JP4478790B2 - Room temperature molten salt and electrochemical device - Google Patents
Room temperature molten salt and electrochemical device Download PDFInfo
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- JP4478790B2 JP4478790B2 JP2005513940A JP2005513940A JP4478790B2 JP 4478790 B2 JP4478790 B2 JP 4478790B2 JP 2005513940 A JP2005513940 A JP 2005513940A JP 2005513940 A JP2005513940 A JP 2005513940A JP 4478790 B2 JP4478790 B2 JP 4478790B2
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- room temperature
- molten salt
- temperature molten
- tfsi
- Prior art date
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- 150000003839 salts Chemical class 0.000 title claims description 36
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- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
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- 229940093499 ethyl acetate Drugs 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- BJEPYKJPYRNKOW-UWTATZPHSA-M malate ion Chemical compound [O-]C(=O)[C@H](O)CC(O)=O BJEPYKJPYRNKOW-UWTATZPHSA-M 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000005649 substituted arylene group Chemical group 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 229940066528 trichloroacetate Drugs 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Description
本発明は、常温容融塩（イオン性液体）及び該常温溶融塩を含む電気化学デバイスに関する。 The present invention relates to an ambient temperature molten salt (ionic liquid) and an electrochemical device containing the ambient temperature molten salt.
有機溶媒は化学合成の媒体として、また高エネルギー密度の電気化学デバイス（リチウム電池等）の電解質溶媒として用いられる。有機溶媒の多くは揮発性であり、また沸点が高く揮発性の少ないものであっても引火性や発火性を示すため安全性に留意する必要があった。
また、本発明者の近年の研究により、リチウム電池にイオン性液体を適用し、安全なリチウム電池を構築する試みが行われ、ハードルの高いリチウム金属負極の利用に対する可能性が拓かれている（特許第２９８１９４５号；特開２００３−３３１９１８；Ｓ．Ｓａｋａｅｂｅ，Ｈ．Ｍａｔｓｕｍｏｔｏ，Ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｃｏｍｍｕｎｉｃａｔｉｏｎ，巻５，５０９頁（２００３年））。
しかしながら、現状では炭素負極等の利用が現実的であり、炭素負極を用いたリチウム電池へのイオン性液体の適用について検討されはじめているが、イオン性液体のみを電解液に用いた場合に、良好な充放電にまでは至っていない。炭素電極を用いたリチウム電池には上記化合物例のなかのラクトンやカーボネート等の溶媒が必ず用いられている。それはこれらの溶媒が炭素負極上で極少量分解され、溶媒の分解を抑制する皮膜を形成するためであるといわれている。イオン性液体にも有機溶媒を添加する試みが知られているが、揮発性、引火性の有機溶媒を加えることは、イオン性液体の特徴である難揮発性、難燃焼性を損なうことになり、また加える量によっては従来の電解質との差がなくなってしまう。
本発明は、難燃性の溶媒として安全性の高い常温溶融塩を提供することを目的とする。Organic solvents are used as chemical synthesis media and as electrolyte solvents in high energy density electrochemical devices (such as lithium batteries). Many of the organic solvents are volatile, and even if they have a high boiling point and a low volatility, they are flammable and ignitable, so it is necessary to pay attention to safety.
In addition, recent studies by the present inventor have attempted to construct a safe lithium battery by applying an ionic liquid to the lithium battery, and have opened up the possibility of using a lithium metal negative electrode with high hurdles ( Patent No. 2981945; JP-A-2003-331918; S. Sakaebe, H. Matsumoto, Electrochemical Communication, Vol. 5, 509 (2003)).
However, at present, the use of a carbon negative electrode is practical, and the application of an ionic liquid to a lithium battery using a carbon negative electrode has begun to be studied, but it is good when only an ionic liquid is used as an electrolyte. It has not yet reached a proper charge / discharge. A lithium battery using a carbon electrode always uses a solvent such as lactone or carbonate in the above compound examples. It is said that these solvents are decomposed in a very small amount on the carbon negative electrode to form a film that suppresses the decomposition of the solvent. Attempts to add organic solvents to ionic liquids are also known, but adding volatile and flammable organic solvents impairs the low volatility and flame retardance characteristic of ionic liquids. Depending on the amount added, the difference from the conventional electrolyte is eliminated.
An object of the present invention is to provide a highly safe room temperature molten salt as a flame retardant solvent.
図１〜４：種々の溶媒及び本発明によって合成された新規イオン性液体の熱重量変化（昇温速度：１０℃／分）（有機溶媒：ＧＢＬ：γ−ブチロラクトン，ＰＣ：プロピレンカーボネート、ＥＣＥＴＭＡ−Ｃｌ：ＥＣＥＴＭＡ−ＴＦＳＩは実施例２で得られた常温溶融塩である。
ＴＭＯＴＦＡ−Ｃｌ：ＴＭＯＴＦＡ−ＴＦＳＩは実施例４で得られた常温溶融塩である。
ＴＭＯＤＡ−Ｃｌ：ＴＭＯＤＡ−ＴＦＳＩは実施例５で得られた常温溶融塩である。）
図５〜図６：充放電特性を示す。縦軸は電圧（Ｖｏｌｔａｇｅ）であり、横軸は比容量（Ｓｐｅｃｉｆｉｃ ｃａｐａｃｉｔｙ）である。1-4: Thermogravimetric change of various solvents and the novel ionic liquid synthesized according to the present invention (heating rate: 10 ° C./min) (organic solvent: GBL: γ-butyrolactone, PC: propylene carbonate, ECETMA- Cl: ECETMA-TFSI is a room temperature molten salt obtained in Example 2.
TMOTFA-Cl: TMOTFA-TFSI is a room temperature molten salt obtained in Example 4.
TMODA-Cl: TMODA-TFSI is a room temperature molten salt obtained in Example 5. )
5 to 6: Charging / discharging characteristics are shown. The vertical axis is voltage (Voltage), and the horizontal axis is specific capacity (Specific capacity).
