CN103682432A - Gel polymer electrolyte and preparation method thereof, and electrochemical power source and application thereof - Google Patents

Gel polymer electrolyte and preparation method thereof, and electrochemical power source and application thereof Download PDF

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CN103682432A
CN103682432A CN201210360673.9A CN201210360673A CN103682432A CN 103682432 A CN103682432 A CN 103682432A CN 201210360673 A CN201210360673 A CN 201210360673A CN 103682432 A CN103682432 A CN 103682432A
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polymer electrolyte
gel polymer
molecular sieve
mesoporous molecular
methoxy ethyl
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周明杰
刘大喜
王要兵
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The invention discloses a gel polymer electrolyte and a preparation method thereof, and an electrochemical power source and application thereof. The gel polymer electrolyte contains an N-methoxyethylpiperidine low-temperature fused salt, a lithium salt, polyvinyl acetate and a mesoporous molecular sieve SBA-15 in a mass ratio of (0.5-1.5):(0.1-0.3):1:(0.1-0.2). The preparation method comprises the following steps: acquiring the mesoporous molecular sieve SBA-15, preparing a first mixed solution containing the polyvinyl acetate, preparing a second mixed solution containing the mesoporous molecular sieve SBA-15, and casting the second mixed solution into a film. The electrochemical power source contains the gel polymer electrolyte. The gel polymer electrolyte has the advantages of high mechanical strength and high conductivity; and the preparation method has the advantages of simple technique, mature technology, high yield and high efficiency. The electrochemical power source containing the gel polymer electrolyte has the advantages of high yield, low production cost, excellent electrochemical properties and wider application range.

Description

Gel polymer electrolyte and preparation method thereof, electrochemical power source and application thereof
Technical field
The invention belongs to electrochemical power source technical field, be specifically related to a kind of gel polymer electrolyte and preparation method thereof, electrochemical power source and application thereof.
Background technology
Lithium ion battery is the advantage such as volume is little, lightweight, high power capacity, memory-less effect owing to having, thereby is widely used in the fields such as mobile phone, mobile phone, military affairs and electric automobile.
Lithium-ion battery electrolytes is divided into organic liquid electrolyte and polymer dielectric.The advantage of now widely used liquid electrolyte is that conductivity is high, but inflammable owing to containing, volatile organic solvent, it discharges fuel gas in charge and discharge process, particularly under some unconventional condition of work, (as high-power, discharge and recharge, super-charge super-discharge etc.) produces the generation that gas is accelerated in large calorimetric meeting, cause inner pressure of battery to increase, Leakage Gas, blast even on fire, thereby there is serious potential safety hazard.
At present, in order to overcome the above-mentioned defect of organic liquid electrolyte, solid gel polymer dielectric is developed in this area.This solid polymer electrolyte because thering is safety, without leaking, leakage current is little, can arbitrary shape etc. the studied persons of advantage pay attention to and apply.But under solid polymer electrolyte room temperature, conductivity is lower by (10 -5~ 10 -4s/cm), can not meet the characteristic of lithium ion battery high current charge-discharge, cause its application to be restricted.
In order to overcome the defect that solid polymer electrolyte conductivity is low, the current gel polymer electrolyte that occurred, this gel polymer electrolyte has advantages of liquid electrolyte and solid electrolyte, can improve the security performance of electric conductivity and the raising liquid electrolyte of solid polymer electrolyte.But it is that its mechanical strength is low that gel polymer electrolyte exists a major defect, therefore, the industrialization that has restricted this gel polymer electrolyte is produced, and causes the production cost of existing gel polymer electrolyte high.Mainly by copolymerization, grafting, generate the mechanical strength that the means such as cross-linked copolymer, dopen Nano metal oxide can improve polymer dielectric to a certain extent at present.But effect is not very desirable, battery rate of finished products is not high.In addition, existing gel polymer electrolyte improves limited to electric conductivity, be not well positioned to meet market to the demand of lithium battery expanding day and range of application.
Summary of the invention
The object of the embodiment of the present invention is to overcome the above-mentioned deficiency of prior art, and gel polymer electrolyte that a kind of mechanical strength and conductance are high and preparation method thereof is provided.
Another object of the embodiment of the present invention is to provide a kind of electrochemical power source and application thereof that comprises gel polymer electrolyte.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A gel polymer electrolyte, contains N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 component; Wherein, the mass ratio of N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 is (0.5 ~ 1.5): (0.1 ~ 0.3): 1:(0.1 ~ 0.2).
And above-mentioned method for preparing gel polymer electrolyte, comprises the steps:
Obtain mesoporous molecular sieve SBA-15;
N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate and organic solvent mix and blend are dissolved, obtain the first mixed liquor;
Described mesoporous molecular sieve SBA-15 is added in described the first mixed liquor, and ultrasonic processing, obtains the second mixed liquor;
By described the second mixed liquor casting film, dry processing, obtains described gel polymer electrolyte;
Wherein, the mass ratio of described N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, organic solvent, polyvinyl acetate and mesoporous molecular sieve SBA-15 is (0.5 ~ 1.5): (0.1 ~ 0.3): (1 ~ 3): 1:(0.1 ~ 0.2).
