CN103840206A - Gel polymer electrolyte and preparation method thereof - Google Patents
Gel polymer electrolyte and preparation method thereof Download PDFInfo
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- CN103840206A CN103840206A CN201210489882.3A CN201210489882A CN103840206A CN 103840206 A CN103840206 A CN 103840206A CN 201210489882 A CN201210489882 A CN 201210489882A CN 103840206 A CN103840206 A CN 103840206A
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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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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Abstract
The invention relates to a gel polymer electrolyte and a preparation method thereof. The preparation method comprises the following steps: (a) preparing a SiO2/PAN (polyacrylonitrile) composite polymer microporous membrane; (b) preparing SiO2 compounded PAN-based gel polymer electrolyte. The invention also relates to a lithium ion battery formed by assembly of the gel polymer electrolyte. According to the gel polymer electrolyte and the preparation method thereof, the problem of potential safety hazards in the exiting liquid electrolyte can be solved, and the conductivity of the gel polymer electrolyte can be effectively improved due to compounding of SiO2 particles in the preparation process.
Description
Technical field
The present invention relates to the field of chemical synthesis, relate in particular to a kind of method for preparing gel polymer electrolyte.
Background technology
Safety problem is the bottleneck of large capacity, high power lithium ion cell application.At present, main potential safety hazard is burning, the blast that leakage, oxidation Decomposition and thermal runaway etc. that widely used liquid electrolyte produces cause.
The liquid electrolyte advantage of current routine is that conductivity is high, but inflammable owing to containing, volatile organic solvent, it discharges fuel gas in charge and discharge process, the generation of gas is accelerated in the large calorimetric meeting that particularly (discharge and recharge as high-power, super-charge super-discharge etc.) produces under some unconventional condition of work, cause inner pressure of battery to increase, Leakage Gas, blast even on fire, thereby there is serious potential safety hazard.And conductivity is lower by (10 under solid polymer electrolyte room temperature
-5～10
-4s/cm), application is restricted.
The studied persons of advantage such as polymer electrolyte lithium-ion battery is safe because having, nothing is leaked, leakage current is little pay attention to, thereby gel polymer electrolyte becomes research emphasis.
Summary of the invention
The object of the invention is to solve the problem and shortage that above-mentioned prior art exists, a kind of method for preparing gel polymer electrolyte is provided, solved existing liquid electrolyte and exist the problem of potential safety hazard, by composite S iO in preparation process
2particle, effectively raises the conductivity of gel polymer electrolyte.
The technical scheme that the present invention is directed to above-mentioned technical problem and propose is: a kind of method for preparing gel polymer electrolyte, comprises the steps: that (a) prepares SiO
2/ PAN composition polymer microporous barrier: PAN is dissolved in organic solvent, and adds tetraethoxysilane and ammoniacal liquor, obtain containing SiO after the hydrolysis that heats up
2slurry, described slurry is coated in and on glass plate, keeps 10～120 min, then remove organic solvent and obtain wet film, to obtaining SiO after its vacuumize
2/ PAN composition polymer microporous barrier.
(b) prepare composite S iO
2pAN base gel polymer electrolyte: by described SiO
2/ PAN composition polymer microporous barrier keeps 5～60min immerse electrolyte under atmosphere of inert gases in, obtains composite S iO after taking-up
2pAN base gel polymer electrolyte.
In described step (a), the thickness of described SiO2/PAN composition polymer microporous barrier is 50～80 μ m.
In described step (a), described organic solvent is 1-METHYLPYRROLIDONE, DMF, acetonitrile or ethanol.
In described step (a), the mass ratio of described polyacrylonitrile, described organic solvent, described tetraethoxysilane and described ammoniacal liquor is 10: (80～100): (5～8): 6.
In described step (a), the temperature of described intensification hydrolysis is 40～60 ℃.
In described step (a), the thickness of described wet film is 80～120 μ m.
In described step (a), described vacuum drying condition is 60 ℃, 0.01 MPa.
In described step (b), the solute of described electrolyte is lithium hexafluoro phosphate, and the concentration of described solute is 0.5～1.5 mol/L; The solvent of described electrolyte is 1:1～1:5 ethylene carbonate and the dimethyl carbonate of volume ratio.
The present invention also comprises the gel polymer electrolyte that utilizes above-mentioned preparation method to make.