本発明は、以下の常温溶融塩及び電気化学デバイスを提供するものである。
項１．揮発性有機溶媒にカチオン性基を導入したカチオン成分と、
無機イオン、スルホンイミドイオン、カルボン酸イオン、１価又は多価スルホン酸イオン、（置換基を有することのあるアルキル、シクロアルキルまたはアリール）４Ｂ−、（Ｒ１ＳＯ２）３Ｃ−｛Ｒ１は置換基を有することのあるアルキル基、置換基を有することのあるハロゲン化アルキル基、置換基を有することのあるアリール基｝、Ｒｆ−ＢＦ３ −（式中、ＲｆはＣｎＦ２ｎ＋１、ｎは１〜４の整数を示す）からなる群から選ばれるアニオン成分を有する常温溶融塩。
項２．項１に記載の常温溶融塩を含む電気化学デバイス。
項３．リチウム二次電池、電気二重層キャパシター、太陽電池またはエレクトロクロミックデバイスである項２に記載の電気化学デバイス。
本発明の常温溶融塩は、難燃性及び不揮発性を有することから、安全性の高い電気化学デバイスを作製することが可能である。
本発明の常温溶融塩の融点は、通常１００℃以下、好ましくは８０℃以下、より好ましくは６０℃以下、さらに好ましくは４０℃以下、特に２５℃以下である。例えば燃料電池に使用する場合には１００℃以下の常温溶融塩を広く使用することができる。一方、太陽電池やエレクトロクロミックデバイス、リチウム電池および電気二重層キャパシターでは常温溶融塩の融点は室温（２５℃）以下が好ましく、より好ましくは０℃以下、特に−２０℃以下であるのがさらに好ましい。
本発明の常温溶融塩のカチオン成分は、揮発性有機溶媒にカチオン性基を導入したものである。
（１）カチオン性基
カチオン性基としては、アンモニウム基、スルホニウム基、ホスホニウム等のオニウムカチオンが例示され、好ましくはアンモニウム基である。カチオン性基は１つの有機溶媒化合物に１個または２個以上、好ましくは１個または２個導入することができる。
本発明の好ましい実施形態において、好ましい有機溶媒化合物としては、酸素原子を１または２以上含む有機溶媒（例えばエーテル、アルコール、エステル、カーボネート、グリコール、グリコールモノエーテルなど）が挙げられる。また、４級アンモニウム基は、酸素原子に結合した炭素原子に導入されるのが好ましい。
このようなカチオン性基は有機溶媒に必要に応じてアルキレン基を介して有機溶媒に導入される。有機溶媒としては、常圧での沸点が−１００℃〜３００℃、好ましくは３０℃〜３００℃であって、常温で固体または液体の化合物が例示され、具体的には以下の化合物が例示される：
・エーテル類：ジエチルエーテル、テトラヒドロフラン、テトラヒドロピラン、ジイソプロピルエーテル、ジフェニルエーテル、アニソール、フェネトール、グアイアコールなど；
・アルキレングリコール類：エチレングリコール、プロピレングリコール、ブチレングリコール、ジエチレングリコール、トリエチレングリコールなど；
・アルキレングリコールモノアルキルエーテル類：エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ブチレングリコールモノメチルエーテル、ブチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテルなど；
・アルキレングリコールジアルキルエーテル類：エチレングリコールジメチルエーテル（ＤＭＥ）、エチレングリコールジエチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、ブチレングリコールジメチルエーテル、ブチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテルなど；
・エステル類：酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸プロピル、プロピオン酸ブチル、ギ酸メチル、ギ酸エチル、ギ酸プロピル、ギ酸ブチル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸ブチルなど；
・ラクトン類：γブチロラクトン（ＧＢＬ）など
・ケトン類：アセトン（ＡＴＮ）、アセチルアセトン、メチルエチルケトン、シクロヘキサノン、シクロペンタノンなど；
・ヘテロ芳香族炭化水素：ピリジンなど
・脂環式炭化水素：シクロペンタン、シクロヘキサン、メチルシクロヘキサンなど：
・ヘテロ脂環式化合物：ジオキサン、モルホリン、ピロリジンなど；
・スルフィド類：ジメチルスルフィド、ジエチルスルフィド、ジ−ｎ−プロピルスルフィド、ジイソプロピルスルフィドなど；
・炭酸エステル類：エチレンカーボネート（ＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート、ジエチルカーボネート（ＤＥＣ）、ジメチルカーボネートなど；
・アルコール類；エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノールなど；
このような有機溶媒にカチオン性基を導入する方法としては、以下の方法が挙げられる。
Ｒ１，Ｒａで表されるアルキル基としては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｓｅｃ−ブチル、イソブチル、ｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、トリデシル、テトラデシル、ヘキサデシル、オクタデシル、エイコシルなどの炭素数１〜２０、好ましくは炭素数１〜６，より好ましくは炭素数１〜３の直鎖又は分枝を有するアルキル基が挙げられる。
ハロアルキル基としては、上記アルキル基の水素原子の少なくとも１つがハロゲン原子（塩素、臭素、フッ素、ヨウ素）、特にフッ素原子で置換された炭素数１〜２０、好ましくは炭素数１〜６，より好ましくは炭素数１〜３の直鎖又は分枝を有するハロアルキル基が挙げられる。
アルコキシ基としては（Ｏ−上記アルキル）構造を有する炭素数１〜２０、好ましくは炭素数１〜６，より好ましくは炭素数１〜３の直鎖又は分枝を有するアルコキシ基が挙げられる。
アルキルチオ基としては、（Ｓ−上記アルキル）構造を有する炭素数１〜２０、好ましくは炭素数１〜６，より好ましくは炭素数１〜３の直鎖又は分枝を有するアルキルチオ基が挙げられる。
アリール基としては、フェニル基、トルイル基、キシリル基、エチルフェニル基、１，３，５−トリメチルフェニル基などの炭素数６〜１０のアリール基が挙げられる。
アラルキル基としては、ベンジル、フェネチル、ナフチルメチルなどの炭素数７〜１５のアラルキル基が挙げられる。
アルコキシアルキル基のアルコキシ基及びアルキル基は前記と同様であり、直鎖又は分枝を有する炭素数１〜２０アルコキシ基で置換された直鎖又は分枝を有する炭素数１〜２０のアルキル基が挙げられ、特にメトキシメチル基（ＣＨ２ＯＣＨ３）、メトキシエチル基（ＣＨ２ＣＨ２ＯＣＨ３）、エトキシメチル基（ＣＨ２ＯＣＨ２ＣＨ３）、エトキシエチル基（ＣＨ２ＣＨ２ＯＣＨ２ＣＨ３）が例示される。