And, a kind of electrochemical power source, described electrochemical power source comprises above-mentioned gel polymer electrolyte.
And, above-mentioned electrochemical power source at mobile terminal product, electric automobile, electrical network, communication equipment, electric tool or/and the application in light fixture.
Above-mentioned gel polymer electrolyte is with polyvinyl acetate matrix, take mesoporous molecular sieve SBA-15 as filler, the N-methoxy ethyl piperidines low-temperature molten salt of take is plasticizer, and by the synergy between N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15, make above-mentioned gel polymer electrolyte conductance high, good mechanical property also makes this gel polymer electrolyte stable chemical performance simultaneously, safe.
Above-mentioned method for preparing gel polymer electrolyte only need be mixed with slurry on request by N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, organic solvent, mesoporous molecular sieve SBA-15 and polyvinyl acetate, then casting film, dry processing, its technique is simple, technology maturation, rate of finished products and efficiency are high, effectively reduce production cost.
Above-mentioned electrochemical power source, due to the gel polymer electrolyte that adopts said method to prepare, because this gel polymer electrolyte has high conductance, thereby has effectively improved electrochemical power supply chemical property, as specific discharge capacity and efficiency for charge-discharge.The high-mechanical property that this gel polymer electrolyte has and low production cost, effectively improved the rate of finished products of this electrochemical power source, reduced the production cost of electrochemical power source, thereby make this electrochemical power source can realize industrialization, produces.
Just because of this electrochemical power source, there is excellent chemical property, thereby effectively expanded the range of application of above-mentioned electrochemical power source.By this electrochemical power source at mobile terminal product, electric automobile, electrical network, communication equipment, electric tool or/and during application in light fixture, this electrochemical power source can be effectively provides stable and lasting electric energy for the operational module in computer, electric automobile, communication equipment, electronic toy and the light source in light fixture, the replacement frequency that reduces electrochemical power source, has reduced this mobile terminal product, electric automobile, electrical network, communication equipment, electric tool or/and the use cost of light fixture.
Accompanying drawing explanation
Fig. 1 is inventive embodiments method for preparing gel polymer electrolyte process chart.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of mechanical strength and the high gel polymer electrolyte of conductance.This gel polymer electrolyte comprises N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 component; Wherein, the mass ratio of N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 is (0.5 ~ 1.5): (0.1 ~ 0.3): 1:(0.1 ~ 0.2).
Particularly, above-mentioned polyvinyl acetate has good film forming and thermal stability and electrochemical stability, matrix as this gel polymer electrolyte, under the acting in conjunction of N-methoxy ethyl piperidines low-temperature molten salt and mesoporous molecular sieve SBA-15, give this gel polymer electrolyte good electrochemical stability performance and mechanical performance.In order further to obtain good mechanical performance and chemically stable gel polymer electrolyte, as preferred embodiment, it is 2～100,000 that this polyvinyl acetate is selected number-average molecular weight.Certainly, iff the film forming of considering polymer, this polyvinyl acetate can also adopt polyvinyl chloride to substitute.
Above-mentioned N-methoxy ethyl piperidines low-temperature molten salt is in embodiments of the present invention as plasticizer function, and this dielectric constant is high, electrode stability good, the more important thing is and polyvinyl acetate matrix between compatibility well.Therefore, this N-methoxy ethyl piperidines low-temperature molten salt and the effect of polyvinyl acetate matrix, effectively improve the mechanical performances such as pliability and the electric conductivity of this gel polymer electrolyte.In a preferred embodiment, this N-methoxy ethyl piperidines low-temperature molten salt is selected from least one in two (fluoroform sulphonyl) inferior amine salts of N-methoxy ethyl-N-methyl piperidine, N-methoxy ethyl-N-methyl piperidine fluoroform sulphonate, two (fluorine sulphonyl) inferior amine salts of N-methoxy ethyl-N-methyl piperidine, N-methoxy ethyl-N-methyl piperidine tetrafluoroborate, N-methoxy ethyl-N-methyl piperidine hexafluorophosphate.This preferred N-methoxy ethyl piperidines low-temperature molten salt can improve this gel polymer electrolyte mechanical performance significantly.Certainly, if can reduce the requirement to mechanical performance, this N-methoxy ethyl piperidines low-temperature molten salt can also be selected well known in the art and be suitable for other N-methoxy ethyl piperidines low-temperature molten salts in the embodiment of the present invention.
Above-mentioned mesoporous molecular sieve SBA-15 is in embodiments of the present invention as filler function, the existence of this mesoporous molecular sieve SBA-15, because mesoporous molecular sieve SBA-15 and polyvinyl acetate polymer matrix have good compatibility, by interacting with this polymeric matrix, increase the content of system amorphous region, thereby improved the wriggling ability of molecule segment.Thereby can increase the conductivity of gel polymer electrolyte.In addition, mesoporous molecular sieve SBA-15 is entrained in this gel polymer electrolyte uniformly, and together with plasticizer, significantly improves the electric conductivity of this gel polymer electrolyte.Meanwhile, this mesoporous molecular sieve SBA-15 can also improve this gel polymer electrolyte mechanical strength.This mesoporous molecular sieve SBA-15 can be commercial, also can adopt method hereinafter to prepare voluntarily.