Compared with prior art, gel polymer electrolyte of the present invention and preparation method thereof, possesses following advantage: (1) gel electrolyte provided by the invention, and through SiO
2after modification, have higher conductivity, security performance is high, has solved existing liquid electrolyte and exist the problem of potential safety hazard, and it has higher specific capacity while being applied to the electrolyte of lithium ion battery.
(2) preparation method of gel electrolyte provided by the invention, simple and quick, possesses low cost, environmental friendliness.
Embodiment
Below in conjunction with embodiment, the present invention is given to elaboration further.
The preparation process of gel polymer electrolyte of the present invention is roughly divided into following steps: (a) prepare SiO
2/ PAN composition polymer microporous barrier: polyacrylonitrile (english abbreviation PAN, molecular weight 30,000) is dissolved in organic solvent and is stirred, and add tetraethoxysilane and ammoniacal liquor, obtain containing SiO after being warmed up to 40～60 ℃ of hydrolysis
2slurry, the slurry obtaining is coated on clean glass plate equably, at room temperature place to insert after 10～120 min and in tank, remove organic solvent, obtain the wet film that thickness is 80～120 μ m, to its vacuumize under 60 ℃, 0.01 MPa, obtain the SiO that thickness is 50～80 μ m
2/ PAN composition polymer microporous barrier.
(b) prepare composite S iO
2pAN base gel polymer electrolyte: by SiO
2/ PAN composition polymer microporous barrier, in the glove box of atmosphere of inert gases, and is immersed electrolyte (LiPF
6/ EC+DMC, wherein, EC+DMC represents the mixed solution of EC and DMC) the middle 5～60min that keeps, after taking-up, obtain composite S iO
2pAN base gel polymer electrolyte.
Wherein, organic solvent is the one in 1-METHYLPYRROLIDONE, DMF, acetonitrile or ethanol.
The mass ratio of polyacrylonitrile, organic solvent, tetraethoxysilane and ammoniacal liquor is 10 g:(80～100) g:(5～8) g:6 g.
Electrolyte (LiPF
6/ EC+DMC) solute be lithium hexafluoro phosphate (LiPF
6), solvent is ethylene carbonate (EC) and dimethyl carbonate (DMC), EC and DMC volume ratio 1:1～1:5, and the concentration of lithium hexafluoro phosphate is 0.5～1.5 mol/L.
The present invention also comprises the gel polymer electrolyte that utilizes above-mentioned preparation method to make.
Be specifically described with the preparation process of 1～4 pair of gel polymer electrolyte of the present invention of embodiment below.
embodiment 1:(a) prepare SiO
2/ PAN composition polymer microporous barrier: by 10 g PAN(molecular weight 30,000) be dissolved in 80 g NMP (1-METHYLPYRROLIDONE) and stir, then add 5 g tetraethoxysilanes and 6 g ammoniacal liquor, and be warmed up to 50 ℃ and be hydrolyzed, obtain containing SiO
2uniform sizing material, the slurry obtaining is coated on clean glass plate equably, at room temperature places after 10min and insert in tank and remove organic solvent, obtain the wet film that thickness is 100 μ m, vacuumize under 60 ℃, 0.01 MPa, obtains the composite S iO that thickness is 70 μ m again
2pAN microporous barrier.
(b) prepare the PAN base gel polymer electrolyte of composite S iO2: dried PAN microporous barrier is put into the glove box that is full of argon gas, and immersed 5min in the electrolyte of LiPF6/ EC+DMC (EC and DMC volume ratio 1:1) of 1 mol/L, after taking-up, obtain the PAN base gel polymer electrolyte of composite S iO2.
embodiment 2:(a) prepare SiO
2/ PAN composition polymer microporous barrier: by 10 g PAN(molecular weight 30,000) be dissolved in 85 g DMF (N, dinethylformamide) in stir, add again 6 g tetraethoxysilanes and 6 g ammoniacal liquor, and be warmed up to 40 ℃ and be hydrolyzed, obtain containing SiO
2uniform sizing material, the slurry obtaining is coated on clean glass plate equably, at room temperature places after 30min and insert in tank and remove organic solvent, obtain the wet film that thickness is 80 μ m, vacuumize under 60 ℃, 0.01 MPa, obtains the composite S iO that thickness is 50 μ m again
2pAN microporous barrier.
