CN103311570A - Blended gel polymer electrolyte thin film with porous appearance and preparation method thereof - Google Patents

Blended gel polymer electrolyte thin film with porous appearance and preparation method thereof Download PDF

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CN103311570A
CN103311570A CN2013101745426A CN201310174542A CN103311570A CN 103311570 A CN103311570 A CN 103311570A CN 2013101745426 A CN2013101745426 A CN 2013101745426A CN 201310174542 A CN201310174542 A CN 201310174542A CN 103311570 A CN103311570 A CN 103311570A
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lithium salts
pvdf
hours
gel polymer
liquid electrolyte
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CN103311570B (en
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李为立
邢玉金
杨刚
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Jiangsu University of Science and Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a blended gel polymer electrolyte thin film with porous appearance and a preparation method thereof. In the composition, a blended polymer film comprises a polyether polyurethane lithium salt and PVDF (polyvinylidene fluoride), the range of the weight ratio of the two is (1: 5)-(1: 10), and an adsorbed liquid electrolyte component in the composition accounts for 40-70% by weight of the total weight. The preparation method comprises the following preparation steps of: firstly preparing the polyether polyurethane lithium salt by condensation polymerization, then mixing the polyether polyurethane lithium salt and the PVDF, dissolving in a mixed solution of N' N-dimethylformamide and glycerol, adopting a thermally induced phase separation method to obtain the blended polymer porous film, drying the thin film, then adsorbing the liquid electrolyte, and activating to obtain the blended gel polymer electrolyte thin film, wherein the optimal ion conductivity can achieve 5.63*10<-3>Scm<-1> at the temperature of 30 DEG C, and an electrochemical window achieves 4.8V. A product disclosed by the invention has good prospects when applied to the fields of polymer lithium ion batteries and the like.

Description

Blended gel polymer electrolyte film of a kind of porous pattern and preparation method thereof
Technical field
The present invention relates to a kind of blended gel polymer electrolyte film that is applied to the porous pattern of polymer Li-ion battery, and relate to the preparation method of this blending type gel electrolyte film.
Background technology
The lithium ion battery excellent performance becomes current secondary cell research and development focus.Electrolyte has played key effect in lithium ion battery, its performance is one of key factor that determines battery performance.At present, lithium rechargeable battery generally all uses liquid electrolyte.Yet the restriction of electrolytical heat-resisting, the withstand voltage properties of liquid body; use the easy leakage defect of liquid electrolyte usually can bring the problem of safety in utilization simultaneously, the accident cause just might be over-charging of battery and the liquid electrolyte that causes leaks when catching fire as the Boeing-737 of recent generation.In order to solve above-mentioned hidden danger, people propose to use solid electrolyte to replace liquid electrolyte.Electrolyte leakage and its machinery generally can not take place in solid electrolyte, withstand voltage properties is good, but its ionic conductivity at room temperature generally has only 10-7～10-6S cm-1, is difficult to satisfy real instructions for use.Gel polymer electrolyte not only has as the high ionic conductivity (10 of liquid electrolyte -4～10 -3Scm -1), and have physical properties such as mechanical performance as solid electrolyte, tensile property.Just because of this, gel polymer electrolyte is widely used in lithium ion battery.Tradition porous gel polymer dielectric is generally used for Kynoar (PVDF) or Kynoar copolymerization perfluoropropene (PVDF-HFP) as polymeric matrix, but this base polymer and liquid electrolyte are because molecular structure difference, compatibility is limited, and polymer matrix cuts any ice hardly to ionic conduction in addition.
