CN103682431A - 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 PDFInfo
- Publication number
- CN103682431A CN103682431A CN201210360661.6A CN201210360661A CN103682431A CN 103682431 A CN103682431 A CN 103682431A CN 201210360661 A CN201210360661 A CN 201210360661A CN 103682431 A CN103682431 A CN 103682431A
- Authority
- CN
- China
- Prior art keywords
- polymer electrolyte
- gel polymer
- preparation
- power source
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a gel polymer electrolyte and a preparation method thereof, and an electrochemical power source and application thereof. The preparation method of the gel polymer electrolyte comprises the following steps: preparing a thick liquid containing PMMA (polymethyl methacrylate) polymer, preparing a gel polymer electrolyte film by running, and impregnating and adsorbing the electrolyte. The electrochemical power source contains the gel polymer electrolyte. The preparation method of the gel polymer electrolyte has the advantages of simple technique, mature technology, high yield and high efficiency, and effectively lowers the production cost. The gel polymer electrolyte prepared by the method has the advantages of high mechanical strength and high conductivity. 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
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, provides a kind of mechanical strength and conductance high, gel polymer electrolyte that cost is low and preparation method thereof.
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 preparation method, comprises the steps:
PMMA polymer and organic plasticizer are mixed with to thick liquid;
Described thick liquid is coated on nonwoven fabrics barrier film, and after casting film-forming, vacuumize, obtains gel polymer electrolyte film;
Under the protection of inert gas, it is that the lithium-ion electrolyte of 0.5～2mol/L floods 5～60min that described gel polymer electrolyte film is placed in to concentration, takes out the described gel polymer electrolyte obtaining.
And, a kind of gel polymer electrolyte, described gel polymer electrolyte is prepared from by above-mentioned gel polymer electrolyte preparation method.
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.
It is substrate that above-mentioned method for preparing gel polymer electrolyte adopts PMMA polymer, nonwoven fabrics is prepared gel polymer electrolyte film as reinforced layer, effectively strengthened the mechanical strength of gel polymer electrolyte film, effectively improved the ability of this gel polymer electrolyte film absorbed electrolyte simultaneously, after gel polymer electrolyte film is flooded in electrolyte, can be effectively by electrolyte absorption and be retained in this gel polymer electrolyte film, thereby effectively raise the electric conductivity of this gel polymer electrolyte.In addition, this method for preparing gel polymer electrolyte, only needs to contain PMMA polymer thick liquid and is coated on nonwoven fabrics, and through casting film, adsorbing electrolyte, 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 the chemical property of chemical power source, 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 provide a kind of mechanical strength and conductance high, gel polymer electrolyte that cost is low and preparation method thereof.As shown in Figure 1, it comprises the steps: in this method for preparing gel polymer electrolyte technological process
Step S01. preparation contains the thick liquid of PMMA polymer: PMMA polymer and organic plasticizer are mixed with to thick liquid;
Step S02. curtain coating is prepared gel polymer electrolyte film: the thick liquid of preparing in step S01 is coated on nonwoven fabrics barrier film, and after casting film-forming, vacuumize, obtains gel polymer electrolyte film;
Step S03. dipping absorption electrolyte: under the protection of inert gas, it is that the lithium-ion electrolyte of 0.5～2mol/L floods 5～60min that described gel polymer electrolyte film is placed in to concentration, takes out the described gel polymer electrolyte obtaining.
Particularly, PMMA polymer in above-mentioned steps S01 and the mass ratio of organic plasticizer are preferably 1:5～1:20, wherein, preferred one or more in 1-METHYLPYRROLIDONE (NMP), acetonitrile (AN), acetone, DMF (DMF) of organic plasticizer.The optimum ratio of this PMMA polymer and organic plasticizer, can make PMMA polymer dissolution in organic plasticizer and prepare dispersed and stable thick liquid, when this thick liquid is carried out to lower step curtain coating processing, can make this contain PMMA polymer thick liquid is uniformly coated on nonwoven fabrics, make the gel polymer electrolyte film even thickness forming, soak and adsorb the equilibrium of electrolyte ability.The thick liquid that PMMA polymer obtains after this preferred organic plasticizer dissolves is water white transparency.Certainly, the application can also be with other organic plasticizer that can dissolve PMMA polymer well known in the art.
