JP2006339010A - Electrolytic solution for electrochemical device - Google Patents
Electrolytic solution for electrochemical device Download PDFInfo
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- JP2006339010A JP2006339010A JP2005161665A JP2005161665A JP2006339010A JP 2006339010 A JP2006339010 A JP 2006339010A JP 2005161665 A JP2005161665 A JP 2005161665A JP 2005161665 A JP2005161665 A JP 2005161665A JP 2006339010 A JP2006339010 A JP 2006339010A
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- nonionic surfactant
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- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 29
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 15
- 229940017219 methyl propionate Drugs 0.000 claims abstract description 12
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 14
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 9
- 229940063013 borate ion Drugs 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- NJQFCQXFOHVYQJ-PMACEKPBSA-N BF 4 Chemical compound C1([C@@H]2CC(=O)C=3C(O)=C(C)C4=C(C=3O2)[C@H](C(C)C)C2=C(O4)C(C)=C(C(C2=O)(C)C)OC)=CC=CC=C1 NJQFCQXFOHVYQJ-PMACEKPBSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical class C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004693 imidazolium salts Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- GVZFDPPAJXHNGL-UHFFFAOYSA-N trifluoromethyl trifluoromethanesulfonate Chemical compound FC(F)(F)OS(=O)(=O)C(F)(F)F GVZFDPPAJXHNGL-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 4
- 239000004327 boric acid Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 229910013075 LiBF Inorganic materials 0.000 description 11
- 238000005470 impregnation Methods 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 10
- -1 borate ions Chemical class 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910013063 LiBF 4 Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000010494 dissociation reaction Methods 0.000 description 4
- 230000005593 dissociations Effects 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 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 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NZPSDGIEKAQVEZ-UHFFFAOYSA-N 1,3-benzodioxol-2-one Chemical compound C1=CC=CC2=C1OC(=O)O2 NZPSDGIEKAQVEZ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KYAJBRQELLCANX-UHFFFAOYSA-N acetic acid acetylene Chemical compound C#C.CC(O)=O KYAJBRQELLCANX-UHFFFAOYSA-N 0.000 description 1
- RDSHARUTTNAPEI-UHFFFAOYSA-N acetylene;butanoic acid Chemical compound C#C.CCCC(O)=O RDSHARUTTNAPEI-UHFFFAOYSA-N 0.000 description 1
- NUJPNLOTBGKWGQ-UHFFFAOYSA-N acetylene;hexanoic acid Chemical compound C#C.CCCCCC(O)=O NUJPNLOTBGKWGQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- FNWIBMVZSHPBBS-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide butyl-ethyl-dimethylazanium Chemical compound CCCC[N+](C)(C)CC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F FNWIBMVZSHPBBS-UHFFFAOYSA-N 0.000 description 1
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- QSSVYRPOXMPNLG-UHFFFAOYSA-N fluoromethyl trifluoromethanesulfonate Chemical compound FCOS(=O)(=O)C(F)(F)F QSSVYRPOXMPNLG-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- GAJQCIFYLSXSEZ-UHFFFAOYSA-L tridecyl phosphate Chemical compound CCCCCCCCCCCCCOP([O-])([O-])=O GAJQCIFYLSXSEZ-UHFFFAOYSA-L 0.000 description 1
- ZOPCDOGRWDSSDQ-UHFFFAOYSA-N trinonyl phosphate Chemical compound CCCCCCCCCOP(=O)(OCCCCCCCCC)OCCCCCCCCC ZOPCDOGRWDSSDQ-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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Abstract
Description
本発明は、電気化学デバイス用電解液に関するものである。 The present invention relates to an electrolyte for an electrochemical device.
現在実用化されているＬｉＰＦ6またはＬｉＢＦ4にかわるＬｉ塩としてジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸リチウム（ＬｉＢＦ2(ＯＯＣＯＣ(ＣＦ3)2)（ＬｉＢＦ2（ＨＨＩＢ）と略す））がある（特許文献１）。このＬｉ塩は、ＬｉＰＦ6及びＬｉＢＦ4に比較して熱安定性が高い。しかしながら、このジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸リチウムを含む電解液は、リチウム塩濃度を高くした場合の粘度上昇が大きいため、電気化学デバイスへの含浸が困難であるという問題を有する。
本発明の目的は、含浸性の高い電気化学デバイス用電解液を提供することにある。 The objective of this invention is providing the electrolyte solution for electrochemical devices with high impregnation property.
