CN104810549A - Method for preparing porous gel polymer electrolyte doped with composite nanoparticles - Google Patents
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Abstract
The invention discloses a method for preparing a porous gel polymer electrolyte, applied to a polymer lithium ion battery, doped with composite nanoparticles. The method comprises the following steps: firstly, carrying out aqueous phase dispersion polymerization to obtain organic nanoparticles of a copolymer of methyl methacrylate and maleic acid lithium; covering the surfaces of the organic nanoparticles with silicon dioxide to obtain composite nanoparticles with core-shell morphology according to a sol-gel method; then, dispersing the composite nanoparticles into an N'N-dimethyl formamide solution of PVDF; preparing PVDF-based composite porous membranes according to an immersion precipitation method; adsorbing liquid electrolyte to obtain composite gel polymer electrolyte membranes after vacuum heating and drying. The thickness of the electrolyte membrane provided by the invention is 30 to 50 microns, the ionic conductivity reaches to 6.31*10<-3>S/cm under the temperature of 30 DEG C, and an electrochemical window reaches 5.4V. The performance of the porous gel polymer electrolyte provided by the invention is superior to that of the conventional gel polymer electrolyte.
Description
Technical field
The invention discloses a kind of porous gel method for preparing polymer electrolytes being applied to a kind of doped compound nano particle of polymer Li-ion battery.
Background technology
More outstanding along with environmental problem, use conventional fossil energy to cause serious air pollution, to new type lithium ion battery, the demand of the environmental protection new forms of energy such as fuel cell is day by day strong.Polymer Li-ion battery is large with its energy density, renewable recycling and be subject to extensive concern.Polymer dielectric, as the important component part of polymer Li-ion battery, in the security reliability of lithium ion battery, the performances such as discharge and recharge has important decisive influence.
Studied, concentrated emphasis is directly adulterated by inorganic nano-particle to be mixed in organic phase polymer to prepare composite polymer electrolyte in the past.Because inorganic nanoparticles is less, be dispersed in polymer matrix and easily nanocluster occur thus cause realizing the homodisperse effect of nano particle.By chemical modification to prepare nucleocapsid pattern nano particle, though analyze it have research to the impact of composite polymer electrolyte performance, as Harbin Institute of Technology professor Tang Dongyan to wait by methyl methacrylate at the in situ Polymerization of inorganic nanoparticles with modified inorganic nanophase.Test finds, polymethyl methacrylate can not evenly be coated on inorganic nanoparticles surface, and percent grafting is also lower simultaneously, really cannot realize the synthesis of the nano particle of homogeneous nucleus shell morphology.Be necessary to design a kind of new synthesizing mean, prepare a kind of composite nanoparticle of homogeneous nucleus shell morphology and be doped in polymer matrix, with Effective Doping composite polymer electrolyte, and its properties effectively being promoted.
Summary of the invention
The object of the invention is the defect for overcoming as above-mentioned prior art, a kind of porous gel method for preparing polymer electrolytes being applied to a kind of doped compound nano particle of polymer Li-ion battery is provided.Described method first synthesizes the nucleocapsid pattern composite nanoparticle that a kind of novel shell is the methyl methacrylate copolymer maleic acid lithium of silicon dioxide stratum nucleare, then adulterated and be dispensed in polyvinylidene fluoride polymer solution, preparation compound polyvinylidene fluoride porous film is sent out by immersion precipitation, after thin film adsorbs Liquid Electrolyte Gels, obtain a kind of composite gel polymer electrolyte with porous pattern.
