO
2(particle diameter is between 3-15nm, and average grain diameter is 5nm) is dispersed in wiring solution-forming B in the mixed solution of 30 weight portion butanone and 25 weight portion butanols, then solution A mixed with B, disperses 1-4 hour again, obtains solute homogeneous polymer slurry.Base film be impregnated in the slurry 25 seconds, taking-up places 80 ℃ of baking oven bakings 5 minutes, place air to shelve again 30 minutes, (the dry 8h of vacuum degree＜0.085Mpa) promptly obtains the polymer composite diaphragm that thickness is about the porous of 50 μ m to place 100 ℃ of vacuum drying ovens then.
Every index of the polymer composite diaphragm that detection obtains, wherein, the barrier film air penetrability adopts the Gurley-ASTM-D726 standard; The barrier film porosity adopts the ASTM-D2873 standard; Barrier film mechanics hot strength adopts the ASTM-D882 standard;
The detection of barrier film absorption electrolyte ability is that the barrier film sample with certain area soaks 1h in the electrolyte, takes out with face tissue and dries surface electrolyte, weighs barrier film weight * 100% of the weight of increase/originally;
The measurement of barrier film ionic conductivity realizes by the impedance response that is clipped in polymer samples between two stainless steel electrodes, by the ac impedance spectroscopy median caudal filament that obtains and the intersection point of real axis, can obtain this volume resistance Ω of sample, again by formula k=d/ (R
bS), can calculate ionic conductivity (d is a thickness of sample, and S is a sample area) with sample.
The result shows this polymer composite diaphragm, and porosity is 52, and air penetrability is 22Sec/100CC, and the absorption electrolyte property reaches 160%, the about 490kg/cm of mechanical strength
2, ionic conductivity is 1.0Scm
-1
This barrier film is assembled into polymer Li-ion battery (LiCoO
2/ polymer composite diaphragm/MCMB), in the 2.75V-4.2V voltage range, when discharging and recharging with the electric current of 0.2C, its 3.6V voltage platform is more than 90%, and this illustrates that this internal resistance of cell is lower, and battery charges and discharge function admirable.
Embodiment 2, be that base film strengthens system and is equipped with polymer composite diaphragm with PVDF-HFP (weight average molecular weight 250,000), PEG (weight average molecular weight 20,000) and MMA and thermal initiator BPO
(benzoyl peroxide for base film strengthens body, is 5nm TiO with the average grain diameter BPO) with polymeric components [PVDF-HFP (weight average molecular weight 250,000) and PEG (weight average molecular weight 20,000)], organic monomer (MMA) and thermal initiator
2Be the ionic conduction reinforcing agent, prepare the polymer dielectric composite membrane according to following method:
Thickness is that the PP nonwoven fabrics of 40-50 μ m cleans after densification (concora crush or roll-in) obtains 30 μ m films is base film; With 3 weight portion weight average molecular weight is that 230,000 poly-(biasfluoroethylene-hexafluoropropylene) and 1 weight portion polyethylene glycol (PEG, weight average molecular weight 1,000 ten thousand) at room temperature are dissolved in wiring solution-forming A in the 40 weight portion butanone; 1 weight portion nano-TiO
2(particle diameter is between 3-15nm, average grain diameter is 5nm), 0.8 weight portion organic monomer methyl methacrylate (MMA), 0.2 weight portion thermal initiator benzoyl peroxide (BPO) be dispersed in wiring solution-forming B in the mixed solution of 30 weight portion acetone and 24 parts by weight of ethanol, then solution A is mixed with B, disperseed again 1-4 hour, and obtained solute homogeneous polymer slurry.Base film be impregnated in the slurry 30 seconds, taking-up places 80 ℃ of baking ovens to toast 5min, place air to shelve 30 fens kinds again, (the dry 8h of vacuum degree＜0.085MPa) promptly obtains the polymer composite diaphragm of the thick porous of about 40 μ m to place 100 ℃ of vacuum drying ovens then.
Press the method assembled battery of embodiment 1, test battery cycle performance (testing standard is with reference to GB2000-T18287), the result shows that this cycle performance of battery is good, after 500 circulations, capacity remains on more than 90%.