Above-mentioned lithium salts is preferably selected from LiBF 4, LiPF 6, LiTFSI, LiCF 3sO 3in at least one.This preferred lithium salts can effectively provide lithium ion.Certainly, this lithium salts can also be selected other lithium salts well known in the art.
As preferred embodiment, the thickness of above-mentioned gel polymer electrolyte is preferably 50～200 μ m.This preferred thickness can make this gel polymer electrolyte not only have good mechanical performance simultaneously but also have less quality, makes the electrochemical capacitor that contains this gel polymer electrolyte both have higher rate of finished products and higher energy density.
From the above mentioned, gel polymer electrolyte in above-described embodiment is with polyvinyl acetate matrix, take mesoporous molecular sieve SBA-15 as filler, the N-methoxy ethyl piperidines low-temperature molten salt of take is plasticizer, and by N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate, synergy between mesoporous molecular sieve SBA-15, make above-mentioned gel polymer electrolyte conductance high, good mechanical property, data in the concrete table that vide infra, compare with existing gel polymer electrolyte, conductance is significantly improved, the conductance that has effectively overcome existing gel polymer electrolyte is low, the defect that mechanical strength is not high.Also make this gel polymer electrolyte stable chemical performance simultaneously, safe.
Correspondingly, the embodiment of the present invention also provides the preparation method that a kind of technique is simple, cost is low of above-mentioned gel polymer electrolyte.As shown in Figure 1, it comprises the steps: in this method for preparing gel polymer electrolyte technological process
Step S01. obtains mesoporous molecular sieve SBA-15;
Step S02. preparation contains the first mixed liquor of polyvinyl acetate: N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate and organic solvent mix and blend are dissolved, obtain the first mixed liquor;
Step S03. preparation contains the second mixed liquor of mesoporous molecular sieve SBA-15: described mesoporous molecular sieve SBA-15 is added in described the first mixed liquor, and ultrasonic processing, obtains the second mixed liquor;
Step S04. is by the second mixed liquor casting film: by described the second mixed liquor casting film, vacuumize, obtains described gel polymer electrolyte;
Particularly, in above-mentioned steps S01, the acquisition methods of mesoporous molecular sieve SBA-15 can be commercial, also can prepare and obtain voluntarily.When preparation is obtained voluntarily, its concrete preparation method is as follows:
Step S011: triblock copolymer P123 be dissolved in the solution (containing dense inorganic aqueous acid) of deionized water and dense inorganic acid and be uniformly mixed, then dripping tetraethoxysilane, continuing to stir 24～48h, forming homogeneous phase solution;
Step S012: add acetic acid in the homogeneous phase solution of preparing in step S011, and continue stirring reaction 8～24h at 30～60 ℃;
Step S013: the reaction solution in step S012 is moved in the autoclave with polytetrafluoroethylsubstrate substrate, and then crystallization 20～60h at 90～120 ℃, cooling, suction filtration, washing, dry, the crystalline product obtaining;
Step S014: the crystalline product obtaining in step S013, at 400～700 ℃ of calcining 4～12h, is obtained to mesoporous molecular sieve SBA-15;
P123 in above-mentioned steps S011 to S014, H 2the mass ratio of O, the acid of dense inorganic acid, tetraethoxysilane, acetic acid consumption is 1:1.5～3:6～8:1～3:0.2～0.7.
Wherein, the triblock copolymer P123 mean molecule quantity in above-mentioned steps S011 is preferably 5800, and dense inorganic acid acid is preferably selected from concentrated hydrochloric acid.The mode that drips tetraethoxysilane should drip while stirring slowly, and triblock copolymer P123, tetraethoxysilane are dissolved completely.Cooling in step S013, suction filtration, washing all can be processed according to the conventional method in this area, and wherein, dry temperature is preferably 90～120 ℃, is preferably 24～48 hours drying time.The object of step S014 calcining is in order to remove triblock copolymer P123, finally obtains white powder mesoporous molecular sieve SBA-15.
Particularly, in above-mentioned steps S02, the mixing of N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate and organic solvent preferably first mixes N-methoxy ethyl piperidines low-temperature molten salt, lithium salts and organic solvent, then add polyvinyl acetate, stir until polyvinyl acetate dissolves completely, to obtain even the first mixed solution.Wherein, organic solvent is preferably at least one in acetonitrile, 1-METHYLPYRROLIDONE (NMP), THF, ethanol, and certainly, this organic solvent also can be selected from other organic solvents well known in the art and that can make polyvinyl acetate dissolve.N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate are selected material as described above separately, in order to save length, do not repeat them here.
The time of the ultrasonic processing in above-mentioned steps S03 is preferably 15～45min.This ultrasonic processing can make each component in mesoporous molecular sieve SBA-15 and the first mixed liquor be dispersed in the second mixed liquor.
N-methoxy ethyl piperidines low-temperature molten salt in above-mentioned steps S02, step S03, lithium salts, organic solvent, mesoporous molecular sieve SBA-15 and the reinforced mass ratio of polyvinyl acetate are (0.5 ~ 1.5): (0.1 ~ 0.3): (1 ~ 3): 1:(0.1 ~ 0.2).According to this preferred proportion, each component is mixed, can obtain dispersed and each second mutually stable mixed liquor, can also make the last gel polymer electrolyte electric conductivity obtaining and mechanical performance excellent.As preferred embodiment, this N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, organic solvent, mesoporous molecular sieve SBA-15 and the reinforced mass ratio of polyvinyl acetate are (0.7 ~ 1.2): (0.18 ~ 0.22): (1.5 ~ 2.5): 1:(0.14 ~ 0.16).