In order to achieve the above object, the technical solution used in the present invention is:
A porous gel method for preparing polymer electrolytes for doped compound nano particle, comprises the steps:
Step one, by mix monomer methyl methacrylate, maleic anhydride mixes according to the ratio of mol ratio 1:1 ~ 100:1, then the dispersant of 3 ~ 10wt% relative to methyl methacrylate and maleic anhydride gross mass is added, mixture is scattered in deionized water under high velocity agitation, monomer total amount is 5 ~ 20wt% relative to the mass ratio of deionized water, add the potassium peroxydisulfate relative to mix monomer quality 1 ~ 3wt%, reaction system temperature elevating range is at 60 ~ 100 DEG C, reaction time controls at 6 ~ 24 hours, 25 DEG C are down to after reaction terminates, add the lithium hydroxide of relative maleic anhydride mole 2 times in reaction system, react 6 ~ 10 hours, obtain the organic nano particle of the methyl methacrylate copolymer maleic acid lithium be scattered in aqueous phase, through freeze drying, obtain the organic nano powder of methyl methacrylate copolymer maleic acid lithium,
Step 2, the organic nano powder dispersion of methyl methacrylate copolymer maleic acid lithium that step one obtained are in ethanol, its concentration controls at 0.01g/ml ~ 0.5g/ml, ultrasonic disperse 0.5h, routine tetraethoxysilane in mass ratio: the organic nano powder of methyl methacrylate copolymer maleic acid lithium is that 10:1 ~ 1:10 adds tetraethoxysilane, dripping ammoniacal liquor makes regulation system pH value control between 8 ~ 11, react 6 ~ 24h at room temperature 25 DEG C, obtain the nucleocapsid pattern composite nanoparticle that shell is the methyl methacrylate copolymer maleic acid lithium of silicon dioxide;
Step 3: be scattered in N by dissolving under Kynoar powder room temperature, in dinethylformamide solution, polymer solution concentration controls at 0.1 ~ 5g/ml, stir after 6 ~ 12 hours, then nucleocapsid pattern composite nanoparticle step 2 obtained adds by 0.01 ~ 10wt% of the doping of Kynoar powder and is distributed to wherein ultrasonic 0.1 ~ 1h, then stirring at room temperature 12 ~ 24h; Again polymer solution is left standstill de-bubbled, utilize the smooth painting of scraper to scrape on glass plate, be soaked in aqueous phase, adopt immersion precipitation to prepare the composite porous film of nucleocapsid pattern composite nanoparticle doping Kynoar;
Step 4: the composite porous film of nucleocapsid pattern composite nanoparticle doping Kynoar step 3 obtained first vacuumizes dry 8 ~ 24 hours at the temperature of 40 DEG C ~ 80 DEG C, then immersion liquid electrolyte 0.5 ~ 1 hour in glove box, obtains the composite gel polymer electrolyte film with loose structure that adsorbed liquid electrolyte component accounts for 40 ~ 70wt% of gross mass.
The thickness of film described above is 30 μm ~ 50 μm.
The mol ratio of the methyl methacrylate described in above-mentioned steps one and maleic anhydride is preferably 5:1 ~ 20:1.
Dispersant described in above-mentioned steps one is polyvinylpyrrolidone, and model is PVP-K30.
The mass ratio of the tetraethoxysilane described in above-mentioned steps two and methyl methacrylate copolymer maleic acid lithium is preferably 5:1 ~ 1:2.
The molecular weight of the Kynoar described in above-mentioned steps three is M
n=4 × 10
5~ 5 × 10
5.
Nucleocapsid pattern composite nanoparticle described in above-mentioned steps three is preferably 1 ~ 10wt% relative to the doping of Kynoar powder.
Liquid electrolyte described in above-mentioned steps four is that 1M hexafluoro closes lithium phosphate carbonate electrolyte.It is close lithium phosphate by hexafluoro to mix the mixed solution that dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate form that described 1M hexafluoro closes lithium phosphate carbonate electrolyte, and its mass ratio is dimethyl carbonate: methyl ethyl carbonate: vinyl carbonate=1:1:1.
The porous gel method for preparing polymer electrolytes beneficial effect of doped compound nano particle of the present invention is:
The research of traditional composite polymer electrolyte is directly adulterated by inorganic phase to be mixed into organic phase and to prepare composite polymer electrolyte, but inorganic phase is to the conduction of lithium ion not contribution, although play certain ion conducting effect at the interface of organic phase and inorganic phase, its effect is also not obvious.In the present invention, the core-shell structure nanometer particle added, plays the effect reducing its degree of crystallinity on the one hand, makes it be more conducive to the conducting of lithium ion in Kynoar matrix, and due to the existence of inorganic phase, decrease to a certain extent and cause intensity to decline because degree of crystallinity reduces; On the other hand, the compatibility of the polymer lithium salt pair electrolyte added is larger, plays better ion conducting effect; Give full play to the feature of the compound two-phase of composite polymer electrolyte; Finally, the effect of compound, the gel polymer electrolyte system obtained after being conducive to adding liquid electrolyte still keeps better mechanical property.