Embodiment 3, be that base film strengthens system and is equipped with polymer composite diaphragm with PVDF-HFP and PMMA
With polymeric components (PVDF-HFP and PMMA) is that base film strengthens body, with nanometer BaTiO
3Be the ionic conduction reinforcing agent, prepare the polymer dielectric composite diaphragm according to following method:
Thickness is that the PE nonwoven fabrics of 40-50 μ m cleans the back to obtain 30 μ m films by example 2 method densifications be base film; The polymeric blends of 4 weight portion PVDF-HFP (weight average molecular weight 250,000) and PMMA (weight average molecular weight 3000) (PVDF-HFP: PMMA=3: 1, weight ratio) at room temperature is dissolved in wiring solution-forming A in the 40 weight portion acetone, 1 weight portion nanometer BaTiO
3(particle diameter between 10-50nm, average grain diameter 30nm) blend is dispersed in wiring solution-forming B in the mixed solution of 30 weight portion butanone and 25 weight portion butanols, then solution A is mixed with B, disperses 1-4h again, obtains solute homogeneous polymer slurry.Base film be impregnated in 5-30 second in the slurry, taking-up places 80 ℃ of baking ovens to toast 5min, place air to shelve again 30 minutes, (the dry 8h of vacuum degree＜0.085MPa) promptly obtains the polymer dielectric composite membrane of the thick porous of about 40 μ m to place 100 ℃ of vacuum drying ovens then.
Embodiment 4, be that base film strengthens system and is equipped with polymer composite diaphragm with polymer P VDF-HFP, PEG and PEGDMA
With polymeric components PVDF-HFP, PEG and polyethylene glycol dimethacrylate (PEGDMA) is that base film strengthens body, is inorganic nano material with CuO, prepares the polymer dielectric composite diaphragm according to following method:
Thickness is the PP/PE compound nonwoven cloth of 50-100 μ m, cleans the back and obtains 35 μ m films as base film by embodiment 1 method densification; With polymer P VDF-HFP (weight average molecular weight 250,000), the PEG (weight average molecular weight 2000) of 4 weight portions and the mixture (PVDF-HFP: PEG: PEGDMA=5: 3: 2 of polyethylene glycol dimethacrylate (PEGDMA), weight ratio), at room temperature be dissolved in 40 weight portion acetone wiring solution-forming A, (particle diameter is between 10-50nm for 1 weight portion nanometer CuO, average grain diameter is 30nm) be dispersed in wiring solution-forming B in the mixed solution of 30 weight portion acetone and 25 weight portion butanols, then solution A is mixed with B, disperse 1-4h again, obtain solute homogeneous polymer slurry.Base film be impregnated in 5-30 second in the slurry, taking-up places 80 ℃ of baking ovens to toast 5min, place air to shelve 30min again, (the dry 8h of vacuum degree＜0.085MPa) promptly obtains the polymer dielectric composite membrane of the thick porous of 50 μ m to place 100 ℃ of vacuum drying ovens then.After tested, its ionic conductivity＞10
-3Scm
-1
Though PEGDMA contains unsaturated double-bond, but under the situation that does not add thermal initiator, polymerization reaction take place hardly in the time of≤70 ℃ utilizes with this understanding PVDF-HFP/PEG/PEGDMA/ inorganic nano material blend to be coated on nonwoven surface and makes film, its ionic conductivity＞10
-3Scm
-1, other physical and chemical performance is all good.Can utilize simultaneously the PEGDMA characteristics of (＞130 ℃) energy rapid polymerization at high temperature, can make film micropore sealing automatically at high temperature, produce the heat-seal blocking effect, prevent the battery combustion explosion, improve the security performance of polymer Li-ion battery.
Because base film is the material PP/PE of two kinds of different melting points, so the polymer composite diaphragm that finally obtains has high temperature self-closing function, can strengthen the security performance of lithium ion battery.The function that this polymer composite diaphragm had is better than the PE micro-pore septum.