The mode of the casting film in above-mentioned steps S04 can select method well known in the art to carry out, as the second mixed liquor of step S03 preparation is cast in to glass plate film forming.The thickness that the amount of this second mixed liquor casting is preferably the rear gained gel polymer electrolyte of drying processing is 50～200 μ m.
The dry vacuum drying mode that preferably adopts of processing of this step S04, its vacuum drying temperature is preferably 80-100 ℃, and vacuum degree can be 0.01MPa, if certain conditions permit, vacuum degree is more high better.This dry processing, can effectively remove organic solvent, accelerates rate of drying, and its dry time is preferably 24～36h.
From the above mentioned, above-mentioned method for preparing gel polymer electrolyte only need be mixed with slurry on request by N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, organic solvent, mesoporous molecular sieve SBA-15 and polyvinyl acetate, then casting film, dry processing, its technique is simple, technology maturation, rate of finished products and efficiency are high, effectively reduce production cost.
The embodiment of the present invention also provides a kind of electrochemical power source, and this electrochemical power source comprises gel polymer electrolyte mentioned above.
As preferred embodiment, this electrochemical power source is lithium polymer battery or gel polymer electrolyte capacitor.
Particularly, when electrochemical power source is lithium polymer battery, the preparation method of this lithium polymer battery is as follows:
Step S05. prepares gel polymer electrolyte: this gel polymer electrolyte is gel polymer electrolyte preparation method be by mentioned earlier prepared from;
Step S06. prepares battery battery core: step S05 is prepared to gel polymer electrolyte and according to positive pole/gel polymer electrolyte/negative pole overlapped way, stack gradually, and reel, make battery battery core;
Step S07. packaged battery: step S06 is prepared to battery battery core and pack in battery container, sealing, makes lithium polymer battery.
Packaged battery method in above-mentioned steps S06 in the preparation method of positive and negative electrode and the preparation method of battery battery core and step S07 all can be according to the method preparation of this area routine.In addition, the battery battery core in step S06 can be circular or other shapes that need according to different lithium battery.
When electrochemical power source is gel polymer electrolyte capacitor, the preparation method of this gel polymer electrolyte capacitor is as follows:
Step S08. prepares gel polymer electrolyte: this gel polymer electrolyte is gel polymer electrolyte preparation method be by mentioned earlier prepared from;
Step S09. prepares battery core: step S08 is prepared to gel polymer electrolyte and according to electrode/gel polymer electrolyte/electrode overlapped way, stack gradually, and reel, make battery core;
Step S10. encapsulated capacitor: step S09 is prepared to battery core and pack in capacitor casing, sealing, makes gel polymer electrolyte capacitor.
Encapsulated capacitor method in above-mentioned steps S09 in the preparation method of electrode and the preparation method of battery core and step S10 all can be according to the method preparation of this area routine.In addition, the battery core in step S09 can be circular or other shapes that need according to different lithium capacitor.
Above-mentioned electrochemical power source, due to the gel polymer electrolyte that adopts said method to prepare, because this gel polymer electrolyte has high conductance, thereby has effectively improved the charge-discharge performance of electrochemical power source.The high-mechanical property that this gel polymer electrolyte has and low production cost, effectively improved the rate of finished products of this electrochemical power source, reduced the production cost of electrochemical power source, thereby make this electrochemical power source can realize industrialization, produces.This electrochemical power source preparation method technology is ripe in addition, and condition is easily controlled, and qualification rate is high.
The embodiment of the present invention further provides the range of application of above-mentioned electrochemical power source, and this range of application comprises that mobile terminal product, electric automobile, electrical network, communication equipment, electric tool are or/and light fixture etc.As when electrochemical power source is lithium polymer battery, the application of this lithium polymer battery in communication equipment.Particularly, this communication equipment comprises operational module and supply module.Wherein, supply module provides electric energy for operational module, and it comprises lithium polymer battery mentioned above, and this lithium polymer battery can be one or more.When supply module comprises plural lithium polymer battery, this lithium polymer battery can be according to the needs of the required electric energy of operational module, with in parallel or series connection or and series connection.The electric energy operation that this operational module is used supply module to provide.Like this, just because of this electrochemical power source, there is excellent charge-discharge performance, thereby effectively expanded the range of application of above-mentioned electrochemical power source.By this electrochemical power source at mobile terminal product, electric automobile, electrical network, communication equipment, electric tool or/and during application in light fixture, this electrochemical power source can be effectively provides stable and lasting electric energy for the operational module in mobile terminal product, electric automobile, electrical network, communication equipment, electric tool and the light source in light fixture, the replacement frequency that reduces electrochemical power source, has reduced this mobile terminal product, electric automobile, electrical network, communication equipment, electric tool or/and the use cost of light fixture.
By a plurality of embodiment, illustrate below the aspects such as above-mentioned gel polymer electrolyte and preparation method thereof, electrochemical power source and application thereof.