Research proves that compound two-phase is continuous phase, and domain size is little, and mixing is comparatively even, system stable performance.Its room-temperature ion conductance of the compound porous gel polymer electrolyte of modified Nano of the present invention reaches 10
-3scm
-1the order of magnitude, electrochemical stability window reaches 5.3V.Realistic polymer Li-ion battery instructions for use.
Accompanying drawing explanation
Fig. 1 is the light microscope figure of core-shell structure nanometer particle doping Kynoar composite polymer electrolyte film prepared by the embodiment of the present invention 1;
Fig. 2 is the electrochemical stability window result of core-shell structure nanometer particle doping Kynoar composite polymer electrolyte film prepared by the embodiment of the present invention 1;
Fig. 3 is different proportion core-shell structure nanometer particle doping Kynoar composite polymer electrolyte film AC impedance spectral curve at different temperatures prepared by the embodiment of the present invention 1;
Fig. 4 is the variation relation curve of ionic conductivity along with temperature of core-shell structure nanometer particle doping Kynoar composite polymer electrolyte film prepared by embodiment of the present invention 1-4;
Embodiment
Below by specific embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit content described in detail in claims of the present invention yet.
Embodiment 1
(1) first by 4g methyl methacrylate, 0.196g maleic anhydride mixes according to the ratio of mol ratio 20:1, mixture is scattered in deionized water under high velocity agitation, monomer total amount is 10wt% relative to the mass ratio of deionized water, namely the quality of water is 41.96g, then adding relative to quality 5% in methyl methacrylate and the maleic anhydride i.e. polyvinylpyrrolidone PVP-K30 of 0.21g is dispersant, the mass fraction 3% i.e. potassium peroxydisulfate of 0.126g is initator, heat up 75 DEG C, react 24 hours, 25 DEG C are down to after reaction terminates, add the relative maleic anhydride mole 2 times i.e. lithium hydroxide of 0.096g in reaction system, react 8 hours, product freeze drying, obtain the organic nano powder of methyl methacrylate copolymer maleic acid lithium.
(2) organic nano powder methyl methacrylate copolymer maleic acid lithium 0.3g is scattered in 25ml absolute ethyl alcohol, its mass ratio is made to control at 0.012g/ml, ultrasonic disperse 0.5h, add tetraethoxysilane, wherein tetraethoxysilane and methyl methacrylate copolymer maleic acid lithium mass ratio are 5:1, namely tetraethoxysilane quality is 1.5g, dripping ammoniacal liquor makes regulation system pH value control about 11, react 24h at room temperature 25 DEG C, to obtain shell be silicon dioxide stratum nucleare is the nucleocapsid pattern composite nanoparticle of methyl methacrylate copolymer maleic acid lithium.
(3) be 4 × 10 by molecular weight
5kynoar powder room temperature under dissolve be scattered in N, in dinethylformamide solution, polymer solution concentration scope control is in 1g/ml, stir after 8 hours, being added by nucleocapsid pattern composite nanoparticle is distributed to wherein again, wherein nucleocapsid pattern composite nanoparticle is 1%wt% relative to the doping of Kynoar, and first ultrasonic 0.4h, and then stirring at room temperature 20h is consequently uniformly dispersed completely.After polymer solution leaves standstill de-bubbled, scrape on glass plate, be soaked in aqueous phase with the smooth painting of scraper, adopt immersion precipitation to prepare the composite porous film of composite nanoparticle doping Kynoar, film thickness is about 30 μm.
(4) the composite nanoparticle doping Kynoar composite porous film obtained vacuumizes dry 20 hours at the temperature of 40 DEG C, again in glove box immersion liquid electrolyte (closing lithium phosphate by hexafluoro, to mix the concentration that dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate form be the mixed solution of 1M, and it is dimethyl carbonate in mass ratio: methyl ethyl carbonate: vinyl carbonate=1:1:1 mixes.) 0.5 hour, by controlling soak time, make the liquid electrolyte component of adsorbing in forming account for the 40wt% of gross mass, obtain the final composite gel polymer electrolyte film with loose structure, film thickness is about 30 μm.