本発明に係る電気化学デバイス用電解液は、下記化３に示されるジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸イオンを０．２Ｍ以上、３Ｍ以下と、
０．１重量％以上、３重量％以下の非イオン性界面活性剤と
を含むことを特徴とする。
And 0.1 wt% or more and 3 wt% or less of a nonionic surfactant.
本発明によれば、含浸性の高い電気化学デバイス用電解液を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the electrolyte solution for electrochemical devices with high impregnation property can be provided.
本発明によれば、含浸性の高い電気化学デバイス用電解液を得ることができる。粘度の大きい電気化学デバイス用電解液の電気化学デバイス内への含浸性を向上させるために鋭意研究を進めた結果、電解質成分としてジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸イオンを０．２Ｍ以上、３Ｍ以下含む電解液に非イオン性界面活性剤を０．１重量％以上、３重量％以下添加することで、電気化学デバイス内への含浸性が大幅に向上されることを見出した。また、この電解液は、高い熱安定性も実現することができる。 ADVANTAGE OF THE INVENTION According to this invention, the electrolyte solution for electrochemical devices with high impregnation property can be obtained. As a result of diligent research in order to improve the impregnation of electrochemical solutions for electrochemical devices with high viscosity into electrochemical devices, difluoro (trifluoro-2-oxide-2-trifluoro-methylpropionate) was used as an electrolyte component. (2-)-0,0) Electrochemical device by adding 0.1 wt% or more and 3 wt% or less of nonionic surfactant to electrolyte containing 0.2M or more and 3M or less of borate ion It has been found that the impregnation property is greatly improved. Moreover, this electrolyte solution can also realize high thermal stability.
上記ホウ酸イオンは、下記化４に示すホウ酸塩から提供されることが望ましい。
但し、Ａa+は、金属イオン、水素イオンまたはオニウムイオンで、ａ及びｂはａ＝ｂで、１以上、３以下を満たす。このホウ酸塩のカチオンは特に限定されないが、リチウムイオンが好ましい。 However, A a + is a metal ion, a hydrogen ion, or an onium ion, and a and b are a = b, and satisfy 1 or more and 3 or less. The cation of the borate is not particularly limited, but lithium ion is preferable.
非イオン性界面活性剤による含浸性向上の効果は、電解質成分であるジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸イオンの濃度を０．２Ｍ以上、３Ｍ以下の範囲内にした際に得ることができる。０．２Ｍより小さいと粘度上昇も小さいため非イオン性界面活性剤の添加による効果は得られない。一方、３Ｍより大きい濃度では、非イオン性界面活性剤を添加しても電解液粘度がほとんど低下しない。より好ましい範囲は、０．５Ｍ以上、３Ｍ以下である。 The effect of improving the impregnation property by the nonionic surfactant is that the concentration of difluoro (trifluoro-2-oxide-2-trifluoro-methylpropionate (2-)-0,0) borate ion as the electrolyte component is adjusted. It can be obtained when it is within the range of 0.2M or more and 3M or less. If it is less than 0.2M, the increase in viscosity is small, so the effect of adding a nonionic surfactant cannot be obtained. On the other hand, at a concentration higher than 3M, the electrolyte solution viscosity hardly decreases even when a nonionic surfactant is added. A more preferable range is 0.5M or more and 3M or less.
また、非イオン性界面活性剤の量は、０．１重量％未満であると含浸性向上の効果は得られず、３重量％より大きいと導電性が低下するため電解液として不利となる。より好ましい範囲は０．５重量％以上、１重量％以下である。また、非イオン性界面活性剤としては、化５に示すトリアルキルフォスフェートが好ましく、中でもトリオクチルフォスフェート（ＴＯＰ）がさらに好ましい。ここに示した界面活性剤を添加することで含浸性の向上を達成することができる。
但し、Ｒはアルキル基である。 However, R is an alkyl group.
また、電解質成分としてジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸イオン以外に、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＣＦ3ＳＯ3、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2及びＬｉ(Ｃ4Ｆ9)ＳＯ3よりなる群から選択される１種類以上を加えてよい。電解質成分を複数種にする場合、電解質成分濃度を１Ｍ以上、３Ｍ以下とし、かつホウ酸イオン濃度を０．２Ｍ以上、３Ｍ以下（より好ましくは０．５Ｍ以上、３Ｍ以下）にすることが望ましい。 In addition to difluoro (trifluoro-2-oxide-2-trifluoro-methylpropionate (2-)-0,0) borate ions as electrolyte components, LiBF 4 , LiPF 6 , LiCF 3 SO 3 , LiN ( One or more selected from the group consisting of CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 and Li (C 4 F 9 ) SO 3 may be added. When a plurality of electrolyte components are used, it is desirable that the electrolyte component concentration be 1M or more and 3M or less and the borate ion concentration be 0.2M or more and 3M or less (more preferably 0.5M or more and 3M or less). .
