US20040096746A1 - Method for drying organic liquid electrolytes - Google Patents
Method for drying organic liquid electrolytes Download PDFInfo
- Publication number
- US20040096746A1 US20040096746A1 US10/381,126 US38112603A US2004096746A1 US 20040096746 A1 US20040096746 A1 US 20040096746A1 US 38112603 A US38112603 A US 38112603A US 2004096746 A1 US2004096746 A1 US 2004096746A1
- Authority
- US
- United States
- Prior art keywords
- metal hydride
- liquid electrolyte
- drying
- organic liquid
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000011244 liquid electrolyte Substances 0.000 title claims abstract description 20
- 238000001035 drying Methods 0.000 title description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims abstract description 7
- 150000008046 alkali metal hydrides Chemical class 0.000 claims abstract description 7
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052987 metal hydride Inorganic materials 0.000 claims description 12
- 150000004681 metal hydrides Chemical class 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 description 13
- 239000008151 electrolyte solution Substances 0.000 description 9
- 229940021013 electrolyte solution Drugs 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000002274 desiccant Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000004678 hydrides Chemical class 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- -1 for example Chemical class 0.000 description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 6
- 238000010981 drying operation Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 238000003109 Karl Fischer titration Methods 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000000010 aprotic solvent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910019256 POF3 Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- FFUQCRZBKUBHQT-UHFFFAOYSA-N phosphoryl fluoride Chemical compound FP(F)(F)=O FFUQCRZBKUBHQT-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 229910012213 MAsF6 Inorganic materials 0.000 description 1
- 229910012226 MBF4 Inorganic materials 0.000 description 1
- 229910018953 MClO4 Inorganic materials 0.000 description 1
- 229910016079 MPF6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-L catecholate(2-) Chemical compound [O-]C1=CC=CC=C1[O-] YCIMNLLNPGFGHC-UHFFFAOYSA-L 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000003446 ligand Substances 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005525 methide group Chemical group 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002825 nitriles 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 239000011877 solvent mixture Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 150000008648 triflates Chemical class 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Definitions
- the present invention relates to a method of removing water and other protic impurities from organic. liquid electrolytes.
- the lithium batteries (both primary and secondary battery cells) commonly used today normally contain anhydrous, liquid, ionically conducting electrolytes in which conducting salts, such as, for example, LiPF 6 , LiBF 4 , LiClO 4 , lithium imides, lithium methides or lithium chelato complexes such as, for example, lithium bis(oxalato)borate, are present in dissolved form.
- conducting salts such as, for example, LiPF 6 , LiBF 4 , LiClO 4 , lithium imides, lithium methides or lithium chelato complexes such as, for example, lithium bis(oxalato)borate.
- protic compounds such as, for example, water, for example according to
- the gaseous products (HF, POF 3 , etc.) formed during the hydrolysis of fluorine-containing conducting salts are highly corrosive and damaging to the other components of the battery, such as, for example, the cathode materials.
- HF leads to the dissolution of manganese spinels and damages the cover layer on the electrode materials that is important for a long service life.
- Borate electrolytes are also sensitive to water. In this case, in part insoluble hydrolysis products form and impair the functional properties.
- JP 208 7473 it is proposed to mix electrolyte solutions with a solvent that forms low-boiling azeotropic mixtures with water, and to remove the water/solvent azeotropic mixture by distillation.
- the disadvantages of this method are the undesired impurities with the entraining solvent and the restriction to high-boiling electrolyte solvents.
- DE 19827630 describes a method of cleaning battery electrolytes that consists in bringing a base, fixed to a solid, for the chemical adsorption of protic impurities into contact with the electrolyte solution and then separating off the solid cleaning agent. It is a disadvantage that the amine-containing cleaning agents fixed to a polymer are expensive and also require pre-treatment (e.g. drying in vacuo for 4 days at 100° C.).
- Modern supercapacitors may also contain an organic electrolyte which is generally the solution of an ammonium salt in an aprotic solvent having a high dielectric constant, such as, for example, acetonitrile or ⁇ -butyrolactone.