Fig. 1 is the light microscope figure of core-shell structure nanometer particle doping Kynoar composite polymer electrolyte film prepared by embodiment 1; Nano particle is dispersed on Kynoar matrix, does not find cluster, and empty size is homogeneous, is evenly distributed.
Fig. 2 is the composite gel polymer electrolyte film linear sweep voltammetry curve test result at room temperature that embodiment 1 prepares (take stainless steel as work positive pole, lithium metal is negative pole and reference electrode, composite gel polymer electrolyte film is sandwiched in period), its electrochemical stability window is 5.4V.
Fig. 3 is that different proportion core-shell structure nanometer particle doping Kynoar composite polymer electrolyte film embodiment 1 prepared is sandwiched between stainless steel electrode, tests the interchange spectral curve obtained at different temperatures.Because what adopt is stainless steel blocking electrode, there is no electrochemical reaction, so the circular arc portion representing electrochemical reaction in impedance spectrum can regard diameter infinity as, show as approximate straight line in the drawings.The resistance R of polymer dielectric is calculated according to the point that Nyquist curve in ac impedance spectroscopy is crossing with real axis on impedance spectrogram
b, by calculating examination
under calculating ionic conductivity (σ) its room temperature of polymer dielectric film, (25 DEG C) ionic conductivity reaches 6.31 × 10
-3scm
-1.
Embodiment 2
(1) first by 4g methyl methacrylate, 0.392g maleic anhydride mixes according to the ratio of mol ratio 10:1, mixture is scattered in deionized water under high velocity agitation, monomer total amount is 5wt% relative to the mass ratio of deionized water, the quality of water is 87.84g, then adding relative to quality 3% in methyl methacrylate and the maleic anhydride i.e. polyvinylpyrrolidone PVP-K30 of 0.132g is dispersant, the mass fraction 2.5% i.e. potassium peroxydisulfate of 0.11g is initator, heat up 85 DEG C, react 6 hours, 25 DEG C are down to after reaction terminates, add the relative maleic anhydride mole 2 times i.e. lithium hydroxide of 0.192g in reaction system, react 6 hours, product freeze drying, obtain the organic nano powder of methyl methacrylate copolymer maleic acid lithium.
(2) organic nano powder methyl methacrylate copolymer maleic acid lithium 0.25g is scattered in 25ml absolute ethyl alcohol, its mass ratio is made to control at 0.01g/ml, ultrasonic disperse 0.5h, add tetraethoxysilane, wherein tetraethoxysilane and methyl methacrylate copolymer maleic acid lithium mass ratio are 3:1, namely tetraethoxysilane quality is 0.75g, dripping ammoniacal liquor makes regulation system pH value control about 9, react 20h at room temperature 25 DEG C, to obtain shell be silicon dioxide stratum nucleare is the nucleocapsid pattern composite nanoparticle of methyl methacrylate copolymer maleic acid lithium.
(3) be 4.5 × 10 by molecular weight
5kynoar powder room temperature under dissolve be scattered in N, in dinethylformamide solution, polymer solution concentration scope control is in 5g/ml, stir after 12 hours, being added by nucleocapsid pattern composite nanoparticle is distributed to wherein again, wherein composite nanoparticle is 0.01wt% relative to the doping of Kynoar, and first ultrasonic 0.1h, and then stirring at room temperature 12h is consequently uniformly dispersed completely.After polymer solution leaves standstill de-bubbled, scrape on glass plate, be soaked in aqueous phase with the smooth painting of scraper, adopt immersion precipitation to prepare the composite porous film of composite nanoparticle doping Kynoar, film thickness is about 50 μm.
(4) the composite nanoparticle doping Kynoar composite porous film obtained vacuumizes dry 8 hours at the temperature of 80 DEG C, again in glove box immersion liquid electrolyte (closing lithium phosphate by hexafluoro, to mix the concentration that dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate form be the mixed solution of 1M, and it is dimethyl carbonate in mass ratio: methyl ethyl carbonate: vinyl carbonate=1:1:1 mixes.) 1 hour, by controlling soak time, make the liquid electrolyte component of adsorbing in forming account for the 70wt% of gross mass, obtain the final composite gel polymer electrolyte film with loose structure, film thickness is about 50 μm.
