JP7429753B2 - Electrolyte and its manufacturing method - Google Patents
Electrolyte and its manufacturing method Download PDFInfo
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- JP7429753B2 JP7429753B2 JP2022169631A JP2022169631A JP7429753B2 JP 7429753 B2 JP7429753 B2 JP 7429753B2 JP 2022169631 A JP2022169631 A JP 2022169631A JP 2022169631 A JP2022169631 A JP 2022169631A JP 7429753 B2 JP7429753 B2 JP 7429753B2
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- colloid
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- colloidal electrolyte
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- 239000003792 electrolyte Substances 0.000 title claims description 130
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 239000000463 material Substances 0.000 claims description 51
- 239000012528 membrane Substances 0.000 claims description 39
- 239000000084 colloidal system Substances 0.000 claims description 38
- 238000001125 extrusion Methods 0.000 claims description 32
- 239000012530 fluid Substances 0.000 claims description 23
- 238000004898 kneading Methods 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 159000000002 lithium salts Chemical class 0.000 claims description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims description 15
- 239000002313 adhesive film Substances 0.000 claims description 14
- 239000004014 plasticizer Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 13
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229920001169 thermoplastic Polymers 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 5
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- 239000011863 silicon-based powder Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 3
- RBYFNZOIUUXJQD-UHFFFAOYSA-J tetralithium oxalate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O RBYFNZOIUUXJQD-UHFFFAOYSA-J 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical group CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical group OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims 1
- 239000004634 thermosetting polymer Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000011244 liquid electrolyte Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910012258 LiPO Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical group O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- IGCKVOUYIUHUIG-UHFFFAOYSA-N [Li]C(F)(F)F Chemical compound [Li]C(F)(F)F IGCKVOUYIUHUIG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
- 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
- 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
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、電解質及びその製造方法、特にコロイド電解質、及び該コロイド電解質を混練方式で製造する製造方法に関する。 The present invention relates to an electrolyte and a method for producing the same, particularly a colloidal electrolyte, and a method for producing the colloidal electrolyte by a kneading method.
現在の電解質の形態には、固体、液体やコロイドなどがある。液体電解質はイオン伝導率が高く、通電の効果が良いが、流動性を有するため、長時間使用されたり外力に押されたりすると、液漏れが生じやすく、電子部品が作動できなくなる。さらに、液体電解質には強酸や強アルカリなどの溶媒が含まれており、これらの溶媒が漏れると安全上のリスクを招く。固体電解質は、液体電解質の代わりに高分子や無機金属酸化物を用いることで、液体電解質の液漏れの問題を解決できるが、固体電解質と電極との間にインタフェース抵抗が存在するため、固体電解質のイオン伝導率が高くなく、電子部品の性能が望ましくない。コロイド電解質は固体電解質と液体電解質の間のものであり、双方の優位性を持ち、将来の電解質材料の主流となる。しかし、現在一般的なコロイド電解質には、濃度分布が不均一であり、光透過性が悪く、伝導率が低いなどの問題があり、このため、従来のコロイド電解質を改良する必要がある。 Current forms of electrolytes include solids, liquids, and colloids. Liquid electrolytes have high ionic conductivity and are effective in conducting electricity, but because they have fluidity, they tend to leak when used for long periods of time or are pushed by external forces, making electronic components inoperable. Furthermore, liquid electrolytes contain solvents such as strong acids and strong alkalis, which pose a safety risk if these solvents leak. Solid electrolytes can solve the leakage problem of liquid electrolytes by using polymers or inorganic metal oxides instead of liquid electrolytes, but since there is an interface resistance between solid electrolytes and electrodes, solid electrolytes Its ionic conductivity is not high, and the performance of electronic components is undesirable. Colloidal electrolytes are between solid electrolytes and liquid electrolytes, have the advantages of both, and will become the mainstream of future electrolyte materials. However, currently common colloidal electrolytes have problems such as non-uniform concentration distribution, poor light transmittance, and low conductivity.Therefore, it is necessary to improve conventional colloidal electrolytes.
本発明の1つの目的は、高粘着性、高透光率及び高伝導率の特性を同時に備える電解質を提供することである。 One objective of the present invention is to provide an electrolyte with the properties of high viscosity, high light transmittance and high conductivity at the same time.
本発明の別の目的は、完成品が保存されやすく、生産力を高めるという特徴がある電解質の製造方法を提供する。 Another object of the present invention is to provide a method for producing an electrolyte, which is characterized in that the finished product is easily preserved and productivity is increased.
本発明のさらなる目的は、エレクトロクロミック技術、ポリマーリチウム電池、スーパーキャパシタンス及びスーパーバッテリーなど、電気化学エネルギー貯蔵や省エネ技術の分野に有用であるコロイド電解質、及び該コロイド電解質を混練方式で製造する製造方法を提供することである。 A further object of the present invention is a colloidal electrolyte useful in the fields of electrochemical energy storage and energy saving technologies, such as electrochromic technology, polymer lithium batteries, supercapacitance and superbatteries, and a manufacturing method for producing the colloidal electrolyte by a kneading method. The goal is to provide the following.
上記及び他の目的を達成させるために、本発明の電解質は、高分子材料と、リチウム塩と、有機溶媒と、可塑剤と、イオン性溶液と、補助材料と、を含み、これらを混練してコロイド状にしたものであり、該高分子材料は約20~45重量%、該リチウム塩は約2~20重量%、該有機溶媒は約10~30重量%、該可塑剤は約10~30重量%、該イオン性溶液は約1~4重量%、該補助材料は約1~4重量%である。 In order to achieve the above and other objects, the electrolyte of the present invention includes a polymeric material, a lithium salt, an organic solvent, a plasticizer, an ionic solution, and an auxiliary material, which are kneaded together. The polymer material is about 20-45% by weight, the lithium salt is about 2-20% by weight, the organic solvent is about 10-30% by weight, and the plasticizer is about 10-45% by weight. 30% by weight, the ionic solution is about 1-4% by weight, and the auxiliary material is about 1-4% by weight.