Based on this, the present invention designs synthetic a kind of being easy to and liquid electrolyte absorption swelling and the Ionomer that simultaneously ionic conduction worked: the EU lithium salts.Research is with itself and PVDF blend and logically be superheated to phase separation method and prepare the porous polymer film, and thin film adsorbs liquid electrolyte swell gelization is to obtain the blended gel polymer dielectric.The EU lithium salts is good with the liquid electrolyte compatibility on the one hand in the polymer blend component, suppresses it and separates out; On the other hand, the disassociation of ion can take place in the EU lithium salts, and itself has ionic conductivity, can further improve the ionic conduction of blended gel polymer dielectric.In the polymer blend component, PVDF and liquid electrolyte compatibility are slightly poor, a main mechanics supporting role in system.Two polyblend film forming, preparation blended gel polymer dielectric has mechanical property and chemical property preferably with guarantee system.
Summary of the invention
The present invention prepares a kind of perforated membrane based on EU lithium salts blend PVDF of porous pattern by thermally induced phase separation, after its adsorptive liquid electrolyte gelization, obtains a kind of blended gel polymer dielectric of porous pattern.Wherein in the blended porous membrane, the quality between EU and the PVDF is 1:5～1:10 than scope, and adsorbed liquid electrolyte accounts for 40～70%wt of its gross mass in the final composition.
In order to achieve the above object, the technical scheme taked of the present invention is:
At first prepare Ionomer EU lithium salts: PEG800 is mixed according to the ratio of mol ratio 1:1.1～1:1.3 with methyl diphenylene diisocyanate (MDI), be warming up to 70～90 ℃, reacted 5～8 hours, under 65～75 ℃ of temperature, add relative MDI mole then and be 10%～30% lithium hydroxide in reaction system, neutralization reaction 4～5 hours obtains the EU lithium salts.
With molecular weight M n=1 * 10 5～1 * 10 7The PVDF powder dissolution in N, in dinethylformamide (DMF) and the glycerol mixed solution according to volume ratio 8:1 composition, stir 12～18 hours under the room temperature until dissolving evenly, the EU lithium salts of Jia Ruing then, the EU lithium salts is 1:5～1:10 with the quality of PVDF than scope.Stirred again 6～12 hours so that dissolving fully, mixture solution concentration is 0.1g/ml, after polymer solution leaves standstill de-bubbled, scrape on glass plate with smooth being coated with of scraper, then in baking oven with 110～150 ℃ of dryings 18～24 hours, the mechanism that is separated according to thermic prepare the porous pattern based on EU lithium salts blend PVDF film.
The porous membrane that obtains vacuumized under 100 ℃～120 ℃ temperature dry 8～12 hours, immersion liquid electrolyte 0.5～1 hour in glove box again, wherein liquid electrolyte be the hexafluoro of 1M concentration close lithium phosphate mix by dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate by 1:1:1 form mixed solution.The adsorbance of control liquid electrolyte makes the adsorbance of liquid electrolyte account for 40%～70%wt of gross mass.
Advantage of the present invention and beneficial effect are:
1, the EU lithium salts on the one hand can effectively adsorb the swelling liquid electrolyte, suppresses liquid electrolyte separating out in use; The dissociable lithium ion that goes out can carry out ionic conduction of EU lithium salts improves system intermediate ion carrier content, to improve the room-temperature ion conductance of blended gel polymer dielectric on the other hand.
2, EU lithium salts and PVDF are dissolved in solvent, prepare porous membrane by thermally induced phase separation, the blend of two kinds of polymeric matrixs, can give full play to the characteristics of the blend two-phase of blended gel polymer dielectric, the blended gel polymer dielectric has higher room-temperature ion conductance when having better mechanical property.
Its room-temperature ion conductance of blended gel polymer dielectric of the present invention reaches the 10-3S cm-1 order of magnitude, and electrochemical stability window reaches 4.8V, realistic polymer Li-ion battery instructions for use.
Description of drawings
Fig. 1 is the flying-spot microscope figure of the EU lithium salts blend PVDF perforated membrane of embodiment 1 preparation;
Fig. 2 is the ac impedance spectroscopy curve chart that the blended gel polymer dielectric of embodiment 1 preparation is tested under different temperatures;
Fig. 3 is the electrochemical stability window result of the blended gel polymer dielectric of embodiment 1 preparation;
Fig. 4 is that the ionic conductivity of blended gel polymer dielectric of embodiment 1-4 preparation is along with the variations in temperature relation curve.