Embodiment 1
Gel polymer electrolyte and preparation method thereof, this gel polymer electrolyte is preparation method comprise the steps:
The preparation of step 11. mesoporous molecular sieve SBA-15:
Step 111: by 10g triblock copolymer P123 (triblock copolymer poly-(1,2-ethylidene glycol)-block-poly-(propylene glycol)-block-poly-(1,2-ethylidene glycol), mean molecule quantity 5800) be dissolved in deionized water (20g) and concentrated hydrochloric acid solution (70g) and be uniformly mixed, then drip lentamente tetraethoxysilane (20g), continue to stir 36h, form homogeneous phase solution;
Step 112: add acetic acid (5g) in the homogeneous phase solution of preparing in step S111, and continue stirring reaction 24h at 40 ℃;
Step 113: reaction solution in step S112 is moved in the autoclave of polytetrafluoroethylsubstrate substrate, then crystallization 48h at 100 ℃, cooling, by the crystalline product suction filtration obtaining, washing and in 100 ℃ of dry 24h, the crystalline product obtaining;
Step 114: the crystalline product obtaining in step S113, at 550 ℃ of calcining 6h, is removed to triblock copolymer, obtain mesoporous molecular sieve SBA-15 white powder;
Step 12. preparation contains the first mixed liquor of polyvinyl acetate:
Two (fluoroform sulphonyl) inferior amine salts of 10g N-methoxy ethyl-N-methyl piperidine, 2.5g LiTFSI and 20g NMP (methyl pyrrolidone) are stirred, then in system, add 10g polyvinyl acetate (molecular weight 2-10 ten thousand), lasting stirring is dissolved polyvinyl acetate, obtains the first mixed liquor;
Step S13. preparation contains the second mixed liquor of mesoporous molecular sieve SBA-15:
Mesoporous molecular sieve SBA-15 1.5g prepared by step S11 adds in step S12 preparation ability the first mixed liquor, and ultrasonic 30min, is dispersed in polymer solution SBA-15, obtains the second mixed liquor;
Step S14. is by the second mixed liquor casting film:
The homodisperse polymer solution of the second mixed liquor of step S13 preparation is cast on clean glass plate, then at 100 ℃, 0.01MPa, after being dried under vacuum, obtain being compounded with the polyvinyl acetate ester group gel polymer electrolyte of mesoporous molecular sieve SBA-15.
The gel polymer electrolyte being prepared by this embodiment 1 contains two (fluoroform sulphonyl) inferior amine salts of N-methoxy ethyl-N-methyl piperidine, LiTFSI lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 component; Wherein, the mass ratio of two (fluoroform sulphonyl) inferior amine salts of N-methoxy ethyl-N-methyl piperidine, LiTFSI lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 is 10:2.5:10:1.5.The thickness of this gel polymer electrolyte is 120 μ m.
The preparation of lithium polymer battery:
Anodal preparation: take 9g LiFePO 4, 0.5g acetylene black and 0.5g PVDF, and add 80gNMP, fully stir and make it to become the slurry mixing, then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into LiFePO in 10～15MPa pressure lower roll 4positive electrode, and be cut into anodal disk;
Negative pole: using lithium sheet as negative pole;
After respectively the stacked order of the gel polymer electrolyte positive/gel polymer electrolyte/negative pole of positive pole, negative pole and the present embodiment 1 preparation being stacked gradually, pack in battery container, on stamping machine, button cell is made in sealing.
Embodiment 2
Gel polymer electrolyte and preparation method thereof, this gel polymer electrolyte is preparation method comprise the steps:
The preparation of step 21. mesoporous molecular sieve SBA-15:
Step 211: by 10g triblock copolymer P123 (triblock copolymer poly-(1,2-ethylidene glycol)-block-poly-(propylene glycol)-block-poly-(1,2-ethylidene glycol), mean molecule quantity 5800) be dissolved in deionized water (15g) and concentrated hydrochloric acid solution (60g) and be uniformly mixed, then drip lentamente tetraethoxysilane (10g), continue to stir 24h, form homogeneous phase solution;
Step 212: add acetic acid (2g) in the homogeneous phase solution of preparing in step S211, and continue stirring reaction 8h at 30 ℃;
Step 213: reaction solution in step S212 is moved in the autoclave of polytetrafluoroethylsubstrate substrate, then crystallization 20h at 90 ℃, cooling, by the crystalline product suction filtration obtaining, washing and in 80 ℃ of dry 24h, the crystalline product obtaining;
Step 214: the crystalline product obtaining in step S213, at 400 ℃ of calcining 4h, is removed to triblock copolymer, obtain mesoporous molecular sieve SBA-15 white powder;
Step 22. preparation contains the first mixed liquor of polyvinyl acetate:
By 5g N-methoxy ethyl-N-methyl piperidine fluoroform sulphonate, 1.0g LiCF 3sO 3stir with 10g AN (acetonitrile), then in system, add 10g polyvinyl acetate ester group (molecular weight 2-10 ten thousand), lasting stirring is dissolved polyvinyl acetate ester group, obtains the first mixed liquor;
Step S23. preparation contains the second mixed liquor of mesoporous molecular sieve SBA-15:
Mesoporous molecular sieve SBA-15 1.0g prepared by step S21 adds in step S22 preparation ability the first mixed liquor, and ultrasonic 15min, is dispersed in polymer solution SBA-15, obtains the second mixed liquor;
Step S24. is by the second mixed liquor casting film:
The homodisperse polymer solution of the second mixed liquor of step S23 preparation is cast on clean glass plate, then after dry under 80 ℃, 0.01MPa vacuum, obtain being compounded with the polyvinyl acetate ester group gel polymer electrolyte of mesoporous molecular sieve SBA-15.