ポリエーテル基としては、−（ＣＨ２）ｎ１−Ｏ−（ＣＨ２ＣＨ２Ｏ）ｎ２−（Ｃ１−Ｃ４アルキル）、または、−（ＣＨ２）ｎ１−Ｏ−（ＣＨ２ＣＨ（ＣＨ３）ｎ２−（Ｃ１−Ｃ４アルキル）で表される基が挙げられ、ｎ１は１〜４の整数、ｎ２は１〜４の整数、Ｃ１−Ｃ４アルキルとしては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチルが例示される。
また、Ｒ１とＲ２は、これらが結合している窒素原子と一緒になって、５〜８員環、好ましくは５員環または６員環の含窒素複素環基（ピロリジニウム、ピペリジニウム、ピロリニウム、ピリジニウム等）を形成してもよい。
前記アルキル基の任意の位置のＣ−Ｃ単結合の間に−Ｏ−、−ＣＯＯ−、−ＣＯ−、を１個または複数個介在させて、エーテル、エステルまたはケトン構造としてもよい。
アリール基、アラルキル基の置換基としては、ハロゲン原子（Ｆ、Ｃｌ、Ｂｒ、Ｉ）、水酸基、メトキシ基、ニトロ基、アセチル基、アセチルアミノ基などが挙げられる。
Ｘは脱離基を表し、具体的には、塩素原子、臭素原子、ヨウ素原子、メタンスルホニル基、ｐ−トルエンスルホニル基などが挙げられる。
好ましい１つの実施形態において、本発明は、低沸点、高揮発性の溶媒に４級アンモニウム基を導入して、常温溶融塩に導く。４級アンモニウム化は、上記のように、脱離基と第三級アミンを反応させて行っても良く、アミノ基を含む溶媒のアミノ基を四級化してもよい。
（２）アニオン成分
本発明の常温溶融塩のアニオン成分としては、以下に例示されるアニオンが使用可能である：
・無機イオン：Ｃｌ−，Ｂｒ−，Ｆ−，Ｉ−、ＳＣＮ−、ＣｌＯ４ −、ＢＦ４ −、ＢＣｌ４ −、ＢＢｒ４ −、ＰＦ６ −、Ａｌ３Ｃｌ８ −，Ａｌ２Ｃｌ７ −，ＡｌＣｌ４ −、ＡｓＦ６ −など；
・スルホンイミドイオン｛（ＲＳＯ２）２Ｎ−、Ｒは置換基を有することのあるアルキル基、置換基を有することのあるハロゲン化アルキル基、置換基を有することのあるアリール基｝、
・１価又は多価カルボン酸イオン；例えば酢酸イオン、ギ酸イオン、プロピオン酸イオン、酪酸イオン、吉草酸イオン、イソ吉草酸イオン、トリフルオロ酢酸イオン、ジフルオロ酢酸イオン、モノフルオロ酢酸イオン、トリクロロ酢酸イオン、ジクロロ酢酸イオン、モノクロロ酢酸イオン、乳酸イオン、グリコール酸イオン、リンゴ酸イオン、
・１価又は多価スルホン酸イオン（Ｒｂ−ＳＯ３−；−Ｏ３Ｓ−Ｒｃ−ＳＯ３−；Ｒｂは置換されていてもよいアルキル基または置換されていてもよいアリール基、Ｒｃは置換されていてもよいアルキレン基または置換されていてもよいアリーレン基、アリール基またはアルキル基は、水酸基、シアノ基、メトキシ基、エトキシ基、メチレンジオキシ基、フッ素原子、塩素原子、臭素原子で置換されていてもよい）；例えばベンゼンスルホン酸イオン、トルエンスルホン酸イオン、
ＣｎＸ１ ２ｎ＋１−ＳＯ３ −（Ｘ１は同一または異なってＨ，ＦまたはＣｌ、ｎ＝１〜６）、ＣｎＸ１ ２ｎ−（ＳＯ３ −）２（Ｘ１は同一または異なってＨ，ＦまたはＣｌ、ｎ＝１〜６）が例示される；
・（置換基を有することのあるアルキル、シクロアルキルまたはアリール）４Ｂ−；
例えば（Ｐｈ）４Ｂ−，（Ｅｔ）３（シクロヘキシル）Ｂ−など、
・（ＲｂＳＯ２）３Ｃ−｛Ｒｂは前記に定義される通りである｝：例えば（ＣＦ３ＳＯ２）３Ｃ−など。
・Ｒｆ−ＢＦ３ −（式中、ＲｆはＣｎＦ２ｎ＋１、ｎは１〜４の整数を示す）、例えばＣＦ３ＢＦ３、Ｃ２Ｆ５ＢＦ３、Ｃ３Ｆ７ＢＦ３、Ｃ４Ｆ９ＢＦ３等が挙げられ、ＣｎＦ２ｎ＋１は直鎖であっても分岐を有していてもよい。
これらのアニオン成分は公知であるか、公知の製法により容易に製造することができる。
本発明の常温溶融塩は、上記のカチオン成分とアニオン成分を混合することにより容易に製造することができる。
上記のカチオン成分及びアニオン成分は、各々単一成分であってもよいが、２種以上の成分を組み合わせて使用しても良く、その配合比率は任意である。
常温溶融塩を得るための塩交換反応は、所望の溶融塩が抽出可能である場合には、溶媒抽出法により行うことができ、或いは、アニオン交換樹脂を通してカチオン成分のカウンターアニオンをＯＨ−に変換した後、Ｈ−（アニオン成分）溶液を当量添加することにより得ることができる。
本発明の常温溶融塩は、リチウム二次電池、電気二重層キャパシター、燃料電池、太陽電池等の電気化学デバイス、化学反応の溶剤として適している。
例えば、本発明の常温溶融塩を、リチウム二次電池に用いる活性の高い炭素負極やリチウム負極に対して電気化学的に不安定な常温溶融塩（例えば、１−エチル−３−メチルイミダゾリウムテトラフルオロボレート等）に添加することにより、負極上への不動態皮膜形成により見掛け上電気化学安定性を大幅に向上させることができる。しかも添加剤となるものも常温溶融塩であるため、全体としての電解液の耐熱性が保たれる。The present invention provides the following room temperature molten salt and electrochemical device.
Inorganic ion, sulfonimide ion, carboxylate ion, monovalent or polyvalent sulfonate ion, (alkyl, cycloalkyl or aryl which may have a substituent) 4 B − , (R 1 SO 2 ) 3 C − {R 1 is an alkyl group which may have a substituent, a halogenated alkyl group which may have a substituent, an aryl group which may have a substituent}, Rf-BF 3 − (wherein Rf is C n F 2n + 1 , N represents an integer of 1 to 4, and a room temperature molten salt having an anionic component selected from the group consisting of:
Item 2. An electrochemical device comprising the room temperature molten salt according to
Item 3. Item 3. The electrochemical device according to Item 2, which is a lithium secondary battery, an electric double layer capacitor, a solar cell, or an electrochromic device.
Since the room temperature molten salt of the present invention has flame retardancy and non-volatility, it is possible to produce a highly safe electrochemical device.
