CN104362003A - Method for manufacturing gel polymer electrolyte - Google Patents
Method for manufacturing gel polymer electrolyte Download PDFInfo
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- CN104362003A CN104362003A CN201410474756.XA CN201410474756A CN104362003A CN 104362003 A CN104362003 A CN 104362003A CN 201410474756 A CN201410474756 A CN 201410474756A CN 104362003 A CN104362003 A CN 104362003A
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- gel polymer
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 31
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000011256 inorganic filler Substances 0.000 claims abstract description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 14
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 13
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000007766 curtain coating Methods 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- TYOCDPIZUIQUSO-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1C TYOCDPIZUIQUSO-UHFFFAOYSA-N 0.000 claims description 3
- -1 1-methyl-3-butyl imidazole hexafluorophosphoric acid Chemical compound 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 150000007984 tetrahydrofuranes Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 13
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000005266 casting Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 12
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 229910013684 LiClO 4 Inorganic materials 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Abstract
The embodiment of the invention discloses a method for manufacturing a gel polymer electrolyte, which comprises the following steps: dissolving electrolyte salt in a plasticizer solvent to obtain a liquid electrolyte solution; adding a polymer matrix material into a liquid electrolyte solution, adding an inorganic filler for composite modification, adding an organic solvent, and uniformly mixing to obtain a first mixed solution; adding ionic liquid into the first mixed solution to obtain a second mixed solution; and carrying out casting treatment on the second mixed solution in a mould and drying to obtain the gel polymer electrolyte. The method for preparing the blended ionic liquid composite gel polymer electrolyte provided by the invention is simple to operate, low in production cost, high in safety, easy to control the preparation process, and widely applicable to the production of electrolytes.
Description
Technical field
The present invention relates to technical field of electronic materials, especially relate to the method for a kind of manufacture for the gel polymer electrolyte of capacitor.
Background technology
Ultracapacitor is primarily of several part composition such as polarizing electrode, collector electrode, electrolyte, barrier film, lead-in wire and encapsulating material, wherein electrolyte needs very high conductivity and enough electrochemical stabilities, to ensure that ultracapacitor can at operating at voltages high as far as possible.Gel polymer electrolyte has above excellent characteristic and no leakage, serviceability temperature wide ranges, and the research therefore using gel polymer electrolyte to improve capacitor performance gets more and more.
Polyblend is a kind of effective ways preparing new type gel polymer dielectric, can improve single a kind of matrix material conductivity low, bad mechanical property, the shortcomings such as electrochemical window is narrow.
In gel polymer electrolyte, add nanometer inorganic filler formation composite gel polymer electrolyte can effectively improve electrolytical conductivity.The high-specific surface area of nanometer inorganic filler can suppress the crystallization behavior of polymer molecular chain, thus increases the ratio of polymer amorphous area, reduces degree of crystallinity and the glass transition temperature of polymer, improves electrolytical conductivity.
Ionic liquid at room temperature has following characteristics: (1) does not almost have vapour pressure, has non-volatile characteristic; (2) conductivity is good; (3) electrochemical window is wider; (4) there is wider stable temperature scope.Therefore in gel polymer electrolyte, introduce ionic liquid, obtaining ionic liquid-gel polymer electrolyte ideally can combine the advantage of ionic liquid and gel polymer electrolyte.
At present the existing method preparing polymer dielectric mostly be blended, compound, introducing ionic liquid.But, merely adopt blended, compound or introduce polymer dielectric prepared by a kind of method of ionic liquid and can not meet that high conductivity required by electrolyte, electrochemical window are wide, the requirement of serviceability temperature wide ranges, electrochemical stability and excellent mechanical properties well.
Summary of the invention
An object of the present invention is to provide a kind of method manufacturing gel polymer electrolyte, according to the gel polymer electrolyte of the method manufacture, there is high conductivity and wider electrochemical window, and thermal stability, electrochemical stability and mechanical performance are all more excellent.
Technical scheme disclosed by the invention comprises:
Provide a kind of method manufacturing gel polymer electrolyte, it is characterized in that, comprising: electrolytic salt is dissolved in plasticizer solvent, obtain liquid electrolyte solution; Matrix material is added in described liquid electrolyte solution, adds inorganic filler and carry out composite modified, and Homogeneous phase mixing after adding organic solvent, obtain the first mixed solution; In described first mixed solution, add ionic liquid, obtain the second mixed solution; Described second mixed solution is carried out in a mold curtain coating process and drying, obtain gel polymer electrolyte.