The gel polymer electrolyte being prepared by this embodiment 2 contains N-methoxy ethyl-N-methyl piperidine fluoroform sulphonate, LiCF 3sO 3lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 component; Wherein, N-methoxy ethyl-N-methyl piperidine fluoroform sulphonate, LiCF 3sO 3the mass ratio of lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 is 5:1.0:10:1.0.The thickness of this gel polymer electrolyte is 50 μ m.
The preparation of lithium polymer battery:
Anodal preparation: with reference to preparation method anodal in embodiment 1 step;
Negative pole: using lithium sheet as negative pole;
After respectively the stacked order of the gel polymer electrolyte positive/gel polymer electrolyte/negative pole of positive pole, negative pole and the present embodiment 2 preparations being stacked gradually, pack in battery container, on stamping machine, button cell is made in sealing.
Embodiment 3
Gel polymer electrolyte and preparation method thereof, this gel polymer electrolyte is preparation method comprise the steps:
The preparation of step 31. mesoporous molecular sieve SBA-15:
Step 311: by 10g triblock copolymer P123 (triblock copolymer poly-(1,2-ethylidene glycol)-block-poly-(propylene glycol)-block-poly-(1,2-ethylidene glycol), mean molecule quantity 5800) be dissolved in deionized water (30g) and concentrated hydrochloric acid solution (80g) and be uniformly mixed, then drip lentamente tetraethoxysilane (25g), continue to stir 48h, form homogeneous phase solution;
Step 312: add acetic acid (7g) in the homogeneous phase solution of preparing in step S311, and continue stirring reaction 60h at 60 ℃;
Step 313: reaction solution in step S312 is moved in the autoclave of polytetrafluoroethylsubstrate substrate, then crystallization 48h at 120 ℃, cooling, by the crystalline product suction filtration obtaining, washing and in 100 ℃ of dry 24h, the crystalline product obtaining;
Step 314: the crystalline product obtaining in step S313, at 700 ℃ of calcining 12h, is removed to triblock copolymer, obtain mesoporous molecular sieve SBA-15 white powder;
Step 32. preparation contains the first mixed liquor of polyvinyl acetate:
By two (fluorine sulphonyl) inferior amine salts of 15g N-methoxy ethyl-N-methyl piperidine, 3.0g LiBF 4with 30gTHF(oxolane) stir, then in system, add 10g polyvinyl acetate (molecular weight 2-10 ten thousand), lasting stirring is dissolved polyvinyl acetate, obtains the first mixed liquor;
Step S33. preparation contains the second mixed liquor of mesoporous molecular sieve SBA-15:
Mesoporous molecular sieve SBA-15 2.0g prepared by step S31 adds in step S32 preparation ability the first mixed liquor, and ultrasonic 45min, is dispersed in polymer solution SBA-15, obtains the second mixed liquor;
Step S34. is by the second mixed liquor casting film:
The homodisperse polymer solution of the second mixed liquor of step S33 preparation is cast on clean glass plate, then after dry under 85 ℃, 0.01MPa vacuum, obtain being compounded with the polyvinyl acetate ester group gel polymer electrolyte of mesoporous molecular sieve SBA-15.
The gel polymer electrolyte being prepared by this embodiment 3 contains two (fluorine sulphonyl) inferior amine salts of N-methoxy ethyl-N-methyl piperidine, LiBF 4lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 component; Wherein, two (fluorine sulphonyl) inferior amine salts of N-methoxy ethyl-N-methyl piperidine, LiBF 4the mass ratio of lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 is 15:3.0:10:2.0.The thickness of this gel polymer electrolyte is 200 μ m.
The preparation of lithium polymer battery:
Anodal preparation: with reference to preparation method anodal in embodiment 1 step;
Negative pole: using lithium sheet as negative pole;
After respectively the stacked order of the gel polymer electrolyte positive/gel polymer electrolyte/negative pole of positive pole, negative pole and the present embodiment 3 preparations being stacked gradually, pack in battery container, on stamping machine, button cell is made in sealing.