The melting point of the room temperature molten salt of the present invention is usually 100 ° C. or lower, preferably 80 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 40 ° C. or lower, particularly 25 ° C. or lower. For example, when used in a fuel cell, a room temperature molten salt at 100 ° C. or lower can be widely used. On the other hand, in solar cells, electrochromic devices, lithium batteries and electric double layer capacitors, the melting point of the room temperature molten salt is preferably room temperature (25 ° C.) or less, more preferably 0 ° C. or less, particularly preferably −20 ° C. or less. .
The cation component of the room temperature molten salt of the present invention is obtained by introducing a cationic group into a volatile organic solvent.
(1) Cationic group Examples of the cationic group include onium cations such as an ammonium group, a sulfonium group, and phosphonium, and an ammonium group is preferable. One or more cationic groups, preferably one or two, can be introduced into one organic solvent compound.
In a preferred embodiment of the present invention, preferred organic solvent compounds include organic solvents containing one or more oxygen atoms (eg ethers, alcohols, esters, carbonates, glycols, glycol monoethers, etc.). The quaternary ammonium group is preferably introduced into a carbon atom bonded to an oxygen atom.
Such a cationic group is introduced into the organic solvent via an alkylene group as necessary. The organic solvent has a boiling point at normal pressure of −100 ° C. to 300 ° C., preferably 30 ° C. to 300 ° C., and is exemplified by a solid or liquid compound at room temperature. Specifically, the following compounds are exemplified. R:
Ethers: diethyl ether, tetrahydrofuran, tetrahydropyran, diisopropyl ether, diphenyl ether, anisole, phenetol, guaiacol, etc .;
Alkylene glycols: ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, etc .;
-Alkylene glycol monoalkyl ethers: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc. ;
Alkylene glycol dialkyl ethers: ethylene glycol dimethyl ether (DME), ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, butylene glycol dimethyl ether, butylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc .;
Esters: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl benzoate, benzoic acid Ethyl, propyl benzoate, butyl benzoate, etc .;
Lactones: γ-butyrolactone (GBL), etc. Ketones: acetone (ATN), acetylacetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, etc.
-Heteroaromatic hydrocarbons: pyridine, etc.-Alicyclic hydrocarbons: cyclopentane, cyclohexane, methylcyclohexane, etc .:
Heteroalicyclic compounds: dioxane, morpholine, pyrrolidine, etc .;
Sulfides: dimethyl sulfide, diethyl sulfide, di-n-propyl sulfide, diisopropyl sulfide, etc .;
Carbonates: ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, diethyl carbonate (DEC), dimethyl carbonate, etc .;
Alcohols: ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and the like;
Examples of methods for introducing a cationic group into such an organic solvent include the following methods.
Examples of the alkyl group represented by R 1 and R a include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, such as undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, and eicosyl. .
As the haloalkyl group, at least one hydrogen atom of the above alkyl group is substituted with a halogen atom (chlorine, bromine, fluorine, iodine), particularly a fluorine atom, and preferably has 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Includes a haloalkyl group having 1 to 3 carbon atoms or a straight chain or branched chain.
Examples of the alkoxy group include straight-chain or branched alkoxy groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms, having an (O-alkyl) structure.
Examples of the alkylthio group include a straight chain or branched alkylthio group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, having an (S-alkyl) structure.
Examples of the aryl group include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, and a 1,3,5-trimethylphenyl group.
Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms such as benzyl, phenethyl and naphthylmethyl.
The alkoxy group and the alkyl group of the alkoxyalkyl group are the same as described above, and a linear or branched alkyl group having 1 to 20 carbon atoms substituted with a linear or branched alkoxy group having 1 to 20 carbon atoms. In particular, methoxymethyl group (CH 2 OCH 3 ), methoxyethyl group (CH 2 CH 2 OCH 3 ), ethoxymethyl group (CH 2 OCH 2 CH 3 ), ethoxyethyl group (CH 2 CH 2 OCH 2 CH 3) ) Is exemplified.
The polyether group, - (CH 2) n1 -O- (CH 2 CH 2 O) n2 - (C 1 -C 4 alkyl), or, - (CH 2) n1 -O- (CH 2 CH (CH 3) n2 - (C 1 -C 4 alkyl) groups represented mentioned in, n1 is an integer from 1 to 4, n2 is an integer from 1 to 4, as a C 1 -C 4 alkyl are methyl, ethyl, Examples are n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.
In addition, R 1 and R 2 together with the nitrogen atom to which they are bonded are a 5- to 8-membered, preferably 5- or 6-membered nitrogen-containing heterocyclic group (pyrrolidinium, piperidinium, pyrrolinium) , Pyridinium, etc.).
One or a plurality of —O—, —COO—, and —CO— may be interposed between C—C single bonds at any position of the alkyl group to form an ether, ester, or ketone structure.
Examples of the substituent for the aryl group and aralkyl group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a methoxy group, a nitro group, an acetyl group, and an acetylamino group.
X represents a leaving group, and specific examples include a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyl group, and a p-toluenesulfonyl group.
In a preferred embodiment, the present invention introduces a quaternary ammonium group into a low boiling point, highly volatile solvent, leading to a room temperature molten salt. As described above, quaternary ammoniumation may be performed by reacting a leaving group with a tertiary amine, or the amino group of a solvent containing an amino group may be quaternized.
(2) Anion component As an anion component of the room temperature molten salt of the present invention, anions exemplified below can be used:
Inorganic ions: Cl − , Br − , F − , I − , SCN − , ClO 4 − , BF 4 − , BCl 4 − , BBr 4 − , PF 6 − , Al 3 Cl 8 − , Al 2 Cl 7 − , AlCl 4 − , AsF 6 − and the like;
Sulfonimide ion {(RSO 2 ) 2 N − , R is an alkyl group that may have a substituent, a halogenated alkyl group that may have a substituent, an aryl group that may have a substituent},
Monovalent or polyvalent carboxylate ions; for example, acetate ion, formate ion, propionate ion, butyrate ion, valerate ion, isovalerate ion, trifluoroacetate ion, difluoroacetate ion, monofluoroacetate ion, trichloroacetate ion , Dichloroacetate ion, monochloroacetate ion, lactate ion, glycolate ion, malate ion,
A monovalent or polyvalent sulfonate ion (R b —SO 3 —; —O 3 S—R c —SO 3 —; R b is an optionally substituted alkyl group or an optionally substituted aryl group; R c represents an optionally substituted alkylene group or an optionally substituted arylene group, aryl group or alkyl group, a hydroxyl group, a cyano group, a methoxy group, an ethoxy group, a methylenedioxy group, a fluorine atom, a chlorine atom, May be substituted with a bromine atom); for example, benzenesulfonate ion, toluenesulfonate ion,
C n X 1 2n + 1 —SO 3 — (X 1 is the same or different, H, F or Cl, n = 1 to 6), C n X 1 2n — (SO 3 − ) 2 (X 1 is the same or different H, F or Cl, n = 1-6) are exemplified;
- (alkyl which may have a substituent, cycloalkyl or aryl) 4 B -;
For example, (Ph) 4 B − , (Et) 3 (cyclohexyl) B − and the like,
· (R b SO 2) 3 C - {R b are as defined above}: for example (CF 3 SO 2) 3 C - like.
