JP2018152291A - Electrolyte - Google Patents
Electrolyte Download PDFInfo
- Publication number
- JP2018152291A JP2018152291A JP2017048934A JP2017048934A JP2018152291A JP 2018152291 A JP2018152291 A JP 2018152291A JP 2017048934 A JP2017048934 A JP 2017048934A JP 2017048934 A JP2017048934 A JP 2017048934A JP 2018152291 A JP2018152291 A JP 2018152291A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- oligoether
- mass
- epnoe
- phosphorus ester
- 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.)
- Granted
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 16
- -1 phosphorus ester compound Chemical class 0.000 claims abstract description 66
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 36
- 239000011574 phosphorus Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 125000005463 sulfonylimide group Chemical group 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 34
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 15
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 14
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 12
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 9
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 9
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 claims description 6
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 claims description 4
- IMDCVAFSSZPRRM-UHFFFAOYSA-N oxo-bis(2,2,2-trifluoroethoxy)phosphanium Chemical compound FC(F)(F)CO[P+](=O)OCC(F)(F)F IMDCVAFSSZPRRM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 abstract description 41
- 150000002500 ions Chemical class 0.000 abstract description 15
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 abstract 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 abstract 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 36
- 229910010941 LiFSI Inorganic materials 0.000 description 35
- 239000007788 liquid Substances 0.000 description 28
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 27
- 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 description 27
- 239000012453 solvate Substances 0.000 description 23
- 238000005259 measurement Methods 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 15
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 150000001450 anions Chemical class 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- YIUFTMLPQFZEFD-UHFFFAOYSA-N 1,1,1-trifluoro-2-[methyl(2,2,2-trifluoroethoxy)phosphoryl]oxyethane Chemical compound FC(F)(F)COP(=O)(C)OCC(F)(F)F YIUFTMLPQFZEFD-UHFFFAOYSA-N 0.000 description 2
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- AVJYNJQKPDKJBG-UHFFFAOYSA-N 1,2,5,8-tetraoxecane Chemical compound C1COCCOOCCO1 AVJYNJQKPDKJBG-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- LIKKZVFVRKNSHY-UHFFFAOYSA-N 2-[ethyl(2,2,2-trifluoroethoxy)phosphoryl]oxy-1,1,1-trifluoroethane Chemical compound FC(F)(F)COP(=O)(CC)OCC(F)(F)F LIKKZVFVRKNSHY-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-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
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WVKUSIAWZULCKO-UHFFFAOYSA-N OP(O)(O)=O.CNC(CC(F)(F)F)CC(F)(F)F Chemical compound OP(O)(O)=O.CNC(CC(F)(F)F)CC(F)(F)F WVKUSIAWZULCKO-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- JLEXUIVKURIPFI-UHFFFAOYSA-N tris phosphate Chemical compound OP(O)(O)=O.OCC(N)(CO)CO JLEXUIVKURIPFI-UHFFFAOYSA-N 0.000 description 1
- ZMQDTYVODWKHNT-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphate Chemical compound FC(F)(F)COP(=O)(OCC(F)(F)F)OCC(F)(F)F ZMQDTYVODWKHNT-UHFFFAOYSA-N 0.000 description 1
- CBIQXUBDNNXYJM-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphite Chemical compound FC(F)(F)COP(OCC(F)(F)F)OCC(F)(F)F CBIQXUBDNNXYJM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
- Fuel Cell (AREA)
Abstract
Description
本明細書で開示する発明である本開示は、電解液に関する。 The present disclosure, which is an invention disclosed herein, relates to an electrolytic solution.
従来、リチウム二次電池などに用いられる電解液としては、グライムとアルカリ金属塩とを有する溶媒和イオン液体が提案されている（例えば、特許文献１参照）。この電解液は熱安定性が高く、高電位の二次電池に利用できるとしている。また、電解液としては、テトラヒドロフランやジオキソラン、ジオキサン、グライムなどのエーテル化合物とリチウム塩とを含むものにハイドロフルオロカーボン又はハイドロフルオロエーテルを添加したものが提案されている（例えば、特許文献２、３参照）。この電解液では、充放電サイクルによる放電容量の低下を抑制することができるとしている。また、電解液としては、グライムとスルホニルイミド塩とを有する溶媒和イオン液体にリン系アルカリ金属塩化合物を添加したものが提案されている（特許文献４参照）。この溶媒和イオン液体では、低温でのイオン伝導度の低下を抑制することができる。 Conventionally, a solvated ionic liquid having glyme and an alkali metal salt has been proposed as an electrolytic solution used for a lithium secondary battery or the like (see, for example, Patent Document 1). This electrolytic solution has high thermal stability, and can be used for a secondary battery having a high potential. In addition, as an electrolytic solution, a solution containing an ether compound such as tetrahydrofuran, dioxolane, dioxane, glyme and a lithium salt and a hydrofluorocarbon or hydrofluoroether added has been proposed (for example, see Patent Documents 2 and 3). ). This electrolyte solution can suppress a decrease in discharge capacity due to a charge / discharge cycle. Moreover, what added the phosphorus alkali metal salt compound to the solvation ionic liquid which has a glyme and a sulfonylimide salt as an electrolyte solution is proposed (refer patent document 4). With this solvated ionic liquid, it is possible to suppress a decrease in ionic conductivity at low temperatures.
しかしながら、上述した特許文献１〜３の電解液では、例えば、−２０℃など、低温ではイオン伝導度が低下する問題があった。また、−２０℃の低温、常温、４０℃以上の高温など温度変化した際にイオン伝導度が大きく変化してしまうヒステリシスがみられることがあった。また、特許文献４の電解液では、低温でのイオン伝導度の低下を抑制することができるものではあるが、まだ十分でなく、更なる改良が望まれていた。 However, the above-described electrolytic solutions of Patent Documents 1 to 3 have a problem that the ionic conductivity decreases at a low temperature such as −20 ° C., for example. Further, there was a case where hysteresis was observed in which the ionic conductivity changed greatly when the temperature changed such as a low temperature of −20 ° C., a normal temperature, and a high temperature of 40 ° C. or higher. Moreover, although the electrolyte solution of patent document 4 can suppress the fall of the ionic conductivity in low temperature, it is still not enough and the further improvement was desired.
本開示は、このような課題を解決するためになされたものであり、低温でのイオン伝導性をより向上させることができる電解液を提供することを主目的とする。 This indication is made in order to solve such a subject, and it aims at providing the electrolyte solution which can improve the ionic conductivity in low temperature more.
上述した目的を達成するために、本発明者らは、グライムとイミド塩とを含む溶媒和イオン液体に所定のリン系エステル化合物を添加したところ、低温でのイオン伝導度をより向上することができることを見いだし本発明を完成するに至った。 In order to achieve the above-mentioned object, the present inventors added a predetermined phosphorus ester compound to a solvated ionic liquid containing glyme and an imide salt, so that the ionic conductivity at low temperature can be further improved. The inventors have found what can be done and have completed the present invention.
即ち、本明細書で開示する電解液は、
アルカリ金属イオンを伝導する電解液であって、
オリゴエーテル化合物と、
アルカリ金属を含むスルホニルイミド塩と、
式（１）〜（１１）に示すリン系エステル化合物と、
を含むものである。
That is, the electrolytic solution disclosed in this specification is
An electrolyte that conducts alkali metal ions,
An oligoether compound,
A sulfonylimide salt containing an alkali metal;
A phosphorus ester compound represented by formulas (1) to (11);
Is included.
この電解液では、低温でのイオン伝導性をより向上させることができる。このような効果が得られる理由は、例えば、以下のように推察される。グライムを含むオリゴエーテル化合物とアルカリ金属を含むスルホニルイミド塩とを含む溶媒和イオン液体としては、例えば、特許文献１〜３に示すように、トリグライム（Ｇ３）又はテトラグライム（Ｇ４）と、Ｌｉイミド塩（ＬｉＴＦＳＩ）とをモル比１：１で混合したものが挙げられる。この溶媒和イオン液体は、低温（−１０〜−３０℃）でイオン伝導度が大きく低下する。特許文献３では、溶媒和イオン液体にハイドロフルオロエーテル（ＨＦＥ−Ａ）で希釈する効果によってイオン伝導性が向上するとしているが、十分ではなかった。また、特許文献４では、リン系アルカリ金属塩を添加して低温でのイオン伝導性の低下を抑制しているが、過冷却で結晶化することもあり、十分ではなかった。本開示の電解液では、溶媒和イオン液体にリン系エステル化合物を含むものとすることにより、Ｐ＝Ｏ結合が溶媒和化合物のＬｉイオンに配位するなどして、新規な溶媒和化合物が形成されると推察される。その結果、Ｌｉ+／オリゴエーテル化合物の錯カチオンがイミドアニオンと解離し易くなり、低温でのイオン伝導性がより向上するものと推察される。また、ジグライム（Ｇ２）や１２−クラウン−４の溶媒和化合物（Ｌｉ塩＋オリゴエーテル化合物）は固体であり、電解液としては従来利用できなかったが、所定のリン系エステル化合物を含むものとすると、Ｐ＝Ｏ結合が溶媒和化合物のＬｉイオンに配位することによって液状となり、新規な電解液として利用可能となるものと推察される。 With this electrolytic solution, ion conductivity at low temperatures can be further improved. The reason why such an effect is obtained is assumed as follows, for example. As a solvated ionic liquid containing an oligoether compound containing glyme and a sulfonylimide salt containing an alkali metal, for example, as shown in Patent Documents 1 to 3, triglyme (G3) or tetraglyme (G4) and Liimide What mixed salt (LiTFSI) by molar ratio 1: 1 is mentioned. This solvated ionic liquid has a significant decrease in ionic conductivity at low temperatures (−10 to −30 ° C.). In Patent Document 3, the ion conductivity is improved by the effect of diluting the solvated ionic liquid with hydrofluoroether (HFE-A), but this is not sufficient. Moreover, in patent document 4, although the phosphorus-based alkali metal salt is added and the fall of the ionic conductivity at low temperature is suppressed, it may crystallize by supercooling and was not enough. In the electrolytic solution of the present disclosure, by including a phosphorus ester compound in the solvated ionic liquid, a novel solvate is formed, for example, by coordination of the P═O bond to the Li ion of the solvate. It is guessed. As a result, it is presumed that the complex cation of the Li + / oligoether compound is easily dissociated from the imide anion, and the ionic conductivity at low temperature is further improved. Further, diglyme (G2) and 12-crown-4 solvate (Li salt + oligoether compound) are solid and cannot be conventionally used as an electrolyte, but include a predetermined phosphorus ester compound. , P = O bond is coordinated to Li ions of the solvate, and is assumed to be liquid and usable as a novel electrolyte.