In one embodiment of the present of invention, described electrolytic salt is lithium perchlorate, lithium hexafluoro phosphate or hexafluorophosphoric acid tetraethyl amine.
In one embodiment of the present of invention, described plasticizer solvent is one or more in propene carbonate, diethyl carbonate, dimethyl carbonate and ethylene carbonate.
In one embodiment of the present of invention, in described liquid electrolyte solution, the concentration of described electrolytic salt is 0.6 mol/L to 1.5 mol/L.
In one embodiment of the present of invention, described matrix material is polymethyl methacrylate and Kynoar-hexafluoropropylene, and the mass ratio of described polymethyl methacrylate and described Kynoar-hexafluoropropylene is 1:10 to 1:4; And: the mass ratio of described matrix material and described electrolytic salt is 1.8:1 to 2.6:1.
In one embodiment of the present of invention, described inorganic filler is nano silicon, nano-aluminium oxide, nano magnesia or nano titanium oxide, and the mass ratio of described inorganic filler and described matrix material is 1:9 to 1:10.5.
In one embodiment of the present of invention, described organic solvent is oxolane, acetonitrile, DMF or 1-Methyl-2-Pyrrolidone, and described organic solvent is 5:1 to 10:1 with the volume mass ratio of described matrix material.
In one embodiment of the present of invention, described ionic liquid is 1,2-dimethyl-3-N-butyl imidazole, 1-methyl-3-ethyl imidazol(e) tetrafluoro boric acid or 1-methyl-3-butyl imidazole hexafluorophosphoric acid, and the mass ratio of described ionic liquid and matrix material is 1.5:1 to 2.2:1.
The method of the manufacture provided in embodiments of the invention blended ionic liquid composite gel polymer electrolyte is simple to operate, production cost is low, fail safe is high and preparation technology is easy to control, and can be widely used in electrolytical production.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the manufacture gel polymer electrolyte of one embodiment of the invention.
Embodiment
The concrete steps of the method for the manufacture gel polymer electrolyte of embodiments of the invention are described in detail below in conjunction with accompanying drawing.
Fig. 1 is the schematic flow sheet of the method for the manufacture gel polymer electrolyte of one embodiment of the invention.Be described in detail below in conjunction with specific embodiment each step to the method.
Step 10: preparation liquid electrolyte solution.
As shown in Figure 1, in step 10, can electrolytic salt be dissolved in plasticizer solvent, obtain liquid electrolyte solution.
In an embodiment, electrolytic salt here can be lithium perchlorate (LiClO
4), lithium hexafluoro phosphate (LiPF
6) or hexafluorophosphoric acid tetraethyl amine ((C
2h
5)
4nPF
6) etc.
In an embodiment, here plasticizer solvent can be one or more in propene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and ethylene carbonate (EC), and in this plasticizer solvent, the volume fraction of each component can be identical.
In an embodiment, in the liquid electrolyte solution obtained in step 10, the concentration of electrolytic salt can be that 0.6 mol/L (mol/L) is to 1.5 mol/L (mol/L).
Step 12: prepare the first mixed solution.
After obtaining liquid electrolyte solution, in step 12, matrix material can be added in this electrolyte solution, and add inorganic filler and carry out composite modified, add Homogeneous phase mixing after organic solvent simultaneously, thus obtain the first mixed solution.
In an embodiment, here matrix material can be polymethyl methacrylate (PMMA) and Kynoar-hexafluoropropylene (PVDF-HFP), and in this matrix material, the mass ratio of PMMA and PVDF-HFP can be 1:10 ~ 1:4.And in an embodiment, total matrix material (i.e. PMMA and PVDF-HFP) can be 1.8:1 ~ 2.6:1 with the mass ratio of aforesaid electrolytic salt.
In an embodiment, inorganic filler here can be nano silicon (SiO
2), nano-aluminium oxide (Al
2o
3), nano magnesia (MgO) or nano titanium oxide (TiO
2) etc., and the mass ratio of this inorganic filler and aforesaid matrix material can be 1:9 ~ 1:10.5.
In an embodiment, here organic solvent can be oxolane (THF), acetonitrile, N, dinethylformamide (DMF) or 1-Methyl-2-Pyrrolidone (NMP) etc., and this organic solvent can be 5:1 ~ 10:1 with the volume mass ratio of aforesaid matrix material.