· Rf-BF 3 - (wherein, Rf is an integer of CnF2n + 1, n is 1 to 4), for example, CF 3 BF 3, C 2 F 5 BF 3, C 3 F 7 BF 3, C 4 F 9 BF 3 and the like, and CnF2n + 1 may be linear or branched.
These anionic components are known or can be easily produced by known production methods.
The room temperature molten salt of the present invention can be easily produced by mixing the cation component and the anion component.
The cation component and the anion component may each be a single component, but may be used in combination of two or more components, and the blending ratio thereof is arbitrary.
When the desired molten salt can be extracted, the salt exchange reaction for obtaining the room temperature molten salt can be performed by a solvent extraction method, or the cation component counter anion is converted to OH- through an anion exchange resin. Then, it can be obtained by adding an equivalent amount of H- (anionic component) solution.
The room temperature molten salt of the present invention is suitable as an electrochemical device such as a lithium secondary battery, an electric double layer capacitor, a fuel cell, and a solar cell, and a solvent for chemical reaction.
For example, the room temperature molten salt of the present invention is used as a highly active carbon negative electrode or lithium negative electrode that is electrochemically unstable for a lithium secondary battery (for example, 1-ethyl-3-methylimidazolium tetra Addition to fluoroborate or the like) can significantly improve the electrochemical stability by forming a passive film on the negative electrode. Moreover, since the additive is also a room temperature molten salt, the heat resistance of the electrolyte as a whole is maintained.
以下、本発明を実施例に基づいて説明するが、本発明はこれら実施例には限定されない。
実施例１ ジメトキシエタン（ＤＭＥ）のイオン性液体化：１−（２−メトキシ−エトキシエチル）−１−メチル−ピペリジニウム−ビス（トリフルオロメチルスルホニル）イミド（ＭＥＥＭＰ−ＴＦＳＩ）の合成
１−ブロモエトキシ−２−メトキシエタン５０ｇをアセトン３００ｍＬに溶解し１Ｌのフラスコにいれ，等モル量のメチルピペリジン（ＭＰ）アセトン溶液を氷浴で冷却しながら滴下混合し，室温下で撹拌。１８ｈ後，アセトン及び水をエバポレータにて留去することにより白色粉末１−（２−メトキシ−エトキシエチル）−１−メチル−ピペリジニウム臭化物（ＭＥＥＭＰ−Ｂｒ）を得る（収率９０％）。アセトン／エタノール混合溶媒にて再結晶を行い精製したものとＬｉ−ＴＦＳＩ（リチウムビス（トリフルオロメシルスルホニルイミド））を超高純度水（以下ｍｉｌｌｉ−Ｑ水と略す）水中で等モル量混合すると，水に不溶の目的生成物（ＭＥＥＭＰ−ＴＦＳＩ）が分離析するのでこれをジクロロメタンで抽出する。抽出したジクロロメタン溶液に当体積のｍｉｌｌｉ−Ｑ水を加え再度撹拌の後，ジクロロメタン相を分液ロートにて分取し、ロータリーエバポレータにてジクロロメタンを留去し，最終的に７０℃に加熱して真空乾燥を行って目的物（ＭＥＥＭＰ−ＴＦＳＩ）を得た（収率７０％）。ＬｉＴＦＳＩのかわりにＬｉＰＦ６を用いることにより室温で溶融するＭＥＥＭＰ−ＰＦ６を得る事ができる。
ＭＥＥＭＰ−ＴＦＳＩのＮＭＲによる分析値は以下の通りである。
１Ｈ−ＮＭＲ［ｐｐｍ］（ｄ−ａｃｅｔｏｎｅ，δ１．７３（ｍ），δ２．０１（ｍ），δ３．３１（ｓ），δ３．３３（ｓ），δ３．５２（ｍ），δ３．５７（ｍ），３．６４（ｍ），δ３．７９，（ｍ），δ４．０６（ｓ））
１３Ｃ−ＮＭＲ［ｐｐｍ］（ｄ−ａｃｅｔｏｎｅ，δ２０．６，δ２１．６，δ４９．８，δ５８．７，δ６２．８，δ６３．４，δ６４．９，δ７０．８，δ７２．２δ１１６．１，δ１１９．３，δ１２２．５，δ１２５．６ｐｐｍ）
実施例２ ジエチルカーボネート（ＤＥＣ）のイオン性液体化：（１−エトキシカルボニロキシエチル）トリメチルアンモニウム−ビス（トリフルオロメチルスルホニル）イミド（ＥＣＥＴＭＡ−ＴＦＳＩ）の合成
実施例１の１−ブロモエトキシ−２−メトキシエタンのかわりに１−クロロエチルカーボネートを使用する以外は同じ手順で標記化合物を得た。収率７７％
１Ｈ−ＮＭＲ［ｐｐｍ］（ｄ−ｍｅｔｈａｎｏｌ，δ１．３４（ｔ），δ１．７１（ｄ），δ３．１８（ｓ），δ４．３１（ｑ），５．９４（ｑ））
１３Ｃ−ＮＭＲ［ｐｐｍ］（ｄ−ｍｅｔｈａｎｏｌ，δ１４．３，δ１４．７，δ４９．６，δ６７．１，δ９３．３，δ１１６．３，δ１１９．５，δ１２２．６７，δ１２５．８，δ１５３．３）
実施例３ アセトンのイオン性液体化：トリメチル（２−オキソプロピル）−アンモニウム−ビス（トリフルオロメチルスルホニル）イミド（ＴＭＯＰＡ−ＴＦＳＩ）の合成
ＴＭＯＰＡ−ＴＦＳＩのＮＭＲによる分析値は以下の通りである。
１Ｈ−ＮＭＲ［ｐｐｍ］（ｄ−ａｃｅｔｏｎｅ，δ２．２６（ｓ），δ３．４７（ｓ），δ４．７６（ｓ））
１３Ｃ−ＮＭＲ［ｐｐｍ］（ｄ−ａｃｅｔｏｎｅ，δ２８．４，δ５４．５，δ７０．４，δ１１６．０，δ１１９．２，δ１２２．４，δ１２５．６，δ２００．０）
実施例４ γ−ブチロラクトンのイオン性液体化：トリメチル（２−オキソ−テトラヒドロフラン−３−イル）アンモニウム−アンモニウム−ビス（トリフルオロメチルスルホニル）のイミド（ＴＭＯＴＦＡ−ＴＦＳＩ）の合成
ＴＭＯＴＦＡ−ＴＦＳＩのＮＭＲによる分析値は以下の通りである。
１Ｈ−ＮＭＲ［ｐｐｍ］（ｄ−ａｃｅｔｏｎｅ）δ３．０１（ｍ），δ３．５５（ｓ），δ４．４３（ｍ），δ４．６３（ｍ），δ５．０７（ｍ））
１３Ｃ−ＮＭＲ［ｐｐｍ］（ｄ−ａｃｅｔｏｎｅ）δ２５．４，δ５２．９，δ５８．４，δ６５．８，δ１１６．３，δ１１９．５，δ１２２．６，δ１２５．８，δ１７０．０）