上記及び他の目的を達成させるために、本発明の電解質の製造方法は、高分子材料を約50~70℃の反応温度で約15~30分間反応させ、脱水乾燥して乾燥高分子材料を得る乾燥ステップと、該乾燥高分子材料をリチウム塩、有機溶媒、可塑剤、イオン性溶液及び補助材料と均一に撹拌し、コロイド電解質を得る材料混合ステップと、該コロイド電解質を70~140℃の反応温度で約2~10分間反応させ、混練して該コロイド電解質を均一にする混練ステップと、を含む。 In order to achieve the above and other objects, the method for producing an electrolyte of the present invention involves reacting a polymeric material at a reaction temperature of about 50 to 70°C for about 15 to 30 minutes, and dehydrating and drying it to obtain a dry polymeric material. a drying step to obtain a colloidal electrolyte by uniformly stirring the dry polymeric material with a lithium salt, an organic solvent, a plasticizer, an ionic solution and an auxiliary material to obtain a colloidal electrolyte; a kneading step of reacting at a reaction temperature for about 2 to 10 minutes and kneading to homogenize the colloidal electrolyte.
本発明のいくつかの実施例では、該高分子材料は熱可塑性高分子材料又は熱硬化性高分子材料であり、ポリビニルブチラール(PVB)、酢酸ビニル共重合体(EVA)、エポキシ樹脂(EP)及びポリエチレン(PE)からなる群から選択される少なくとも1種の材料又は他の代替可能な材料である。 In some embodiments of the invention, the polymeric material is a thermoplastic polymeric material or a thermoset polymeric material, such as polyvinyl butyral (PVB), vinyl acetate copolymer (EVA), epoxy resin (EP), etc. and polyethylene (PE) or other alternative materials.
本発明のいくつかの実施例では、該リチウム塩は、ヘキサフルオロリン酸リチウム(LiPF6)、テトラフルオロホウ酸リチウム(LiBF4)、過塩素酸リチウム(LiClO4)、ヘキサフルオロヒ素酸リチウム(LiAsF6)、トリフルオロメチルスルホン酸リチウム(LiCF3SO3)、ビス(シュウ酸)ホウ酸リチウム(LiBOB)、リチウムジフルオロ(オキサラト)ボレート(LiODFB)、ビス(トリフルオロメタンスルホニル)イミドリチウム(LiTFSI)、リチウムビス(フルオロスルホニル)イミド(LiFSI)、ジフルオロリン酸リチウム(LiPO2F2)及びテトラフルオロシュウ酸リン酸リチウム(LiFOP)からなる群から選択される少なくとも1種の材料又は他の代替可能な材料である。 In some embodiments of the invention, the lithium salt is lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate ( LiAsF 6 ), lithium trifluoromethylsulfonate (LiCF 3 SO 3 ), lithium bis(oxalate)borate (LiBOB), lithium difluoro(oxalato)borate (LiODFB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) , lithium bis(fluorosulfonyl)imide (LiFSI), lithium difluorophosphate (LiPO 2 F 2 ), and lithium tetrafluorooxalate phosphate (LiFOP) or other possible substitutes. It is a good material.
本発明のいくつかの実施例では、該有機溶媒はプロピレンカーボネート(PC)、エチレンカーボネート(EC)、酪酸プロピル(γ-BL)、N-メチル-ピロリジン(NMP)及びジメチルカーボネート(DMC)からなる群から選択される少なくとも1種の材料又は他の代替可能な材料である。 In some embodiments of the invention, the organic solvent consists of propylene carbonate (PC), ethylene carbonate (EC), propyl butyrate (γ-BL), N-methyl-pyrrolidine (NMP), and dimethyl carbonate (DMC). at least one material selected from the group or other alternative materials.
本発明のいくつかの実施例では、該可塑剤は、ジエチレングリコールブチルエーテル(Diethylene Glycol Monobutyl Ether)又はアジピン酸(Adipic acid)から選択される。 In some embodiments of the invention, the plasticizer is selected from Diethylene Glycol Monobutyl Ether or Adipic acid.
本発明のいくつかの実施例では、該イオン性溶液は、実質的には、主シクロプロピルから構成される。 In some embodiments of the invention, the ionic solution consists essentially of primarily cyclopropyl.
本発明のいくつかの実施例では、該補助材料はトナー、UV吸収剤、光安定剤、温度安定剤及びシリコン粉末からなる群から選択される少なくとも1種の材料である。 In some embodiments of the invention, the auxiliary material is at least one material selected from the group consisting of toner, UV absorber, light stabilizer, temperature stabilizer, and silicon powder.
本発明のいくつかの実施例では、該混練ステップで混練した該コロイド電解質を押し出し、高速カッターを利用して造粒しながら、急速な降温及び乾燥をし、顆粒状電解質を製造する押出造粒ステップをさらに含む。 In some embodiments of the present invention, the colloidal electrolyte kneaded in the kneading step is extruded and granulated using a high-speed cutter while rapidly cooling and drying to produce a granular electrolyte. further including steps.
本発明のいくつかの実施例では、該押出造粒ステップでは、作動温度は約100~140℃であり、押出圧力は約0.2~1メガパスカル(MPa)であり、製造された該顆粒状電解質の顆粒のサイズが約1~30mmである。 In some embodiments of the invention, in the extrusion granulation step, the operating temperature is about 100-140° C., the extrusion pressure is about 0.2-1 megapascals (MPa), and the granules produced The size of the electrolyte granules is approximately 1 to 30 mm.