In one embodiment of the present of invention, in step 12, can stir after aforesaid each component mixing 12 to 15 hours on magnetic stirring apparatus, each component fully be mixed, thus obtains aforesaid first mixed solution.
Step 14: prepare the second mixed solution.
After having prepared the first mixture solution in step 12, at step 14, ionic liquid can be added in this first mixture solution, thus obtain the second mixture solution.
In an embodiment, ionic liquid here can be 1,2-dimethyl-3-N-butyl imidazole (DMBITFSI), 1-methyl-3-ethyl imidazol(e) tetrafluoro boric acid (EMIBF
4) or 1-methyl-3-butyl imidazole hexafluorophosphoric acid (BMIPF
6) etc., and the mass ratio of this ionic liquid and aforesaid matrix material can be 1.5:1 ~ 2.2:1.
In an embodiment, add aforesaid ionic liquid in the first mixed solution after, can also stir at ambient temperature on magnetic stirring apparatus after 1 ~ 2 hour and leave standstill 5 minutes removal bubbles, thus obtain the second mixture solution.
Step 16: the second mixed solution is carried out curtain coating process and drying, obtain gel polymer electrolyte.
After obtaining the second mixture solution at step 14, in step 16, the second mixture solution can be placed in mould curtain coating, then insert in drying box, drying 40 to 50 hours at the temperature of 60 to 120 degrees Celsius.
Like this, through each step aforesaid, required gel polymer electrolyte can be obtained.
The following detailed description of several concrete example of the present invention.
Example 1:
Take 0.6g LiClO
4be dissolved in (wherein the volume ratio of PC and DEC is 1:1) in the mixed solution of 9.43ml PC and DEC, fully dissolve the liquid electrolyte being mixed with 0.6mol/L; Separately take the mixed polymer matrix of 0.098g PMMA and 0.982g PVDF-HFP, 0.108g Al
2o
3join in aforesaid liquid electrolyte, separately add 10ml NMP and mix, room temperature lower magnetic force stirs 12h and obtains solution A; Get 1.62g EMIBF
4add in solution A, stirred at ambient temperature 1h, leave standstill 5 minutes and remove bubble, obtain solution B; By solution B curtain coating in Teflon mould, move in 80 DEG C of drying boxes, take off after drying 40h, just obtain blended ionic liquid composite gel polymer electrolyte film.
Obtained blended ionic liquid composite gel polymer electrolyte film and stainless steel electrode are formed and block battery and test at electrochemical workstation, conductivity is 3.5mS/cm, and electrochemical operation window is 4.2V.
Example 2:
Take 0.8g LiClO
4be dissolved in (wherein the volume ratio of PC and DEC is 1:1) in the mixed solution of 9.43ml PC and DEC, fully dissolve the liquid electrolyte being mixed with 0.8mol/L; Separately take the mixed polymer matrix of 0.13g PMMA and 1.31g PVDF-HFP, 0.137g Al
2o
3join in aforesaid liquid electrolyte, separately add 10ml NMP and mix, room temperature lower magnetic force stirs 12h and obtains solution A; Get 2.2g EMIBF
4add in solution A, stirred at ambient temperature 1h, leave standstill 5 minutes and remove bubble, obtain solution B; By solution B curtain coating in Teflon mould, move in 80 DEG C of drying boxes, take off after drying 40h, just obtain blended ionic liquid composite gel polymer electrolyte film.
Obtained blended ionic liquid composite gel polymer electrolyte film and stainless steel electrode are formed and block battery and test at electrochemical workstation, conductivity is 5.22mS/cm, and electrochemical operation window is 4.1V.
Example 3:
Take 1g LiClO
4be dissolved in (wherein the volume ratio of PC and DEC is 1:1) in the mixed solution of 9.43ml PC and DEC, fully dissolve the liquid electrolyte being mixed with 1mol/L; Separately take the mixed polymer matrix of 0.182g PMMA and 1.818g PVDF-HFP, 0.2g Al
2o
3join in aforesaid liquid electrolyte, separately add 10ml NMP and mix, room temperature lower magnetic force stirs 12h and obtains solution A; Get 3g EMIBF
4add in solution A, stirred at ambient temperature 1h, leave standstill 5 minutes and remove bubble, obtain solution B; By solution B curtain coating in Teflon mould, move in 80 DEG C of drying boxes, take off after drying 40h, just obtain blended ionic liquid composite gel polymer electrolyte film.