実施例５ エチレンカーボネート（ＥＣ）のイオン性液体化：トリメチル（２−オキソ−［１，３］−ジオキソラン−４−イル）アンモニウム−ビス（トリフルオロメチルスルホニル）イミド（ＴＭＯＤＡ−ＴＦＳＩ）の合成
ＴＭＯＤＡ−ＴＦＳＩのＮＭＲによる分析値は以下の通りである。
１Ｈ−ＮＭＲ［ｐｐｍ］（ｄ−ａｃｅｔｏｎｅ，δ３．２１（ｓ），δ４．８８（ｍ），δ５．１２（ｍ），δ５．９０（ｍ））
１３Ｃ−ＮＭＲ［ｐｐｍ］（ｄ−ａｃｅｔｏｎｅ，δ４５．５，δ６５．８，δ９４．０，δ１１６．３，δ１１９．５，δ１２２．７，δ１２５．９，δ１５２．５）EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to these Examples.
Example 1 Ionic Liquefaction of Dimethoxyethane (DME): Synthesis of 1- (2-methoxy-ethoxyethyl) -1-methyl-piperidinium-bis (trifluoromethylsulfonyl) imide (MEEMP-TFSI) 1-Bromoethoxy 2-Methoxyethane (50 g) is dissolved in acetone (300 mL), placed in a 1 L flask, an equimolar amount of methylpiperidine (MP) acetone solution is added dropwise with cooling in an ice bath, and the mixture is stirred at room temperature. After 18 h, acetone and water are distilled off with an evaporator to obtain white powder 1- (2-methoxy-ethoxyethyl) -1-methyl-piperidinium bromide (MEEMP-Br) (yield 90%). When recrystallized with an acetone / ethanol mixed solvent and purified, and Li-TFSI (lithium bis (trifluoromesylsulfonylimide)) are mixed in equimolar amounts in ultrahigh-purity water (hereinafter abbreviated as milli-Q water). The target product (MEEMP-TFSI) which is insoluble in water separates out and is extracted with dichloromethane. After adding this volume of milli-Q water to the extracted dichloromethane solution and stirring again, the dichloromethane phase was separated with a separatory funnel, the dichloromethane was distilled off with a rotary evaporator, and finally heated to 70 ° C. It vacuum-dried and obtained the target object (MEEMP-TFSI) (yield 70%). By using LiPF 6 instead of LiTFSI, MEEMP-PF 6 that melts at room temperature can be obtained.
The analysis value by NMR of MEEMP-TFSI is as follows.
1 H-NMR [ppm] (d-acetone, δ1.73 (m), δ2.01 (m), δ3.31 (s), δ3.33 (s), δ3.52 (m), δ3.57 (M), 3.64 (m), δ 3.79, (m), δ 4.06 (s))
13 C-NMR [ppm] (d-acetone, δ20.6, δ21.6, δ49.8, δ58.7, δ62.8, δ63.4, δ64.9, δ70.8, δ72.2 δ116.1, (δ119.3, δ122.5, δ125.6 ppm)
Example 2 Ionic liquefaction of diethyl carbonate (DEC): Synthesis of (1-ethoxycarbonyloxyethyl) trimethylammonium-bis (trifluoromethylsulfonyl) imide (ECETMA-TFSI) 1-Bromoethoxy- of Example 1 The title compound was obtained in the same procedure except that 1-chloroethyl carbonate was used instead of 2-methoxyethane. Yield 77%
1 H-NMR [ppm] (d-ethanol, δ 1.34 (t), δ 1.71 (d), δ 3.18 (s), δ 4.31 (q), 5.94 (q))
13 C-NMR [ppm] (d-ethanol, δ14.3, δ14.7, δ49.6, δ67.1, δ93.3, δ116.3, δ119.5, δ122.67, δ125.8, δ153. 3)
Example 3 Ionic liquefaction of acetone: Synthesis of trimethyl (2-oxopropyl) -ammonium-bis (trifluoromethylsulfonyl) imide (TMOPA-TFSI)
The analysis values by NMR of TMOPA-TFSI are as follows.
1 H-NMR [ppm] (d-acetone, δ 2.26 (s), δ 3.47 (s), δ 4.76 (s))
13 C-NMR [ppm] (d-acetone, δ28.4, δ54.5, δ70.4, δ116.0, δ119.2, δ122.4, δ125.6, δ200.0)
Example 4 Ionic Liquefaction of γ-Butyrolactone: Synthesis of Trimethyl (2-oxo-tetrahydrofuran-3-yl) ammonium-ammonium-bis (trifluoromethylsulfonyl) imide (TMOTFA-TFSI)
The analysis values by NMR of TMOTFA-TFSI are as follows.
1 H-NMR [ppm] (d-acetone) δ 3.01 (m), δ 3.55 (s), δ 4.43 (m), δ 4.63 (m), δ 5.07 (m))
13 C-NMR [ppm] (d-acetone) δ25.4, δ52.9, δ58.4, δ65.8, δ116.3, δ119.5, δ122.6, δ125.8, δ170.0)
Example 5 Ionic liquefaction of ethylene carbonate (EC): Synthesis of trimethyl (2-oxo- [1,3] -dioxolan-4-yl) ammonium-bis (trifluoromethylsulfonyl) imide (TMODA-TFSI)
The analysis values by NMR of TMODA-TFSI are as follows.