溶媒成分としては、例えば、有機溶媒、イオン性液体等を挙げることができる。有機溶媒としては、特に限定されるものではないが、プロピレンカーボネート（ＰＣ）、エチレンカーボネート（ＥＣ）、１，２−ジメトキシエタン（ＤＭＥ）、γ−ブチロラクトン（ＧＢＬ）、テトラヒドロフラン（ＴＨＦ）、２−メチルテトラヒドロフラン（２−ＭｅＨＦ）、１，３−ジオキソラン、スルホラン、アセトニトリル（ＡＮ）、ジエチルカーボネート（ＤＥＣ）、ジメチルカーボネイト（ＤＭＣ）、メチルエチルカーボネイト（ＭＥＣ）、ジプロピルカーボネート（ＤＰＣ）などを挙げることができる。また、イオン性液体としては、イミダゾリウム塩、四級アンモニウム塩、ピロリジウム塩及びピペリジウム塩よりなる群から選択されるカチオン種と、ＢＦ4、ＰＦ6、ビストリフルオロメタンスルホニルアミドアニオン（ＴＦＳＩ）、トリフルオロメチルトリフレート（ＴＦＳ）、ビスペンタフルオロエタンスルホニルアミドアニオン（ＢＥＴＩ）、ジシアナミドアニオン（ＤＣＡ）及びＣｌよりなる群から選択されるアニオン種とを備えるものを挙げることができる。前記溶媒成分は１種類でもよいし２種類以上含んでもよい。この中でも、エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）およびγ−ブチロラクトン（ＧＢＬ）よりなる群から選択される少なくとも２種類の溶媒を含むことが望ましい。ＥＣ、ＰＣ、ＧＢＬの誘電率は、それぞれ９０，６５，４２と大きい。一方、ジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸塩は、フッ素塩であるテトラフルオロホウ酸塩やヘキサフルオロリン酸塩に比して解離度が小さい。ＥＣ、ＰＣ及びＧＢＬのうちから２種類以上を組み合わせて使用することにより、溶媒の誘電率と併せてエントロピーを向上させることができるため、ジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸塩の解離を促すことができる。ＥＣ、ＰＣ及びＧＢＬの三種類全てを使用することにより、ホウ酸塩の解離促進と電解液の熱安定性をさらに向上することができる。 Examples of the solvent component include organic solvents and ionic liquids. The organic solvent is not particularly limited, but propylene carbonate (PC), ethylene carbonate (EC), 1,2-dimethoxyethane (DME), γ-butyrolactone (GBL), tetrahydrofuran (THF), 2- Examples include methyltetrahydrofuran (2-MeHF), 1,3-dioxolane, sulfolane, acetonitrile (AN), diethyl carbonate (DEC), dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), dipropyl carbonate (DPC) and the like. Can do. Examples of the ionic liquid include cation species selected from the group consisting of imidazolium salts, quaternary ammonium salts, pyrrolidinium salts, and piperidinium salts, BF 4 , PF 6 , bistrifluoromethanesulfonylamide anion (TFSI), And an anionic species selected from the group consisting of fluoromethyl triflate (TFS), bispentafluoroethanesulfonylamide anion (BETI), dicyanamide anion (DCA) and Cl. The solvent component may be one kind or two or more kinds. Among these, it is desirable to include at least two types of solvents selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), and γ-butyrolactone (GBL). The dielectric constants of EC, PC, and GBL are as large as 90, 65, and 42, respectively. On the other hand, difluoro (trifluoro-2-oxide-2-trifluoro-methylpropionate (2-)-0,0) borate is different from tetrafluoroborate and hexafluorophosphate which are fluorine salts. The degree of dissociation is small. By using two or more of EC, PC and GBL in combination, the entropy can be improved together with the dielectric constant of the solvent, so difluoro (trifluoro-2-oxide-2-trifluoro-methyl Dissociation of propionate (2-)-0,0) borate can be promoted. By using all three types of EC, PC and GBL, it is possible to further improve the borate dissociation promotion and the thermal stability of the electrolyte.