- the ammonium salts generally have perfluorinated anions such as PF 6 ⁇ or BF 4 ⁇ . These are electrochemically stable, not very nucleophilic and do not become incorporated into the active electrode masses.
- JP 11054378 and JP 11008163 propose adding to the electrolyte adsorbents based on inorganic oxides, for example aluminosilicates. Such adsorbents are able to lower the water content and hence improve the reliability, safety and current characteristics.
- the disadvantages of this method are on the one hand that the adsorbents must be pre-treated and on the other hand that adsorbent remains in the finished capacitor, so that the specific storage capacity is reduced.
- the object of the present invention is to avoid the disadvantages of the prior art and to provide a method of removing water and other protic impurities from organic liquid electrolytes.
- Organic liquid electrolytes are to be understood as being solutions containing lithium salts and/or ammonium salts with electrochemically resistant anions in aprotic, polar, organic solvents.
- [0019] is to yield product solutions having water contents down to ⁇ 20 ppm.
- the object is achieved by a method of removing water and other protic impurities from an organic liquid electrolyte, wherein the organic liquid electrolyte is brought into contact with one or more insoluble alkali metal hydride(s) and the insoluble reaction by-products formed thereby are separated off.
- the removal of water and other protic impurities is to be understood as meaning the partial removal to the complete removal.
- the binary hydrides of lithium (LiH) and sodium (NaH) that are used as the preferred drying agents are relatively inexpensive in large amounts and are available in pure form. Although they are completely insoluble in the aprotic solvents used for lithium batteries, it has been found that LiH, NaH and the other alkali metal hydrides KH, RbH and CsH are rapidly effective insofar as the drying operation is concerned, and very low residual contents of protic impurities can be achieved.
- the drying agents in hydride form used according to the invention are substantially more advantageous in terms of safety than the alkali metals themselves.
- the method according to the invention can be used with all organic liquid electrolytes, that is to say, for example, solutions of
- fluorides such as MPF 6 , MAsF 6 , MBF 4
- R F perfluorinated alkyl radical having from 1 to 10 carbon atoms, also cyclic
- L identity ligand having two O atoms, such as, for example, oxalate, catecholate, salicylate, also partially or wholly fluorinated
- carbonates e.g. dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethylmethyl carbonate,
- nitriles e.g. acetonitrile, adipic acid dinitrile, glutaric acid dinitrile,
- lactones e.g. ⁇ -butyrolactone
- amides e.g. dimethylformamide, N-methylpyrrolidone,
- ethers e.g. tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane (monoglyme), 1,3-dioxolan,
- carbonic acid esters e.g. ethyl formate, propyl formate, diethyl oxalate
- boric acid esters e.g. tributyl borate, trimethyl borate
- phosphoric acid esters e.g. tributyl phosphate, trimethyl phosphate
- sulfur compounds e.g. dimethyl sulfoxide, sulfolane
- the alkali metal reacts energetically and irreversibly with proton-active substances according to;
- the hydride is preferably added in portions to the liquid electrolyte.
- the content of proton-active substances for example water, is not to exceed a particular upper limit of 0.6 mmol/g active H concentration, for example 1% water.
- drying method according to the invention can be carried out as described below by way of example.
- An alkali metal hydride is added in portions, preferably with stirring, to the moist liquid electrolyte optionally contaminated with other proton-active substances.
- This operation is preferably carried out in a temperature range from ⁇ 20 to 150° C., particularly preferably from 0 to 90° C.
- the drying operation can readily be monitored by measuring the volume of gas that develops. In some cases (mainly when significant amounts of acid are present, e.g. 0.1 mmol/g HCl), the evolution of gas is very vigorous and foaming occurs. Cooling is then necessary. Otherwise, the reaction is scarcely noticeably exothermic.
- a subsequent reaction phase at room temperature or elevated temperature (up to 90° C., sometimes up to 120 20 C.) is necessary to complete the drying.