Embodiment
Embodiment 1
(1) 80g PEG800 is mixed with 27.5g MDI, heat up 75 ℃, reacted 7 hours, form performed polymer.With adjustment to 75 ℃, 2.4g LiOH progressively joins in the reaction system then, and reaction was carried out 4 hours, to obtain the EU lithium salts.
(2) be that Mn=1 * 105PVDF powder joins in 60ml DMF and the mixed solution of glycerol according to volume ratio 8:1 composition with the 5g molecular weight, stir under the room temperature after 12 hours, add EU lithium salts 1g and stirred again 12 hours so that dissolve fully.Polymer solution leaves standstill de-bubbled, scrape on glass plate with smooth being coated with of scraper again, then in baking oven with 110 ℃ of dryings 24 hours, by thermally induced phase separation prepare the porous pattern based on EU lithium salts blend PVDF film.
(3) with vacuumize dry 8 hour of EU lithium salts blend PVDF film at 120 ℃, the hexafluoro that soaks 1M concentration again in glove box closes lithium phosphate and mixed the liquid electrolyte be made up of by 1:1:1 dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate 1 hour, the adsorbance of liquid electrolyte accounts for the 70%wt of gross mass, to obtain the final blended gel polymer electrolyte film based on EU lithium salts blend PVDF.
Fig. 1 is the ESEM picture of the EU lithium salts blend PVDF perforated membrane for preparing of embodiment 1, and the mixture two-phase mixes, and obvious two-phase incompatibility is not arranged, the cluster phenomenon takes place occur; Pore size homogeneous in the thin polymer film and being evenly distributed is conducive to the absorption of liquid electrolyte, with the guarantee system stable performance.
Fig. 2 is sandwiched in the blended gel polymer electrolyte film based on EU lithium salts blend polyvinylidene fluoride (PVDF) that embodiment 1 prepares between the stainless steel electrode, the interchange spectral curve that test obtains under different temperatures.Because what adopt is the stainless steel blocking electrode, there is not electrochemical reaction, can regard the diameter infinity as so in impedance spectrum, represent the circular arc portion of electrochemical reaction, show as approximate straight line in the drawings.Calculate the resistance R of polymer dielectric according to the crossing point of real axis on Nyquist curve in the ac impedance spectroscopy and the impedance spectrogram b, by Examination is calculated based on the ionic conductivity (σ) of the blended gel polymer electrolyte film of EU lithium salts blend polyvinylidene fluoride (PVDF) (wherein, L is film thickness, A is the area of film), (30 ℃) ionic conductivity reaches 3.87 * 10 under its room temperature -3S cm -1
What Fig. 3 prepared for embodiment 1 (is that work positive pole, lithium metal are negative pole and reference electrode with the stainless steel based at room temperature linear scan volt-ampere curve test result of the blended gel polymer electrolyte film of EU lithium salts blend polyvinylidene fluoride (PVDF), during EU lithium salts blend PVDF gel polymer electrolyte film is sandwiched in), its electrochemical stability window is 4.8V.
Embodiment 2
(1) 80g PEG800 is mixed with 32.5g MDI, heat up 90 ℃, reacted 5 hours, form performed polymer.With adjustment to 70 ℃, 7.2g LiOH progressively joins in the reaction system then, and reaction was carried out 4.5 hours, to obtain the EU lithium salts.
(2) be that Mn=1 * 106PVDF powder joins in 110ml DMF and the mixed solution of glycerol according to volume ratio 8:1 composition with the 10g molecular weight, stir under the room temperature after 18 hours, add EU lithium salts 1g, stirred again 8 hours, so that dissolving fully.Polymer solution leaves standstill de-bubbled, scrape on glass plate with smooth being coated with of scraper again, then in baking oven with 150 ℃ of dryings 18 hours, by thermally induced phase separation prepare the porous pattern based on EU lithium salts blend PVDF film.