(b) prepare the PAN base gel polymer electrolyte of composite S iO2: dried PAN microporous barrier is put into the glove box that is full of neon, and the LiPF6/ EC+DMC that is immersed 0.5mol/L (represents the mixed solution of EC and DMC, volume ratio 1:2) electrolyte in 30min, after taking-up, obtain the PAN base gel polymer electrolyte of composite S iO2.
embodiment 3:(a) prepare SiO
2/ PAN composition polymer microporous barrier:
By 10 g PAN(molecular weight 30,000) be dissolved in the AN (acetonitrile) of 90 g and stir, then add 7g tetraethoxysilane and 6g ammoniacal liquor, and be warmed up to 55 ℃ and be hydrolyzed, obtain containing SiO
2uniform sizing material, the slurry obtaining is coated on clean glass plate equably, at room temperature places after 50min and insert in tank and remove organic solvent, obtain the wet film that thickness is 110 μ m, vacuumize under 60 ℃, 0.01 MPa, obtains the composite S iO that thickness is 50 μ m again
2pAN microporous barrier.
(b) prepare the PAN base gel polymer electrolyte of composite S iO2: dried PAN microporous barrier is put into the glove box that is full of helium, and the LiPF6/ EC+DMC that is immersed 1.5 mol/L (represents the mixed solution of EC and DMC, volume ratio 1:3) electrolyte in 50min, after taking-up, obtain the PAN base gel polymer electrolyte of composite S iO2.
embodiment 4:(a) prepare SiO
2/ PAN composition polymer microporous barrier: by 10 g PAN(molecular weight 30,000) be dissolved in 100 g EtOH (ethanol) and stir, then add 7g tetraethoxysilane and 6g ammoniacal liquor, and be warmed up to 60 ℃ and be hydrolyzed, obtain containing SiO
2uniform sizing material, the slurry obtaining is coated on clean glass plate equably, at room temperature places after 120min and insert in tank and remove organic solvent, obtain the wet film that thickness is 120 μ m, vacuumize under 60 ℃, 0.01 MPa, obtains the composite S iO that thickness is 60 μ m again
2pAN microporous barrier.
(b) prepare the PAN base gel polymer electrolyte of composite S iO2: dried PAN microporous barrier is put into the glove box that is full of nitrogen, and the LiPF6/ EC+DMC that is immersed 0.8mol/L (represents the mixed solution of EC and DMC, volume ratio 1:5) electrolyte in 60min, after taking-up, obtain the PAN base gel polymer electrolyte of composite S iO2.
comparative example:in comparative example of the present invention, as follows to method for preparing gel polymer electrolyte.
1. by 10 g PAN(molecular weight 30,000) be dissolved in approximately 80 g NMP (1-METHYLPYRROLIDONE), and be warmed up to 50 ℃ and stir.The slurry obtaining is coated on clean glass plate equably, then after dry under 100 ℃, 0.01 MPa vacuum, obtains the PAN gel mould of thickness approximately 45 μ m.
2. PAN microporous barrier is put into the glove box that is full of argon gas, and immersed the LiPF of 1 mol/L
65～60 min in the electrolyte of/EC+DMC (representing the mixed solution of EC and DMC, volume ratio 1:1), are taken out and are obtained PAN base gel polymer electrolyte.
conductivity test:the PAN base gel polymer electrolyte of preparing in embodiment 1～4 and comparative example is carried out respectively to conductivity test with four point probe tester, table 1 is the result of test.
Table 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example |
| Conductivity ms/cm | 4.8 | 4.1 | 3.8 | 3.3 | 0.9 |
Find by Data Comparison, the PAN base gel polymer electrolyte of embodiment 1～4 preparation, in conductivity far above the PAN base gel polymer electrolyte of preparing in comparative example.This illustrates in method for preparing gel polymer electrolyte of the present invention, by composite S iO
2particle has improved the conductivity of gel polymer electrolyte effectively, and simultaneously method of operation is safe and reliable, has solved existing liquid electrolyte and exist the problem of potential safety hazard.
charge-discharge test:table 2 is applied to respectively the data of carrying out charge-discharge test in lithium ion battery for gel polymer electrolyte prepared by embodiment 1～4 and comparative example.
The preparation of lithium ion battery comprises the following steps: take 9.0 g LiCoO
2, 0.5 g acetylene black and 0.5 g Kynoar (PVDF), and add 20 g methyl pyrrolidones (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 0.01 MPa, 80 ℃ are dried to constant weight, and are pressed into LiCoO in 10 ~ 15 MPa pressure lower rolls
2electrode, and be cut into anodal disk, lithium sheet is as negative pole.The gel electrolyte having prepared in embodiment 1 ~ 4 and comparative example is placed between both positive and negative polarity, and on stamping machine, button cell is made in sealing.