本発明のいくつかの実施例では、該混練ステップで混練した該コロイド電解質を80~150℃で加熱して溶融し、流動性コロイドとし、開口径サイズを調整可能なスリット状吐出口を先端に有する塗布ヘッドのキャビティに該流動性コロイドを前記キャビティの圧力により注入し、該流動性コロイドを該スリット状吐出口から均一に流出させ、離型膜上に塗布して粘着膜構造を形成し、次に、エアナイフにより急速に降温し、厚さを制御してコロイド電解質膜を形成する第1コロイド電解質膜形成ステップをさらに含む。 In some embodiments of the present invention, the colloidal electrolyte kneaded in the kneading step is heated at 80 to 150° C. to melt it to form a fluid colloid, and a slit-like discharge port whose opening diameter size can be adjusted is disposed at the tip. Injecting the fluid colloid into a cavity of a coating head having a coating head using the pressure of the cavity, causing the fluid colloid to uniformly flow out from the slit-shaped discharge port, and applying the fluid colloid onto a release film to form an adhesive film structure; Next, the method further includes forming a first colloidal electrolyte membrane by rapidly lowering the temperature using an air knife and controlling the thickness to form a colloidal electrolyte membrane.
本発明のいくつかの実施例では、該押出造粒ステップで製造された該顆粒状電解質を約70~140℃の反応温度で約2~10分間反応させ、混練して該顆粒状電解質を第2コロイド電解質とし、該第2コロイド電解質を約80~150℃で加熱して溶融し、流動性コロイドとし、開口径サイズを調整可能なスリット状吐出口を先端に有する塗布ヘッドのキャビティに該流動性コロイドを前記キャビティの圧力により注入し、該流動性コロイドを該スリット状吐出口から均一に流出させ、離型膜上に塗布して粘着膜構造を形成し、エアナイフにより急速に降温し、粘着膜の厚さを制御してコロイド電解質膜を形成する第2コロイド電解質膜形成ステップをさらに含む。 In some embodiments of the invention, the granular electrolyte produced in the extrusion granulation step is reacted at a reaction temperature of about 70-140° C. for about 2-10 minutes and kneaded to form the granular electrolyte. The second colloidal electrolyte is heated at about 80 to 150°C to melt it and become a fluid colloid, which is then flowed into a cavity of a coating head having a slit-shaped discharge port with an adjustable opening diameter at the tip. The fluid colloid is injected by the pressure of the cavity, the fluid colloid is uniformly flowed out from the slit-shaped discharge port, and is applied onto the release film to form an adhesive film structure. The method further includes forming a second colloidal electrolyte membrane by controlling the thickness of the membrane.
本発明のいくつかの実施例では、該混練ステップで混練した該コロイド電解質体を押出温度約80~160℃、エアナイフ噴射口の風圧約95~1000キロパスカル(kPa)、押出圧力約0.5~1メガパスカル(MPa)で加熱して押し出し、厚さ約0.005~3mmのコロイド電解質膜を形成する、第3コロイド電解質膜形成ステップをさらに含む。 In some embodiments of the present invention, the colloidal electrolyte body kneaded in the kneading step is extruded at a temperature of about 80 to 160°C, a wind pressure of an air knife jet of about 95 to 1000 kilopascals (kPa), and an extrusion pressure of about 0.5 The method further includes a third colloidal electrolyte membrane forming step of heating and extruding at ~1 megapascal (MPa) to form a colloidal electrolyte membrane having a thickness of approximately 0.005 to 3 mm.
本発明のいくつかの実施例では、該押出造粒ステップで製造された該顆粒状電解質を、押出延流法により約70~140℃で加熱して粘稠状コロイドとし、次に、該粘稠状コロイドを押出温度約80~160℃、エアナイフ噴射口の風圧約95~1000キロパスカル(kPa)、押出圧力約0.5~1メガパスカル(MPa)で加熱して押し出し、厚さ約0.005~3mmのコロイド電解質膜を形成する、第4コロイド電解質膜形成ステップをさらに含む。 In some embodiments of the invention, the granular electrolyte produced in the extrusion granulation step is heated to a viscous colloid by an extrusion flow process at about 70-140°C; The viscous colloid is heated and extruded at an extrusion temperature of about 80 to 160°C, a wind pressure of about 95 to 1000 kilopascals (kPa) from the air knife nozzle, and an extrusion pressure of about 0.5 to 1 megapascal (MPa) to a thickness of about 0. The method further includes a fourth colloidal electrolyte membrane forming step of forming a colloidal electrolyte membrane with a thickness of .005 to 3 mm.
本発明の有益な効果は以下の通りである。 The beneficial effects of the present invention are as follows.
本発明のコロイド電解質では、特定成分及び各成分間の特定の割合を採用し、混練により各成分を均一に分散させることによって、該コロイド電解質は、凝集機械的性質が高いため低流動性を有する。イオン伝導率も固体電解質よりも明らかに向上し、イオン伝導率が高い、スペーサを必要としない、ガラスやプラスチックなどの粘着に有用であるなどの特性を実現する。安全性が高いので液漏れを回避し、また、高粘着性、高透光率及び高伝導率を有する。 In the colloidal electrolyte of the present invention, by employing specific components and specific ratios between each component and uniformly dispersing each component by kneading, the colloidal electrolyte has low fluidity due to high cohesive mechanical properties. . The ionic conductivity is also clearly improved compared to solid electrolytes, realizing properties such as high ionic conductivity, no need for spacers, and useful for adhesion to glass, plastic, etc. It is highly safe to avoid liquid leakage, and also has high adhesiveness, high light transmittance and high conductivity.
本発明の電解質は、エレクトロクロミックデバイスの電解質層に利用可能であり、また、粘着技術を利用して作製できる。また、従来のエネルギー貯蔵部品例えばスーパーキャパシタンス、リチウムポリマー電池、スーパーバッテリーの電解質は全てセパレータと組み合わせて電極から隔離されて、電極導通を回避することができる。これらを比較すると、本発明の電解質は粘着膜にした場合、2つの電極間にスペーサ及びイオン伝達や電子バリアのためのものとして使用できる。 The electrolyte of the present invention can be used as an electrolyte layer of an electrochromic device, and can also be produced using adhesive technology. Additionally, the electrolytes of conventional energy storage components such as supercapacitances, lithium polymer batteries, and superbatteries can all be isolated from the electrodes in combination with separators to avoid electrode conduction. Comparing these, when the electrolyte of the present invention is made into an adhesive film, it can be used as a spacer between two electrodes and as a barrier for ion transfer and electrons.