本明細書で開示する電解液は、アルカリ金属イオンを伝導する電解液であって、オリゴエーテル化合物と、アルカリ金属を含むスルホニルイミド塩と、リン系エステル化合物と、を含むものである。この電解液は、アルカリ金属として、リチウムイオン、ナトリウムイオン、カリウムイオンなどを伝導するが、このうちリチウムイオンであることが好ましい。 The electrolytic solution disclosed in the present specification is an electrolytic solution that conducts alkali metal ions, and includes an oligoether compound, a sulfonylimide salt containing an alkali metal, and a phosphorus ester compound. This electrolyte conducts lithium ions, sodium ions, potassium ions, and the like as alkali metals, and among these, lithium ions are preferable.
オリゴエーテル化合物としては、例えば、グライムや、トリグライムモノメチルエーテル、テトラグライムモノメチルエーテル及び１２−クラウン−４などが挙げられ、このうち１以上を含むことが好ましい。グライムは、直鎖状の対称グリコールジエーテルの総称であり、例えば、Ｒ−Ｏ（ＣＨ2ＣＨ2Ｏ）n−Ｒで表されるものとしてもよい。式中、Ｒは、アルキル基又はアリール基であり、ｎは１以上の整数である。アルキル基としては、メチル、エチル、プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチルなどが挙げられる。アリール基としては、フェニル、ナフチル、アントリルなどが挙げられる。ｎは、１以上の整数であればよいが、３又は４であることが好ましい。グライムは、ジグライム（Ｇ２）、トリグライム（Ｇ３）、テトラグライム（Ｇ４）のうち１以上であるものとしてもよい。オリゴエーテル化合物は１種を単独で用いてもよいし、２種以上を混合して用いてもよい。 Examples of the oligoether compound include glyme, triglyme monomethyl ether, tetraglyme monomethyl ether, 12-crown-4, and the like, and it is preferable to include one or more of these. Glyme is a general term for linear symmetric glycol diethers, and may be represented by, for example, R—O (CH 2 CH 2 O) n —R. In the formula, R is an alkyl group or an aryl group, and n is an integer of 1 or more. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Aryl groups include phenyl, naphthyl, anthryl and the like. n may be an integer of 1 or more, but is preferably 3 or 4. The glyme may be one or more of diglyme (G2), triglyme (G3), and tetraglyme (G4). An oligo ether compound may be used individually by 1 type, and 2 or more types may be mixed and used for it.
スルホニルイミド塩は、例えば、イミド構造を含むアニオンを含むものとしてもよい。このアニオンとしては、例えば、窒素にカルボニル基が２つ結合したイミドアニオンのほか、窒素に２つのスルホニル基が結合したスルホニルイミドアニオンや、窒素に１つのスルホニル基と１つのカルボニル基が結合したスルホニルカルボニルイミドアニオンなどを含むものとしてもよい。イミド構造を含むアニオンとしては、スルホニルイミドアニオンやスルホニルカルボニルイミドアニオンが好ましく、スルホニルイミドアニオンがより好ましい。スルホニルイミドアニオンとしては、例えば、ビス（トリフルオロメタンスルホニル）イミドアニオン（ＴＦＳＩ） やビス（ペンタフルオロエタンスルホニル）イミドアニオン（ＢＥＴＩ）、ビス（フルオロスルホニル）イミドアニオン（ＦＳＩ）、フルオロスルホニルトリフルオロメタンスルホニルイミドアニオン（ＦＴＡ）、４，４，５，５，−テトラフルオロ−１，３，２−ジチアゾリン−１，１，３，３−テトラオキシドアニオン（ＣＴＦＳＩ）等が挙げられる。スルホニルカルボニルイミドアニオンとしては、例えば、２，２，２−トリフルオロ−Ｎ−（トリフルオロメチルスルホニル）アセトアミドアニオン（ＴＳＡＣ）等が挙げられる。このうち、オリゴエーテル化合物に対する溶解性や、錯体形成しやすさなどの観点からは、ＴＦＳＩやＦＳＩが好ましい。このイミド構造を含むアニオンは、アルカリ金属イオンを対カチオンとしてもよい。アルカリ金属としては、例えば、リチウム、ナトリウム、カリウムなどが好ましく、リチウムがより好ましい。このスルホニルイミド塩としては、例えば、ＬｉＦＳＩやＬｉＴＦＳＩなどが好ましい。 The sulfonylimide salt may contain, for example, an anion containing an imide structure. Examples of the anion include an imide anion in which two carbonyl groups are bonded to nitrogen, a sulfonylimide anion in which two sulfonyl groups are bonded to nitrogen, and a sulfonyl in which one sulfonyl group and one carbonyl group are bonded to nitrogen. A carbonylimide anion or the like may be included. As an anion containing an imide structure, a sulfonylimide anion and a sulfonylcarbonylimide anion are preferable, and a sulfonylimide anion is more preferable. Examples of the sulfonylimide anion include bis (trifluoromethanesulfonyl) imide anion (TFSI), bis (pentafluoroethanesulfonyl) imide anion (BETI), bis (fluorosulfonyl) imide anion (FSI), and fluorosulfonyltrifluoromethanesulfonylimide. Anion (FTA), 4,4,5,5, -tetrafluoro-1,3,2-dithiazoline-1,1,3,3-tetraoxide anion (CTFSI) and the like can be mentioned. Examples of the sulfonylcarbonylimide anion include 2,2,2-trifluoro-N- (trifluoromethylsulfonyl) acetamide anion (TSAC). Among these, TFSI and FSI are preferable from the viewpoint of solubility in the oligoether compound and ease of complex formation. The anion containing this imide structure may have an alkali metal ion as a counter cation. As the alkali metal, for example, lithium, sodium, potassium and the like are preferable, and lithium is more preferable. As this sulfonylimide salt, for example, LiFSI and LiTFSI are preferable.
リン系エステル化合物としては、式（１）〜（１１）に示す化合物が挙げられる。具体的には、エチルホスホン酸ジエチル（ＥＰｎＯＥ）、メチルホスホン酸ジメチル（ＭＰｎＯＭ）、フェニルホスホン酸ジエチル（ＰｈＰｎＯＥ）、メチルホスホン酸ビス（トリフルオロエチル）（ＭＰｎＯＥＦ）、エチルホスホン酸ビス（トリフルオロエチル）（ＥＰｎＯＥＦ）、ホスホン酸ビス（トリフルオロエチル）（ＨＰｎＯＥＦ）、リン酸トリス（トリフルオロエチル）（ＴＦＥＰａ）、リン酸トリフェニル（ＴＰＰａ）、リン酸トリエチル（ＴＥＰａ）、亜リン酸トリス（トリフルオロエチル）（ＴＦＥＰｉ）、リン酸ビス（２，２，２−トリフルオロエチル）ジメチルアミド（ＰＦ−３９；Ｐａｍ）などが挙げられる。リン系エステル化合物としては、リン酸トリエチル（ＴＥＰａ）と、ホスホン酸ビス（トリフルオロエチル）（ＨＰｎＯＥＦ）と、メチルホスホン酸ジメチル（ＭＰｎＯＭ）と、エチルホスホン酸ジエチル（ＥＰｎＯＥ）とのうち２以上が電解液に含まれていることが好ましい。特に、リン系エステル化合物としては、エチルホスホン酸ジエチル（ＥＰｎＯＥ）を含むものとすることが好ましい。このリン系エステル化合物は、オリゴエーテル化合物とスルホニルイミド塩との全体に対して２０質量％以上３００質量％以下の範囲で含まれていることが好ましい。この範囲では、−１０℃以下など低温領域でのイオン伝導性をより向上でき好ましい。このリン系エステル化合物の含有量は、２５０質量％以下であることがより好ましく、２００質量％以下であることが更に好ましい。また、この含有量は、３０質量％以上であることがより好ましく、５０質量％以上であることが更に好ましい。 As a phosphorus ester compound, the compound shown to Formula (1)-(11) is mentioned. Specifically, diethyl ethylphosphonate (EPnOE), dimethyl methylphosphonate (MPnOM), diethyl phenylphosphonate (PhPnOE), bis (trifluoroethyl) methylphosphonate (MPnOEF), bis (trifluoroethyl) ethylphosphonate ( EPnOEF), bis (trifluoroethyl) phosphonate (HPnOEF), tris phosphate (trifluoroethyl) (TFEPa), triphenyl phosphate (TPPa), triethyl phosphate (TEPa), tris phosphite (trifluoroethyl) ) (TFEPi), bis (2,2,2-trifluoroethyl) dimethylamide phosphate (PF-39; Pam), and the like. As the phosphorus ester compound, two or more of triethyl phosphate (TEPa), bis (trifluoroethyl) phosphonate (HPnOEF), dimethyl methylphosphonate (MPnOM) and diethyl ethylphosphonate (EPnOE) are electrolyzed. It is preferably contained in the liquid. In particular, the phosphorus ester compound preferably contains diethyl ethylphosphonate (EPnOE). The phosphorus ester compound is preferably contained in the range of 20% by mass or more and 300% by mass or less with respect to the whole of the oligoether compound and the sulfonylimide salt. In this range, the ion conductivity in a low temperature region such as −10 ° C. or lower can be further improved, which is preferable. The content of the phosphorus ester compound is more preferably 250% by mass or less, and further preferably 200% by mass or less. Further, this content is more preferably 30% by mass or more, and further preferably 50% by mass or more.