Obtained blended ionic liquid composite gel polymer electrolyte film and stainless steel electrode are formed and block battery and test at electrochemical workstation, conductivity is 7.36mS/cm, and electrochemical operation window is 4.5V.
Example 4:
Take 1.2g LiClO
4be dissolved in (wherein the volume ratio of PC and DEC is 1:1) in the mixed solution of 9.43ml PC and DEC, fully dissolve the liquid electrolyte being mixed with 1.2mol/L; Separately take the mixed polymer matrix of 0.4g PMMA and 2g PVDF-HFP, 0.24g Al
2o
3join in aforesaid liquid electrolyte, separately add 10ml NMP and mix, room temperature lower magnetic force stirs 12h and obtains solution A; Get 3.6g EMIBF
4add in solution A, stirred at ambient temperature 1h, leave standstill 5 minutes and remove bubble, obtain solution B; By solution B curtain coating in Teflon mould, move in 80 DEG C of drying boxes, take off after drying 40h, just obtain blended ionic liquid composite gel polymer electrolyte film.
Obtained blended ionic liquid composite gel polymer electrolyte film and stainless steel electrode are formed and block battery and test at electrochemical workstation, conductivity is 4.3mS/cm, and electrochemical operation window is 4.05V.
Example 5:
Take 1.5g LiClO
4be dissolved in (wherein the volume ratio of PC and DEC is 1:1) in the mixed solution of 9.43ml PC and DEC, fully dissolve the liquid electrolyte being mixed with 1.5mol/L; Separately take the mixed polymer matrix of 0.5g PMMA and 2.5g PVDF-HFP, 0.3g Al
2o
3join in aforesaid liquid electrolyte, separately add 10ml NMP and mix, room temperature lower magnetic force stirs 12h and obtains solution A; Get 4.5g EMIBF
4add in solution A, stirred at ambient temperature 1h, leave standstill 5 minutes and remove bubble, obtain solution B; By solution B curtain coating in Teflon mould, move in 80 DEG C of drying boxes, take off after drying 40h, just obtain blended ionic liquid composite gel polymer electrolyte film.
Obtained blended ionic liquid composite gel polymer electrolyte film and stainless steel electrode are formed and block battery and test at electrochemical workstation, conductivity is 3.4mS/cm, and electrochemical operation window is 4.1V.
In embodiments of the invention, the advantages such as thermal stability, high conductivity and wider electrochemical window can not be possessed for conventional gel polymer dielectric simultaneously, propose to carry out modification by blended and method that is compound to gel polymer electrolyte, and introduce ionic liquid at room temperature to prepare blended ionic liquid composite gel polymer electrolyte.The electrolytic conductivity prepared by the method for the embodiment of the present invention is higher, and Heat stability is good, electrochemical window are wider, satisfactory mechanical property and can be well compatible etc. with electrode material, can meet the instructions for use of ultracapacitor and lithium ion battery etc.
The method of the manufacture provided in embodiments of the invention blended ionic liquid composite gel polymer electrolyte is simple to operate, production cost is low, fail safe is high and preparation technology is easy to control, and can be widely used in electrolytical production.
Described the present invention by specific embodiment above, but the present invention is not limited to these specific embodiments.It will be understood by those skilled in the art that and can also make various amendment, equivalent replacement, change etc. to the present invention, as long as these conversion do not deviate from spirit of the present invention, all should within protection scope of the present invention.In addition, " embodiment " described in above many places represents different embodiments, can certainly by its all or part of combination in one embodiment.
Claims (8)
1. manufacture a method for gel polymer electrolyte, it is characterized in that, comprising:
Electrolytic salt is dissolved in plasticizer solvent, obtains liquid electrolyte solution;
Matrix material is added in described liquid electrolyte solution, adds inorganic filler and carry out composite modified, and Homogeneous phase mixing after adding organic solvent, obtain the first mixed solution;
In described first mixed solution, add ionic liquid, obtain the second mixed solution;
Described second mixed solution is carried out in a mold curtain coating process and drying, obtain gel polymer electrolyte.
2. the method for claim 1, is characterized in that: described electrolytic salt is lithium perchlorate, lithium hexafluoro phosphate or hexafluorophosphoric acid tetraethyl amine.