Preferably; as the preferred embodiment of the present invention; in this step S01, preparation is preferably carried out containing the thick liquid of PMMA polymer in the environment of Buchholz protection that is dried inertia; concrete method is: under the Buchholz protection of dry inertia; by PMMA polymer, according to mass ratio, be that 1:5～1:20 mixes with organic plasticizer; and follow agitating procedure to stir 1～10 hour, PMMA polymer is dissolved completely, to form uniform and stable transparent thick liquid.In this embodiment; the object of carrying out in the environment containing the Buchholz protection that is formulated in dry inertia of the thick liquid of PMMA polymer is in order to prevent that airborne moisture from being adsorbed by the thick liquid containing PMMA polymer, thereby affects the performance that obtains gel polymer electrolyte film after the stability of this thick liquid and casting film-forming.
In above-mentioned steps S02, the mode that in step S01, preparation is coated on nonwoven fabrics barrier film containing thick liquid can be adopted to the modes such as cast, certainly can also adopt other modes well known in the art that thick liquid is coated on nonwoven fabrics barrier film.Wherein, the preferred PET nonwoven fabrics of nonwoven fabrics barrier film barrier film, this nonwoven fabrics barrier film can also be selected the nonwoven fabrics barrier film of conventional other materials in this area certainly.Through being coated with thick liquid nonwoven fabrics barrier film, directly through curtain coating, process again, this thick liquid is evenly distributed on nonwoven fabrics barrier film.Like this, drying is processed rear formed gel polymer electrolyte film even thickness, stable electrochemical property, and process the more firm of energy reinforced PMMA polymer and the combination of nonwoven fabrics barrier film through curtain coating, thereby strengthened gel polymer electrolyte film sound construction, mechanical strength is high.It is 50～200um that thick liquid is coated in the thicknesses of layers that amount on barrier film is preferably after curtain coating is processed.This preferred thickness can effectively improve the transmission performance of gel polymer electrolyte to electric charge, thereby improves the chemical property of the ultracapacitor that hereinafter contains this gel polymer electrolyte.
In this step S02, vacuum drying temperature is preferably 60 ℃～100 ℃, is preferably 24～48 hours drying time; Vacuum degree can be 0.01MPa, if certain conditions permit, vacuum degree is more high better.This preferred drying condition, can effectively remove the organic plasticizer in thick liquid, can further improve the correlated performance of this gel polymer electrolyte film simultaneously, as to the absorption property of electrolyte etc.In order better to remove organic plasticizer, obtain the gel polymer electrolyte film of excellent performance, after casting film-forming, first naturally evaporate into film and become after white, then be that 0.01MPa, temperature are vacuumize 24～48 hours at 60～100 ℃ in vacuum degree.
In above-mentioned steps S03, the Buchholz protection object of dry inertia is in order to prevent that airborne moisture from together being adsorbed wherein by gel polymer electrolyte film in company with electrolyte, thereby guarantees the electric property of gel polymer electrolyte.Gel polymer electrolyte film is in electrolyte after fully adsorbing, and electrolyte is adsorbed and is fixed in this gel polymer electrolyte film, thereby forms mechanical strength and the high gel polymer electrolyte of conductance.
In this step S03, electrolyte is selected from and contains LiPF
6, LiBF
4, at least one lithium salts in LiBOB organic liquid electrolyte.Particularly, this electrolyte is LiPF
6/ EC+DMC lithium-ion battery electrolytes, LiBF
4/ EC+DMC and LiBOB/EC+DMC also can; Wherein, the volume ratio of EC and DMC is 1:1～1:2.In addition, for this electrolyte can better be adsorbed by gel polymer electrolyte film and fix, in a preferred embodiment, the concentration of this electrolyte is 1mol/L.