この電解液において、オリゴエーテル化合物は、トリグライム、テトラグライム、トリグライムモノメチルエーテル及びテトラグライムモノメチルエーテルのうち１以上であり、このオリゴエーテル化合物は、スルホニルイミド塩に対してモル比で０．８以上１．２以下の範囲で含まれていることが好ましい。これらのオリゴエーテル化合物とスルホニルイミド塩とがモル比で１：１近傍で含まれると、溶媒和イオン液体となりやすい。あるいは、この電解液において、オリゴエーテル化合物は、ジグライム及び１２−クラウン−４のうち１以上であり、このオリゴエーテル化合物は、スルホニルイミド塩に対してモル比で１．８以上２．２以下の範囲で含まれていることが好ましい。これらのオリゴエーテル化合物とスルホニルイミド塩とがモル比で２：１近傍で含まれると、溶媒和化合物となりやすい。オリゴエーテル化合物は、ジグライム及び１２−クラウン−４である場合は、そのままでは固体で有り電解液として利用できないが、この固体に上述したリン系エステル化合物を添加すると、液状になり、電解液として利用できるようになる。 In this electrolytic solution, the oligoether compound is one or more of triglyme, tetraglyme, triglyme monomethyl ether and tetraglyme monomethyl ether, and the oligoether compound is 0.8 or more in molar ratio to the sulfonylimide salt. It is preferably included in the range of 1.2 or less. When these oligoether compounds and the sulfonylimide salt are contained in a molar ratio of about 1: 1, a solvated ionic liquid tends to be formed. Alternatively, in this electrolytic solution, the oligoether compound is one or more of diglyme and 12-crown-4, and the oligoether compound has a molar ratio of 1.8 to 2.2 with respect to the sulfonylimide salt. It is preferable that it is included in the range. When these oligoether compounds and sulfonylimide salts are contained in a molar ratio of around 2: 1, solvates are easily formed. When the oligoether compound is diglyme and 12-crown-4, it is solid as it is and cannot be used as an electrolytic solution. However, when the above-described phosphorus ester compound is added to this solid, it becomes a liquid and is used as an electrolytic solution. become able to.
この電解液の用途としては、例えば、リチウムイオン電池等のアルカリ金属イオン電池や、コンデンサー、燃料電池、太陽電池などの構成材料などが挙げられる。 Examples of the use of the electrolytic solution include alkali metal ion batteries such as lithium ion batteries, and constituent materials such as capacitors, fuel cells, and solar cells.
以上説明した電解液では、低温でのイオン伝導性をより向上することができる。このような効果が得られる理由は、例えば、以下のように推察される。グライムを含むオリゴエーテル化合物とアルカリ金属を含むスルホニルイミド塩とを含む溶媒和イオン液体としては、例えば、トリグライム（Ｇ３）又はテトラグライム（Ｇ４）と、Ｌｉイミド塩（ＬｉＴＦＳＩ）とをモル比１：１で混合したものが挙げられる。この溶媒和イオン液体は、低温（−１０℃〜−３０℃）でイオン伝導度が大きく低下する。この電解液では、溶媒和イオン液体にリン系エステル化合物を含むものとすることにより、Ｐ＝Ｏ結合が溶媒和化合物のＬｉイオンに配位するなどして、新規な溶媒和化合物が形成されると推察される。その結果、Ｌｉ+／オリゴエーテル化合物の錯カチオンがイミドアニオンと解離し易くなり、低温でのイオン伝導性がより向上するものと推察される。また、ジグライム（Ｇ２）や１２−クラウン−４の溶媒和化合物（Ｌｉ塩＋オリゴエーテル化合物）は固体であり、電解液としては従来利用できなかったが、上述したリン系エステル化合物を含むものとすると、Ｐ＝Ｏ結合が溶媒和化合物のＬｉイオンに配位することによって液状となり、新規な電解液として利用可能となるものと推察される。 In the electrolytic solution described above, the ion conductivity at a low temperature can be further improved. The reason why such an effect is obtained is assumed as follows, for example. As a solvated ionic liquid containing an oligoether compound containing glyme and a sulfonylimide salt containing an alkali metal, for example, a molar ratio of triglyme (G3) or tetraglyme (G4) and Liimide salt (LiTFSI) is 1: What was mixed in 1 is mentioned. This solvated ionic liquid has a significant decrease in ionic conductivity at low temperatures (−10 ° C. to −30 ° C.). In this electrolytic solution, it is assumed that a solvated ionic liquid contains a phosphorus ester compound, whereby a P = O bond is coordinated to a Li ion of the solvated compound and a new solvated compound is formed. Is done. As a result, it is presumed that the complex cation of the Li + / oligoether compound is easily dissociated from the imide anion, and the ionic conductivity at low temperature is further improved. Further, diglyme (G2) and solvate of 12-crown-4 (Li salt + oligoether compound) are solid and cannot be conventionally used as an electrolyte, but include the above-described phosphorus ester compounds. , P = O bond is coordinated to Li ions of the solvate, and is assumed to be liquid and usable as a novel electrolyte.
なお、本発明は上述した実施形態に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.
以下では上述した電解液を具体的に作製した例について説明する。なお、実験例１−１〜８、６−１〜５が参考例に相当し、それ以外が実施例に相当する。 Below, the example which produced the electrolyte solution mentioned above concretely is demonstrated. Experimental examples 1-1 to 8 and 6-1 to 5 correspond to reference examples, and the others correspond to examples.
