TWI232126B - Method of removing water and other protic impurities from organic liquid electrolytes - Google Patents
Method of removing water and other protic impurities from organic liquid electrolytes Download PDFInfo
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- TWI232126B TWI232126B TW090122346A TW90122346A TWI232126B TW I232126 B TWI232126 B TW I232126B TW 090122346 A TW090122346 A TW 090122346A TW 90122346 A TW90122346 A TW 90122346A TW I232126 B TWI232126 B TW I232126B
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000011244 liquid electrolyte Substances 0.000 title claims abstract description 19
- 239000012535 impurity Substances 0.000 title claims abstract description 16
- 229910001868 water Inorganic materials 0.000 title abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 241001674048 Phthiraptera Species 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 230000000422 nocturnal effect Effects 0.000 claims 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 abstract description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 17
- -1 lithium imine Chemical class 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000002274 desiccant Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000004678 hydrides Chemical class 0.000 description 7
- 229910052987 metal hydride Inorganic materials 0.000 description 6
- 150000004681 metal hydrides Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 238000010981 drying operation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- NPAXBRSUVYCZGM-UHFFFAOYSA-N carbonic acid;propane-1,2-diol Chemical compound OC(O)=O.CC(O)CO NPAXBRSUVYCZGM-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- HZONRRHNQILCNO-UHFFFAOYSA-N 1-methyl-2h-pyridine Chemical compound CN1CC=CC=C1 HZONRRHNQILCNO-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 229910013462 LiC104 Inorganic materials 0.000 description 1
- 229910012213 MAsF6 Inorganic materials 0.000 description 1
- 229910012226 MBF4 Inorganic materials 0.000 description 1