Embodiment 3
(1) first by 5g methyl methacrylate, 0.98g maleic anhydride mixes according to the ratio of mol ratio 5:1, mixture is scattered in deionized water under high velocity agitation, monomer total amount is 20wt% relative to the mass ratio of deionized water, namely the quality of water is 29.9g, then adding relative to quality 10% in methyl methacrylate and the maleic anhydride i.e. polyvinylpyrrolidone PVP-K30 of 0.598g is dispersant, mass fraction 1% i.e. 0.0598g potassium peroxydisulfate is initator, heat up 100 DEG C, react 10 hours, 25 DEG C are down to after reaction terminates, add the relative maleic anhydride mole 2 times i.e. lithium hydroxide of 0.48g in reaction system, react 24 hours, product freeze drying, obtain the organic nano powder of methyl methacrylate copolymer maleic acid lithium.
(2) organic nano powder methyl methacrylate copolymer maleic acid lithium 12.5g is scattered in 25ml absolute ethyl alcohol, its mass ratio is made to control at 0.5g/ml, ultrasonic disperse 0.5h, add tetraethoxysilane, wherein tetraethoxysilane and methyl methacrylate copolymer maleic acid lithium mass ratio are 1:2, and namely tetraethoxysilane quality is 6.25g, drip ammoniacal liquor and make regulation system pH value control about 8, react 6h at room temperature 25 DEG C, obtaining shell is silicon dioxide (SiO
2) stratum nucleare is the nucleocapsid pattern composite nanoparticle of methyl methacrylate copolymer maleic acid lithium.
(3) be 5 × 10 by molecular weight
5kynoar powder room temperature under dissolve be scattered in N, dinethylformamide (N, dinethylformamide) in solution, polymer solution concentration scope control is in 0.1g/ml, stir after 6 hours, then added by nucleocapsid pattern composite nanoparticle and be distributed to wherein, wherein composite nanoparticle is 10wt% relative to the doping of Kynoar, first ultrasonic 1h, and then stirring at room temperature 24h is consequently uniformly dispersed completely.After polymer solution leaves standstill de-bubbled, scrape on glass plate with the smooth painting of scraper, be soaked in aqueous phase, adopt immersion precipitation to prepare the composite porous film of composite nanoparticle doping Kynoar.
(4) the composite nanoparticle doping Kynoar composite porous film obtained vacuumizes dry 24 hours at the temperature of 60 DEG C, again in glove box immersion liquid electrolyte (closing lithium phosphate by hexafluoro, to mix the concentration that dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate form be the mixed solution of 1M, and it is dimethyl carbonate in mass ratio: methyl ethyl carbonate: vinyl carbonate=1:1:1 mixes.) 0.7 hour, by controlling soak time, make the liquid electrolyte component of adsorbing in forming account for the 60wt% of gross mass, obtain the final composite gel polymer electrolyte film with loose structure, film thickness is about 40 μm.
Embodiment 4
(1) first by 8g methyl methacrylate, 0.98g maleic anhydride mixes according to the ratio of mol ratio 8:1, mixture is scattered in deionized water under high velocity agitation, monomer total amount is 15wt% relative to the mass ratio of deionized water, namely the quality of water is 59.9g, then adding relative to quality 6% in methyl methacrylate and the maleic anhydride i.e. polyvinylpyrrolidone PVP-K30 of 0.539g is dispersant, mass fraction 1.5% i.e. 0.135g potassium peroxydisulfate is initator, heat up 100 DEG C, react 10 hours, 25 DEG C are down to after reaction terminates, add the relative maleic anhydride mole 2 times i.e. lithium hydroxide of 0.48g in reaction system, react 20 hours, product freeze drying, obtain the organic nano powder of methyl methacrylate copolymer maleic acid lithium.