With this barrier film assembling polymer Li-ion battery (LiCoO
2/ polymer composite diaphragm/MCMB), ionic conductivity reaches 1.5Scm after tested
-1
Embodiment 5, be that base film strengthens system and is equipped with the polymer dielectric composite diaphragm with the polymeric components
With polymer P VDF-HFP, polyethylene glycol dimethyl ether (PEGDME) and polymethyl methacrylate (PMMA) is that base film strengthens body, with inorganic nano material nanometer Al
2O
3For the ionic conduction reinforcing agent prepares the polymer dielectric composite diaphragm according to following method:
Thickness is the PP nonwoven fabrics of 40-50 μ m, and obtaining 20 μ m films by embodiment 1 method densification after cleaning is base film; Three kinds of mixture of polymers of 4 weight portions (PVDF-HFP: PEGDME: PMMA=5: 4: 1, weight ratio, three's weight average molecular weight was respectively 250,000,2000 and 2000) at room temperature are dissolved in wiring solution-forming A in the 40 weight portion butanone, 1 weight portion nanometer Al
2O
3(particle diameter is between 5-20nm, and average grain diameter is 10nm) is dispersed in wiring solution-forming B in the mixed solution of 30 weight portion butanone and 25 weight portion butanols, then solution A mixed with B, stirs 4h again, obtains solute homogeneous polymer slurry.With slurry dip-coating base film two sides, rolling is placed in 100 ℃ of vacuum drying ovens that (the dry 8h of vacuum degree＜0.085MPa) promptly obtains the polymer dielectric composite diaphragm of the thick porous of 40 μ m.
Adopt this polymer dielectric composite diaphragm to be assembled into button cell, at Voltammetry Analyzer (Model-601A, CH Instruments) recording electrochemical window on is 4.8V (sweep speed is 1mV/s, and work electrode is a stainless steel electrode, and reference electrode is a lithium electrode).
Embodiment 6, be that base film strengthens body with the polymeric components, preparation polymer dielectric composite membrane
With polymer P VDF-HFP, polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA) is that base film strengthens body, with inorganic nano material nanometer SiO
2Be the ionic conduction reinforcing agent, prepare the polymer dielectric composite membrane according to following method:
Thickness is the PP nonwoven fabrics of 90-100 μ m, cleans after to obtain 50 μ m films by embodiment 1 method after closely knit be base film; With three kinds of polymeric blends of 3 weight portions (PVDF-HFP: polyacrylonitrile (PAN): polymethyl methacrylate (PMMA)=5: 2: 3, weight ratio, three's weight average molecular weight is respectively 200,000,8000 and 2000) at room temperature be dissolved in wiring solution-forming A in the 40 weight portion N-methyl pyrrolidones (NMP); With 1 weight portion nanometer SiO
2(particle diameter is between 2-10nm, and average grain diameter is 5nm) is dispersed in wiring solution-forming B in the mixed solution of 30 weight portion NMP and 26 weight portion butanols, then solution A mixed with B, disperses 1-4h again, obtains solute homogeneous polymer slurry.In the base film surface, rolling is placed on 100 ℃ of vacuum drying ovens, and (dry 8h in the vacuum degree＜0.085MPa) promptly obtains the polymer composite diaphragm of the thick porous of 70 μ m with the slurry blade coating.
Embodiment 7, be that base film strengthens body with organic monomer and thermal initiator, preparation polymer dielectric composite membrane
With organic monomer methyl methacrylate (MMA) and neopentylglycol diacrylate (NPGDA) and thermal initiator BPO is that base film strengthens body, with inorganic nano material nanometer SiO
2Be the ionic conduction reinforcing agent, prepare the polymer dielectric composite membrane according to following method:
Thickness is the PP/PE/PP nonwoven fabrics of 80-100 μ m, cleans after to obtain 50 μ m films by embodiment 1 method densification be base film; 1.8 parts by weight of methylmethacrylate (MMA), 0.2 weight portion thermal initiator BPO and 1 weight portion neopentylglycol diacrylate (NPGDA) at room temperature are dissolved in wiring solution-forming A in the 40 weight portion butanone; With 1 weight portion nanometer SiO
2(particle diameter is between 2-10nm, and average grain diameter is 5nm) is dispersed in wiring solution-forming B in the mixed solution of 30 weight portion butanone and 26 weight portion butanols, then solution A mixed with B, stirs 1-4h again, obtains solute homogeneous polymer slurry.In the base film surface, rolling is placed on 100 ℃ of vacuum drying ovens, and (dry 9h in the vacuum degree＜0.085MPa) promptly obtains the polymer composite diaphragm of the thick porous of 70 μ m with the slurry blade coating.