- 229910016079 MPF6 Inorganic materials 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019256 POF3 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 101100408805 Schizosaccharomyces pombe (strain 972 / ATCC 24843) pof3 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RPXKKUZDTAOVEQ-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O.OC(=O)C(O)=O RPXKKUZDTAOVEQ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- HXVSHYULHRMHAV-UHFFFAOYSA-N dicyano pentanedioate Chemical compound N#COC(=O)CCCC(=O)OC#N HXVSHYULHRMHAV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012771 household material Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Inorganic materials [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FFUQCRZBKUBHQT-UHFFFAOYSA-N phosphoryl fluoride Chemical compound FP(F)(F)=O FFUQCRZBKUBHQT-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
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- 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
- H01G11/04—Hybrid capacitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
- H01G11/20—Reformation or processes for removal of impurities, e.g. scavenging
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- 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
- H01G11/58—Liquid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/02—Diaphragms; Separators
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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
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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
- H01M10/0566—Liquid materials
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the 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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- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
1232126
本發明係關於移除有機液體電解質中水分和其他人μ 不純物之方法。 通常現今使用的鋰電池(主要與二極電池元件兩者)之導 體鹽類,含有無水的、液體、離子導體電解質,像是,例 如,LiPF6、LiBF4、LiC104、亞胺鋰、甲基鋰、或螯合鋰 錯化合物,(像是,雙草酸硼酸鋰),係呈現溶解的型二。 多數此類導體鹽類’在含有質子化合物存在時,咬多或少 會很快地分解,像是,例如,有水分時,例如,根據
LiPF6 + H20—LiF + 2HF t +POF3 丨
L]HC2〇4 γ 〇、r-〇 ' Β -OH〇〆、〇 (2) 況下’形成某種侵佔性和損害性之機能上特性。雖炊,有 導電鹽類與水不反應,像是,例如,uno4,係可預期在 有水存在下,亦有負面的影響’料負面的影響,係主要 歸屬於擾動覆蓋層之形成,其根據與陽極的反應而增加歷 力0 在含氟鹽類的水解反應期間,所形成之氣體產物 (hf,p〇F3,等),係、具有高度腐純,且會傷害到冑池其他部 分,像是,例如,陽極材料。例如,HF將導致於鎮失晶石 的溶解’及傷害電極材料覆蓋層,其對長使用生命期為重 要的。最I ’則使二極電池之循環穩定性受才員。领酸電解 質亦對水分敏感^在M例中,—些不可溶之水解產物的狀 ________ _ 4 _ 本紙張尺度適用巾國g家料(CNS) A4規格 1232126