(2) organic nano powder methyl methacrylate copolymer maleic acid lithium 2.5g is scattered in 25ml absolute ethyl alcohol, its mass ratio is made to control at 0.1g/ml, ultrasonic disperse 0.5h, add tetraethoxysilane, wherein tetraethoxysilane and methyl methacrylate copolymer maleic acid lithium mass ratio are 1:1, namely tetraethoxysilane quality is 2.5g, dripping ammoniacal liquor makes regulation system pH value control about 10, react 15h at room temperature 25 DEG C, to obtain shell be silicon dioxide stratum nucleare is the composite nanoparticle of methyl methacrylate copolymer maleic acid lithium.
(3) be 4.5 × 10 by molecular weight
5kynoar powder room temperature under dissolve be scattered in N, dinethylformamide (N, dinethylformamide) in solution, polymer solution concentration scope control is in 0.5g/ml, stir after 10 hours, then added by nucleocapsid pattern composite nanoparticle and be distributed to wherein, wherein nucleocapsid pattern composite nanoparticle is 2wt% relative to the doping of Kynoar, first ultrasonic 0.8h, and then stirring at room temperature 20h is consequently uniformly dispersed completely.After polymer solution leaves standstill de-bubbled, scrape on glass plate with the smooth painting of scraper, be soaked in aqueous phase, adopt immersion precipitation to prepare the composite porous film of composite nanoparticle doping Kynoar.
(4) the composite nanoparticle doping Kynoar composite porous film obtained vacuumizes dry 18 hours at the temperature of 50 DEG C, again in glove box immersion liquid electrolyte (closing lithium phosphate by hexafluoro, to mix the concentration that dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate form be the mixed solution of 1M, and it is dimethyl carbonate in mass ratio: methyl ethyl carbonate: vinyl carbonate=1:1:1 mixes.) 0.9 hour, by controlling soak time, make the liquid electrolyte component of adsorbing in forming account for the 65wt% of gross mass, obtain the final composite gel polymer electrolyte film with loose structure, film thickness is about 45 μm.
Fig. 4 is the ionic conductivity variation with temperature situation of the core-shell structure nanometer particle doping Kynoar composite polymer electrolyte film of embodiment 1-4.Its linear relationship shows, the ionic conductivity of composite gel polymer electrolyte film varies with temperature the Arrhenius equation meeting experiment, meets the universal law of gel polymer electrolyte ionic conduction.Conductive ion carrier is transmitted mutually by the gel phase in system and absorption liquid state in the inner, and macromolecular chain contributes to it around lithium ion folding and separates with macroanion, and polymer segment wriggling can promote lithium ion transmission wherein.The volume of material is expanded along with the rising of temperature, makes the space free volume expansion of ionic conduction, and the energy of ion motion also raises along with the rising of temperature simultaneously, and these factors all promote the motion of conductive ion carrier.Therefore, along with the rising of temperature, R
bdecline.
Claims (9)
1. a porous gel method for preparing polymer electrolytes for doped compound nano particle, it is characterized in that, step is as follows:
Step one, by mix monomer methyl methacrylate, maleic anhydride mixes according to the ratio of mol ratio 1:1 ~ 100:1, then the dispersant of 3 ~ 10wt% relative to methyl methacrylate and maleic anhydride gross mass is added, mixture is scattered in deionized water under high velocity agitation, monomer total amount is 5 ~ 20wt% relative to the mass ratio of deionized water, add the potassium peroxydisulfate relative to mix monomer quality 1 ~ 3wt%, reaction system temperature elevating range is at 60 ~ 100 DEG C, reaction time controls at 6 ~ 24 hours, 25 DEG C are down to after reaction terminates, add the lithium hydroxide of relative maleic anhydride mole 2 times in reaction system, react 6 ~ 10 hours, obtain the organic nano particle of the methyl methacrylate copolymer maleic acid lithium be scattered in aqueous phase, through freeze drying, obtain the organic nano powder of methyl methacrylate copolymer maleic acid lithium,