ホウ酸塩の解離促進のため、ＥＣ、ＰＣ及びＧＢＬのうちの２種類以上の溶媒は、溶媒成分中に３３体積％以上、１００体積％以下含むことが望ましい。より好ましい範囲は、８０体積％以上、１００体積％以下である。 In order to promote dissociation of borate, it is desirable that two or more kinds of solvents among EC, PC, and GBL are contained in the solvent component in an amount of 33% by volume to 100% by volume. A more preferable range is 80 volume% or more and 100 volume% or less.
また電気化学デバイス用電解液内に添加剤を含んでもよい。添加剤としては、特に限定されるものではないが、ビニレンカーボネイト（ＶＣ）、ビニレンアセテート（ＶＡ）、ビニレンブチレート、ビニレンヘキサネート、ビニレンクロトネート、カテコールカーボネートなどが挙げられる。添加剤の種類は１種類もしくは２種類以上にすることができる。添加剤の濃度は、電解液の０．１重量％以上、３重量％以下の間が好ましい。さらに好ましい範囲は、０．５〜１重量％である。 Moreover, you may include an additive in the electrolyte solution for electrochemical devices. Although it does not specifically limit as an additive, Vinylene carbonate (VC), vinylene acetate (VA), vinylene butyrate, vinylene hexanate, vinylene crotonate, catechol carbonate, etc. are mentioned. One kind or two or more kinds of additives can be used. The concentration of the additive is preferably between 0.1% by weight and 3% by weight of the electrolytic solution. A more preferable range is 0.5 to 1% by weight.
本発明における電気化学デバイス用電解液に最適な電気化学デバイスとしては、電気化学反応を応用した発光素子、発電素子、蓄電素子、センサー等が挙げられる。中でもリチウムイオン二次電池、電気二重層キャパシタが好ましい。最も好ましいのは、リチウムイオン二次電池である。また、電気化学デバイスは、高温環境下での使用が想定されるものに組み込まれることが好ましい。具体的には、二輪乃至四輪のハイブリッド電気自動車、二輪乃至四輪の電気自動車、アシスト自転車等の車載用や電子機器の非常用が挙げられる。 Examples of the electrochemical device most suitable for the electrolytic solution for electrochemical devices in the present invention include a light emitting device, a power generation device, a storage device, a sensor, and the like applying an electrochemical reaction. Of these, lithium ion secondary batteries and electric double layer capacitors are preferred. Most preferred is a lithium ion secondary battery. Moreover, it is preferable that an electrochemical device is incorporated in the thing assumed to be used in a high temperature environment. Specific examples include in-vehicle use such as two-wheel to four-wheel hybrid electric vehicles, two-wheel to four-wheel electric vehicles, and assist bicycles, and emergency use of electronic devices.
[実施例]
以下、本発明の実施例を図面を参照して詳細に説明する。
[Example]
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
（実施例１）
エチレンカーボネート（ＥＣ）とγ−ブチロラクトン（ＧＢＬ）の体積比が１：２である混合溶媒に１Ｍのジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸リチウム｛ＬｉＢＦ2（ＨＨＩＢ）｝を溶かしたものに、０．５重量％のトリオクチルフォスフェートを混合した電気化学デバイス用電解液を調製した。
Example 1
In a mixed solvent in which the volume ratio of ethylene carbonate (EC) and γ-butyrolactone (GBL) is 1: 2, 1M difluoro (trifluoro-2-oxide-2-trifluoro-methylpropionate (2-)-0, 0) An electrolytic solution for an electrochemical device was prepared by mixing 0.5% by weight of trioctyl phosphate with a solution of lithium borate {LiBF 2 (HHIB)}.
（実施例２〜１９）
溶媒および電解質成分とその濃度および界面活性剤の種類とその量を表１〜２に示すような電気化学デバイス用電解液を調製した。実施例８，９においては、ＬｉＢＦ2（ＨＨＩＢ）を０．５Ｍと、ＬｉＰＦ6またはＬｉＴＦＳＩを０．５Ｍとを混合し、Ｌｉ濃度が１Ｍになるように調製した電解液を用いた。
(Examples 2 to 19)
Electrolytes for electrochemical devices as shown in Tables 1 and 2 were prepared with the solvent and electrolyte components, their concentrations, and the types and amounts of surfactants. In Examples 8 and 9, an electrolytic solution prepared by mixing LiBF 2 (HHIB) with 0.5M and LiPF 6 or LiTFSI with 0.5M to have a Li concentration of 1M was used.