Li+H20—LiOH + H2 t (3) 因此必須將降低含質子不純物到最少(H2〇〈 2〇 ppm HF <約30Ppm)。為此已經發明有一些方法,但其都有缺點。 在日本專利208 7473提出,將電解質溶液與溶劑混合, 以形成與水之共彿混合物’且可以蒸顧法移除共滩混合物 之水分/溶劑。該方法的缺點,係為溶劑中帶有不希望得到 之不純物,且受限於高沸點之電解質溶劑。 在美國專利5,395,486和WO 2000038813,以鈍性之氟化液 體,像是例如以CsFu為共乘者。彼等方法的缺點,尤其係 為關於隨其物質之氟化物的放射。 在日本專利1〇3 38653所提出的方法,係經由乾燥鈍性 氣體吹拂,以達成電解液之乾燥,其缺點為必須使用非常 昂貴(隨即要純化)之鈍性氣體,且會發生損失大量的溶劑 ,或是必須排出凝結之溶劑蒸氣與反饋之複雜操作。 另一在德國專利1 9 8 2 7 6 3 1和一形式相類似之日本專利 2 0 0 0 0 5 81 19所敘述之方法,係根據水分和[JF,在特別前處 理過氧化鋁之物理吸附。此吸附方法的缺點,係在A丨氧化 物複雜之前處理(在4〇〇°C,氮氣流中,乾燥四星期)。 德國專利1 9827630敘述清潔電池電解液的方法,含有以 驗’利用與電解質接觸時,含質子不純物,係以化學吸附 ’固定在固體上,隨即將此固體清潔劑分開。其缺點為含 有氨類固定在聚合物上之清潔劑很貴且也需要前處理(例 如’在10 0 °C真空下乾燥4天)。 最後,藉由以鹼性金屬乾燥電解液的方法則為人所知。 -5- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
裝 訂
1232126 五、發明説明(4 本方法 一 可為一般性適用的, —不會導致於額外的污染, 可使用商業上提供之乾燥劑,不需要另外之處理, 一在安全考量上沒有危機, ―、可得到=含量<2〇 PPm之溶液產物。
該目的係藉由移除有機液體電解質中水分和其他含質子 不純物之方法達成,其中將有機液體電解質,與一或多不 互/合之驗金屬氫化物接觸,由此將所形成不互溶之反應副 產物分開。應了解該水分和其他含質子不純物之移除,係 為部份移除對全部移除的方法。
寺 口之使用趣一元氳化物(LiH)和鋼氫化物(NaH),係 為較佳足乾燥劑’其在大量的考量上較便宜,且提供有純 化的形式。雖然該在鋰電池無質子溶劑完全不溶解,頃發 現’以乾燥操作考量程度範圍而言,該LiH、NaH和其他鹼 金屬氫化物,KH、RbH和CsH,可很快地有效率達成,且 剩餘非常少的質子不純物含量。此外,令人驚訝地發現, 使用根據本發明之氫化物形式之乾燥劑,在安全上比鹼金 屬本身更有實質上的優點。以DSC (熱差分析儀,在Systag/ 瑞士RADEX儀器中心執行)量測LiH混合物,或個別!^金屬 ’和二草酸硼酸魏溶液,發現反應一開始係為危險的,高 度放熱分解反應,如所謂的起始溫度所敘(Tqnse〇,係顯著 地高於氫化物的例子(見表1)。 表1 ··電解液與LiH和Li金屬接觸的熱分解(Radex實驗) 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 1232126 A7 ____ _B7__._ 五、發明説明(6 ) 嵌入磷 m[l3p] 其中 M=Li或NR4(R = H或為1到1〇碳之烷基,亦環烷)
Rf全氟烷自由基,為1到1〇碳之烷基,亦環烷 L =有2個〇之雙齒狀配位基,像是,例如,草酸根,鄰苯 二翁,水楊酸,亦部份或完全氟化。
在非質子溶劑,有高介電常數像是 碳酸鹽,例如:二甲基碳酸鹽,二乙基碳酸鹽,乙二醇 碳酸醋,丙二醇碳酸酯,乙基甲基碳酸鹽, 氰’例如:乙氰,乙二酸二氰,戊二酸二氰, 内酯,例如:7 -丁酸丙酯, 氣化物,例如··二甲醯氨,N_甲基吡p各燒酮 醚,例如:四氫呋喃,2-甲基四氫呋喃,丨,2—甲氧基乙 坑(monoglyme) ’ 1, 3-dioxolan ,
乙縮酸,例如:1, 1二乙氧基甲烷 硫化合物,例如:二甲基亞颯,酚烷 和其混合物 驗金屬劇烈地且不可逆與質子活性物質反應,其根據 MH+X-Η—MX 丨 +H2 t (4) X = H0,自素、RC00、R〇和相類似 R =烷基 為了使反應4中不會太劇烈地放出之氣體,氫化物較佳係 以相對液體電解質等比例加入。在本發明另一較佳之實施 例中,該含質子活性物質的量,例如水,不會超過特定舌 -9 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1232126 A7 B7 五、發明説明(7 性Η;辰度0· 6毫莫耳/克的上限。雖然,該含有較多不純物之 液體電解質,亦可由熟知此技藝者觀察安全之預防措施下 乾燥’其建議在此類情況下,先以不同之乾燥方法且僅在 最後執行根據本發明之乾燥方法。 以下用實例敘述根據本發明方法所執行之乾燥方式。 將鹼金屬依比例,較佳以攪拌,加入潮濕之液體電解質 ,可視情況而定,以其他質子活性物質污染之。該操作較 佳係在溫度範圍從-20到15〇。〇執行,最好係從〇到9〇。(:。隨 即可藉由量測所產生之氣體體積,監測其乾燥操作。在一 些例子中,(王要係當有特定量之酸存在,亦即〇 ·丨毫莫耳/ 克HC1),該氣體係為非常劇烈且有泡沐發生。其必要隨即 冷卻。否貝|卜該反應決不顯著地放熱。根據乾燥劑的活性 ,ρ遺即係必要在室溫或高溫(高於9(rc有時高於⑽。c)下的 反應相,完成乾燥。 在-万面係藉由所用之金屬氫化物的活性,另一方面係 =子活性不純物,通常為水之濃度,來^乾燥劑的使用 里。通常係以Karl Fischer滴定儀來決定水含量。所用之乾 燥劑之水含量’較佳係為相對應於KadFischer滴定儀 能偵測之最少量(或是其他水分決㈣)。為了能縮短反庫 的時間’(例如,從2到1〇〇次),較佳㈣以化學計量上過量 使用乾燥劑。