(3) with vacuumize dry 10 hour of EU lithium salts blend PVDF film at 110 ℃, the hexafluoro that soaks 1M concentration again in glove box closes lithium phosphate and mixed the liquid electrolyte be made up of by 1:1:1 dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate 0.8 hour, the adsorbance of liquid electrolyte accounts for the 60%wt of gross mass, to obtain the final blended gel polymer electrolyte film based on EU lithium salts blend PVDF.
Embodiment 3
(1) 80g PEG800 is mixed with 30g MDI, heat up 70 ℃, reacted 8 hours, form performed polymer.With adjustment to 65 ℃, 4.8g LiOH progressively joins in the reaction system then, and reaction was carried out 5 hours, to obtain the EU lithium salts.
(2) be M with the 8g molecular weight n=1 * 10 7The PVDF powder joins in 90ml DMF and the mixed solution of glycerol according to volume ratio 8:1 composition, stirs under the room temperature after 15 hours, adds EU lithium salts 1g, stirs 6 hours, so that dissolving fully again.Polymer solution leaves standstill de-bubbled, scrape on glass plate with smooth being coated with of scraper again, then in baking oven with 120 ℃ of dryings 20 hours, by thermally induced phase separation prepare the porous pattern based on EU lithium salts blend PVDF film.
(3) with vacuumize dry 9 hour of EU lithium salts blend PVDF film at 115 ℃, the hexafluoro that soaks 1M concentration again in glove box closes lithium phosphate and mixed the liquid electrolyte be made up of by 1:1:1 dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate 0.6 hour, the adsorbance of liquid electrolyte accounts for the 50%wt of gross mass, to obtain the final blended gel polymer electrolyte film based on EU lithium salts blend PVDF.
Embodiment 4
(1) 80g PEG800 is mixed with 27.5g MDI, heat up 85 ℃, reacted 6 hours, form performed polymer.Under this temperature 2.4g LiOH is progressively joined in the reaction system then, reaction was carried out 5 hours, to obtain the EU lithium salts.
(2) be M with the 7g molecular weight n=6 * 10 5The PVDF powder joins in 80ml DMF and the mixed solution of glycerol according to volume ratio 8:1 composition, stirs under the room temperature after 12 hours, adds EU lithium salts 1g, stirs 12 hours, so that dissolving fully again.Polymer solution leaves standstill de-bubbled, scrape on glass plate with smooth being coated with of scraper again, then in baking oven with 110 ℃ of dryings 24 hours, by thermally induced phase separation prepare the porous pattern based on EU lithium salts blend PVDF film.
(3) with vacuumize dry 12 hour of EU lithium salts blend PVDF film at 110 ℃, the hexafluoro that soaks 1M concentration again in glove box closes lithium phosphate and mixed the liquid electrolyte be made up of by 1:1:1 dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate 0.5 hour, the adsorbance of liquid electrolyte accounts for the 40%wt of gross mass, to obtain the final blended gel polymer electrolyte film based on EU lithium salts blend PVDF.
Fig. 4 be embodiment 1-4 based on the ionic conductivity of the blended gel polymer electrolyte film of EU lithium salts blend polyvinylidene fluoride (PVDF) with the variation of temperature situation.Its linear relationship shows that the ionic conductivity of this blended gel polymer electrolyte film varies with temperature consistent with the Arrhenius equation of testing, and meets the universal law of gel polymer electrolyte ionic conduction.As everyone knows, temperature raises and causes material volume to expand, and causes producing the more freedom space, promotes the migration of polymer segment and lithium ion.In addition, along with the rising of temperature, R bReduce.This phenomenon has shown that also charge carrier from the polymer segment motion with shifting the decomplexing activation takes place.Common this phenomenon can be observed in liquid electrolyte and gel polymer electrolyte.