1 H-NMR [ppm] (d-acetone, δ 3.21 (s), δ 4.88 (m), δ 5.12 (m), δ 5.90 (m))
13 C-NMR [ppm] (d-acetone, δ45.5, δ65.8, δ94.0, δ116.3, δ119.5, δ122.7, δ125.9, δ152.5)
原料の溶媒としてプロピレンカーボネート（ＰＣ）を使用し、常法に従いメチル基に塩素原子を導入し、さらにトリエチルアミンを反応させ、さらにアニオン交換を行うことにより、以下のプロピレンカーボネート（ＰＣ）のイオン性液体を得ることができる。
γ−ブチロラクトン（ＧＢＬ）、プロピレンカーボネート（ＰＣ），実施例３で得られたＥＣＥＴＭＡ−Ｃｌ（カウンターアニオンがＣｌである実施例２の常温溶融塩の製造中間体）及びＥＣＥＴＭＡ−ＴＦＳＩ（実施例２で得られた常温溶融塩）を加熱し、重量変化を調べることで、耐熱性を評価した。
結果を図１に示す。
図１は、物質に熱をかけた場合の重量変化をあらわしたものであり，耐熱性の指針となる。ＧＢＬやＰＣなどの電池電解液として用いられる有機溶媒は沸点が２００℃以上であるが，揮発性があるために，１００℃より前から揮発して重量が減少している。ＤＥＣもＧＢＬやＰＣのような有機溶媒である。ＤＥＣを塩に変換したものＥＣＥＴＭＡ−Ｃｌは常温で固体の塩であるが，１５０℃付近まで安定であること，さらに対アニオンをＣｌからＴＦＳＩにアニオン交換したもの（ＥＣＥＴＭＡ−ＴＦＳＩ，室温で液体）ではさらに耐熱性が向上していることが、図１から明らかである。本発明の常温溶融塩を電池電解液として用いた場合，安全性が向上することが、図１の結果から明らかにされた。
試験例２
リチウム電池で良く使われる溶媒分子は揮発性が高く、発火性を有する（ＤＥＣ：ジエチルカーボネート，ＧＢＬ：γ−ブチロラクトン，ＥＣ：エチレンカーボネート）。先ず、これらの溶媒を加熱し、重量変化を調べることで、耐熱性を評価した。結果を図２に示す。
次に、上記の３つの溶媒分子にトリメチルアンモニウム基を修飾してカチオン化し、且つ、アニオンをハロゲンとすると固体の塩となり、２００℃でも揮発しない。該固体の塩についての熱分析測定結果を図３に示す。
さらに、アニオンをハロゲンからＴＦＳＩに交換するとさらに耐熱性が向上する。対応するＴＦＳＩ塩の熱分析測定結果を図４に示す。なお、該ＴＦＳＩ塩は、室温でも溶融するイオン性液体を形成する。
試険例３
以下の条件で、リチウム電池を作製し、充放電特性を調べた。結果を図５及び図６に示す。
充電・放電レート０．１Ｃ（３００ｍＡｈ／ｇを理論値として）
充電はＣＣＣＶモード５ｍＶ，１０時間
放電は１．２Ｖカットオフ
電極：９５ｗｔ％ＭＣＭＢ２８００＋５ｗｔ％ＰＶｄＦ、集電体は銅箔、対極はＬｉ箔を用いた２極セル（ラミネート）
電解質組成：ＥＭＩ−ＴＦＳＩ＋ＬｉＴＦＳＩ（１０ｗｔ％，およそ０．４Ｍ）
ＥＭＩ−ＴＦＳＩ＋ＥＣＥＴＭＡ−ＴＦＳＩ（体積比５：１）＋１０ｗｔ％ＬｉＴＦＳＩ
ＥＭＩ−ＴＦＳＩは電気化学安定性がアンモニウム系よりも劣っているが、粘性が比較的低いという長所がある。電気化学安定性が悪い点は、炭素を負極に用いた場合に如実に現れる。すなわち、図５において、充電時（点線）に５００ｍＡｈ／ｇもの大きな容量を示すが、これはＥＭＩカチオンの不可逆的な還元反応が起こっていること、あるいは炭素負極へのＥＭＩカチオンの挿入反応が起こっていること、その両方が起きていることを示唆する。また、放電時（実線）にはまったく容量が無く、ＥＭＩ−ＴＦＳＩのような電気化学安定性に劣る系は、全く炭素負極を用いる事が不可能である。
ところが、今回開発した溶媒構造を有するイオン性液体（ＥＣＥＴＭＡ−ＴＦＳＩ）を少量添加することにより、図６に示すように、ＥＭＩ−ＴＦＳＩにおいても良好な充放電特性を示しうることがわかった。これはＥＣＥＴＭＡ−ＴＦＳＩの分解により炭素負極上にいわゆるＳＥＩ皮膜を形成し、ＥＭＩの分解や炭素材料への挿入を抑制したためである。このような効果は従来、ＤＥＣやＧＢＬ，ＥＣのようなカルボニル構造を有する有機溶媒で知られていた。ＧＢＬ，ＥＣのような有機溶媒は、耐熱性や引火性に問題があるが今回合成した有機溶媒構造を有するイオン性液体では、難粘性でありかつ耐熱性が大幅に向上し、安全性に大きく寄与するものである。
電気化学安定性に優れるアンモニウム系イオン液体においても同様の効果が期待される。Using propylene carbonate (PC) as a raw material solvent, introducing a chlorine atom into a methyl group according to a conventional method, further reacting with triethylamine, and further performing anion exchange, the following ionic liquid of propylene carbonate (PC) Can be obtained.
γ-butyrolactone (GBL), propylene carbonate (PC), ECETMA-Cl obtained in Example 3 (production intermediate of room temperature molten salt of Example 2 in which counter anion is Cl) and ECETMA-TFSI (Example 2) The heat resistance was evaluated by heating the room temperature molten salt obtained in
The results are shown in FIG.
FIG. 1 shows a change in weight when a substance is heated, and serves as a guideline for heat resistance. Although organic solvents used as battery electrolytes such as GBL and PC have a boiling point of 200 ° C. or higher, they are volatile and thus volatilize from before 100 ° C. to reduce their weight. DEC is also an organic solvent such as GBL and PC. DEC converted to salt ECETMA-Cl is a solid salt at room temperature, but is stable up to around 150 ° C, and the anion exchanged from Cl to TFSI (ECETMA-TFSI, liquid at room temperature) Then, it is clear from FIG. 1 that the heat resistance is further improved. From the results of FIG. 1, it was clarified that the safety is improved when the room temperature molten salt of the present invention is used as a battery electrolyte.