図1は本発明の電解質の製造方法の一実施例のフローチャートである。図1に示すように、本実施例の電解質は、高分子材料と、リチウム塩と、有機溶媒と、可塑剤と、イオン性溶液と、補助材料と、を含み、これらを混練してコロイド状にしたものである。該高分子材料は約20~45重量%、該リチウム塩は約2~20重量%、該有機溶媒は約10~30重量%、該可塑剤は約10~30重量%、該イオン性溶液は約1~4重量%、該補助材料は約1~4重量%である。 FIG. 1 is a flowchart of an embodiment of the electrolyte manufacturing method of the present invention. As shown in FIG. 1, the electrolyte of this example includes a polymer material, a lithium salt, an organic solvent, a plasticizer, an ionic solution, and an auxiliary material, which are kneaded to form a colloid. This is what I did. The polymeric material is about 20-45% by weight, the lithium salt is about 2-20% by weight, the organic solvent is about 10-30% by weight, the plasticizer is about 10-30% by weight, and the ionic solution is about 10-30% by weight. About 1-4% by weight, the supplementary material about 1-4% by weight.
好ましくは、該高分子材料は、熱可塑性高分子材料又は熱硬化性高分子材料であり、ポリビニルブチラール(PVB)、酢酸ビニル共重合体(EVA)、エポキシ樹脂(EP)及びポリエチレン(PE)からなる群から選択される少なくとも1種の材料又は他の代替可能な材料である。本実施例では、該熱可塑性高分子材料はポリビニルブチラール(PVB)であり、主にイオン伝導経路を提供するものとして機能し、コロイド電解質の粘着度及びイオン伝導率を向上させるとともに、優れた電子絶縁性を有する。 Preferably, the polymeric material is a thermoplastic polymeric material or a thermosetting polymeric material, and is selected from polyvinyl butyral (PVB), vinyl acetate copolymer (EVA), epoxy resin (EP) and polyethylene (PE). or other alternative materials. In this example, the thermoplastic polymeric material is polyvinyl butyral (PVB), which primarily functions as providing an ionic conduction path, improving the cohesiveness and ionic conductivity of the colloidal electrolyte, as well as providing excellent electronic Has insulation properties.
好ましくは、該リチウム塩は、ヘキサフルオロリン酸リチウム(LiPF6)、テトラフルオロホウ酸リチウム(LiBF4)、過塩素酸リチウム(LiClO4)、ヘキサフルオロヒ素酸リチウム(LiAsF6)、トリフルオロメチルスルホン酸リチウム(LiCF3SO3)、ビス(シュウ酸)ホウ酸リチウム(LiBOB)、リチウムジフルオロ(オキサラト)ボレート(LiODFB)、ビス(トリフルオロメタンスルホニル)イミドリチウム(LiTFSI)、リチウムビス(フルオロスルホニル)イミド(LiFSI)、ジフルオロリン酸リチウム(LiPO2F2)及びテトラフルオロシュウ酸リン酸リチウム(LiFOP)からなる群から選択される少なくとも1種の材料又は他の代替可能な材料である。本実施例では、該リチウム塩は過塩素酸リチウム(LiClO4)であり、解離してイオンを生成することができ、該熱可塑性高分子間で移動することで好ましいイオン伝導機能を付与する。 Preferably, the lithium salt is lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium hexafluoroarsenate (LiAsF 6 ), trifluoromethyl Lithium sulfonate (LiCF 3 SO 3 ), lithium bis(oxalate)borate (LiBOB), lithium difluoro(oxalato)borate (LiODFB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl) At least one material selected from the group consisting of imide (LiFSI), lithium difluorophosphate (LiPO 2 F 2 ), and lithium tetrafluorooxalate phosphate (LiFOP) or other alternative materials. In this example, the lithium salt is lithium perchlorate (LiClO4), which can dissociate to generate ions, which impart a desirable ion conduction function by moving between the thermoplastic polymers.
好ましくは、該有機溶媒はプロピレンカーボネート(PC)、エチレンカーボネート(EC)、酪酸プロピル(γ-BL)、N-メチル-ピロリジン(NMP)及びジメチルカーボネート(DMC)からなる群から選択される少なくとも1種の材料又は他の代替可能な材料である。該有機溶媒はリチウムイオンを伝達する場所を提供し、イオンが該リチウム塩から解離することを補助する。該有機溶媒は好ましくは高沸点の特性を有する。 Preferably, the organic solvent is at least one selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), propyl butyrate (γ-BL), N-methyl-pyrrolidine (NMP) and dimethyl carbonate (DMC). seed material or other alternative materials. The organic solvent provides a transport site for the lithium ions and assists in their dissociation from the lithium salt. The organic solvent preferably has high boiling characteristics.
好ましくは、該可塑剤はジエチレングリコールブチルエーテル(Diethylene Glycol Monobutyl Ether)又はアジピン酸(Adipic acid)から選ばれる。本実施例では、該可塑剤はジエチレングリコールブチルエーテルである。該可塑剤の添加により電解質の透光性が向上し、電解質の適用性が向上し、特にエレクトロクロミックデバイス(Electrochromic device/ECD)への適用が可能になる。 Preferably, the plasticizer is selected from Diethylene Glycol Monobutyl Ether or Adipic acid. In this example, the plasticizer is diethylene glycol butyl ether. Addition of the plasticizer improves the translucency of the electrolyte, improving the applicability of the electrolyte, and particularly making it possible to apply it to electrochromic devices (ECD).
好ましくは、該イオン性溶液は実質的には主シクロプロピルから構成される。本実施例では、該イオン性溶液は主シクロプロピルに塩素酸根を持つ〔(Pmim)(ClO4)〕ものである。該イオン性溶液は、リチウムイオン以外の伝導イオンを提供し、電解質のイオン濃度を高め、また、リチウムイオンの環境安定性を高める。 Preferably, the ionic solution consists essentially of cyclopropyl. In this example, the ionic solution has a chlorate group in the main cyclopropyl group [(Pmim)(ClO 4 )]. The ionic solution provides conductive ions other than lithium ions, increases the ionic concentration of the electrolyte, and also increases the environmental stability of lithium ions.