From the above, it is substrate that above-described embodiment method for preparing gel polymer electrolyte adopts PMMA polymer, nonwoven fabrics is prepared gel polymer electrolyte film as reinforced layer, effectively strengthened the mechanical strength of gel polymer electrolyte film, effectively improved the ability of this gel polymer electrolyte film absorbed electrolyte simultaneously, after gel polymer electrolyte film is flooded in electrolyte, can be effectively by electrolyte absorption and be retained in this gel polymer electrolyte film, thereby effectively raise the electric conductivity of this gel polymer electrolyte.The not high deficiency of conductance of effective like this mechanical strength that has overcome existing gel polymer electrolyte not high and existing gel polymer electrolyte and solid electrolyte.In addition, this method for preparing gel polymer electrolyte, only needs to contain PMMA polymer thick liquid and is coated on nonwoven fabrics, and through casting film, adsorbing electrolyte, its technique is simple, technology maturation, rate of finished products and efficiency are high, effectively reduce production cost.
Correspondingly, the embodiment of the present invention also provides a kind of gel polymer electrolyte, and this gel polymer electrolyte is prepared from by above-mentioned gel polymer electrolyte preparation method.Particularly, this gel polymer electrolyte preparation method as described above, in order to save length, does not repeat them here.Like this, it is substrate that embodiment of the present invention gel polymer electrolyte adopts PMMA polymer, nonwoven fabrics is that reinforced layer is to form gel polymer electrolyte film, and adsorb and fixed electrolyte in this gel polymer electrolyte film, therefore, this gel polymer electrolyte machinery machine intensity and conductance are high.
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 S04. prepares gel polymer electrolyte: this gel polymer electrolyte is gel polymer electrolyte preparation method be by mentioned earlier prepared from;
Step S05. prepares battery battery core: step S04 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 S06. packaged battery: step S05 is prepared to battery battery core and pack in battery container, sealing, makes lithium polymer battery.
Packaged battery method in above-mentioned steps S05 in the preparation method of positive and negative electrode and the preparation method of battery battery core and step S06 all can be according to the method preparation of this area routine.In addition, the battery battery core in step S05 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 S07. prepares gel polymer electrolyte: this gel polymer electrolyte is gel polymer electrolyte preparation method be by mentioned earlier prepared from;
Step S08. prepares battery core: step S07 is prepared to gel polymer electrolyte and according to electrode/gel polymer electrolyte/electrode overlapped way, stack gradually, and reel, make battery core;
Step S09. encapsulated capacitor: step S08 is prepared to battery core and pack in capacitor casing, sealing, makes gel polymer electrolyte capacitor.
Encapsulated capacitor method in above-mentioned steps S08 in the preparation method of electrode and the preparation method of battery core and step S09 all can be according to the method preparation of this area routine.In addition, the battery core in step S08 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:
Step 11. preparation is containing the thick liquid of PMMA: in flask, add respectively 10g PMMA and 120g NMP, and under the protection of inert gas, stir 8h and make it mix the thick liquid that obtains homogeneous transparent;
Step 12. curtain coating is prepared gel polymer electrolyte film: the mucus of step 11 preparation is cast in to casting film-forming on PET nonwoven fabrics barrier film, naturally evaporate into film and become white, and vacuum degree is 0.01MPa vacuumize 48h at 100 ℃, obtain the PMMA polymeric substrates gel film that PET nonwoven fabrics strengthens;
Step 13. is prepared the PMMA base gel polymer electrolyte that PET nonwoven fabrics strengthens: dried PMMA base gel film is transferred in the glove box that is full of argon gas, and is immersed the LiPF of 1mol/L
630min in (volume ratio of EC and DMC is 1:1) in/EC+DMC lithium-ion battery electrolytes, is taken out and is obtained the PMMA base gel polymer electrolyte that PET nonwoven fabrics strengthens.
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:
Step 21. preparation is containing the thick liquid of PMMA: in flask, add respectively 10g PMMA and 50gAN, and under the protection of inert gas, stir 10h and make it mix the thick liquid that obtains homogeneous transparent;
Step 22. curtain coating is prepared gel polymer electrolyte film: the mucus of step 21 preparation is cast in to casting film-forming on PET nonwoven fabrics barrier film, naturally evaporate into film and become white, and vacuum degree is 0.01MPa vacuumize 24h at 60 ℃, obtain the PMMA polymeric substrates gel film that PET nonwoven fabrics strengthens;
Step 23. is prepared the PMMA base gel polymer electrolyte that PET nonwoven fabrics strengthens: dried PMMA base gel film is transferred in the glove box that is full of argon gas, and is immersed the LiPF of 1mol/L
65min in (volume ratio of EC and DMC is 1:2) in/EC+DMC lithium-ion battery electrolytes.Taken out and obtained the PMMA base gel polymer electrolyte that PET nonwoven fabrics strengthens.