（比較例１）
エチレンカーボネートとγ−ブチロラクトンの体積比１：２である混合溶媒に１Ｍのジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸リチウムを溶かした電気化学デバイス用電解液を調製した。
(Comparative Example 1)
Dissolve 1M lithium difluoro (trifluoro-2-oxide-2-trifluoro-methylpropionate (2-)-0,0) borate in a mixed solvent of ethylene carbonate and γ-butyrolactone in a volume ratio of 1: 2. An electrolyte for an electrochemical device was prepared.
（比較例２〜９）
溶媒および電解質成分とその濃度および界面活性剤の種類とその量を表１に示すような電気化学デバイス用電解液を調製した。
(Comparative Examples 2-9)
Electrolytes for electrochemical devices as shown in Table 1 were prepared with the solvent and electrolyte components, their concentrations, and the types and amounts of surfactants.
下記表１，２において、ＬｉＴＦＳＩはビストリフルオロメタンスルホニルアミドリチウム、ＥＭＩＢＦ4は４フッ化ホウ酸１−エチル３−メチルイミダゾリウム、ＥＭＩＴＦＳＩは１−エチル３−メチルイミダゾリウムビストリフルオロメタンスルホニルアミド、
１１２４ＮＴＦＳＩはジメチルエチルブチルアンモニウムビストリフルオロメタンスルホニルアミドを示す。
In Tables 1 and 2 below, LiTFSI is bistrifluoromethanesulfonylamide lithium, EMIBF 4 is 1-ethyl 3-methylimidazolium tetrafluoroborate, EMITFSI is 1-ethyl 3-methylimidazolium bistrifluoromethanesulfonylamide,
1124NTFSI indicates dimethylethylbutylammonium bistrifluoromethanesulfonylamide.
（含浸性の評価）
グラファイト粉末（ＫＳ−６）を９０重量部と、結着剤としてＰＶｄＦを１０重量部とを、Ｎ−メチルピロリドン（ＮＭＰ）溶液中で混合することによりスラリーを調製した。得られたスラリーを厚さ１５μｍのアルミニウム箔からなる集電体に塗布し、乾燥し、プレスすることによりグラファイト電極を作製した。作製したグラファイト電極１を二枚用意し、図１に示す試験セルを作製した。グラファイト電極１の間にセパレータとして厚さ３０μｍのポリプロピレンフィルム２を挟み、得られた電極体をガラス容器３内の電解液４に浸漬した。電解液４には、実施例１〜１９及び比較例１〜９で調製した電気化学デバイス用電解液を使用した。インピーダンスアナライザー５により電極体のインピーダンスの経時変化を測定することにより含浸性の評価を行った。なお、インピーダンスの値はＣｏｌｅ−ｃｏｌｅプロットから求めた。Ｃｏｌｅ−ｃｏｌｅプロットの一例を図２に示す。Ｃｏｌｅ−ｃｏｌｅプロットにおけるＲｃの値は、ポリプロピレンフィルム２からなるセパレータの抵抗値を近似的に表している。試験セルを作製してから１０分後及び１２０分後のＲｃの抵抗値と、１０分後から１２０分後までの抵抗減少率（％）を下記表１〜２に示す。
A slurry was prepared by mixing 90 parts by weight of graphite powder (KS-6) and 10 parts by weight of PVdF as a binder in an N-methylpyrrolidone (NMP) solution. The obtained slurry was applied to a current collector made of an aluminum foil having a thickness of 15 μm, dried and pressed to produce a graphite electrode. Two prepared graphite electrodes 1 were prepared, and a test cell shown in FIG. 1 was prepared. A
表１及び表２から明らかなように、非イオン性界面活性剤の量を０．１重量％以上、３重量％以下の範囲内にし、かつＬｉＢＦ2（ＨＨＩＢ）濃度を０．２Ｍ以上、３Ｍ以下とした実施例１〜１９の電解液によると、抵抗減少率が、比較例１〜９に比較して大きくなった。 As apparent from Tables 1 and 2, the amount of the nonionic surfactant is within the range of 0.1 wt% or more and 3 wt% or less, and the LiBF 2 (HHIB) concentration is 0.2 M or more, 3 M According to the electrolytic solutions of Examples 1 to 19 described below, the resistance reduction rate was larger than those of Comparative Examples 1 to 9.