好ましくは、該補助材料はトナー、UV吸収剤、光安定剤、温度安定剤及びシリコン粉末からなる群から選択される少なくとも1種の材料である。該トナーは任意の色の色材であってもよく、フィルタリングや深さの調整用として有用である。該UV吸収剤は二酸化チタン、2-(2'-ヒドロキシ-5'-tert-オクチルフェニル)ベンゾトリアゾール、2-(2'-ヒドロキシ-5'-tert-オクチルフェニル)ベンゾトリアゾールとトリアゾールとの混合物から構成され、接着材の寿命を延ばし、耐候性を向上させることができる。該光安定剤はペンタエリトリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオナートを主材料として構成され、UV光を吸収した高分子の酸化分解による変質を回避できる。該温度安定剤はエチレングリコール(EG)を主材料として構成され、接着材の耐低温凍結性や耐高温揮発性を向上させる。シリコン粉末は105~10ナノサイズの任意の形状の粒子であってもよく、接着材の機械的特性や電気絶縁特性を向上させる。 Preferably, the auxiliary material is at least one material selected from the group consisting of toner, UV absorber, light stabilizer, temperature stabilizer and silicon powder. The toner may be a colorant of any color and is useful for filtering and depth adjustment. The UV absorber is titanium dioxide, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, a mixture of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and triazole. It can extend the life of the adhesive and improve its weather resistance. The light stabilizer is mainly composed of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and can avoid deterioration due to oxidative decomposition of polymers that absorb UV light. . The temperature stabilizer is mainly composed of ethylene glycol (EG) and improves the low-temperature freezing resistance and high-temperature volatility resistance of the adhesive. The silicon powder may be particles of any shape from 10 5 to 10 nanometers, and improves the mechanical and electrical insulation properties of the adhesive.
該熱可塑性高分子、該リチウム塩及び該有機溶媒を混合した後、該熱可塑性高分子は該有機溶媒で膨潤させて高分子網目を形成する。該熱可塑性高分子の主鎖又は側鎖上の高陰電性原子(例えば酸素)又はヒドロキシ基(即ちOH-)は不対電子(unpaired electron)を有する。このため、該リチウム塩から解離されたリチウムイオン(Li+)は該熱可塑性高分子と一時的な配位結合を形成し、該高分子網目内を伝達しやすくなる。該有機溶媒の存在はリチウムイオンの別の伝導方式を提供し、リチウムイオンが該有機溶媒を介して上記コロイド状高分子電解質内を移動できるようにする。 After mixing the thermoplastic polymer, the lithium salt, and the organic solvent, the thermoplastic polymer is swollen with the organic solvent to form a polymer network. Highly electronegative atoms (eg, oxygen) or hydroxy groups (ie, OH-) on the main chain or side chain of the thermoplastic polymer have unpaired electrons. Therefore, the lithium ions (Li+) dissociated from the lithium salt form temporary coordination bonds with the thermoplastic polymer, and are easily transmitted within the polymer network. The presence of the organic solvent provides another mode of conduction for lithium ions, allowing them to move through the colloidal polyelectrolyte through the organic solvent.
本実施例の電解質の製造方法は、高分子材料を約50~70℃の反応温度で約15~30分間反応させ、脱水乾燥して乾燥高分子材料を得る乾燥ステップS0と、該乾燥高分子材料をリチウム塩、有機溶媒、可塑剤、イオン性溶液及び補助材料と均一に撹拌し、コロイド電解質を得る材料混合ステップS1と、該コロイド電解質を約70~140℃の反応温度で約2~10分間反応させ、混練して該コロイド電解質を均一にする混練ステップS2と、を含む。本実施例では、該材料混合ステップS1では、撹拌器により撹拌し、該混練ステップS2では、混練機を利用して該コロイド電解質を機械力及び化学作用により均一に混合する。 The method for producing an electrolyte of this embodiment includes a drying step S0 in which a polymeric material is reacted at a reaction temperature of approximately 50 to 70°C for approximately 15 to 30 minutes, and then dehydrated and dried to obtain a dry polymeric material; A material mixing step S1 of uniformly stirring the material with a lithium salt, an organic solvent, a plasticizer, an ionic solution and an auxiliary material to obtain a colloidal electrolyte; The method includes a kneading step S2 in which the colloidal electrolyte is made uniform by reacting for a minute and kneading the colloidal electrolyte. In this embodiment, in the material mixing step S1, stirring is performed using a stirrer, and in the kneading step S2, a kneader is used to uniformly mix the colloidal electrolyte by mechanical force and chemical action.
図2は本発明の電解質の製造方法の別の実施例のフローチャートである。図2に示すように、好ましくは、本実施例の方法は、該混練ステップS2で混練した該コロイド電解質を押し出し、高速カッターを利用して造粒しながら、急速な降温及び乾燥をし、顆粒状電解質を製造する押出造粒ステップS3をさらに含む。本実施例では、該コロイド電解質はスクリューにより押し出された後、造粒機を利用して高速カッターにより急速な降温及び乾燥をし、顆粒状電解質となり、このようにして、完成品の保存が容易になり、後続のプロセスへの利用に有利である。降温及び乾燥に関しては、例えば水又は有機溶媒で降温してから、風乾方式で乾燥してもよい。 FIG. 2 is a flowchart of another embodiment of the electrolyte manufacturing method of the present invention. As shown in FIG. 2, preferably, in the method of this embodiment, the colloidal electrolyte kneaded in the kneading step S2 is extruded, and while granulating using a high-speed cutter, the temperature is rapidly lowered and dried to form granules. The method further includes an extrusion granulation step S3 for producing a shaped electrolyte. In this example, the colloidal electrolyte is extruded by a screw, and then rapidly cooled down and dried by a high-speed cutter using a granulator to become a granular electrolyte, thus making it easy to store the finished product. This makes it advantageous for use in subsequent processes. Regarding temperature lowering and drying, for example, after lowering the temperature with water or an organic solvent, drying may be performed by an air drying method.