The preparation of lithium polymer battery:
Anodal preparation: take 8.5g LiFePO
4, 0.3g acetylene black and 0.3g PVDF, and add 17gNMP, 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, 80 ℃ are dried to constant weight, and are pressed into LiFePO in 10～15MPa pressure lower roll
4electrode, 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 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:
Step 31. preparation is containing the thick liquid of PMMA: in flask, add respectively 10g PMMA and 200g acetone, and under the protection of inert gas, stir 1h and make it mix the thick liquid that obtains homogeneous transparent;
Step 32. curtain coating is prepared gel polymer electrolyte film: the mucus of step 31 preparation is cast in to casting film-forming on PET nonwoven fabrics barrier film, naturally evaporate into film and become white, and vacuum degree is 0.01MPa vacuumize 36h at 80 ℃, obtain the PMMA polymeric substrates gel film that PET nonwoven fabrics strengthens;
Step 33. is prepared the PMMA base gel polymer electrolyte that PET nonwoven fabrics strengthens: dried PMMA base gel film is transferred in the glove box that is full of argon gas, and is immersed the LiPF of 1mol/L
660min in (volume ratio of EC and DMC is 1:1) in/EC+DMC lithium-ion battery electrolytes.Taken out and obtained the PMMA base gel polymer electrolyte that PET nonwoven fabrics strengthens.
The preparation of lithium polymer battery:
Anodal preparation: take 8.8gLiFePO
4, 0.7g acetylene black and 1.0g PVDF, and add 176gDMF, 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, 120 ℃ are dried to constant weight, and are pressed into LiFePO in 10～15MPa pressure lower roll
4electrode, 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 3 preparations being stacked gradually, be wound into a rectangular cell pole piece, and 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:
Step 41. preparation is containing the thick liquid of PMMA: in flask, add respectively 10g PMMA and 160g DMF, and under the protection of inert gas, stir 5h and make it mix the thick liquid that obtains homogeneous transparent;
Step 42. curtain coating is prepared gel polymer electrolyte film: the mucus of step 41 preparation is cast in to casting film-forming on PET nonwoven fabrics barrier film, naturally evaporate into film and become white, and vacuum degree is 0.01MPa vacuumize 24h at 100 ℃, obtain the PMMA polymeric substrates gel film that PET nonwoven fabrics strengthens;
Step 43. is prepared the PMMA base gel polymer electrolyte that PET nonwoven fabrics strengthens: dried PMMA base gel film is transferred in the glove box that is full of argon gas, and is immersed the LiPF of 1mol/L
645min in (volume ratio of EC and DMC is 1:2) in/EC+DMC lithium-ion battery electrolytes.Taken out and obtained the PMMA base gel polymer electrolyte that PET nonwoven fabrics strengthens.
The preparation of lithium polymer battery:
Anodal preparation: take 9g LiFePO
4, 0.7g acetylene black and 0.7g PVDF, and add 150g NMP, 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, 110 ℃ are dried to constant weight, and are pressed into LiFePO4 electrode in 10～15MPa pressure lower roll, and are 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 4 preparations being stacked gradually, be wound into a rectangular cell pole piece, and pack in battery container, on stamping machine, button cell is made in sealing.
Embodiment 5
Gel polymer electrolyte and preparation method thereof, this gel polymer electrolyte is preparation method comprise the steps:
Step 51. preparation contains the thick liquid of PMMA: with reference to embodiment 1 step 11;
Step 52. curtain coating is prepared gel polymer electrolyte film: with reference to embodiment 1 step 12;
Step 53. is prepared the PMMA base gel polymer electrolyte that PET nonwoven fabrics strengthens: dried PMMA base gel film is transferred in the glove box that is full of argon gas, and is immersed (volume ratio of EC and DMC is 1:1) middle 45min in the LiBOB/EC+DMC lithium-ion battery electrolytes of 2mol/L.Taken out and obtained the PMMA base gel polymer electrolyte that PET nonwoven fabrics strengthens.