ＬｉＢＦ2（ＨＨＩＢ）濃度について検討するため、実施例１，８，９，１３〜１６及び比較例４，５を比較する。ＬｉＢＦ2（ＨＨＩＢ）濃度が０．２Ｍ未満の比較例４の電解液では、非イオン性界面活性剤が０．５重量％添加されているものの、抵抗変化が全く見られなかった。また、ＬｉＢＦ2（ＨＨＩＢ）濃度が３Ｍを超えている比較例５の電解液では、抵抗減少率が２０％と少なかった。ＬｉＢＦ2（ＨＨＩＢ）濃度が０．２Ｍ以上、３Ｍ以下の実施例１，８，９，１３〜１６では、比較例４，５に比較して抵抗減少率が大きくなったものの、ＬｉＢＦ2（ＨＨＩＢ）濃度が０．２Ｍの実施例１３の抵抗減少率は他の実施例に比べて十分でなかった。よって、含浸性を向上させるには、ＬｉＢＦ2（ＨＨＩＢ）濃度を０．５Ｍ以上、３Ｍ以下にすることが望ましい。 In order to examine the LiBF 2 (HHIB) concentration, Examples 1, 8, 9, 13 to 16 and Comparative Examples 4 and 5 are compared. In the electrolytic solution of Comparative Example 4 having a LiBF 2 (HHIB) concentration of less than 0.2M, no change in resistance was observed although 0.5% by weight of the nonionic surfactant was added. Further, in the electrolytic solution of Comparative Example 5 in which the LiBF 2 (HHIB) concentration exceeded 3M, the resistance reduction rate was as small as 20%. In Examples 1, 8, 9, and 13 to 16 in which the LiBF 2 (HHIB) concentration was 0.2 M or more and 3 M or less, the resistance reduction rate was larger than that of Comparative Examples 4 and 5, but LiBF 2 (HHIB) ) The resistance reduction rate of Example 13 having a concentration of 0.2M was not sufficient as compared with the other examples. Therefore, in order to improve the impregnation property, it is desirable that the LiBF 2 (HHIB) concentration be 0.5 M or more and 3 M or less.
非イオン性界面活性剤濃度について検討するため、電解質塩、溶媒組成及び界面活性剤の種類が同じ実施例１，１０〜１２及び比較例２，３を比較する。界面活性剤濃度が０．１重量％未満の比較例２と、界面活性剤濃度が３重量％を超える比較例３は、いずれも、抵抗減少率が１０％台と小さかった。界面活性剤濃度が０．１重量％以上、３重量％以下の実施例１，１０〜１２によると、抵抗減少率が比較例２，３に比して大きくなり、中でも、界面活性剤濃度が０．５重量％以上、１重量％以下の実施例１，１１において大きな抵抗減少率が得られた。 In order to examine the nonionic surfactant concentration, Examples 1, 10 to 12 and Comparative Examples 2 and 3 having the same electrolyte salt, solvent composition and surfactant type are compared. In Comparative Example 2 in which the surfactant concentration was less than 0.1% by weight and Comparative Example 3 in which the surfactant concentration exceeded 3% by weight, the resistance reduction rate was as small as 10%. According to Examples 1 to 10-12 in which the surfactant concentration is 0.1 wt% or more and 3 wt% or less, the resistance reduction rate is larger than that of Comparative Examples 2 and 3, and among them, the surfactant concentration is In Examples 1 and 11 of 0.5% by weight or more and 1% by weight or less, a large resistance reduction rate was obtained.
界面活性剤の種類については、実施例１〜５のうち、トリオクチルフォスフェートを使用した実施例１、トリノニルフォスフェートを使用した実施例４、トリデシルフォスフェートを使用した実施例５において、大きな抵抗減少率が得られた。 Regarding the type of surfactant, in Examples 1 to 5, Example 1 using trioctyl phosphate, Example 4 using trinonyl phosphate, Example 5 using tridecyl phosphate, A large resistance reduction rate was obtained.
非水溶媒の種類については、実施例１，６，７のうち、ＥＣ，ＰＣ及びＧＢＬの三成分を使用した実施例６において、最も大きな抵抗減少率が得られた。 About the kind of nonaqueous solvent, the largest resistance reduction rate was obtained in Example 6 using three components of EC, PC, and GBL among Examples 1, 6, and 7.