Embodiment 4
Gel polymer electrolyte and preparation method thereof, this gel polymer electrolyte is preparation method comprise the steps:
The preparation of step 41. mesoporous molecular sieve SBA-15:
Step 411: by 10g triblock copolymer P123 (triblock copolymer poly-(1,2-ethylidene glycol)-block-poly-(propylene glycol)-block-poly-(1,2-ethylidene glycol), mean molecule quantity 5800) be dissolved in deionized water (20g) and concentrated hydrochloric acid solution (75g) and be uniformly mixed, then drip lentamente tetraethoxysilane (20g), continue to stir 24h, form homogeneous phase solution;
Step 412: add acetic acid (5g) in the homogeneous phase solution of preparing in step S411, and continue stirring reaction 40h at 40 ℃;
Step 413: reaction solution in step S412 is moved in the autoclave of polytetrafluoroethylsubstrate substrate, then crystallization 48h at 100 ℃, cooling, by the crystalline product suction filtration obtaining, washing and in 100 ℃ of dry 24h, the crystalline product obtaining;
Step 414: the crystalline product obtaining in step S413, at 550 ℃ of calcining 8h, is removed to triblock copolymer, obtain mesoporous molecular sieve SBA-15 white powder;
Step 42. preparation contains the first mixed liquor of polyvinyl acetate:
By 8g N-methoxy ethyl-N-methyl piperidine hexafluorophosphate, 1.8g LiPF 6stir with 20g ethanol, then in system, add 10g polyvinyl acetate (molecular weight 2-10 ten thousand), lasting stirring is dissolved polyvinyl acetate, obtains the first mixed liquor;
Step S43. preparation contains the second mixed liquor of mesoporous molecular sieve SBA-15: mesoporous molecular sieve SBA-15 1.3g prepared by step S31 adds in step S42 preparation ability the first mixed liquor, ultrasonic 35min, SBA-15 is dispersed in polymer solution, obtains the second mixed liquor;
Step S44. is by the second mixed liquor casting film:
The homodisperse polymer solution of the second mixed liquor of step S43 preparation is cast on clean glass plate, then after dry under 90 ℃, 0.01MPa vacuum, obtain being compounded with the polyvinyl acetate ester group gel polymer electrolyte of mesoporous molecular sieve SBA-15.
The gel polymer electrolyte being prepared by this embodiment 4 contains N-methoxy ethyl-N-methyl piperidine hexafluorophosphate, LiPF 6lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 component; Wherein, N-methoxy ethyl-N-methyl piperidine hexafluorophosphate, LiPF 6the mass ratio of lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 is 8:1.8:10:1.3.The thickness of this gel polymer electrolyte is 170 μ m.
The preparation of lithium polymer battery:
Anodal preparation: with reference to preparation method anodal in embodiment 1 step;
Negative pole: using lithium sheet as negative pole;
After respectively the stacked order of the gel polymer electrolyte positive/gel polymer electrolyte/negative pole of positive pole, negative pole and the present embodiment 4 preparations being stacked gradually, pack in battery container, on stamping machine, button cell is made in sealing.
Comparison example:
Gel polymer electrolyte and preparation method thereof, this gel polymer electrolyte is preparation method comprise the steps:
Two (fluoroform sulphonyl) inferior amine salts of 10g N-methoxy ethyl-N-methyl piperidine, 2.5g LiTFSI and 20g NMP (methyl pyrrolidone) are stirred, then in system, add 10g polyvinyl acetate (molecular weight 2-10 ten thousand), lasting stirring is dissolved polyvinyl acetate, and ultrasonic 30min, homodisperse polymer solution is cast on clean glass plate, after dry under 100 ℃, 0.01MPa vacuum again, obtain polyvinyl acetate ester group gel polymer electrolyte.
The preparation of lithium polymer battery:
Anodal preparation: with reference to preparation method anodal in embodiment 1 step;
Negative pole: using lithium sheet as negative pole;
After the stacked order of gel polymer electrolyte positive/gel polymer electrolyte/negative pole of respectively being prepared by positive pole, negative pole and this comparison example stacks gradually, pack in battery container, on stamping machine, button cell is made in sealing.
Performance test:
Be that gel polymer electrolyte and the lithium polymer battery of preparing for the various embodiments described above and comparative example carries out performance test below, method of testing is as follows:
1. the test of the conductance of gel polymer electrolyte: add the electrolyte preparing between two stainless steel blocking electrodes, form polymer dielectric blocking electrode system, do ac impedance measurement, obtain the complex impedance plane graph of GPE, curve is body impedance in the intersection value of high frequency region and transverse axis.According to body impedance (R b) and ionic conductivity (σ) between relation:
σ=d/(S*R b)
Can calculate ionic conductivity, the thickness that wherein d is polymer dielectric film, S are the contact area of polymer dielectric dielectric film and electrode.
The gel polymer electrolyte that utilizes said method to prepare embodiment 1 ~ 4 and comparative example carries out conductivity test, and test result is shown in as following table 1.
Table 1
Figure BDA00002175435600161
2. the mechanical strength test of gel polymer electrolyte: the gel polymer electrolyte that utilizes film stretching strength tester to prepare embodiment 1 ~ 4 and comparative example carries out hot strength test, and test result sees the following form 2.
Table 2
Embodiment Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparison example
Hot strength Mpa 5.5 5.3 5.7 5.2 2.2
3. lithium polymer battery electrochemical property test: in the voltage range of 2.5 ~ 4.2V, utilize charge-discharge test instrument to carry out 0.1C charge-discharge test to the lithium polymer battery of the present embodiment 1～4 preparation, the data obtained is as following table 3.