［原料の略称等］
Ｇ４ Tetraethylene glycol dimethyl ether：東京化成製
Ｇ３ Triethylene glycol dimethyl ether：東京化成製
Ｇ３ＯＨ Triethylene glycol monomethyl ether：東京化成製
Ｇ２ Diethylene glycol dimethyl ether：東京化成製
１２−Ｃ−４ 12-Crown-4 (1,4,7,10-Tetraoxacyclodecane)：東京化成製
ＬｉＴＦＳＩ Lithium Bis(trifluoromethanesulfonyl)imide：キシダ化学製
ＬｉＦＳＩ Lithium Bis(fluorosulfonyl)imide：キシダ化学製
ＥＰｎＯＥ Diethyl ethlphosphonate：Aldrich製
ＭＰｎＯＭ Dimethyl methlphosphonate：Aldrich製
ＰｈＰｎＯＥ Diethyl Phenylphosphonate：東京化成製
ＴＭＰａ Trimethyl phosphate：東京化成製
ＴＥＰａ Triethyl phosphate：東京化成製
ＴＰＰａ Triphenyl phosphate：東京化成製
ＭＰｎＯＥＦ Bis(2,2,2-trifluoroethyl)methylphosphonate：Aldrich製
ＨＰｎＯＥＦ Bis(2,2,2-trifluoroethyl)phosphonate：Aldrich製
ＴＦＥＰａ Tris(2,2,2-trifluoroethyl)phosphate：東京化成製
ＴＦＥＰｉ Tris(2,2,2-trifluoroethyl)phosphite：Aldrich製
ＰＦ−３９（Ｐａｍ） O,O-Bis(2,2,2-trifluoroethyl)N,N-dimethylphosphoramodate：東ソーエフテック製
ＨＦＥ−Ａ 1,1,2,2-Tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether：東京化成製
（リン系エステル化合物の略号）
Ｐａ：phosphate（リン酸エステル），Ｐｎ：phosphonate（ホスホン酸エステル），
Ｐｉ：phosphite（亜リン酸エステル），Ｐａｍ：phosphoramide（リン酸アミドエステル）
[Abbreviations of raw materials]
G4 Tetraethylene glycol dimethyl ether: Tokyo Kasei G3 Triethylene glycol dimethyl ether: Tokyo Kasei G3OH Triethylene glycol monomethyl ether: Tokyo Kasei G2 Diethylene glycol dimethyl ether: Tokyo Kasei 12-C-4 12-Crown-4 (1,4 , 7,10-Tetraoxacyclodecane): Tokyo Chemical LiTFSI Lithium Bis (trifluoromethanesulfonyl) imide: Kishida Chemical LiFSI Lithium Bis (fluorosulfonyl) imide: Kishida Chemical EPnOE Diethyl ethlphosphonate: Aldrich MPnOM Dimethyl methlphosphonate: Aldrich PhPnOE Diethyl Phenylphosphonate Kasei TMPa Trimethyl phosphate: Tokyo Kasei TEPa Triethyl phosphate: Tokyo Kasei TPPa Triphenyl phosphate: Tokyo Kasei MPnOEF Bis (2,2,2-trifluoroethyl) methylphosphonate: Aldrich HPnOEF Bis (2,2,2-trifluoroethyl) phosphonate : TFEPa Tris (2,2,2-trifluoroethyl) phosphate manufactured by Aldrich: manufactured by Tokyo Chemical Industry FEPi Tris (2,2,2-trifluoroethyl) phosphite: PF-39 (Pam) from Aldrich O, O-Bis (2,2,2-trifluoroethyl) N, N-dimethylphosphoramodate: HFE-A 1,1 from Tosoh F-Tech , 2,2-Tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether: manufactured by Tokyo Chemical Industry (abbreviation for phosphorus ester compounds)
Pa: phosphate (phosphate ester), Pn: phosphonate (phosphonate ester),
Pi: phosphite (Phosphite), Pam: phosphoramide (Phosphate amide)
（比較試料：４種の溶媒和イオン液体（ＩＬａ，ＩＬｂ，ＩＬｃ，ＩＬｄ）の作製）
Ａｒガスを充填したグローブボックス内で、２０ｍＬサンプル瓶に等モル量（５０．０ｍｍｏｌ）のＧ４（１１．１１ｇ）又はＧ３（８．９１ｇ）とＬｉＴＦＳＩ（１４．３６ｇ） 又はＬｉＦＳＩ（９．３６ｇ）をとり、サンプル瓶を密封して取り出し、加熱により均一溶液として４種の溶媒和イオン液体（ＩＬ）を得た。それぞれ、ａ：Ｇ３＋ＬｉＦＳＩ、ｂ：Ｇ３＋ＬｉＴＦＳＩ、ｃ：Ｇ４＋ＬｉＦＳＩ、ｄ：Ｇ４＋ＬｉＴＦＳＩと略称する。なお、溶媒和ＩＬａを調製後に、冬季（気温１０℃以下）２ヵ月間放置したところ、凍結・固化したが、結晶化であることがＸＲＤ測定で判った。
(Comparative sample: Preparation of four solvated ionic liquids (ILa, ILb, ILc, ILd))
In a glove box filled with Ar gas, equimolar amounts (50.0 mmol) of G4 (11.11 g) or G3 (8.91 g) and LiTFSI (14.36 g) or LiFSI (9.36 g) in a 20 mL sample bottle The sample bottle was sealed and taken out, and four solvated ionic liquids (IL) were obtained as a uniform solution by heating. They are abbreviated as a: G3 + LiFSI, b: G3 + LiTFSI, c: G4 + LiFSI, and d: G4 + LiTFSI, respectively. After preparation of the solvated ILa, it was allowed to stand for 2 months in the winter (at a temperature of 10 ° C. or less) for 2 months, but it was frozen and solidified, but was found to be crystallized by XRD measurement.
（各種リン系エステル化合物、ＨＦＥ−Ａを添加した溶媒和イオン液体の作製）
Ａｒガスを充填したグローブボックス内で、撹拌子を入れたサンプル瓶中に、溶媒和イオン液体ＩＬａ：（Ｇ３＋ＬｉＦＳＩ）又はＩＬｄ：（Ｇ４＋ＬｉＴＦＳＩ）に対して、所定量の各種リン系エステル化合物又はＨＦＥ−Ａを加えて、撹拌により均一に混合して電解液を調製した。
(Preparation of solvated ionic liquid to which various phosphorus ester compounds and HFE-A were added)
In a glove box filled with Ar gas, in a sample bottle containing a stirring bar, a predetermined amount of various phosphorus ester compounds or HFE- with respect to the solvated ionic liquid ILa: (G3 + LiFSI) or ILd: (G4 + LiTFSI). A was added and mixed uniformly by stirring to prepare an electrolytic solution.
（イオン伝導度の測定）
Ａｒガスを充填したグローブボックス内で、測定セル（ポリマーセルと称する）の内部（直径１０ｍｍ）に電解液を入れてステンレス製電極で挟み、気泡を抜き密封した。このときに電解液中にセパレータ（直径１０ｍｍ；ポリエチレンＰＥ製気孔率８２％）を配置しないものとするものとで別個に測定した。測定セルを恒温槽内に置いて、２５℃、１０℃、−１０℃、−３０℃、−１０℃、１０℃、２５℃、４５℃、６０℃、７０℃、８０℃、８０℃、７０℃、６０℃、４５℃、２５℃となるようにしてインピーダンス測定した。その測定は、振幅電圧を１００ｍＶにして、０．１Ｍｈｚ−１Ｈｚの間で０．５ｐｔｓ／ｓｅｃで行った。得られたＣｏｌｅ−ＣｏｌｅプロットのＺ’の実軸切片の値もしくはＢｏｄｅ線図でθが最小になる｜Ｚ｜を抵抗値（Ｒ）として求めた。この値（Ｒ）と膜厚ｔ（ｃｍ）及び電極面積Ｓ（ｃｍ2）から次式に従いイオン伝導度σ（Ｓ／ｃｍ）を算出した。
イオン伝導度σ（Ｓ／ｃｍ）＝１／Ｒ×ｔ／Ｓ
(Ion conductivity measurement)
In a glove box filled with Ar gas, an electrolytic solution was put in a measurement cell (referred to as a polymer cell) (diameter 10 mm) and sandwiched between stainless steel electrodes, and air bubbles were removed and sealed. At this time, it was measured separately with a separator (diameter 10 mm; polyethylene PE porosity 82%) not disposed in the electrolyte. Place the measurement cell in a constant temperature bath, 25 ° C, 10 ° C, -10 ° C, -30 ° C, -10 ° C, 10 ° C, 25 ° C, 45 ° C, 60 ° C, 70 ° C, 80 ° C, 80 ° C, 70 ° C. Impedance measurement was performed at temperatures of 60 ° C., 60 ° C., 45 ° C., and 25 ° C. The measurement was performed at 0.5 pts / sec between 0.1 Mhz-1 Hz with an amplitude voltage of 100 mV. In the obtained Cole-Cole plot, the value of the Z ′ real axis intercept or | Z | at which θ is minimized in the Body diagram was obtained as the resistance value (R). Ion conductivity σ (S / cm) was calculated from this value (R), film thickness t (cm), and electrode area S (cm 2 ) according to the following equation.
Ionic conductivity σ (S / cm) = 1 / R × t / S
また、別種の測定セル（液体セルと称する）を用いて、同様にイオン伝導度の温度依存性を測定した。このセルは直径２ｍｍ、長さ６．５ｍｍの円筒状空隙に液状電解質を入れて白金電極で上下を挟む構造である。上記２種類の測定セルを用いて測定したσ−Ｔ値を表記する際に、その頭に下記略号を付して測定セルを区別した。２５℃〜−３０℃〜８０℃〜２５℃の１サイクル測定で得られるσ値（ｍＳ／ｃｍ）について、２５℃のσ値３つ；−３０℃のσ値１つ；８０℃のσ値１つを表１〜１０中に記載した。なお、２５℃のσ値３つの中で特に低下が大きい値がある場合、このσ−Ｔ曲線はヒステリシスを示す。
（ｎ） ：ポリマーセルでセパレータ無し
（ｓｐ）：ポリマーセルでセパレータ有り
（Ｌ） ：液体セルでセパレータ無し
Moreover, the temperature dependence of the ionic conductivity was similarly measured using another type of measurement cell (referred to as a liquid cell). This cell has a structure in which a liquid electrolyte is placed in a cylindrical gap having a diameter of 2 mm and a length of 6.5 mm, and is sandwiched between platinum electrodes. When the σ-T values measured using the two types of measurement cells were described, the following abbreviations were attached to the heads to distinguish the measurement cells. For σ values (mS / cm) obtained by one cycle measurement from 25 ° C. to −30 ° C. to 80 ° C. to 25 ° C., three σ values at 25 ° C .; one σ value at −30 ° C .; One is listed in Tables 1-10. Note that this σ-T curve exhibits hysteresis when there is a particularly large decrease among the three σ values at 25 ° C.
(N): Polymer cell without separator (sp): Polymer cell with separator (L): Liquid cell with no separator
（ラマン分光測定）
Ａｒガスを充填したグローブボックス内で、１ｍＬサンプル瓶に試料を１／３体積以上の量を入れて、レーザー・ラマン分光測定を実施した。測定装置は、日本分光社製ＮＲＳ−３３００を用いた。
(Raman spectroscopy measurement)
In a glove box filled with Ar gas, a sample of 1/3 volume or more was put into a 1 mL sample bottle, and laser Raman spectroscopic measurement was performed. As a measuring device, NRS-3300 manufactured by JASCO Corporation was used.