さらに、比較例６〜９の結果から、電解質成分としてＬｉＰＦ6やＬｉＢＦ4のようなフッ素系のリチウム塩を用いる電解液においては、もともと低粘度であるために界面活性剤添加の効果を得られず、一方、ＬｉＰＦ4（ＯＯＣＯＣ（ＣＦ3）2）あるいはＬｉＢ（ＣＨ（ＣＦ3）2Ｏ）2（ＯＯＣＯＣ（ＣＦ3）2を用いる電解液においては、元の粘度が高すぎるために界面活性剤で効果が得られないことが理解できる。 Furthermore, from the results of Comparative Examples 6 to 9, in the electrolytic solution using a fluorine-based lithium salt such as LiPF 6 or LiBF 4 as an electrolyte component, the effect of adding a surfactant can be obtained because it is originally low in viscosity. On the other hand, in the electrolyte solution using LiPF 4 (OOCOC (CF 3 ) 2 ) or LiB (CH (CF 3 ) 2 O) 2 (OOCOC (CF 3 ) 2 , the surface viscosity is too high. It can be understood that the effect cannot be obtained with the agent.
（導電率の測定）
実施例１および比較例３，５の電気化学デバイス用電解液について、東亜電波工業社製ディジタル電気伝導率計ＣＭ−３０Ｖにより測定した２５℃の導電率の結果を表３に示す。
Table 3 shows the results of electrical conductivity at 25 ° C. measured for the electrolytic devices for electrochemical devices of Example 1 and Comparative Examples 3 and 5 using a digital conductivity meter CM-30V manufactured by Toa Denpa Kogyo Co., Ltd.
表３を見てわかるように、比較例３のように非イオン性界面活性剤の濃度が３重量％を超えると導電率が大きく下がる。また、比較例５のようにジフルオロ（トリフルオロ−２−オキシド−２−トリフルオロ−メチルプロピオナト（２−）−０，０）ホウ酸イオンの濃度が３Ｍを超えると導電率が大きく下がり電気化学デバイス用電解液としては不利となる。 As can be seen from Table 3, when the concentration of the nonionic surfactant exceeds 3% by weight as in Comparative Example 3, the conductivity greatly decreases. Further, as in Comparative Example 5, when the concentration of difluoro (trifluoro-2-oxide-2-trifluoro-methylpropionate (2-)-0,0) borate ion exceeds 3M, the conductivity is greatly reduced and electricity is reduced. This is disadvantageous as an electrolyte for chemical devices.
なお、本発明は上記実施形態そのままに限定されるものではなく、実施段階ではその要旨を逸脱しない範囲で構成要素を変形して具体化できる。また、上記実施形態に開示されている複数の構成要素の適宜な組み合わせにより、種々の発明を形成できる。例えば、実施形態に示される全構成要素から幾つかの構成要素を削除してもよい。さらに、異なる実施形態にわたる構成要素を適宜組み合わせてもよい。 Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage. In addition, various inventions can be formed by appropriately combining a plurality of components disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, constituent elements over different embodiments may be appropriately combined.
１…グラファイト電極、２…プロピレンフィルム、３…容器、４…電解液、５…インピーダンスアナライザー。 DESCRIPTION OF SYMBOLS 1 ... Graphite electrode, 2 ... Propylene film, 3 ... Container, 4 ... Electrolyte solution, 5 ... Impedance analyzer.
Claims (5)
０．１重量％以上、３重量％以下の非イオン性界面活性剤と
を含むことを特徴とする電気化学デバイス用電解液。
An electrolyte solution for electrochemical devices, comprising 0.1% by weight or more and 3% by weight or less of a nonionic surfactant.