該過量係從藉由氫化物的活性,和所 燥操㈣確方式之特定例子+給定。該㈣能力,係㈣ 金屬氫化物之活性表面積’亦即較細分散程度之金屬氮化 物’有較佳之活性。該乾燥能力,更進一#,根據前處理 -10- 1232126 A7 B7 五、發明説明(9 ) 放置未經加工之有問題的電解溶液,在鈍性多頸燒瓶中 ,其裝設有KPG攪拌器、加入固體的裝置、和熱偶計。以 塑膠注射器移除樣品,且以Karl Fischer滴定儀來確認其水 含量。 P远即加入如表2所示之l i Η的量,且亦如表2所示之條件執 行揽拌。在給定的乾燥次數後,再次移除樣品,及藉由注 射器附屬之過濾器過濾澄清之。(例如,Minisart SRP, Sartorius 0.45微米孔徑大),且再次確認其水含量。 隨即再次藉由經過玻璃過濾熔塊澄清乾燥溶液。 表2 ··不同電解液之乾燥條件 t例 電解質 H20 量 LiH 乾燥 乾燥 H20 溶液 含量 量 溫度 時間 含量 (ppm) (g) (g) α) (hrs) (ppm) 1 LiC10"P〇DME 870 150 0· 8 室溫 2. 5 265 2 ” ” ” ,, ” 15 15 3 LiC10"PC - DME 340 8000 3. 4 70 2 100 4 ” 340 8000 4. 7 70 5 10 5 L0B/PC-DME 340 1010 4. 8 40 24 55 6 L0B/PC-DMC 120 2600 15. 4 70 24 <20 裝 訂 將可見表2,乾燥的程度係根據每一例子所給定的條件。 為了要達到剩餘水含量< 2〇 ppm,在所述實例之乾燥時間 從5到24小時,係為必要的。 -12- 本紙張尺度適用中國國家標準(CNs) A4規格(210X297公釐) 修正/更士 申請曰期 __^fo v °\ κ ι〇 · * 案 犹 ------- 090122346 —-----一 類 別 (以上各棚由本局填註)
公告本I A4 C4 1232126 中文說明書替換頁(93年5月)
l專利説明書 中 文 自有機液體電解質中移除水分和其他含質子不純物之方法 英 文
METHOD OF REMOVING WATER AND OTHER PROTIC IMPURITIES FROM ORGANIC LIQUID ELECTROLYTES 姓 名 國 1·歐瑞曲懷特曼ULRICH WIETELMANN 2. 克拉斯史庫德KLAUS SCHADE 3. 悠威里斯許達UWELISCHKA 均德國 發明 住、居所 1·德國弗瑞得瑞取多夫市羅海默街19號 2·德國威斯巴登市瓦魯爾路12G號 3·德國尼德許貝斯市剛特渥特玲路79號 裝 姓 么 (名稱f 國 籍 德商開麥妥公司 CHEMETALL GMBH 德國 線 申請人 德國法蘭克福市崔肯那路3號
1. 湯瑪士克拉特 THOMAS KLATT 2. H.-P.羅森伯格博士 DR.H.-P. ROSENBERGER 本紙張尺度適用中g g *操準(Cns) μ規格(⑽χ挪公發) 1232 126 第 090122346 號申請案 年^月 修正 中文說明書替換頁(93年5月)A7 五、發明説明(3 ) 例如,F.P. Dousek et al.(Chem. Listy (1973),67(4)427-432) ’提出最前面以分子篩乾燥,隨即藉由液體K/Na合金進行 最後乾燥。此方式係類似於日本專利〇1 122566之原理,其 敘述以經過用鹼性金屬填充之層析管,過濾乾淨之電解液 。然而,在安全考量上,將鹼性金屬與相對上易反應之溶 劑接觸’並不會沒有風險的。因此,四氫咬喃,例如在約 高於1 oo°c與鋰金屬接觸已為吾人所知。其他鹼性金屬,也 可在適當的高溫下,與用在鐘電池電解液溶劑,超越平常 活潑地反應。 近代的超電容也含有有機電解液,及通常為高介電常數 在非質子溶劑中之銨鹽,像是,例如,乙氰或7 -丁酸丙酉旨 。該銨鹽通常有全氟離子像是PF,或是BF4·。此等係為電 化學穩定’不是非常親核性,且不會介入於活性電極主體。 該型電解液也須為低水含量(<20 ppm)。為了能達到此 目的,日本專利1 1054378和日本專利1 1008 163提出,基 於無機氧化物加入電解液吸收劑像是,矽酸鋁。此類吸收 劑係為低水含量,因此能改進可信度、安全和電流特性。 此方法的缺點為,一方面該吸收劑必須經由前處理,另— 方面’該吸收劑係存在於最終之電容中,以至於降低特定 儲存客積。 本發明的目的,係要避免先前技藝之缺點,以提供從有 機液體電解質中移除水分與含質子不純物的方法。應了解 ’有機液體電解質,係為含有電化學抵抗離子,在無質子 、極性、有機溶劑之鋰鹽和/或氨鹽。
本紙張尺度適用中國國家襟準(Cns) A4規格(210χ 297公策) 1232126 第090122346號申請案f多年;月7^修正/更 中文說明書替換頁(93年5月)Α7 Β7 五、發明説明(5 ) ΕΟ乙二醇碳酸醋,DMC =二甲基酸醋,PC=丙二醇碳酸 醋,DME=1,2-二甲氧基乙烷,L〇B =二草酸硼酸鋰。 導體鹽類 電解質 濃度 (Wt.%) Li金屬 T ONSET Τ MAX LiH T ONSET Tmax LiPF6/EC-DMC 11 145 160 230 (240)1) L1CIO4/PC-DME 6 160 165 255 265 LOB/EC-DMC 10.5 180 220 240 ./.1) 1}Tmax : 因為樣品容器開放性,所以不能或不易得到。 T〇NSET * 第一個放熱反應的起始溫度。