- the amount of drying agent to be used is determined on the one hand by the “activity” of the metal hydride used and on the other hand by the concentration of the proton-active impurity—generally water.
- the water content is normally determined by Karl Fischer titration.
- the amount of drying agent used is preferably such that it corresponds at least to the amount of water determined by Karl Fischer titration (or an alternative water determination).
- the drying agent can preferably be used in a stoichiometric excess (e.g. from 2 to 100 times).
- the excess to be used in a particular case is given by the activity of the hydride and the precise manner in which the drying operation is carried out.
- the drying ability is dependent on the “active surface area” of the metal hydride, i.e. the activity is better the finer the degree of distribution of the metal hydride.
- the drying ability of the metal hydride is additionally dependent on the nature of the pre-treatment,
- the “fresher” a metal hydride the more active it is in general.
- Metal hydrides that have been in contact with air or moisture are “passivated” and must generally be activated. This may be effected by milling under an inert gas atmosphere. This operation may take place separately from the point of view of space or in situ, i.e. during drying of the electrolyte.
- the commercially available hydride grades are sufficiently active to dry an electrolyte to water contents ⁇ 20 ppm within a few hours.
- intensive stirring is preferably carried out, on a laboratory scale, for example, using a high-speed propeller stirrer. Drying may also be carried out by passing the liquid electrolyte over a fixed bed containing the metal hydride (e.g. a column).
- the clear solutions prepared in this manner have extremely low water contents (and equally low contents of other proton-active substances). They can be used without further treatment as electrolytes for electrolytic cells, preferably lithium batteries, or electrolytic two-layer capacitors (supercapacitors).
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- Secondary Cells (AREA)
- Primary Cells (AREA)
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/355,828 US7666310B2 (en) | 2000-09-27 | 2006-02-16 | Method of drying organic liquid electrolytes |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE10049097A DE10049097B4 (de) | 2000-09-27 | 2000-09-27 | Verfahren zur Trocknung von organischen Flüssigelektrolyten |
DE10049097.2 | 2000-09-27 | ||
PCT/EP2001/010924 WO2002028500A1 (de) | 2000-09-27 | 2001-09-21 | Verfahren zur trocknung von organischen flüssigelektrolyten |
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US11/355,828 Continuation US7666310B2 (en) | 2000-09-27 | 2006-02-16 | Method of drying organic liquid electrolytes |
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US20040096746A1 true US20040096746A1 (en) | 2004-05-20 |
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US10/381,126 Abandoned US20040096746A1 (en) | 2000-09-27 | 2001-09-21 | Method for drying organic liquid electrolytes |
US11/355,828 Expired - Fee Related US7666310B2 (en) | 2000-09-27 | 2006-02-16 | Method of drying organic liquid electrolytes |
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US11/355,828 Expired - Fee Related US7666310B2 (en) | 2000-09-27 | 2006-02-16 | Method of drying organic liquid electrolytes |
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US (2) | US20040096746A1 (ja) |
EP (1) | EP1330299A1 (ja) |
JP (1) | JP5021147B2 (ja) |
KR (1) | KR20030039376A (ja) |
CN (1) | CN1476343A (ja) |
AU (1) | AU2002214984A1 (ja) |
CA (1) | CA2424361C (ja) |
DE (1) | DE10049097B4 (ja) |
TW (1) | TWI232126B (ja) |
WO (1) | WO2002028500A1 (ja) |
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US20030124421A1 (en) * | 2001-12-14 | 2003-07-03 | Issaev Nikolai N. | Non-aqueous electrochemical cells |