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 5 preparations being stacked 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 above-described embodiment 1 ~ 5 carries out performance test below, method of testing is as follows:
1. the mechanical strength test of gel polymer electrolyte: the measurement specimen size of the hot strength of film is 3cm * 5cm, and hot strength is by formula σ
t=G/S obtains, and wherein G is heavy burden (N), the sectional area that S is film, σ
thot strength for film.According to this method of testing, the mechanical strength test of the gelatin polymer of embodiment 1 ~ 5 preparation be the results are shown in to following table 1.
Table 1
2. 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.
Utilize said method to carry out conductivity test to the gel polymer electrolyte of embodiment 1 ~ 5 preparation, test result is shown in as following table 2.
Table 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 1～5 preparation, the data obtained is as following table.
Table 3
In table 1,2, data are known, and gel polymer electrolyte prepared by above-described embodiment has excellent mechanical performance, also have good electric conductivity simultaneously.
From table 3, data are known, and the prepared lithium polymer battery of the embodiment of the present invention, due to the gel polymer electrolyte that contains the embodiment of the present invention and prepare, makes lithium polymer battery have higher specific discharge capacity and efficiency for charge-discharge.In addition, can also draw, the gel polymer electrolyte that lithium polymer battery adopts the embodiment of the present invention to prepare, effectively raises lithium polymer battery rate of finished products, has reduced its production cost, thereby make this lithium polymer battery can realize industrialization, produces.
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 preparation method, comprises the steps:
PMMA polymer and organic plasticizer are mixed with to thick liquid;
Described thick liquid is coated on nonwoven fabrics barrier film, and after casting film-forming, vacuumize, obtains gel polymer electrolyte film;
Under the protection of dry inert gas, it is that the lithium-ion electrolyte of 0.5～2mol/L floods 5～60min that described gel polymer electrolyte film is placed in to concentration, takes out the described gel polymer electrolyte obtaining.
2. gel polymer electrolyte preparation method as claimed in claim 1, is characterized in that, the mass ratio of described PMMA polymer and organic plasticizer is 1:5～1:20.
3. gel polymer electrolyte preparation method as claimed in claim 1 or 2, is characterized in that, one or more in described organic plasticizer 1-METHYLPYRROLIDONE, acetonitrile, acetone, DMF.
4. gel polymer electrolyte preparation method as claimed in claim 1 or 2, is characterized in that, described thick liquid be coated in amount on nonwoven fabrics barrier film for the thickness through casting film-forming be 50um～200um.
5. gel polymer electrolyte preparation method as claimed in claim 1, is characterized in that, described vacuum drying temperature is 60 ℃～100 ℃, and be 24～48 hours drying time.
6. gel polymer electrolyte preparation method as claimed in claim 1, is characterized in that, described lithium-ion electrolyte is for containing LiPF
6, LiBF
4, at least one lithium salts in LiBOB organic liquid electrolyte.
7. a gel polymer electrolyte, is characterized in that, described gel polymer electrolyte is prepared from by the arbitrary described gel polymer electrolyte preparation method of claim 1～6.