Tmax : 放熱反應溫度的最大值。 從該相較的數據確定得知氫化物具有高度操作安全性, 其在相當大量製造實例下,係為非常重要的。 根據本發明所使用的皆為有機液體電解質也就是,例如 ,為以下之溶液 氟化物,像是 MPF6,MAsF6,MBF4 全氯酸 MC104 破化鋰 Lil
三石黃酸 MSO3RF 亞胺鹽 mn(so2rf)2 甲基鹽 m[c(so2rf)3] 嵌入砸1 M [L2B ] -8- 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公釐) J232126,修至 090122346號中請案 尤說明書替換頁(92年1〇月) A7 B7 煩請委員明示,本案修正後是否變更原:r質内容 五、發明説明(8 ) 的本質。 “新鮮’’之金屬氫化物,通常有較多之活性。已經接觸過 空氣或溼氣之金屬氫化物,係被“保護”,通常必須要活 化之。其可藉由在鈍氣環境中研磨來達成I從空間的觀點 上,孩操作可以分開或同時,亦即在乾燥電解質的期間進 行。 頃發現,商業上所提供之氫化物等級,係有足夠的活性 (在數小時中,水含量〈2〇 PPm),以乾燥電解質。為了能 促進實驗室規模之乾燥操作,較佳係執行密集的攪拌,例 如使用同速之螺旋槳攪摔器《也可藉由將液體電解質通 過含有金屬氫化物固定床來執行(例如,層析管)。 當完成乾燥操作時,必須將乾燥劑殘留物和不可溶之反 應產物分離《頃發現根據反應4所形成之鹼金屬氫氧化物, 係完全不溶解於溶劑和上述之溶劑中。因此,藉由簡單之 固/液分離操作,像是過濾或離心器,可將不希望得到之反 應副產物分離。 乂此方法所製備之澄清溶液,具有相當低的水含量(相等 於其他質子活性物質之低含量)。其不需經由進一步之處理 ’即可使用在電解電池,較佳係链電池,或是電解雙層電 谷器(超級電容器)之電解液。 以實例的方式,更詳細解釋本發明的主體。 實例1至6 :乾燥不同電解液 。藉由根據本發明方法的協助,在不同的乾燥狀況下,乾 燥表2所不〈不同電解液溶劑。如下為一般之實驗裝置: ^紙張尺度適用中國國家標準X 297:ϋ---—----
Claims (1)
12靴 90122346號申請案 中文申凊專利範圍替換本(93年申請專利範圍 A8 B8 5月) •一種自有#液體電解質中#除水分和其他含質子不純 之方法其特彳政為在-20至150。(:之溫度下將電解液與 (鋰虱化物)接觸,並且將所形成之不可溶反應副產 物以及LiH殘留物移除。 根據申凊專利範圍第丨項之方法,其特徵為在欲乾燥之 1〉夜體電解質之質子化合物的含量係<0.6毫莫耳/克。 根據申#專利範圍第丨項之方法,其特徵為溫度係從〇 到 90°(:〇 j據申5目專利㈣第丨或2項之方法,其特徵為僅的含 里至少在化學計量上,係相對應於質子不純物的含量。 根據申叫專利範圍第4項之方法,其特徵為LiH的含量 在化學計量上,係相對於質子不純物的含量之2到1〇〇 倍。 ,,申叫專利範圍第1或2項之方法,其特徵為藉由在鈍 氣環境中研磨以活化LiH。 根據申μ專利知圍第〗或2項之方法,其特徵為在中 攪拌液體電解質。 2據申叩專利範圍第丨或2項之方法,其特徵為使液體電 解質通過含有UH之固定床。 才艮據申叫專利範圍第丨或2項之方法,其特徵為藉由過濾 或離心器移除不可溶之反應副產物。 ^據申μ專利範圍第丨或2項之方法,其中該有機液體電 解質係用於電解電池或超級電容器。 U·,申請專利範圍第…項之方法,其中該有機液體電 科質係用於鐘電池。
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TW090122346A TWI232126B (en) | 2000-09-27 | 2001-09-10 | Method of removing water and other protic impurities from organic liquid electrolytes |
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US (2) | US20040096746A1 (zh) |
EP (1) | EP1330299A1 (zh) |
JP (1) | JP5021147B2 (zh) |
KR (1) | KR20030039376A (zh) |
CN (1) | CN1476343A (zh) |
AU (1) | AU2002214984A1 (zh) |
CA (1) | CA2424361C (zh) |
DE (1) | DE10049097B4 (zh) |
TW (1) | TWI232126B (zh) |
WO (1) | WO2002028500A1 (zh) |
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US7285356B2 (en) * | 2004-07-23 | 2007-10-23 | The Gillette Company | Non-aqueous electrochemical cells |