Table 3
Embodiment 1 2 3 4 Comparison example
Discharge capacity (3th) mAh/g 108 105 107 104 92
In table 1,2, Data Comparison is found, adds mesoporous molecular sieve SBA-15 can improve significantly the electric conductivity of mechanical performance and the electric conductivity, particularly gel polymer electrolyte film of gel polymer electrolyte film.Hence one can see that, has good synergy in the various embodiments described above between piperidines low-temperature molten salt, lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15, jointly given electric conductivity and the mechanical performance of this gel polymer electrolyte excellence.
As shown in Table 3, the discharge capacity that embodiment 1 ~ 4 prepares lithium polymer battery is prepared the discharge capacity of lithium polymer battery apparently higher than comparison example.Further illustrate the gel polymer electrolyte of preparing in above-described embodiment and there is excellent electric conductivity.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. a gel polymer electrolyte, contains N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 component; Wherein, the mass ratio of N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate, mesoporous molecular sieve SBA-15 is (0.5 ~ 1.5): (0.1 ~ 0.3): 1:(0.1 ~ 0.2).
2. gel polymer electrolyte as claimed in claim 1, is characterized in that: described N-methoxy ethyl piperidines low-temperature molten salt is at least one in two (fluoroform sulphonyl) inferior amine salts of N-methoxy ethyl-N-methyl piperidine, N-methoxy ethyl-N-methyl piperidine fluoroform sulphonate, two (fluorine sulphonyl) inferior amine salts of N-methoxy ethyl-N-methyl piperidine, N-methoxy ethyl-N-methyl piperidine tetrafluoroborate, N-methoxy ethyl-N-methyl piperidine hexafluorophosphate.
3. gel polymer electrolyte as claimed in claim 1, is characterized in that: described lithium salts is LiBF 4, LiPF 6, LiTFSI, LiCF 3sO 3in at least one.
4. gel polymer electrolyte as claimed in claim 1, is characterized in that: the thickness of described gel polymer electrolyte is 50～200 μ m.
5. the method for preparing gel polymer electrolyte as described in as arbitrary in claim 1～4, comprises the steps:
Obtain mesoporous molecular sieve SBA-15;
N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, polyvinyl acetate and organic solvent mix and blend are dissolved, obtain the first mixed liquor;
Described mesoporous molecular sieve SBA-15 is added in described the first mixed liquor, and ultrasonic processing, obtains the second mixed liquor;
By described the second mixed liquor casting film, dry processing, obtains described gel polymer electrolyte;
Wherein, the mass ratio of described N-methoxy ethyl piperidines low-temperature molten salt, lithium salts, organic solvent, polyvinyl acetate and mesoporous molecular sieve SBA-15 is (0.5 ~ 1.5): (0.1 ~ 0.3): (1 ~ 3): 1:(0.1 ~ 0.2).
6. method for preparing gel polymer electrolyte as claimed in claim 5, is characterized in that: described mesoporous molecular sieve SBA-15 acquisition methods is:
Triblock copolymer P123 be dissolved in the solution of deionized water and dense inorganic acid and be uniformly mixed, then dripping tetraethoxysilane, continuing to stir 24～48h, forming homogeneous phase solution;
In described homogeneous phase solution, add acetic acid, and continue stirring reaction 8～24h at 30～60 ℃, obtain reactant liquor;
Described reaction solution is moved in the autoclave with polytetrafluoroethylsubstrate substrate, and then crystallization 20～60h at 90～120 ℃, cooling, suction filtration, washing, dry, the crystalline product obtaining;
Described crystalline product, at 400～700 ℃ of calcining 4～12h, is obtained to mesoporous molecular sieve SBA-15;
Wherein, described P123, H 2o: dense inorganic acid acid: tetraethoxysilane: the mass ratio of acetic acid consumption is 1:1.5～3:6～8:1～3:0.2～0.7.
7. method for preparing gel polymer electrolyte as claimed in claim 5, is characterized in that: in the preparation steps of described the second mixed liquor, the time of ultrasonic processing is 15～45min.
8. an electrochemical power source, is characterized in that, described electrochemical power source comprises the arbitrary described gel polymer electrolyte of claim 1～4.
9. electrochemical power source as claimed in claim 8, is characterized in that, described electrochemical power source is lithium polymer battery or gel polymer electrolyte capacitor.
As claimed in claim 8 or 9 electrochemical power source at mobile terminal product, electric automobile, electrical network, communication equipment, electric tool or/and the application in light fixture.
CN201210360673.9A 2012-09-21 2012-09-21 Gel polymer electrolyte and preparation method thereof, and electrochemical power source and application thereof Pending CN103682432A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10483049B2 (en) 2016-05-30 2019-11-19 Taiyo Yuden Co., Ltd. Lithium ion capacitor
CN110931844A (en) * 2019-12-25 2020-03-27 西安大工迅驰材料科技有限公司 All-solid-state composite polymer electrolyte containing modified molecular sieve

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10483049B2 (en) 2016-05-30 2019-11-19 Taiyo Yuden Co., Ltd. Lithium ion capacitor
CN110931844A (en) * 2019-12-25 2020-03-27 西安大工迅驰材料科技有限公司 All-solid-state composite polymer electrolyte containing modified molecular sieve
CN110931844B (en) * 2019-12-25 2022-12-23 西安大工迅驰材料科技有限公司 All-solid-state composite polymer electrolyte containing modified molecular sieve

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