3. as described in claim 1 or 2 method, is characterized in that: described plasticizer solvent is one or more in propene carbonate, diethyl carbonate, dimethyl carbonate and ethylene carbonate.
4. method as claimed any one in claims 1 to 3, it is characterized in that: in described liquid electrolyte solution, the concentration of described electrolytic salt is 0.6 mol/L to 1.5 mol/L.
5. the method according to any one of Claims 1-4, it is characterized in that: described matrix material is polymethyl methacrylate and Kynoar-hexafluoropropylene, and the mass ratio of described polymethyl methacrylate and described Kynoar-hexafluoropropylene is 1:10 to 1:4; And: the mass ratio of described matrix material and described electrolytic salt is 1.8:1 to 2.6:1.
6. the method for claim 1, it is characterized in that: described inorganic filler is nano silicon, nano-aluminium oxide, nano magnesia or nano titanium oxide, and the mass ratio of described inorganic filler and described matrix material is 1:9 to 1:10.5.
7. the method according to any one of claim 1 to 6, it is characterized in that: described organic solvent is oxolane, acetonitrile, N, dinethylformamide or 1-Methyl-2-Pyrrolidone, and described organic solvent is 5:1 to 10:1 with the volume mass ratio of described matrix material.
8. the method for claim 1, it is characterized in that: described ionic liquid is 1,2-dimethyl-3-N-butyl imidazole, 1-methyl-3-ethyl imidazol(e) tetrafluoro boric acid or 1-methyl-3-butyl imidazole hexafluorophosphoric acid, and the mass ratio of described ionic liquid and matrix material is 1.5:1 to 2.2:1.
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|---|---|---|---|
| CN201410474756.XA CN104362003A (en) | 2014-09-18 | 2014-09-18 | Method for manufacturing gel polymer electrolyte |
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|---|---|---|---|
| CN201410474756.XA CN104362003A (en) | 2014-09-18 | 2014-09-18 | Method for manufacturing gel polymer electrolyte |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107039680A (en) * | 2016-02-03 | 2017-08-11 | 三星电子株式会社 | Solid electrolyte and the lithium battery for including the solid electrolyte |
| CN110783114A (en) * | 2019-11-20 | 2020-02-11 | 西安合容新能源科技有限公司 | High-voltage-resistant aqueous electrolyte and application thereof in high-voltage super capacitor |
| CN113035587A (en) * | 2021-03-12 | 2021-06-25 | 西安交通大学 | Preparation method of low-temperature solid electrolyte and application of low-temperature solid electrolyte in low-temperature solid supercapacitor |
| TWI760922B (en) * | 2020-11-17 | 2022-04-11 | 國立成功大學 | Electrolyte and fabricating method thereof, and lithium battery |
| CN115472907A (en) * | 2022-11-03 | 2022-12-13 | 河南省法恩莱特新能源科技有限公司 | Preparation method of gel polymer electrolyte |
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| CN102130364A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | Gel-type polymer electrolyte used for lithium-sulfur secondary battery system and preparation method |
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| CN101740813A (en) * | 2009-12-16 | 2010-06-16 | 北京理工大学 | Ionic liquid compound electrolyte material |
| CN102130364A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | Gel-type polymer electrolyte used for lithium-sulfur secondary battery system and preparation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107039680A (en) * | 2016-02-03 | 2017-08-11 | 三星电子株式会社 | Solid electrolyte and the lithium battery for including the solid electrolyte |
| CN110783114A (en) * | 2019-11-20 | 2020-02-11 | 西安合容新能源科技有限公司 | High-voltage-resistant aqueous electrolyte and application thereof in high-voltage super capacitor |
| CN110783114B (en) * | 2019-11-20 | 2021-10-22 | 西安合容新能源科技有限公司 | High-voltage-resistant aqueous electrolyte and application thereof in high-voltage super capacitor |
| TWI760922B (en) * | 2020-11-17 | 2022-04-11 | 國立成功大學 | Electrolyte and fabricating method thereof, and lithium battery |
| CN113035587A (en) * | 2021-03-12 | 2021-06-25 | 西安交通大学 | Preparation method of low-temperature solid electrolyte and application of low-temperature solid electrolyte in low-temperature solid supercapacitor |
| CN115472907A (en) * | 2022-11-03 | 2022-12-13 | 河南省法恩莱特新能源科技有限公司 | Preparation method of gel polymer electrolyte |
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