好ましくは、該押出造粒ステップS3は、作動温度約100~140℃、押出圧力約0.2~1メガパスカル(MPa)であり、製造された該顆粒状コロイド電解質の顆粒サイズは約1~30mmである。本実施例では、電解質顆粒のサイズは4mmであり、作動温度は105℃であり、押出圧力は0.8メガパスカル(MPa)である。 Preferably, the extrusion granulation step S3 has an operating temperature of about 100-140° C., an extrusion pressure of about 0.2-1 megapascals (MPa), and a granule size of the produced granular colloidal electrolyte of about 1-140° C. It is 30mm. In this example, the size of the electrolyte granules is 4 mm, the operating temperature is 105° C., and the extrusion pressure is 0.8 megapascals (MPa).
図3は本発明の電解質の製造方法の別の実施例のフローチャートである。図3に示すように、好ましくは、後続のプロセスでの取り扱い性から、本実施例の電解質の製造方法は、該混練ステップS2で混練した該コロイド電解質を約80~150℃で加熱して溶融し、流動性コロイドとし、開口径サイズを調整可能なスリット状吐出口を先端に有する塗布ヘッドのキャビティに該流動性コロイドを上記キャビティの圧力により注入し、該流動性コロイドを該スリット状吐出口から均一に流出させ、離型膜上に塗布して粘着膜構造を形成し、エアナイフにより急速に降温し、厚さを制御してコロイド電解質膜を形成する第1コロイド電解質膜形成ステップS41をさらに含む。本実施例では、加熱溶融温度を95℃とし、開口径サイズを調整可能なスリット状吐出口を先端に有する塗布ヘッドのキャビティに該流動性コロイドを上記キャビティの圧力により注入し、該流動性コロイドを塗布ヘッドのスリット状吐出口から均一に流出させ、該流動性コロイドを離型膜上に塗布するにつれて粘着膜構造を構成し、粘着膜をエアナイフにより急速に降温し、粘着膜の厚さを制御して、コロイド電解質膜を形成する。 FIG. 3 is a flowchart of another embodiment of the electrolyte manufacturing method of the present invention. As shown in FIG. 3, preferably, from the viewpoint of ease of handling in subsequent processes, the electrolyte manufacturing method of this embodiment is such that the colloidal electrolyte kneaded in the kneading step S2 is heated at about 80 to 150°C to melt it. The fluid colloid is made into a fluid colloid, and the fluid colloid is injected into a cavity of a coating head having a slit-shaped discharge port at the tip with an adjustable opening diameter by the pressure of the cavity. Further, a first colloidal electrolyte membrane forming step S41 is performed, in which the colloidal electrolyte membrane is uniformly flowed out, coated on a release membrane to form an adhesive membrane structure, and rapidly cooled with an air knife to form a colloidal electrolyte membrane by controlling the thickness. include. In this example, the heating and melting temperature was set to 95°C, and the fluid colloid was injected into the cavity of the coating head having a slit-shaped discharge port at the tip with an adjustable opening diameter by the pressure of the cavity. uniformly flows out from the slit-shaped discharge port of the coating head, and as the fluid colloid is applied onto the release film, it forms an adhesive film structure, and the temperature of the adhesive film is rapidly lowered using an air knife to reduce the thickness of the adhesive film. control to form a colloidal electrolyte membrane.
図4は本発明の電解質の製造方法の別の実施例のフローチャート。図4に示すように、好ましくは、後続のプロセスでの取り扱い性から、本実施例の電解質の製造方法は、該押出造粒ステップS3で製造された該顆粒状電解質置を約70~140℃の反応温度で約2~10分間反応させ、混練して該顆粒状電解質を第2コロイド電解質とし、該第2コロイド電解質を約80~150℃で加熱して溶融し、流動性コロイドとし、開口径サイズを調整可能なスリット状吐出口を先端に有する塗布ヘッドのキャビティに該流動性コロイドを上記キャビティの圧力により注入し、該流動性コロイドを該スリット状吐出口から均一に流出させ、離型膜上に塗布して粘着膜構造を形成し、エアナイフにより急速に降温し、粘着膜の厚さを制御して、コロイド電解質膜を形成する第2コロイド電解質膜形成ステップS42をさらに含む。本実施例では、反応温度を90℃、反応時間を5分間とし、また、混練機を利用して、該顆粒状電解質をコロイド電解質にし、次に、該コロイド電解質を95℃で加熱して溶融し、流動性コロイドとし、塗布ヘッドのキャビティに該流動性コロイドを上記キャビティの圧力により注入する。塗布ヘッドの先端は開口径サイズを調整可能なスリット状吐出口であり、該流動性コロイドは塗布ヘッドのスリット状吐出口から流出し、離型膜上に塗布されるにつれて粘着膜構造を形成する。ここで、離型膜は紙膜、布膜又はプラスチック膜である。粘着膜をエアナイフにより急速に降温し、粘着膜の厚さを制御して、コロイド電解質膜を形成し、最後に、離型膜を被覆し、粘着膜巻き取り装置によりコロイド電解質膜を得る。 FIG. 4 is a flowchart of another embodiment of the electrolyte manufacturing method of the present invention. As shown in FIG. 4, preferably, from the viewpoint of ease of handling in subsequent processes, the electrolyte production method of this embodiment is performed by heating the granular electrolyte produced in the extrusion granulation step S3 at a temperature of about 70 to 140°C. The granular electrolyte is reacted for about 2 to 10 minutes at a reaction temperature of The fluid colloid is injected into the cavity of the coating head which has a slit-shaped discharge port at the tip whose diameter size can be adjusted by the pressure of the cavity, the fluid colloid is uniformly flowed out from the slit-shaped discharge port, and the mold is released. It further includes a second colloidal electrolyte membrane forming step S42 of coating the membrane to form an adhesive membrane structure, rapidly lowering the temperature using an air knife, and controlling the thickness of the adhesive membrane to form a colloidal electrolyte membrane. In this example, the reaction temperature was 90°C and the reaction time was 5 minutes, and the granular electrolyte was made into a colloidal electrolyte using a kneader, and then the colloidal electrolyte was heated at 95°C to melt it. Then, the fluid colloid is made into a fluid colloid, and the fluid colloid is injected into the cavity of the coating head by the pressure of the cavity. The tip of the coating head is a slit-shaped discharge port whose opening diameter size can be adjusted, and the fluid colloid flows out from the slit-shaped discharge port of the coating head and forms an adhesive film structure as it is coated onto the release film. . Here, the release film is a paper film, a cloth film, or a plastic film. The temperature of the adhesive film is rapidly lowered using an air knife, and the thickness of the adhesive film is controlled to form a colloidal electrolyte membrane.Finally, a release film is coated, and a colloidal electrolyte membrane is obtained using an adhesive film winding device.