（実験例１−１〜５）
上述した２種類のイオン伝導度測定セル（ポリマーセルと液体セル）を３個ずつ用いて、標準電解液のイオン伝導度の温度依存性（２５℃→−３０℃→８０℃→２５℃）を評価した。標準電解液は、エチレンカーボネート（ＥＣ）、ジメチルカーボネート（ＤＭＣ）、エチルメチルカーボネート（ＥＭＣ）を体積比で３：４：３で混合した混合溶媒にＬｉＰＦ6を１Ｍ溶解したものを用いた。測定結果を表１に示した。図１は、実験例１−１，１−５のイオン伝導度σ−温度Ｔ曲線である。２５℃でのイオン伝導度は、ポリマーセルで４〜８ｍＳ／ｃｍであり、液体セルでは８〜１０ｍＳ／ｃｍであった。なお、液体セル測定では昇温過程６０℃から先のステップの測定値が乱れたので、ここでは除外した。この原因は電解質の粘性が低い場合にセルから漏れが生じる為と推定した。なお、表中の「ｅ（−ｎ）」は、１０-nを表す。
(Experimental Examples 1-1 to 5)
Using the two types of ion conductivity measurement cells (polymer cell and liquid cell) described above, the temperature dependence of the ionic conductivity of the standard electrolyte (25 ° C → -30 ° C → 80 ° C → 25 ° C) evaluated. The standard electrolyte used was a solution obtained by dissolving 1M LiPF 6 in a mixed solvent in which ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 3: 4: 3. The measurement results are shown in Table 1. FIG. 1 is an ionic conductivity σ-temperature T curve of Experimental Examples 1-1 and 1-5. The ionic conductivity at 25 ° C. was 4 to 8 mS / cm in the polymer cell and 8 to 10 mS / cm in the liquid cell. In the liquid cell measurement, since the measured value of the previous step was disturbed from the temperature rising process of 60 ° C., it was excluded here. This is presumed to be due to leakage from the cell when the electrolyte viscosity is low. In the table, “e (−n)” represents 10 −n .
（実験例１−６〜８）
溶媒和イオン液体は、グライム（Ｇ３、Ｇ４）とＬｉイミド塩塩（ＬｉＦＳＩ、ＬｉＴＦＳＩ）とを１：１モル比で混合したものであり、室温付近で液状であり、１５０℃以下の雰囲気で不揮発性であることが知られている。図２は、グライム（Ｇ３、Ｇ４）とＬｉイミド塩塩（ＬｉＦＳＩ、ＬｉＴＦＳＩ）から得られる４種類の溶媒和イオン液体について、ポリマーセル（セパレータ）で測定したσ−Ｔ曲線である。また、実験例１−６、７（Ｇ３＋ＬｉＦＳＩ）と実験例１−８（Ｇ４＋ＬｉＴＦＳＩ）について、ポリマーセル（セパレータ有・無）及び液体セルで測定したイオン伝導度σを表１に示した。図２において、Ｇ３＋ＬｉＦＳＩ、Ｇ３＋ＬｉＴＦＳＩ及びＧ４＋ＬｉＦＳＩのσ−Ｔ曲線は降温過程と昇温過程でσ値が乖離するヒステリシスを示した。なお、これらの溶媒和イオン液体では、冬場に１０℃以下の雰囲気に放置すると結晶化した。したがって調製時や降温時の液状（室温）は過冷却状態と考えられる。一方、Ｇ４＋ＬｉＴＦＳＩのσ−Ｔ曲線は、ヒステリシスを示さずに冬場でも固化しない安定な液状であった。
(Experimental Examples 1-6 to 8)
The solvated ionic liquid is a mixture of glyme (G3, G4) and Li imide salt (LiFSI, LiTFSI) in a 1: 1 molar ratio, is liquid near room temperature, and is non-volatile in an atmosphere of 150 ° C. or lower. It is known to be sex. FIG. 2 is a σ-T curve measured with a polymer cell (separator) for four types of solvated ionic liquids obtained from glyme (G3, G4) and Li imide salt (LiFSI, LiTFSI). Table 1 shows the ionic conductivity σ measured in the polymer cell (with / without separator) and the liquid cell for Experimental Examples 1-6 and 7 (G3 + LiFSI) and Experimental Example 1-8 (G4 + LiTFSI). In FIG. 2, the σ-T curves of G3 + LiFSI, G3 + LiTFSI, and G4 + LiFSI showed hysteresis in which the σ value deviates between the temperature decreasing process and the temperature increasing process. These solvated ionic liquids crystallized when left in an atmosphere of 10 ° C. or lower in winter. Therefore, the liquid state (room temperature) at the time of preparation or when the temperature is lowered is considered to be a supercooled state. On the other hand, the σ-T curve of G4 + LiTFSI did not show hysteresis and was a stable liquid that did not solidify even in winter.
（実験例２−１〜９、３−１〜４）
安定な液状を示す溶媒和イオン液体（Ｇ４＋ＬｉＴＦＳＩ）のオリゴエーテル化合物（グライム）とスルホニルイミド塩との全体に対して各種のリン系エステル化合物を２０質量％又は３０質量％添加したものについて、ポリマーセル（セパレータ有・無）及び液体セルで測定したσ−Ｔの値を表２、３にまとめて示した。表２、３に示すように、ポリマーセル（セパレータｓｐ無）で測定した−３０℃のσ値は、いずれのリン系エステル化合物を添加した場合も、無添加の溶媒和イオン液体（ｎ）の値（０．００３ｍＳ／ｃｍ）を上回った。この結果から、溶媒和イオン液体（Ｇ４＋ＬｉＴＦＳＩ）にリン系エステル化合物を添加することで、低温域でのイオン伝導性が向上することがわかった。特に、リン系エステル化合物（ＴＥＰａ、ＥＰｎＯＥ、ＴＦＥＰｉ、ＨＰｎＯＥＦ）は顕著な添加効果を示した。図３は、実験例１−８、２−２，５，９、３−４のσ−Ｔ曲線である。
(Experimental examples 2-1 to 9, 3-1 to 4)
Polymer cell in which 20% by mass or 30% by mass of various phosphorus ester compounds are added to the entire oligoether compound (glyme) and sulfonylimide salt of solvated ionic liquid (G4 + LiTFSI) showing a stable liquid state Tables 2 and 3 collectively show the values of σ-T measured with (with / without separator) and the liquid cell. As shown in Tables 2 and 3, the σ value at −30 ° C. measured in the polymer cell (without separator sp) is the value of the solvated ionic liquid (n) with no addition when any phosphorus ester compound is added. The value (0.003 mS / cm) was exceeded. From this result, it was found that the ion conductivity in a low temperature region was improved by adding a phosphorus ester compound to the solvated ionic liquid (G4 + LiTFSI). In particular, phosphorus ester compounds (TEPa, EPnOE, TFEPi, HPnOEF) showed a remarkable effect of addition. FIG. 3 is a σ-T curve of Experimental Examples 1-8, 2-2, 5, 9, 3-4.
（実験例４−１〜４）
優れた添加効果を示したリン系エステル化合物の中で、ＥＰｎＯＥ（エチルホスホン酸ジエチルエステル）は、ポリマーセル（セパレータ無）だけでなく液体セルで測定したσ値も最大となった（表２）。そこで、安定な液状を示す溶媒和イオン液体（Ｇ４＋ＬｉＴＦＳＩ）にＥＰｎＯＥを添加する際に、その添加量効果を２０質量％〜２００質量％としてσ−Ｔ測定を行った。ポリマーセル（セパレータ有・無）又は液体セルで測定したσ値を表４にまとめて示した。これらの値を一定条件で比較することは難しいが、表４に示したように、ＥＰｎＯＥを２００質量％添加しても良好なイオン伝導度を示すことがわかった。
(Experimental examples 4-1 to 4)
Among the phosphorus ester compounds that showed an excellent addition effect, EPnOE (ethylphosphonic acid diethyl ester) had the maximum σ value measured not only in the polymer cell (without separator) but also in the liquid cell (Table 2). . Then, when adding EPnOE to the solvated ionic liquid (G4 + LiTFSI) which shows a stable liquid state, the addition amount effect was 20 mass%-200 mass%, and (sigma) -T measurement was performed. Table 4 summarizes the σ values measured in a polymer cell (with or without a separator) or a liquid cell. Although it is difficult to compare these values under constant conditions, as shown in Table 4, it was found that even when 200% by mass of EPnOE was added, good ionic conductivity was exhibited.