Embodiment 8, be that base film strengthens body with organic monomer methyl methacrylate (MMA) and diethylene glycol diacrylate (DEGDA) and thermal initiator azodiisobutyronitrile (ALBN), with inorganic nano material nanometer SiO
2Be the ionic conduction reinforcing agent, prepare the polymer dielectric composite membrane according to following method:
Thickness is the PP/PE/PP nonwoven fabrics of 80-100 μ m, cleans after to obtain 50 μ m films by embodiment 1 method densification be base film; 1.8 parts by weight of methylmethacrylate (MMA), 0.2 weight portion thermal initiator ALBN and 1 weight portion diethylene glycol diacrylate (DEGDA) at room temperature are dissolved in wiring solution-forming A in the 40 weight portion butanone; With 1 weight portion nanometer SiO
2(particle diameter is between 2-10nm, and average grain diameter is 5nm) is dispersed in wiring solution-forming B in the mixed solution of 30 weight portion butanone and 26 weight portion butanols, then solution A mixed with B, stirs 1-4h again, obtains solute homogeneous polymer slurry.In the base film surface, rolling is placed on 100 ℃ of vacuum drying ovens, and (dry 9h in the vacuum degree＜0.085MPa) promptly obtains the polymer composite diaphragm of the thick porous of 70 μ m with the slurry blade coating.
Claims (10)
1, a kind of method for preparing polymer composite diaphragm is base film to be strengthened body and inorganic nano material mixing in organic solvent obtains uniform sizing material, and this slurry coating in nonwoven fabrics matrix film two sides, is after heat treatment obtained polymer composite diaphragm;
Described base film strengthens body and is selected from following 1) to) in any one: 1) organic monomer and its corresponding initator; 2) two or more polymer; 3) organic monomer and its corresponding initator and two or more polymer; 4) organic monomer and two or more polymer.
2, method according to claim 1 is characterized in that: described nonwoven fabrics matrix film is PP nonwoven fabrics or PE nonwoven fabrics or PP/PE compound nonwoven cloth or PP/PE/PP compound nonwoven cloth to be carried out densification to handle the thickness of making be the film of 10-50 μ m.
3, method according to claim 2, it is characterized in that: described organic monomer is an acrylic ester monomer, and described acrylic ester monomer is selected from a kind of or its combination in any in the following substances group: neopentylglycol diacrylate, polyethylene glycol dimethacrylate, diethylene glycol diacrylate and methyl methacrylate.
4, method according to claim 3 is characterized in that: it is organic monomer and its corresponding initator that described base film strengthens body; Described polymer composite diaphragm is according to following A) or method B) be prepared:
A) described organic monomer and its corresponding initator and inorganic nano material in organic solvent copolyreaction 2-4 hour must uniform sizing material, this slurry coating is obtained composite membrane of polymer after the drying of nonwoven fabrics matrix film two sides;
B) after described organic monomer and its corresponding initator and inorganic nano material mixing in organic solvent are coated on nonwoven fabrics matrix film two sides, again by heating or illumination polymerization film formation.
5, method according to claim 2 is characterized in that: described polymer comprises: Kynoar, polyacrylonitrile, polyoxyethylene, polyethylene glycol, polyethylene glycol dimethyl ether, polyacrylate and copolymerization class fluorine compounds.
6, method according to claim 2 is characterized in that: described organic solvent is divided into solvent composition and pore creating material component; Described solvent composition is acetone, N-methyl pyrrolidone or butanone; Described pore creating material component is methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or butanols; Described inorganic nano material is nanometer SiO
2, nanometer Al
2O
3, nano-TiO
2, nanometer BaTiO
3With a kind of or its combination in any among the nanometer CuO, the particle size range of described nano particle is 5-100nm.
7, method according to claim 6 is characterized in that: the addition that described base film strengthens body is the 2.5-16 weight portion, and the addition of inorganic nano material is the 1-8 weight portion; Described solvent composition addition be the 40-70 weight portion, the addition of described pore creating material is the 10-30 weight portion.
8, method according to claim 7 is characterized in that: the mass ratio of described organic monomer and initator is 95: 5-80: 20; The mode of described polymer composite diaphragm coating coating slurry adopts infusion process or dip coating or knife coating or spraying process.
9, the polymer composite diaphragm of arbitrary described method preparation among the claim 1-8.
10, utilize the polymer Li-ion battery of the described polymer composite diaphragm preparation of claim 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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