図5は本発明の電解質の製造方法の別の実施例のフローチャートである。図5に示すように、好ましくは、後続のプロセスでの取り扱い性から、本実施例の電解質の製造方法は、該混練ステップS2で混練した該コロイド電解質体を押出温度約80~160℃、エアナイフ噴射口の風圧約95~1000キロパスカル(kPa)、押出圧力約0.5~1メガパスカル(MPa)で加熱して押出し、厚さ約0.005~3mmのコロイド電解質膜を形成する、第3コロイド電解質膜形成ステップS43をさらに含む。本実施例では、押出温度は120℃であり、エアナイフ噴射口の吹き角度は90°~105°であり、押出噴射口のキャップは1mmであり、押出圧力は0.6メガパスカル(MPa)であり、最後には、厚さ0.6mmのコロイド電解質膜が形成される。 FIG. 5 is a flowchart of another embodiment of the electrolyte manufacturing method of the present invention. As shown in FIG. 5, preferably, from the viewpoint of ease of handling in subsequent processes, the electrolyte manufacturing method of this embodiment is such that the colloidal electrolyte body kneaded in the kneading step S2 is extruded at a temperature of about 80 to 160° C. with an air knife. A colloidal electrolyte membrane having a thickness of about 0.005 to 3 mm is formed by heating and extruding at an air pressure of about 95 to 1000 kilopascals (kPa) at the injection port and an extrusion pressure of about 0.5 to 1 megapascals (MPa). The method further includes a step S43 of forming a three-colloidal electrolyte membrane. In this example, the extrusion temperature was 120°C, the blowing angle of the air knife nozzle was 90° to 105°, the cap of the extrusion nozzle was 1 mm, and the extrusion pressure was 0.6 megapascals (MPa). Finally, a colloidal electrolyte membrane with a thickness of 0.6 mm is formed.
図6は本発明の電解質の製造方法の別の実施例のフローチャートである。図6に示すように、好ましくは、後続のプロセスでの取り扱い性から、本実施例の電解質の製造方法は、該押出造粒ステップS3で製造された該顆粒状電解質を、押出延流法により約70~140℃で加熱して粘稠状コロイドとし、次に、該粘稠状コロイドを押出温度約80~160℃、エアナイフ噴射口の風圧約95~1000キロパスカル(kPa)、押出圧力約0.5~1メガパスカル(MPa)で加熱して押出し、厚さ約0.005~3mmのコロイド電解質膜を形成する、第4コロイド電解質膜形成ステップS44をさらに含む。本実施例では、該顆粒状電解質を100℃で加熱して粘稠状コロイドとし、押出温度は120℃であり、エアナイフ噴射口の風圧は約100キロパスカル(kPa)であり、風は押出噴射口の幅全体にわたって存在し、エアナイフ噴射口の吹き角度は90°~105°であり、押出噴射口のキャップは約1mmであり、押出圧力は0.6メガパスカル(MPa)であり、最後に、厚さ0.6mmのコロイド電解質膜が形成される。 FIG. 6 is a flowchart of another embodiment of the electrolyte manufacturing method of the present invention. As shown in FIG. 6, preferably, from the viewpoint of ease of handling in subsequent processes, the electrolyte manufacturing method of this example is such that the granular electrolyte manufactured in the extrusion granulation step S3 is subjected to an extrusion flow spreading method. The viscous colloid is heated at about 70 to 140°C, and then the viscous colloid is extruded at a temperature of about 80 to 160°C, a wind pressure of about 95 to 1000 kilopascals (kPa) at the air knife nozzle, and an extrusion pressure of about 80 to 160°C. The method further includes a fourth colloidal electrolyte membrane forming step S44 of heating and extruding at 0.5 to 1 megapascal (MPa) to form a colloidal electrolyte membrane having a thickness of about 0.005 to 3 mm. In this example, the granular electrolyte was heated at 100°C to form a viscous colloid, the extrusion temperature was 120°C, the wind pressure at the air knife jet was about 100 kilopascals (kPa), and the wind was extruded into a viscous colloid. Exists across the width of the mouth, the blowing angle of the air knife jet is 90° to 105°, the cap of the extrusion jet is about 1 mm, the extrusion pressure is 0.6 megapascals (MPa), and finally , a colloidal electrolyte membrane with a thickness of 0.6 mm is formed.
本発明のコロイド電解質では、特定成分及び各成分間の特定の割合を採用し、混練により各成分を均一に分散させることによって、該コロイド電解質は、凝集機械的性質が高いため低流動性を有する。イオン伝導率も固体電解質よりも明らかに向上し、イオン伝導率が高い、スペーサを必要としない、ガラスやプラスチックなどの粘着に有用であるなどの特性を実現する。安全性が高いので液漏れを回避し、また、高粘着性、高透光率及び高伝導率を有する。 In the colloidal electrolyte of the present invention, by employing specific components and specific ratios between each component and uniformly dispersing each component by kneading, the colloidal electrolyte has low fluidity due to high cohesive mechanical properties. . The ionic conductivity is also clearly improved compared to solid electrolytes, realizing properties such as high ionic conductivity, no need for spacers, and useful for adhesion to glass, plastic, etc. It is highly safe to avoid liquid leakage, and also has high adhesiveness, high light transmittance and high conductivity.