（実験例５−１〜５）
溶媒和イオン液体（Ｇ３＋ＬｉＦＳＩ）は、最も高温の６０℃未満までσ−Ｔ曲線がヒステリシス形状を示しており（図２）、最も不安定な液状の溶媒和イオン液体といえる。一方、構成物のＧ３やＬｉＦＳＩは電気化学的に安定性が高いと報告されているので、この溶媒和イオン液体を安定な液状とすることを検討した。溶媒和イオン液体（Ｇ３＋ＬｉＦＳＩ）にＥＰｎＯＥを添加する際に、その添加量を２０質量％〜４００質量％としてσ−Ｔを測定した。ポリマーセル（セパレータ有）及び液体セルで測定したσ値を表５にまとめて示した。図４は、液体セルで測定した実験例１−７、５−２〜４のσ−Ｔ曲線である。溶媒和イオン液体（Ｇ３＋ＬｉＦＳＩ）にＥＰｎＯＥを添加すると、２０質量％から２００質量％の間でイオン伝導度が順次増大し、しかもσ−Ｔ曲線でヒステリシスが消失して安定な液状となることが、ポリマーセル（セパレータ有）及び液体セルによるσ−Ｔ測定の両方で認められた。なお、実験例５−１（Ｌ）の−３０℃でσ値が急激に低下する事象や、実験例５−３（ｓｐ）でσ値が小さい事象は、他の測定法によるこれらの結果と比べると、イレギュラーな測定エラーかもしれない。一方、ＥＰｎＯＥを４００質量％添加した実験例５−５では、両セルの測定方法で非常に小さいσ値が得られたことから、ＥＰｎＯＥ添加量は２００質量％付近でσ最大値を与えることがわかった。そのポリマーセル（セパレータ有）での測定値は、約３．５ｍＳ／ｃｍ（２５℃）であり、液体セル測定値は、約５ｍＳ／ｃｍ（２５℃）であった。表１に示したＥＰｎＯＥ無添加の溶媒和イオン液体（Ｇ３＋ＬｉＦＳＩ）のσ値と比較すると、それぞれ約２倍強と約４倍弱に増大していた。また表１に示した標準電解液のσ値に比較すると、おおよそ０．５倍の大きさに相当する。図４に示すように、実験例５−２〜４では、ヒステリシスが消失し、ＥＰｎＯＥ添加による低温域でのイオン伝導性向上が明瞭であった。
(Experimental Examples 5-1 to 5)
The solvated ionic liquid (G3 + LiFSI) can be said to be the most unstable liquid solvated ionic liquid, with the σ-T curve showing a hysteresis shape up to the highest temperature of less than 60 ° C. (FIG. 2). On the other hand, since G3 and LiFSI as constituents have been reported to have high electrochemical stability, it was examined to make this solvated ionic liquid a stable liquid. When EPnOE was added to the solvated ionic liquid (G3 + LiFSI), σ-T was measured with an addition amount of 20% by mass to 400% by mass. Table 5 summarizes the σ values measured in the polymer cell (with separator) and the liquid cell. FIG. 4 is a σ-T curve of Experimental Examples 1-7 and 5-2 to 4 measured in the liquid cell. When EPnOE is added to the solvated ionic liquid (G3 + LiFSI), the ionic conductivity sequentially increases between 20% by mass and 200% by mass, and the hysteresis disappears in the σ-T curve to become a stable liquid. It was observed in both the σ-T measurement by the polymer cell (with separator) and the liquid cell. In addition, the phenomenon in which the σ value suddenly decreases at −30 ° C. in Experimental Example 5-1 (L) and the event in which the σ value is small in Experimental Example 5-3 (sp) are the results of these other measurement methods. It may be an irregular measurement error. On the other hand, in Experimental Example 5-5 in which 400% by mass of EPnOE was added, a very small σ value was obtained by the measurement method of both cells. Therefore, the added amount of EPnOE can give a σ maximum value in the vicinity of 200% by mass. all right. The measured value in the polymer cell (with separator) was about 3.5 mS / cm (25 ° C.), and the measured value in the liquid cell was about 5 mS / cm (25 ° C.). When compared with the σ value of the solvated ionic liquid (G3 + LiFSI) without addition of EPnOE shown in Table 1, they were increased by about 2 times and about 4 times, respectively. Further, when compared with the σ value of the standard electrolyte shown in Table 1, it corresponds to approximately 0.5 times the size. As shown in FIG. 4, in Experimental Examples 5-2 to 4, the hysteresis disappeared, and the ion conductivity improvement in the low temperature region by adding EPnOE was clear.
（実験例６−１〜５）
次に、溶媒和イオン液体（Ｇ３＋ＬｉＦＳＩ）にハイドロフルオロエーテル（ＨＦＥ−Ａ）を添加したものについて検討した。ＨＦＥ−Ａは、添加溶媒和化合物に対して反応することなく、単なる希釈する効果によって、添加量に応じてイオン伝導性が向上すると考えられる（特許文献３など参照）。そこで、より不安定な液状を示した溶媒和イオン液体（Ｇ３＋ＬｉＦＳＩ）を用いて、ＨＦＥ−Ａの添加量を２２質量％から４９０質量％まで変化させて、ポリマーセル（セパレータ有）でσ−Ｔを測定した。表６に測定結果をまとめた。また、図５は、実験例１−６、６−１〜４（セパレータ有）のσ−Ｔ曲線である。溶媒和イオン液体（Ｇ３＋ＬｉＦＳＩ）へのＨＦＥ−Ａ添加においては、添加量２２質量％から４９０質量％まで、σ値は増大せずに一定であった。また添加量２２質量％から１００質量％まで、σ−Ｔ曲線上にヒステリシスが残留していた。即ち、ＨＦＥ−Ａを添加した溶媒和イオン液体において、セパレータを挟んだセルを用いると、ＨＦＥ−Ａ量の増加に対しイオン伝導度は一定値であり、温度変化によるσ−Ｔ曲線のヒステリシスは消失しないことがわかった。これらの結果より、ＨＦＥ−Ａの添加効果が溶媒和イオン液体の液状の安定性向上に対し効果が小さいことと同時に、イオン伝導性の向上に対しても効果が小さいことが示唆された。これは、リン系エステル化合物の添加効果とは対照的な結果であった。この違いは、リン系エステル化合物が溶媒和イオン液体と相互作用するためではないかと推定する。これについては、後述のラマン分光分析で検討した。
(Experimental examples 6-1 to 5)
Next, what added hydrofluoroether (HFE-A) to the solvation ionic liquid (G3 + LiFSI) was examined. It is thought that HFE-A improves ion conductivity according to the addition amount by the effect of simply diluting without reacting with the added solvate (see Patent Document 3, etc.). Therefore, using a solvated ionic liquid (G3 + LiFSI) showing a more unstable liquid state, the amount of HFE-A added was changed from 22% by mass to 490% by mass, and σ-T was used in the polymer cell (with separator). Was measured. Table 6 summarizes the measurement results. FIG. 5 is a σ-T curve of Experimental Examples 1-6 and 6-1 to 4 (with a separator). In addition of HFE-A to the solvated ionic liquid (G3 + LiFSI), the σ value was constant without increasing from 22 mass% to 490 mass%. Further, hysteresis remained on the σ-T curve from the addition amount of 22% by mass to 100% by mass. That is, in a solvated ionic liquid to which HFE-A is added, when a cell sandwiched between separators is used, the ionic conductivity is a constant value as the amount of HFE-A increases, and the hysteresis of the σ-T curve due to temperature change is It turns out not to disappear. From these results, it was suggested that the effect of addition of HFE-A is small for improving the stability of the solvated ionic liquid, and at the same time, the effect for improving the ion conductivity is small. This was in contrast to the effect of adding the phosphorus ester compound. This difference is presumed to be because the phosphorus ester compound interacts with the solvated ionic liquid. This was examined by Raman spectroscopy described later.
（実験例７−１〜３、８−１〜４、９−１〜４）
グライムＧ３、Ｇ４に代るオリゴエーテル化合物を用いてＬｉＦＳＩと溶媒和化合物を形成させ、ＥＰｎＯＥの添加効果を検討した。トリグライムモノメチルエーテル（Ｇ３ＯＨ）、ジグライム（Ｇ２）、及び１２−クラウン−４（１２−Ｃ−４）をオリゴエーテル化合物として用いた。（Ｇ３ＯＨ＋ＬｉＦＳＩ）にＥＰｎＯＥを２０質量％、２００質量％添加した場合のσ−Ｔ測定結果を表７にまとめて示した。表７に示すように、２００質量％添加のσ値（３ｍＳ／ｃｍ）が最も大きく、添加効果を確認できた。Ｇ２や１２−Ｃ−４では、ＬｉＦＳＩに対して２：１（モル比）で混合すると、溶媒和化合物が形成されることが報告されている。そこで、その溶媒和化合物に対してＥＰｎＯＥを２０質量％、３０質量％、５０質量％添加した場合のσ−Ｔ測定結果を表８、９にまとめた。（２×Ｇ２＋ＬｉＦＳＩ）と（２×１２−Ｃ−４＋ＬｉＦＳＩ）の溶媒和化合物は共に固体であったが、ＥＰｎＯＥを添加すると溶解して液状物となり、イオン伝導性が増大した。後述のラマン分光分析の結果では、これらの場合にも添加効果が発揮されてσ増大したことが示唆された。（２×Ｇ２＋ＬｉＦＳＩ）＋ＥＰｎＯＥ（３０％）では、１．５ｍＳ／ｃｍの値を示し、また（２×１２−Ｃ−４＋ＬｉＦＳＩ）＋ＥＰｎＯＥ（３０−５０％）では、０．４ｍＳ／ｃｍの値を示した。
(Experimental examples 7-1 to 3, 8-1 to 4, 9-1 to 4)
LiFSI and a solvate were formed using an oligoether compound instead of glyme G3 and G4, and the effect of adding EPnOE was examined. Triglyme monomethyl ether (G3OH), diglyme (G2), and 12-crown-4 (12-C-4) were used as oligoether compounds. Table 7 summarizes the σ-T measurement results when 20 mass% and 200 mass% of EPnOE were added to (G3OH + LiFSI). As shown in Table 7, the σ value (3 mS / cm) of the addition of 200% by mass was the largest, confirming the addition effect. In G2 and 12-C-4, it is reported that a solvate is formed when mixed at 2: 1 (molar ratio) with respect to LiFSI. Accordingly, Tables 8 and 9 summarize the σ-T measurement results when 20 mass%, 30 mass%, and 50 mass% of EPnOE are added to the solvate. The solvates of (2 × G2 + LiFSI) and (2 × 12−C-4 + LiFSI) were both solids, but when EPnOE was added, the solvates were dissolved to become liquids, and the ionic conductivity was increased. From the results of Raman spectroscopy described later, it was suggested that the effect of addition was also exhibited in these cases and σ increased. (2 × G2 + LiFSI) + EPnOE (30%) shows a value of 1.5 mS / cm, and (2 × 12−C-4 + LiFSI) + EPnOE (30-50%) shows a value of 0.4 mS / cm. It was.