8. an electrochemical power source, is characterized in that, described electrochemical power source comprises gel polymer electrolyte claimed in claim 7.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210360661.6A CN103682431A (en) | 2012-09-21 | 2012-09-21 | Gel polymer electrolyte and preparation method thereof, and electrochemical power source and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210360661.6A CN103682431A (en) | 2012-09-21 | 2012-09-21 | Gel polymer electrolyte and preparation method thereof, and electrochemical power source and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103682431A true CN103682431A (en) | 2014-03-26 |
Family
ID=50319240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210360661.6A Pending CN103682431A (en) | 2012-09-21 | 2012-09-21 | Gel polymer electrolyte and preparation method thereof, and electrochemical power source and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103682431A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108352585A (en) * | 2016-01-06 | 2018-07-31 | 株式会社Lg化学 | Include the secondary cell of gas absorption polymer |
| CN108649240A (en) * | 2018-05-15 | 2018-10-12 | 常州大学 | A kind of fuel cell |
| CN109119680A (en) * | 2018-08-27 | 2019-01-01 | 江苏中兴派能电池有限公司 | A kind of preparation method of lithium ion battery with high energy density |
| US10483049B2 (en) | 2016-05-30 | 2019-11-19 | Taiyo Yuden Co., Ltd. | Lithium ion capacitor |
| CN111834667A (en) * | 2019-04-16 | 2020-10-27 | 深圳新宙邦科技股份有限公司 | Preparation method of polymer electrolyte membrane |
-
2012
- 2012-09-21 CN CN201210360661.6A patent/CN103682431A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108352585A (en) * | 2016-01-06 | 2018-07-31 | 株式会社Lg化学 | Include the secondary cell of gas absorption polymer |
| CN108352585B (en) * | 2016-01-06 | 2021-05-25 | 株式会社Lg化学 | Secondary battery comprising gas-adsorbing polymer |
| US10483049B2 (en) | 2016-05-30 | 2019-11-19 | Taiyo Yuden Co., Ltd. | Lithium ion capacitor |
| CN108649240A (en) * | 2018-05-15 | 2018-10-12 | 常州大学 | A kind of fuel cell |
| CN109119680A (en) * | 2018-08-27 | 2019-01-01 | 江苏中兴派能电池有限公司 | A kind of preparation method of lithium ion battery with high energy density |
| CN111834667A (en) * | 2019-04-16 | 2020-10-27 | 深圳新宙邦科技股份有限公司 | Preparation method of polymer electrolyte membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108963327B (en) | Inorganic filler composite PEO solid electrolyte material, preparation method and all-solid-state battery | |
| WO2022041702A1 (en) | Gel electrolyte precursor and application thereof | |
| CN103904291A (en) | Aqueous lithium ion battery electrode, preparation method of electrode and aqueous lithium ion battery | |
| CN110311130B (en) | Titanium niobate negative electrode material and preparation method thereof | |
| JP2016532996A (en) | Method for producing electrode-separation membrane composite, electrode-separation membrane composite produced by the production method, and lithium secondary battery including the same | |
| CN101841013B (en) | Polymer isolating membrane and lithium ion battery applying same | |
| CN103682431A (en) | Gel polymer electrolyte and preparation method thereof, and electrochemical power source and application thereof | |
| CN103680968A (en) | Gel polymer electrolyte, preparation method for the same, super capacitor and application thereof | |
| CN103151563A (en) | Polymer cell and preparation method thereof | |
| CN114400372B (en) | Preparation method of solid electrolyte film of anisotropic ion transmission channel | |
| WO2022161438A1 (en) | Boron-containing modified diaphragm and preparation method and application therefor, and battery including diaphragm | |
| CN105161761A (en) | Preparation method of gel polymer electrolyte and application | |
| CN109616655B (en) | Double-layer coated lithium iron borate/nickel pyrophosphate lithium battery positive electrode material and preparation method thereof | |
| CN103855427A (en) | Modified polymethyl methacrylate electrolyte as well as preparation method, lithium ion battery and application thereof | |
| CN114069037A (en) | Gel polymer electrolyte, preparation method and application thereof, solid-state lithium battery and preparation method thereof | |
| CN103804708A (en) | Poly(vinylidene fluoride-hexafluoropropenyl) gel polymer film as well as preparation and application thereof | |
| CN103840109A (en) | Polyvinyl-acetate-based gel polymer electrolyte membrane, preparation method of membrane, and lithium-ion battery | |
| CN103840201A (en) | P(VDF-HFP) (Polyvinylidene Fluoride-Hexafluoropropylene)-based gel polymer electrolyte membrane, and preparation method thereof and lithium ion battery | |
| CN103923333A (en) | Polyacrylonitrile gel thin film and preparation method thereof, corresponding electrolyte and preparation method thereof, and lithium ion battery | |
| CN103779089A (en) | Gel polymer dielectric and preparation method for the same, super capacitor and application thereof | |
| CN104124415A (en) | Composite gel polymer electrolyte as well as preparation method and application thereof | |
| CN103834153A (en) | Gel polymer electrolyte and preparation method thereof | |
| CN103840193A (en) | Gel polymer electrolyte and preparation method thereof | |
| CN110994016A (en) | Polymer solid electrolyte and preparation method and application thereof | |
| CN105826598A (en) | PVDF-P(VC-VAc)-based blended gel polymer electrolyte and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140326 |