本発明の電解質は、エレクトロクロミックデバイスの電解質層に利用可能であり、また、粘着技術を利用して作製できる。また、従来のエネルギー貯蔵部品例えばスーパーキャパシタンス、リチウムポリマー電池、スーパーバッテリーの電解質は全てセパレータと組み合わせて電極から隔離されて、電極導通を回避することができる。これらを比較すると、本発明の電解質は粘着膜にした場合、2つの電極間にスペーサ及びイオン伝達や電子バリアのためのものとして使用できる。 The electrolyte of the present invention can be used as an electrolyte layer of an electrochromic device, and can also be produced using adhesive technology. Additionally, the electrolytes of conventional energy storage components such as supercapacitances, lithium polymer batteries, and superbatteries can all be isolated from the electrodes in combination with separators to avoid electrode conduction. Comparing these, when the electrolyte of the present invention is made into an adhesive film, it can be used as a spacer between two electrodes and as a barrier for ion transfer and electrons.
S0 乾燥ステップ
S1 材料混合ステップ
S2 混練ステップ
S3 押出造粒ステップ
S41 第1コロイド電解質膜形成ステップ
S42 第2コロイド電解質膜形成ステップ
S43 第3コロイド電解質膜形成ステップ
S44 第4コロイド電解質膜形成ステップ
S0 Drying step S1 Material mixing step S2 Kneading step S3 Extrusion granulation step S41 First colloidal electrolyte membrane forming step S42 Second colloidal electrolyte membrane forming step S43 Third colloidal electrolyte membrane forming step S44 Fourth colloidal electrolyte membrane forming step
Claims (7)
該高分子材料は、熱可塑性高分子材料又は熱硬化性高分子材料であり、ポリビニルブチラール、酢酸ビニル共重合体、エポキシ樹脂及びポリエチレンからなる群から選択される少なくとも1種の材料であり、
該リチウム塩は、ヘキサフルオロリン酸リチウム、テトラフルオロホウ酸リチウム、過塩素酸リチウム、ヘキサフルオロヒ素酸リチウム、トリフルオロメチルスルホン酸リチウム、ビス(シュウ酸)ホウ酸リチウム、リチウムジフルオロ(オキサラト)ボレート、ビス(トリフルオロメタンスルホニル)イミドリチウム、リチウムビス(フルオロスルホニル)イミド、ジフルオロリン酸リチウム及びテトラフルオロシュウ酸リン酸リチウムからなる群から選択される少なくとも1種の材料であり、
該有機溶媒はプロピレンカーボネート、エチレンカーボネート、酪酸プロピル、N-メチル-ピロリジン及びジメチルカーボネートからなる群から選択される少なくとも1種の材料であり、
該可塑剤はジエチレングリコールブチルエーテル又はアジピン酸から選択され、
該イオン性溶液は主シクロプロピルに塩素酸根を持つ〔(Pmim)(ClO 4 )〕であり、
該補助材料は任意の色の色材であるトナー、UV吸収剤、光安定剤、温度安定剤及び10 5 ~10ナノサイズの任意の形状の粒子で構成されるシリコン粉末からなる群から選択される少なくとも1種の材料であることを特徴とする電解質。 It contains a polymeric material, a lithium salt, an organic solvent, a plasticizer, an ionic solution, and an auxiliary material, and these are kneaded into a colloid, and the polymeric material is 20% by weight. The lithium salt is 2% to 20% by weight, the organic solvent is 10% to 30% by weight, the plasticizer is 10% to 30% by weight, the ionic solution is 1% by weight or more and 2% by weight or less, and the auxiliary material is 1% by weight or more and 2% by weight or less,
The polymer material is a thermoplastic polymer material or a thermosetting polymer material, and is at least one material selected from the group consisting of polyvinyl butyral, vinyl acetate copolymer, epoxy resin, and polyethylene,
The lithium salts include lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium bis(oxalate)borate, and lithium difluoro(oxalato)borate. , at least one material selected from the group consisting of lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium difluorophosphate, and lithium tetrafluorooxalate phosphate,
The organic solvent is at least one material selected from the group consisting of propylene carbonate, ethylene carbonate, propyl butyrate, N-methyl-pyrrolidine, and dimethyl carbonate,
the plasticizer is selected from diethylene glycol butyl ether or adipic acid;
The ionic solution has a chlorate group in the main cyclopropyl [(Pmim)(ClO 4 )],
The auxiliary material is selected from the group consisting of a toner as a colorant of any color, a UV absorber, a light stabilizer, a temperature stabilizer, and a silicon powder consisting of particles of any shape between 10 and 10 nanometers. 1. An electrolyte comprising at least one material .
該乾燥高分子材料をリチウム塩、有機溶媒、可塑剤、イオン性溶液及び補助材料と均一に撹拌し、コロイド電解質を得る材料混合ステップと、
該コロイド電解質を70~140℃の反応温度で2~10分間反応させ、混練機を利用して該コロイド電解質を機械力及び化学作用により均一に混合する混練ステップと、を含むことを特徴とする請求項1に記載の電解質の製造方法。 A drying step of reacting the polymeric material at a reaction temperature of 50 to 70°C for 15 to 30 minutes and dehydrating and drying it to obtain a dry polymeric material;
a material mixing step of uniformly stirring the dry polymeric material with a lithium salt, an organic solvent, a plasticizer, an ionic solution and an auxiliary material to obtain a colloidal electrolyte;
A kneading step of reacting the colloidal electrolyte at a reaction temperature of 70 to 140° C. for 2 to 10 minutes and uniformly mixing the colloidal electrolyte using a kneader by mechanical force and chemical action. A method for producing the electrolyte according to claim 1.
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