US7479348B2 (en) * | 2005-04-08 | 2009-01-20 | The Gillette Company | Non-aqueous electrochemical cells |
CA2517248A1 (fr) | 2005-08-29 | 2007-02-28 | Hydro-Quebec | Procede de purification d'un electrolyte, electrolyte ainsi obtenu et ses utilisations |
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US10343964B2 (en) | 2016-07-26 | 2019-07-09 | Lockheed Martin Energy, Llc | Processes for forming titanium catechol complexes |
US10065977B2 (en) | 2016-10-19 | 2018-09-04 | Lockheed Martin Advanced Energy Storage, Llc | Concerted processes for forming 1,2,4-trihydroxybenzene from hydroquinone |
US10930937B2 (en) | 2016-11-23 | 2021-02-23 | Lockheed Martin Energy, Llc | Flow batteries incorporating active materials containing doubly bridged aromatic groups |
US10497958B2 (en) | 2016-12-14 | 2019-12-03 | Lockheed Martin Energy, Llc | Coordinatively unsaturated titanium catecholate complexes and processes associated therewith |
US10741864B2 (en) | 2016-12-30 | 2020-08-11 | Lockheed Martin Energy, Llc | Aqueous methods for forming titanium catecholate complexes and associated compositions |
US10320023B2 (en) | 2017-02-16 | 2019-06-11 | Lockheed Martin Energy, Llc | Neat methods for forming titanium catecholate complexes and associated compositions |
CN110310842B (zh) * | 2018-03-20 | 2022-03-18 | 中天超容科技有限公司 | 高电压电容的电解液及其制备方法和电容器件 |
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2000
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- 2001-09-21 CN CNA018195288A patent/CN1476343A/zh active Pending
- 2001-09-21 US US10/381,126 patent/US20040096746A1/en not_active Abandoned
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- 2001-09-21 KR KR10-2003-7004375A patent/KR20030039376A/ko not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
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DE10049097B4 (de) | 2004-08-26 |
US20060138056A1 (en) | 2006-06-29 |
EP1330299A1 (de) | 2003-07-30 |
CA2424361A1 (en) | 2003-03-25 |
CN1476343A (zh) | 2004-02-18 |
DE10049097A1 (de) | 2002-04-25 |
US20040096746A1 (en) | 2004-05-20 |
AU2002214984A1 (en) | 2002-04-15 |
CA2424361C (en) | 2010-04-06 |
US7666310B2 (en) | 2010-02-23 |
JP5021147B2 (ja) | 2012-09-05 |
KR20030039376A (ko) | 2003-05-17 |
JP2004511068A (ja) | 2004-04-08 |
WO2002028500A1 (de) | 2002-04-11 |
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