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 ion battery assembling, its performance data is listed in the table below 2.
Table 2
| Embodiment | 1 | 2 | 3 | 4 | Comparative example |
| The specific capacity (mAh/g) of electric discharge first | 120 | 116 | 112 | 107 | 95 |
As can be seen from Table 2, adopt the specific capacity of electric discharge first of the gel polymer electrolyte lithium-ion battery of embodiment 1 ~ 4 preparation all far above the specific capacity of electric discharge first of gel polymer electrolyte that adopts comparative example.Illustrate that gel polymer electrolyte of the present invention is through SiO
2after modification, security performance is high, and it has higher specific capacity after being applied to lithium ion battery.
Foregoing; it is only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skills are according to main design of the present invention and spirit; can carry out very easily corresponding flexible or modification, therefore protection scope of the present invention should be as the criterion with the desired protection range of claims.
Claims (9)
1. a method for preparing gel polymer electrolyte, is characterized in that, comprises the steps:
(a) prepare SiO
2/ PAN composition polymer microporous barrier: PAN is dissolved in organic solvent, and adds tetraethoxysilane and ammoniacal liquor, obtain containing SiO after the hydrolysis that heats up
2slurry, described slurry is coated in and on glass plate, keeps 10～120 min, then remove organic solvent and obtain wet film, to obtaining SiO after its vacuumize
2/ PAN composition polymer microporous barrier;
(b) prepare composite S iO
2pAN base gel polymer electrolyte: by described SiO
2/ PAN composition polymer microporous barrier keeps 5～60min immerse electrolyte under atmosphere of inert gases in, obtains composite S iO after taking-up
2pAN base gel polymer electrolyte.
2. preparation method according to claim 1, is characterized in that, in described step (a), the thickness of described wet film is 80～120 μ m.
3. preparation method according to claim 1, is characterized in that, in described step (a), and described SiO
2the thickness of/PAN composition polymer microporous barrier is 50～80 μ m.
4. preparation method according to claim 1, is characterized in that, in described step (a), described organic solvent is 1-METHYLPYRROLIDONE, DMF, acetonitrile or ethanol.
5. preparation method according to claim 1, it is characterized in that, in described step (a), the mass ratio of described polyacrylonitrile, described organic solvent, described tetraethoxysilane and described ammoniacal liquor is 10: (80～100): (5～8): 6.
6. preparation method according to claim 1, is characterized in that, in described step (a), the temperature of described intensification hydrolysis is 40～60 ℃.
7. preparation method according to claim 1, is characterized in that, in described step (a), described vacuum drying condition is 60 ℃, 0.01 MPa.
8. preparation method according to claim 1, is characterized in that, in described step (b), the solute of described electrolyte is lithium hexafluoro phosphate, and the concentration of described solute is 0.5～1.5 mol/L; The solvent of described electrolyte is ethylene carbonate and the dimethyl carbonate of volume ratio 1:1～1:5.
9. the gel polymer electrolyte that the arbitrary described preparation method of claim 1 to 8 makes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210489882.3A CN103840206A (en) | 2012-11-27 | 2012-11-27 | Gel polymer electrolyte and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210489882.3A CN103840206A (en) | 2012-11-27 | 2012-11-27 | Gel polymer electrolyte and preparation method thereof |
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| CN103840206A true CN103840206A (en) | 2014-06-04 |
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| CN201210489882.3A Pending CN103840206A (en) | 2012-11-27 | 2012-11-27 | Gel polymer electrolyte and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005609A (en) * | 2010-10-20 | 2011-04-06 | 浙江工业大学 | Composite gel polymer electrolyte membrane and application thereof |
| US20110206994A1 (en) * | 2008-01-16 | 2011-08-25 | Seeo, Inc | Gel polymer electrolytes for batteries |
-
2012
- 2012-11-27 CN CN201210489882.3A patent/CN103840206A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110206994A1 (en) * | 2008-01-16 | 2011-08-25 | Seeo, Inc | Gel polymer electrolytes for batteries |
| CN102005609A (en) * | 2010-10-20 | 2011-04-06 | 浙江工业大学 | Composite gel polymer electrolyte membrane and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 蒲薇华等: "原位复合SiO2的P(AN-MMA)凝胶电解质", 《电池》 * |
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Application publication date: 20140604 |