Claims (3)

1. the blended gel polymer electrolyte film of a porous pattern, the polymer blend film that it is characterized in that the porous pattern in its composition is EU lithium salts and PVDF, quality between the two is 1:5～1:10 than scope, 40～70%wt of adsorbed liquid electrolyte ingredients constitute gross mass in the composition.
2. the preparation method of the blended gel polymer electrolyte film of a kind of porous pattern as claimed in claim 1 is characterized in that comprising the steps:
Step 1: preparation EU lithium salts: PEG800 is mixed according to the ratio of mol ratio 1:1.1～1:1.3 with methyl diphenylene diisocyanate (MDI), be warming up to 70～90 ℃, condensation polymerization reaction 5～8 hours, under 65～75 ℃ of temperature, add relative MDI mole then and be 10%～30% lithium hydroxide in reaction system, neutralization reaction 4～5 hours obtains the EU lithium salts;
Step 2: with molecular weight M n=1 * 10 5～1 * 10 7The PVDF powder dissolution in N, in dinethylformamide (DMF) solution, stir under the room temperature and add the EU lithium salts after 12～18 hours, its EU lithium salts is 1:5～1:10 with respect to the quality of PVDF than scope, stirred again 6～12 hours so that dissolving fully, mixture solution concentration is 0.1g/ml, after polymer solution leaves standstill de-bubbled, scrape on glass plate with smooth being coated with of scraper, then in baking oven with 110 ℃ of dryings 18～24 hours, adopt thermally induced phase separation to prepare the EU lithium salts blend PVDF film of porous pattern;
Step 3: the EU lithium salts blend PVDF perforated membrane that step 2 is prepared vacuumized under 110 ℃～120 ℃ temperature dry 8～12 hours, immersion liquid electrolyte 0.5～1 hour in glove box again, the adsorbance of control liquid electrolyte, adsorbed liquid electrolyte ingredients constitute gross mass 40～70%wt in feasible the composition is to obtain the blended gel polymer dielectric.
3. the preparation method of the blended gel polymer electrolyte film of a kind of porous pattern according to claim 2 is characterized in that: the described liquid electrolyte of step 3 be the hexafluoro of 1M concentration close lithium phosphate mix by dimethyl carbonate, methyl ethyl carbonate and vinyl carbonate by 1:1:1 form mixed solution.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104900913A (en) * 2015-05-12 2015-09-09 江苏科技大学 Preparation method of porous fiber gel polymer electrolyte
CN108630987A (en) * 2017-03-17 2018-10-09 四川大学 A kind of gel polymer electrolyte and its preparation method and application
CN110951036A (en) * 2019-12-29 2020-04-03 太原理工大学 Casting polyurethane elastomer electrolyte and preparation method thereof
CN111786016A (en) * 2019-04-03 2020-10-16 深圳格林德能源集团有限公司 Fluorine-containing polyurethane solid composite electrolyte and preparation method thereof
CN115000349A (en) * 2022-06-27 2022-09-02 中国电子科技集团公司第十八研究所 Metal lithium cathode coated with phase separation polymer protective film and preparation method thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104900913A (en) * 2015-05-12 2015-09-09 江苏科技大学 Preparation method of porous fiber gel polymer electrolyte
CN108630987A (en) * 2017-03-17 2018-10-09 四川大学 A kind of gel polymer electrolyte and its preparation method and application
CN111786016A (en) * 2019-04-03 2020-10-16 深圳格林德能源集团有限公司 Fluorine-containing polyurethane solid composite electrolyte and preparation method thereof
CN111786016B (en) * 2019-04-03 2021-08-03 深圳格林德能源集团有限公司 Fluorine-containing polyurethane solid composite electrolyte and preparation method thereof
CN110951036A (en) * 2019-12-29 2020-04-03 太原理工大学 Casting polyurethane elastomer electrolyte and preparation method thereof
CN115000349A (en) * 2022-06-27 2022-09-02 中国电子科技集团公司第十八研究所 Metal lithium cathode coated with phase separation polymer protective film and preparation method thereof

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