Priority Applications (1)
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| JP2005161665A JP2006339010A (en) | 2005-06-01 | 2005-06-01 | Electrolytic solution for electrochemical device |
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| JP2005161665A JP2006339010A (en) | 2005-06-01 | 2005-06-01 | Electrolytic solution for electrochemical device |
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| JP2006339010A true JP2006339010A (en) | 2006-12-14 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009054288A (en) * | 2007-08-23 | 2009-03-12 | Sony Corp | Electrolyte and secondary battery |
| JP2009054407A (en) * | 2007-08-27 | 2009-03-12 | Sony Corp | Electrolyte solution and secondary battery |
| WO2010004012A1 (en) * | 2008-07-11 | 2010-01-14 | Commissariat A L'energie Atomique | Ionic liquid electrolytes that include an anionic surfactant and electrochemical devices such as storage batteries comprising them |
| US9153836B2 (en) | 2007-08-23 | 2015-10-06 | Sony Corporation | Electrolytic solutions and battery |
| WO2016125770A1 (en) * | 2015-02-02 | 2016-08-11 | 日立化成株式会社 | Electrolyte for lithium ion capacitor and lithium ion capacitor |
| WO2017018328A1 (en) * | 2015-07-27 | 2017-02-02 | 日本化学工業株式会社 | Additive for light-emitting layer in electrochemiluminescent cell, composition for forming light-emitting layer in electrochemiluminescent cell, and electrochemiluminescent cell |
| CN107851725A (en) * | 2015-07-27 | 2018-03-27 | 日本化学工业株式会社 | Electrochemical luminescence unit luminescent layer additive, electrochemical luminescence unit luminescent layer formation composition and electrochemical luminescence unit |
| CN111448691A (en) * | 2017-12-26 | 2020-07-24 | 昭和电工株式会社 | Binder for nonaqueous battery electrode, slurry for nonaqueous battery electrode, and nonaqueous battery |
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2005
- 2005-06-01 JP JP2005161665A patent/JP2006339010A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009054288A (en) * | 2007-08-23 | 2009-03-12 | Sony Corp | Electrolyte and secondary battery |
| US9153836B2 (en) | 2007-08-23 | 2015-10-06 | Sony Corporation | Electrolytic solutions and battery |
| JP2009054407A (en) * | 2007-08-27 | 2009-03-12 | Sony Corp | Electrolyte solution and secondary battery |
| FR2933814A1 (en) * | 2008-07-11 | 2010-01-15 | Commissariat Energie Atomique | IONIC LIQUID ELECTROLYTES COMPRISING A SURFACTANT AND ELECTROCHEMICAL DEVICES SUCH AS ACCUMULATORS COMPRISING THEM |
| JP2011527495A (en) * | 2008-07-11 | 2011-10-27 | コミサリア ア レネルジ アトミ−ク エ オエネルジー アルテルナティヴ | Electrochemical devices such as ionic liquid electrolytes containing anionic surfactants and storage batteries containing them |
| US9123972B2 (en) | 2008-07-11 | 2015-09-01 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Ionic liquid electrolytes comprising an anionic surfactant and electrochemical devices such as accumulators comprising them |
| WO2010004012A1 (en) * | 2008-07-11 | 2010-01-14 | Commissariat A L'energie Atomique | Ionic liquid electrolytes that include an anionic surfactant and electrochemical devices such as storage batteries comprising them |
| WO2016125770A1 (en) * | 2015-02-02 | 2016-08-11 | 日立化成株式会社 | Electrolyte for lithium ion capacitor and lithium ion capacitor |
| WO2017018328A1 (en) * | 2015-07-27 | 2017-02-02 | 日本化学工業株式会社 | Additive for light-emitting layer in electrochemiluminescent cell, composition for forming light-emitting layer in electrochemiluminescent cell, and electrochemiluminescent cell |
| CN107851725A (en) * | 2015-07-27 | 2018-03-27 | 日本化学工业株式会社 | Electrochemical luminescence unit luminescent layer additive, electrochemical luminescence unit luminescent layer formation composition and electrochemical luminescence unit |
| US20180366646A1 (en) * | 2015-07-27 | 2018-12-20 | Nippon Chemical Industrial Co., Ltd. | Additive for light-emitting layer in light-emitting electrochemical cell, composition for forming light-emitting layer in light-emitting electrochemical cell, and light-emitting electrochemical cell |
| US10439143B2 (en) | 2015-07-27 | 2019-10-08 | Nippon Chemical Industrial Co., Ltd. | Additive for light-emitting layer in light-emitting electrochemical cell, composition for forming light-emitting layer in light-emitting electrochemical cell, and light-emitting electrochemical cell |
| CN107851725B (en) * | 2015-07-27 | 2019-12-10 | 日本化学工业株式会社 | Additive for light-emitting layer of electrochemiluminescence unit, composition for forming light-emitting layer of electrochemiluminescence unit, and electrochemiluminescence unit |
| CN111448691A (en) * | 2017-12-26 | 2020-07-24 | 昭和电工株式会社 | Binder for nonaqueous battery electrode, slurry for nonaqueous battery electrode, and nonaqueous battery |
| US11764359B2 (en) | 2017-12-26 | 2023-09-19 | Resonac Corporation | Binder including copolymer of styrene, (meth)acrylate, and surfactant having unsaturated bond, slurry having the same, nonaqueous battery electrode using the same, and nonaqueous battery using the same |
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