Step 2, the organic nano powder dispersion of methyl methacrylate copolymer maleic acid lithium that step one obtained are in ethanol, its concentration controls at 0.01g/ml ~ 0.5g/ml, ultrasonic disperse 0.5h, routine tetraethoxysilane in mass ratio: the organic nano powder of methyl methacrylate copolymer maleic acid lithium is that 10:1 ~ 1:10 adds tetraethoxysilane, dripping ammoniacal liquor makes regulation system pH value control between 8 ~ 11, react 6 ~ 24h at room temperature 25 DEG C, obtain the nucleocapsid pattern composite nanoparticle that shell is the methyl methacrylate copolymer maleic acid lithium of silicon dioxide;
Step 3: be scattered in N by dissolving under Kynoar powder room temperature, in dinethylformamide solution, polymer solution concentration controls at 0.1 ~ 5g/ml, stir after 6 ~ 12 hours, then nucleocapsid pattern composite nanoparticle step 2 obtained adds by 0.01 ~ 10wt% of the doping of Kynoar powder and is distributed to wherein ultrasonic 0.1 ~ 1h, then stirring at room temperature 12 ~ 24h; Again polymer solution is left standstill de-bubbled, utilize the smooth painting of scraper to scrape on glass plate, be soaked in aqueous phase, adopt immersion precipitation to prepare the composite porous film of nucleocapsid pattern composite nanoparticle doping Kynoar;
Step 4: the composite porous film of nucleocapsid pattern composite nanoparticle doping Kynoar step 3 obtained first vacuumizes dry 8 ~ 24 hours at the temperature of 40 DEG C ~ 80 DEG C, then immersion liquid electrolyte 0.5 ~ 1 hour in glove box, obtains the composite gel polymer electrolyte film with loose structure that adsorbed liquid electrolyte component accounts for 40 ~ 70wt% of gross mass.
2. according to the porous gel method for preparing polymer electrolytes of a kind of doped compound nano particle according to claim 1, it is characterized in that, the thickness of described film is 30 μm ~ 50 μm.
3., according to the porous gel method for preparing polymer electrolytes of a kind of doped compound nano particle according to claim 1, it is characterized in that, the mol ratio of the methyl methacrylate described in step one and maleic anhydride is preferably 5:1 ~ 20:1.
4. according to the porous gel method for preparing polymer electrolytes of a kind of doped compound nano particle according to claim 1, it is characterized in that, the dispersant described in step one is polyvinylpyrrolidone, and model is PVP-K30.
5. according to the porous gel method for preparing polymer electrolytes of a kind of doped compound nano particle according to claim 1, it is characterized in that, the mass ratio of the tetraethoxysilane described in step 2 and methyl methacrylate copolymer maleic acid lithium is preferably 5:1 ~ 1:2.
6. according to the porous gel method for preparing polymer electrolytes of a kind of doped compound nano particle according to claim 1, it is characterized in that, the molecular weight of the Kynoar described in step 3 is M
n=4 × 10
5~ 5 × 10
5.
7. according to the porous gel method for preparing polymer electrolytes of a kind of doped compound nano particle according to claim 1, it is characterized in that, the nucleocapsid pattern composite nanoparticle described in step 3 is preferably 1 ~ 10wt% relative to the doping of Kynoar powder.
8. according to the porous gel method for preparing polymer electrolytes of a kind of doped compound nano particle according to claim 1, it is characterized in that, the liquid electrolyte described in step 4 is that 1M hexafluoro closes lithium phosphate carbonate electrolyte.
9. according to the porous gel method for preparing polymer electrolytes of a kind of doped compound nano particle according to claim 8, it is characterized in that, it is close lithium phosphate by hexafluoro to mix the mixed solution that dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate form that described 1M hexafluoro closes lithium phosphate carbonate electrolyte, and its mass ratio is dimethyl carbonate: methyl ethyl carbonate: vinyl carbonate=1:1:1.
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| CN110492175A (en) * | 2019-08-13 | 2019-11-22 | 中北大学 | All solid state alkali metal battery organic nano composite electrolyte membrane and preparation method thereof |
| CN113346131A (en) * | 2021-05-12 | 2021-09-03 | 北京理工大学 | Composite polymer gel solid electrolyte, preparation method thereof and application of lithium metal battery |
| CN115732770A (en) * | 2022-12-07 | 2023-03-03 | 北京理工大学 | Flexible self-healing electrolyte membrane, preparation method thereof and battery |
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| CN115732770B (en) * | 2022-12-07 | 2024-07-19 | 北京理工大学 | Flexible self-healing electrolyte membrane, preparation method thereof and battery |
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