US20030180625A1 (en) * | 2002-03-22 | 2003-09-25 | Bookeun Oh | Nonaqueous liquid electrolyte |
US20060019161A1 (en) * | 2004-07-23 | 2006-01-26 | Issaev Nikolai N | Non-aqueous electrochemical cells |
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US20070000121A1 (en) * | 2002-02-28 | 2007-01-04 | The Gillette Company, A Delaware Corporation | Method of making non-aqueous electrochemical cell |
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JP5794028B2 (ja) * | 2011-08-03 | 2015-10-14 | セントラル硝子株式会社 | テトラフルオロホウ酸リチウム溶液の製造方法 |
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US7927739B2 (en) | 2001-12-14 | 2011-04-19 | The Gillette Company | Non-aqueous electrochemical cells |
US20050089760A1 (en) * | 2001-12-14 | 2005-04-28 | The Gillette Company, A Delaware Corporation | Electrolyte additive for non-aqueous electrochemical cells |
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US7566350B2 (en) | 2002-02-28 | 2009-07-28 | The Gillette Company | Method of making non-aqueous electrochemical cell |
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US7498102B2 (en) * | 2002-03-22 | 2009-03-03 | Bookeun Oh | Nonaqueous liquid electrolyte |
US20030180625A1 (en) * | 2002-03-22 | 2003-09-25 | Bookeun Oh | Nonaqueous liquid electrolyte |
US7473491B1 (en) * | 2003-09-15 | 2009-01-06 | Quallion Llc | Electrolyte for electrochemical cell |
US20080088278A1 (en) * | 2004-07-23 | 2008-04-17 | The Gillette Company, A Delaware Corporation | Non-aqueous electrochemical cells |
US7524581B2 (en) | 2004-07-23 | 2009-04-28 | The Gillette Company | Non-aqueous electrochemical cells |
US20060019161A1 (en) * | 2004-07-23 | 2006-01-26 | Issaev Nikolai N | Non-aqueous electrochemical cells |
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US20060228624A1 (en) * | 2005-04-08 | 2006-10-12 | Issaev Nikolai N | Non-aqueous electrochemical cells |
US9847552B2 (en) | 2007-07-04 | 2017-12-19 | Albermarle Germany Gmbh | Method for producing low-acid lithium borate salts and mixtures of low-acid lithium borate salts and lithium hydride |
US9200013B2 (en) | 2011-11-22 | 2015-12-01 | Wacker Chemie Ag | Method for producing solids from alkali salts of silanols |
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US10734666B2 (en) | 2014-11-26 | 2020-08-04 | Lockheed Martin Energy, Llc | Metal complexes of substituted catecholates and redox flow batteries containing the same |
US10253051B2 (en) | 2015-03-16 | 2019-04-09 | Lockheed Martin Energy, Llc | Preparation of titanium catecholate complexes in aqueous solution using titanium tetrachloride or titanium oxychloride |
US10316047B2 (en) | 2016-03-03 | 2019-06-11 | Lockheed Martin Energy, Llc | Processes for forming coordination complexes containing monosulfonated catecholate ligands |
US10644342B2 (en) | 2016-03-03 | 2020-05-05 | Lockheed Martin Energy, Llc | Coordination complexes containing monosulfonated catecholate ligands and methods for producing the same |
US9938308B2 (en) | 2016-04-07 | 2018-04-10 | Lockheed Martin Energy, Llc | Coordination compounds having redox non-innocent ligands and flow batteries containing the same |
US10343964B2 (en) | 2016-07-26 | 2019-07-09 | Lockheed Martin Energy, Llc | Processes for forming titanium catechol complexes |
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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 |
Also Published As
Publication number | Publication date |
---|---|
EP1330299A1 (de) | 2003-07-30 |
DE10049097A1 (de) | 2002-04-25 |
WO2002028500A1 (de) | 2002-04-11 |
TWI232126B (en) | 2005-05-11 |
CA2424361A1 (en) | 2003-03-25 |
CN1476343A (zh) | 2004-02-18 |
DE10049097B4 (de) | 2004-08-26 |
US20060138056A1 (en) | 2006-06-29 |
US7666310B2 (en) | 2010-02-23 |
AU2002214984A1 (en) | 2002-04-15 |
KR20030039376A (ko) | 2003-05-17 |
CA2424361C (en) | 2010-04-06 |
JP5021147B2 (ja) | 2012-09-05 |
JP2004511068A (ja) | 2004-04-08 |
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