（実験例１０−１〜４）
溶媒和イオン液体（Ｇ３＋ＬｉＦＳＩ）へのリン系エステル化合物の添加においては、これまでＥＰｎＯＥを中心に用いてきたが、２種類のリン系エステル化合物の添加について検討する。（Ｇ３＋ＬｉＦＳＩ）＋ＥＰｎＯＥ（２００％）を基準とし、ＥＰｎＯＥの含有量中の１５０質量％を、優れた添加効果を示したリン系エステル化合物（ＴＥＰａ、ＴＦＥＰｉ、ＨＰｎＯＥｆ）、及びＭＰｎＯＭ（メチルホスホン酸ジメチル）に代替する検討を行った。測定結果を表１０にまとめて示した。表５の実験例５−２（（Ｇ３＋ＬｉＦＳＩ）＋ＥＰｎＯＥ（５０％））の値２．１ｍＳ／ｃｍに比べると、表１０に示すリン系エステル化合物（１５０質量％）の追加によってσ値が増大したのは、ＥＰｎＯＥ、ＴＥＦａ、ＭＰｎＯＭであった。更に実験例５−４（（Ｇ３＋ＬｉＦＳＩ）＋ＥＰｎＯＥ（２００％））の値３．５ｍＳ／ｃｍに比べると、ＴＥＰａで同程度で、ＭＰｎＯＭで上回る。これらの結果は、有効な２種類のリン系エステル化合物の添加効果があることが示唆された。
(Experimental examples 10-1 to 4)
In the addition of the phosphorus ester compound to the solvated ionic liquid (G3 + LiFSI), EPnOE has been mainly used so far, but the addition of two types of phosphorus ester compounds will be examined. Based on (G3 + LiFSI) + EPnOE (200%), 150 mass% in the content of EPnOE is added to phosphorus ester compounds (TEPa, TFEPi, HPnOEf) and MPnOM (dimethyl methylphosphonate) that showed an excellent additive effect. Considered alternatives. The measurement results are summarized in Table 10. Compared with the value 2.1 mS / cm of Experimental Example 5-2 ((G3 + LiFSI) + EPnOE (50%)) in Table 5, the addition of the phosphorus ester compound (150% by mass) shown in Table 10 increased the σ value. Were EPnOE, TEFa and MPnOM. Furthermore, when compared with the value 3.5 mS / cm of Experimental Example 5-4 ((G3 + LiFSI) + EPnOE (200%)), it is about the same at TEPa and higher at MPnOM. These results suggest that there is an effect of adding two effective phosphorus ester compounds.
（添加効果の考察）
溶媒和イオン液体（Ｇ４＋ＬｉＴＦＳＩ）に関して溶媒和化合物の構造検討をラマン分光分析で実施した。Ｌｉ+−グライムのカチオン錯体に対してＴＦＳＩアニオンがＬｉ+←Ｏ＝Ｓによって配位すると、Ｏ＝Ｓ結合に由来する特性吸収（１２５０ｃｍ-1付近と７６０ｃｍ-1付近）が高波数側にシフトすると考えられる。ここでは、（Ｇ４＋ＬｉＴＦＳＩ）、（Ｇ３＋ＬｉＦＳＩ）、（２×Ｇ２＋ＬｉＴＦＳＩ）、（２×１２−Ｃ−４＋ＬｉＴＦＳＩ）の溶媒和化合物、及び（Ｇ４＋ＬｉＴＦＳＩ）、（Ｇ３＋ＬｉＦＳＩ）へのＥＰｎＯＥ添加物（２０質量％、５０質量％、２００質量％）に関して、ラマン分光分析を実施した。なお、比較試料として各構成成分化合物及びＧ４＋ＥＰｎＯＥ（２０質量％、５０質量％、２００質量％）についても測定した。図６は、各電解液の全波数領域でのラマンスペクトルである。ＬｉＦＳＩを含む系では蛍光が生じる場合があり、分析できない場合が３件あった。図７は、イミドアニオンのＯ＝Ｓに由来する７４０ｃｍ-1付近の吸収スペクトルである。図８は、イミドアニオンのＯ＝Ｓに由来する１２５０ｃｍ-1付近の吸収スペクトルである。ＬｉＴＦＳＩとＧ４、及びＧ３とＬｉＦＳＩを１：１モル比で混合すると、Ｏ＝Ｓ由来の７６０ｃｍ-1付近の吸収は大きく低波数側にシフトした。またＯ＝Ｓ由来の１２５０ｃｍ-1付近の吸収も少ないが低波数側にシフトした。そして、その溶媒和イオン液体にＥＰｎＯＥを添加すると、その添加量に応じて更に低波数側へのシフトが、Ｏ＝Ｓ由来の７６０ｃｍ-1付近の吸収でのみ見られた。この結果は、（Ｌｉ+−グライム）のカチオン錯体の形成と、イミドアニオンがそこからよりフリーな状態へ変化する様子を反映すると考えられた。即ち、溶媒和化合物が会合型（ＡＧＧ）から接触イオン対型（ＣＩＰ）を経て溶媒分離イオン対型（ＳＳＩＰ）になることが示唆された。図９は、溶媒和化合物の説明図であり、図９（ａ）がカチオン錯体、図９（ｂ）がＣＩＰ溶媒和化合物、図９（ｃ）がＳＳＩＰ溶媒和化合物、図９（ｄ）が溶媒和化合物の種別の説明図である。
(Consideration of additive effect)
The structure of the solvate was studied by Raman spectroscopy for the solvated ionic liquid (G4 + LiTFSI). Li + - the TFSI anion against a cationic complex of glyme is coordinated by Li + ← O = S, the shift characteristic absorption derived from O = S bond (1250 cm around -1 and near 760 cm -1) is the high wave number side I think that. Here, solvates of (G4 + LiTFSI), (G3 + LiFSI), (2 × G2 + LiTFSI), (2 × 12−C-4 + LiTFSI), and EPnOE additives to (G4 + LiTFSI), (G3 + LiFSI) (20% by mass, 50%) Mass spectrometry, 200 mass%), Raman spectroscopy analysis was carried out. In addition, it measured also about each structural-component compound and G4 + EPnOE (20 mass%, 50 mass%, 200 mass%) as a comparative sample. FIG. 6 is a Raman spectrum of each electrolytic solution in the full wavenumber region. In the system containing LiFSI, fluorescence sometimes occurred and there were 3 cases where analysis was impossible. FIG. 7 is an absorption spectrum near 740 cm −1 derived from O═S of the imide anion. FIG. 8 is an absorption spectrum near 1250 cm −1 derived from O═S of the imide anion. When LiTFSI and G4, and G3 and LiFSI were mixed at a 1: 1 molar ratio, the absorption near 760 cm −1 derived from O═S was greatly shifted to the low wavenumber side. Further, although the absorption near 1250 cm −1 derived from O = S was small, it shifted to the low wavenumber side. When EPnOE was added to the solvated ionic liquid, a shift toward a lower wavenumber side was further observed only in the vicinity of 760 cm −1 derived from O═S depending on the addition amount. This result was considered to reflect the formation of a cation complex of (Li + -glyme) and the state of the imide anion changing from there to a more free state. That is, it was suggested that the solvate is changed from the association type (AGG) to the contact ion pair type (CIP) to the solvent separation ion pair type (SSIP). FIG. 9 is an explanatory diagram of a solvate, in which FIG. 9 (a) is a cation complex, FIG. 9 (b) is a CIP solvate, FIG. 9 (c) is an SSIP solvate, and FIG. It is explanatory drawing of the kind of solvate.