Test example 2
Solvent molecules often used in lithium batteries are highly volatile and ignitable (DEC: diethyl carbonate, GBL: γ-butyrolactone, EC: ethylene carbonate). First, the heat resistance was evaluated by heating these solvents and examining the change in weight. The results are shown in FIG.
Next, if the trimethylammonium group is modified to cationize the above three solvent molecules and the anion is halogenated, it becomes a solid salt and does not volatilize even at 200 ° C. The result of thermal analysis measurement for the solid salt is shown in FIG.
Furthermore, when the anion is exchanged from halogen to TFSI, the heat resistance is further improved. The thermal analysis measurement results of the corresponding TFSI salt are shown in FIG. The TFSI salt forms an ionic liquid that melts even at room temperature.
Trial example 3
A lithium battery was fabricated under the following conditions and the charge / discharge characteristics were examined. The results are shown in FIGS.
Charging / discharging rate 0.1C (300mAh / g as theoretical value)
Charging is CCCV mode 5 mV, 10-hour discharging is 1.2 V cutoff electrode: 95 wt% MCMB2800 + 5 wt% PVdF, current collector is copper foil, counter electrode is a bipolar cell using Li foil (laminate)
Electrolyte composition: EMI-TFSI + LiTFSI (10 wt%, approximately 0.4 M)
EMI-TFSI + ECETMA-TFSI (volume ratio 5: 1) +10 wt% LiTFSI
Although EMI-TFSI is inferior in electrochemical stability to ammonium, it has the advantage of relatively low viscosity. The point of poor electrochemical stability is apparent when carbon is used for the negative electrode. That is, in FIG. 5, a large capacity of 500 mAh / g is shown at the time of charging (dotted line). This indicates that an irreversible reduction reaction of the EMI cation occurs, or an insertion reaction of the EMI cation into the carbon anode occurs. Suggest that both are happening. Further, a system having no capacity at the time of discharge (solid line) and inferior in electrochemical stability such as EMI-TFSI cannot use a carbon negative electrode at all.
However, it was found that by adding a small amount of the ionic liquid (ECETMA-TFSI) having a solvent structure developed this time, good charge / discharge characteristics can be exhibited even in EMI-TFSI as shown in FIG. This is because the so-called SEI film was formed on the carbon negative electrode by the decomposition of ECETMA-TFSI, and the decomposition of EMI and the insertion into the carbon material were suppressed. Such an effect has been conventionally known for organic solvents having a carbonyl structure such as DEC, GBL, and EC. Organic solvents such as GBL and EC have problems with heat resistance and flammability, but the ionic liquids having the organic solvent structure synthesized this time are hard to be viscous and have significantly improved heat resistance. It contributes.
The same effect is expected even in an ammonium-based ionic liquid having excellent electrochemical stability.
Claims (4)
る。The
ＴＦＳＩTFSI −− はビス（トリフルオロメチルスルホニル）イミドを表す。）Represents bis (trifluoromethylsulfonyl) imide. )
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| FR3002086A1 (en) * | 2013-02-13 | 2014-08-15 | Commissariat Energie Atomique | PROCESS FOR THE SYNTHESIS OF IONIC LIQUIDS WITH CARBONATE FUNCTIONAL GROUP AND IONIC LIQUIDS THUS OBTAINED |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102008021271A1 (en) * | 2008-04-29 | 2010-01-28 | Merck Patent Gmbh | Reactive ionic liquids |
| JP2012116802A (en) * | 2010-12-02 | 2012-06-21 | Nitto Boseki Co Ltd | Ionic liquid and production method of the same |
| CN103130777A (en) * | 2011-12-01 | 2013-06-05 | 海洋王照明科技股份有限公司 | Pyridines ionic liquid containing carbonic ester group and preparation method and application thereof |
| CN103130764A (en) * | 2011-12-01 | 2013-06-05 | 海洋王照明科技股份有限公司 | Quaternary ammonium salt ionic liquid containing carbonic ester group and preparation method and application thereof |
| CN103130778B (en) * | 2011-12-01 | 2016-02-10 | 海洋王照明科技股份有限公司 | Pyrazine ionic liquid of carbonate-containing group and its preparation method and application |
| CN103130776A (en) * | 2011-12-01 | 2013-06-05 | 海洋王照明科技股份有限公司 | Imidazoles ionic liquid containing carbonic ester perssad and preparation method and application thereof |
| CN103130779B (en) * | 2011-12-01 | 2015-08-05 | 海洋王照明科技股份有限公司 | Maleimide ionic liquid of carbonate-containing group and its preparation method and application |
| CN103130783B (en) * | 2011-12-01 | 2016-04-13 | 海洋王照明科技股份有限公司 | Tetramethylene sulfide class ionic liquid of carbonate-containing group and its preparation method and application |
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| JP2001035253A (en) * | 1999-07-19 | 2001-02-09 | Fuji Photo Film Co Ltd | Electrolyte composition, photoelectric transfer element and photo-electrochemical battery |
| JP5081345B2 (en) * | 2000-06-13 | 2012-11-28 | 富士フイルム株式会社 | Method for manufacturing photoelectric conversion element |
| JP4637334B2 (en) * | 2000-08-29 | 2011-02-23 | 富士フイルム株式会社 | Electrolyte composition and electrochemical cell |
| JP4240263B2 (en) * | 2000-12-22 | 2009-03-18 | 富士フイルム株式会社 | Electrolyte composition and non-aqueous electrolyte secondary battery |
| JP2003201272A (en) * | 2001-07-31 | 2003-07-18 | Tokuyama Corp | Onium salt |
| EP1595863B1 (en) * | 2003-02-13 | 2010-12-29 | Koei Chemical Co., Ltd. | Quaternary ammonium salts |
| JP2004262897A (en) * | 2003-03-04 | 2004-09-24 | Tosoh Corp | Quaternary ammonium room temperature molten salt and method for producing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3002086A1 (en) * | 2013-02-13 | 2014-08-15 | Commissariat Energie Atomique | PROCESS FOR THE SYNTHESIS OF IONIC LIQUIDS WITH CARBONATE FUNCTIONAL GROUP AND IONIC LIQUIDS THUS OBTAINED |
| WO2014124892A1 (en) * | 2013-02-13 | 2014-08-21 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for synthesising ionic liquids having a carbonate functional group and resulting ionic liquids. |
| US10026993B2 (en) | 2013-02-13 | 2018-07-17 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for synthesizing ionic liquids having a carbonate functional group and ionic liquids thus obtained |
Also Published As
| Publication number | Publication date |
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| JPWO2005027157A1 (en) | 2006-11-24 |
| WO2005027157A3 (en) | 2005-05-06 |
| WO2005027157A2 (en) | 2005-03-24 |
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