図１０は、（Ｌｉ+−グライム）のカチオン錯体の−Ｏ−結合由来の８５０ｃｍ-1付近の吸収スペクトルである。４種の溶媒和化合物において、混合前後で−Ｏ−結合由来の高波数側へのシフトが見られた。この結果も、（Ｌｉ+−グライム）のカチオン錯体の形成を示唆するものであった。図１１は、ＥＰｎＯＥのＯ＝Ｐ結合由来の７００ｃｍ-1付近の吸収スペクトルである。ここでは、逆にＥＰｎＯＥに（Ｇ４＋ＬｉＴＦＳＩ）を添加していくと見做すと、シフト量は僅かであるが、（Ｇ４＋ＬｉＴＦＳＩ）＋ＥＰｎＯＥ（０質量％、２０質量％、５０質量％、２００質量％）で（Ｇ４＋ＬｉＴＦＳＩ）の添加量に応じた高波数側へのシフトが見られた。一方、Ｇ４を含まないＬｉＴＦＳＩ＋ＥＰｎＯＥ（２０質量％、５０質量％、２００質量％）ではシフトは全く観測されなかった。したがって、ＥＰｎＯＥがＬｉ+←Ｏ＝Ｐによって、（Ｌｉ+−グライム）のカチオン錯体に配位することが示唆された。（Ｇ３＋ＬｉＦＳＩ）＋ＥＰｎＯＥ（０質量％、２０質量％、５０質量％、２００質量％）においても、明瞭ではないが、この傾向が見られることから、ＥＰｎＯＥの溶媒和化合物への関与が示唆された。 FIG. 10 is an absorption spectrum near 850 cm −1 derived from the —O— bond of a cation complex of (Li + -glyme). In the four solvates, a shift toward the high wavenumber derived from the —O— bond was observed before and after mixing. This result also suggested the formation of a cation complex of (Li + -glyme). FIG. 11 is an absorption spectrum around 700 cm −1 derived from the O═P bond of EPnOE. Here, conversely, assuming that (G4 + LiTFSI) is added to EPnOE, the shift amount is slight, but (G4 + LiTFSI) + EPnOE (0 mass%, 20 mass%, 50 mass%, 200 mass%) A shift toward the high wave number according to the amount of (G4 + LiTFSI) added was observed. On the other hand, no shift was observed in LiTFSI + EPnOE (20 mass%, 50 mass%, 200 mass%) not containing G4. Therefore, it was suggested that EPnOE coordinates to the (Li + -glyme) cation complex by Li + ← O = P. Even in (G3 + LiFSI) + EPnOE (0% by mass, 20% by mass, 50% by mass, 200% by mass), although this tendency is not clear, participation of EPnOE in the solvate was suggested.
本明細書で開示する電解液は、例えばアルカリ金属イオン二次電池、コンデンサ、燃料電池、太陽電池などの構成材料として利用可能である。 The electrolytic solution disclosed in the present specification can be used as a constituent material of, for example, an alkali metal ion secondary battery, a capacitor, a fuel cell, and a solar cell.
Claims (8)
オリゴエーテル化合物と、
アルカリ金属を含むスルホニルイミド塩と、
式（１）〜（１１）に示すリン系エステル化合物と、
を含む電解液。
An oligoether compound,
A sulfonylimide salt containing an alkali metal;
A phosphorus ester compound represented by formulas (1) to (11);
An electrolyte solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017048934A JP6790934B2 (en) | 2017-03-14 | 2017-03-14 | Electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017048934A JP6790934B2 (en) | 2017-03-14 | 2017-03-14 | Electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018152291A true JP2018152291A (en) | 2018-09-27 |
| JP6790934B2 JP6790934B2 (en) | 2020-11-25 |
Family
ID=63681848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017048934A Active JP6790934B2 (en) | 2017-03-14 | 2017-03-14 | Electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6790934B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018170230A (en) * | 2017-03-30 | 2018-11-01 | 株式会社豊田中央研究所 | Lithium secondary battery |
| WO2019188360A1 (en) * | 2018-03-26 | 2019-10-03 | Tdk株式会社 | Secondary battery electrolyte and secondary battery |
| JP2020129496A (en) * | 2019-02-08 | 2020-08-27 | 株式会社豊田自動織機 | Electrolyte solution and secondary battery |
| JP2020135992A (en) * | 2019-02-15 | 2020-08-31 | 株式会社豊田中央研究所 | Electrolyte solution and lithium secondary battery |
| CN114552000A (en) * | 2022-02-15 | 2022-05-27 | 北京航空航天大学 | Ultralow-temperature graphite-based lithium ion battery and preparation method of electrolyte thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005063871A (en) * | 2003-08-19 | 2005-03-10 | Sanyo Electric Co Ltd | Lithium secondary battery |
| WO2009133899A1 (en) * | 2008-04-28 | 2009-11-05 | 旭硝子株式会社 | Secondary cell nonaqueous electrolyte and secondary cell |
| JP2014116077A (en) * | 2012-12-06 | 2014-06-26 | Shin Kobe Electric Mach Co Ltd | Lithium ion secondary battery, secondary battery system including the same, nonaqueous electrolytic solution for lithium ion secondary battery |
| WO2015008496A1 (en) * | 2013-07-19 | 2015-01-22 | パナソニック株式会社 | Non-aqueous electrolytic solution, and non-aqueous electrolyte secondary cell using same |
| JP2016219422A (en) * | 2015-05-25 | 2016-12-22 | パナソニックＩｐマネジメント株式会社 | Electrolytic solution for battery and battery |
| JP2017004603A (en) * | 2015-06-04 | 2017-01-05 | 東ソ−・エフテック株式会社 | Non-aqueous electrolyte and non-aqueous secondary battery |
-
2017
- 2017-03-14 JP JP2017048934A patent/JP6790934B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005063871A (en) * | 2003-08-19 | 2005-03-10 | Sanyo Electric Co Ltd | Lithium secondary battery |
| WO2009133899A1 (en) * | 2008-04-28 | 2009-11-05 | 旭硝子株式会社 | Secondary cell nonaqueous electrolyte and secondary cell |
| JP2014116077A (en) * | 2012-12-06 | 2014-06-26 | Shin Kobe Electric Mach Co Ltd | Lithium ion secondary battery, secondary battery system including the same, nonaqueous electrolytic solution for lithium ion secondary battery |
| WO2015008496A1 (en) * | 2013-07-19 | 2015-01-22 | パナソニック株式会社 | Non-aqueous electrolytic solution, and non-aqueous electrolyte secondary cell using same |
| JP2016219422A (en) * | 2015-05-25 | 2016-12-22 | パナソニックＩｐマネジメント株式会社 | Electrolytic solution for battery and battery |
| JP2017004603A (en) * | 2015-06-04 | 2017-01-05 | 東ソ−・エフテック株式会社 | Non-aqueous electrolyte and non-aqueous secondary battery |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018170230A (en) * | 2017-03-30 | 2018-11-01 | 株式会社豊田中央研究所 | Lithium secondary battery |
| WO2019188360A1 (en) * | 2018-03-26 | 2019-10-03 | Tdk株式会社 | Secondary battery electrolyte and secondary battery |
| JPWO2019188360A1 (en) * | 2018-03-26 | 2021-03-11 | Tdk株式会社 | Rechargeable battery electrolyte and secondary battery |
| JP7014290B2 (en) | 2018-03-26 | 2022-02-01 | Tdk株式会社 | Electrolyte for secondary batteries and secondary batteries |
| JP2020129496A (en) * | 2019-02-08 | 2020-08-27 | 株式会社豊田自動織機 | Electrolyte solution and secondary battery |
| JP2020135992A (en) * | 2019-02-15 | 2020-08-31 | 株式会社豊田中央研究所 | Electrolyte solution and lithium secondary battery |
| JP7295652B2 (en) | 2019-02-15 | 2023-06-21 | 株式会社豊田中央研究所 | Electrolyte and lithium secondary battery |
| CN114552000A (en) * | 2022-02-15 | 2022-05-27 | 北京航空航天大学 | Ultralow-temperature graphite-based lithium ion battery and preparation method of electrolyte thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6790934B2 (en) | 2020-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6790934B2 (en) | Electrolyte | |
| US10308587B2 (en) | Functionalized fluoropolymers and electrolyte compositions | |
| EP4106070A1 (en) | Phosphorus-containing electrolytes | |
| JP5725510B2 (en) | Solvent for electrolytic solution, electrolytic solution, and gel electrolyte | |
| US9543619B2 (en) | Functionalized phosphorus containing fluoropolymers and electrolyte compositions | |
| JP7209688B2 (en) | Modified triazine functional compound | |
| KR102669779B1 (en) | Ionic liquids with silane functional groups | |
| JP2022084688A (en) | Nonaqueous electrolyte composition comprising silyl oxalate | |
| US5660947A (en) | Electrolyte for use in a galvanic cell | |
| Xu et al. | A fusible orthoborate lithium salt with high conductivity in solutions | |
| JP2002033127A (en) | Silane compound to be used as electrolyte additive for electrochemical cell | |
| US20020022182A1 (en) | Fluoroalkyl phosphates for use in electrochemical cells | |
| KR20020036760A (en) | Tetrakisfluoroalkylborate salts and their use as conducting salts | |
| KR102631722B1 (en) | Denatured ionic liquid containing triazine | |
| WO2004059782A1 (en) | Additive for nonaqueous electrolytic solution of secondary battery and nonaqueous electrolyte secondary battery | |
| KR20010095331A (en) | Lithium salts, process for preparing them, nonaqueous electrolyte and electrochemical cell | |
| KR20010040169A (en) | Complex salts for use in electrochemical cells | |
| JP6435235B2 (en) | Fluorine-containing phosphate ester cyanoalkylamide, nonaqueous electrolyte containing the same, and nonaqueous secondary battery | |
| WO2015069854A1 (en) | Electrolyte solution for capacitors and batteries | |
| JP2019064923A (en) | Ionic compound, nonaqueous electrolyte including ionic compound and electricity storage device using nonaqueous electrolyte | |
| KR20210107060A (en) | Modified Ionic Liquids Containing Boron | |
| KR101614017B1 (en) | Method for Preparation of Ionic Liquids Containing Ether Substituted Anion and Liquid or Ionogel Electrolytes Prepared Using the Same | |
| EP4315476A1 (en) | Flame retardants for battery electrolytes | |
| KR20220101630A (en) | Flame Retardant for Lithium Battery | |
| McOwen | Developing New Electrolytes for Advanced Li-ion Batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20191216 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200914 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201006 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20201019 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6790934 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |