WO2009136608A1 - Ionic liquid - Google Patents

Ionic liquid Download PDF

Info

Publication number
WO2009136608A1
WO2009136608A1 PCT/JP2009/058579 JP2009058579W WO2009136608A1 WO 2009136608 A1 WO2009136608 A1 WO 2009136608A1 JP 2009058579 W JP2009058579 W JP 2009058579W WO 2009136608 A1 WO2009136608 A1 WO 2009136608A1
Authority
WO
WIPO (PCT)
Prior art keywords
fta
ionic liquid
fsa
found
anal calcd
Prior art date
Application number
PCT/JP2009/058579
Other languages
French (fr)
Japanese (ja)
Inventor
松本　一
寺澤　直弘
栄部　比夏里
誠二 都築
Original Assignee
独立行政法人産業技術総合研究所
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 独立行政法人産業技術総合研究所 filed Critical 独立行政法人産業技術総合研究所
Priority to JP2010511070A priority Critical patent/JP5339542B2/en
Priority to US12/991,817 priority patent/US20110070486A1/en
Publication of WO2009136608A1 publication Critical patent/WO2009136608A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/002—Inorganic electrolyte
    • H01M2300/0022—Room temperature molten salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to an ionic liquid, and particularly relates to an ionic liquid having a low viscosity, a low melting point, and a high conductivity.
  • Ionic liquids have been special in recent years due to their potential applications as electrolytes, reaction media, and catalysts for organic synthesis for various electrochemical devices such as lithium secondary batteries, dye-sensitized solar cells, actuators and electric double layer capacitors. Has attracted a lot of attention. Compared to conventional organic liquid electrolytes, the main advantages of ionic liquids as electrolytes are non-flammability, non-volatility and high thermal stability.
  • the anion of the ionic liquid is bistrifluoromethylsulfonylamide (* conventionally the same as what is called bistrifluoromethylsulfonylimide, TFSI, but in recent years, Since it is recommended by IUPAC to call it amide, it is referred to as amide in this patent.) ([(CF 3 SO 2 ) 2 N] ⁇ ; [TFSA] ⁇ ) and tetrafluoroborate (BF 4 ⁇ ) has attracted attention because of its high electrochemical stability and thermal stability (Patent Documents 1 and 2).
  • Patent Document 4 discloses a salt containing fluorosulfonyl (trifluoromethylsulfonylamide) (FTA), but there is no disclosure of the melting point of the salt obtained in the examples, and this salt is an ionic liquid. Has not been demonstrated.
  • An object of the present invention is to provide an ionic liquid having a low viscosity, a low melting point, high conductivity, and high thermal stability.
  • an ionic liquid composed of a fluorosulfonyl (trifluoromethylsulfonylamide) (FTA) anion and a specific cation having a low viscosity, a low melting point, and a high conductivity at a low temperature. And it discovered that it had comparatively high thermal stability.
  • FFA fluorosulfonyl (trifluoromethylsulfonylamide)
  • An ionic liquid comprising a fluorosulfonyl (trifluoromethylsulfonylamide) (FTA) anion and one of the following cations: Tetramethylammonium (N1111); Ethyltrimethylammonium (N1112); n-propyltrimethylammonium (N1113); Diethyldimethylammonium (N1122); Di-n-propyldimethylammonium (N1133); Triethylmethylammonium (N2221); n-butyldiethylmethylammonium (N1224); N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (DEME); Tetraethylammonium (N2222); Tetra n-propylammonium (N3333); Tetra n-butylammonium (N4444); Tetra n-pent
  • Item 2. The ionic liquid according to Item 1, wherein the cation is tetraethylammonium (N2222) or triethylmethylammonium (N2221).
  • Item 3. Item 2. The ionic liquid according to Item 1, wherein the cation is tetramethylammonium (N1111), ethyltrimethylammonium (N1112), or n-propyltrimethylammonium (N1113).
  • Item 4. Item 2. The ionic liquid according to Item 1, wherein the cation is N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (DEME).
  • Item 4. The ionic liquid according to Item 1, wherein the cation is N-methyl-N-propyl-piperidinium (PP13).
  • Item 7. Item 4. The ionic liquid according to Item 1, wherein the cation is 5-azoniaspiro [4.4] nonane (AS44).
  • the ionic liquid of the present invention is suitable as an electrochemical device such as a lithium secondary battery, a fuel cell, a dye-sensitized solar cell, and an electric double layer capacitor, a solvent for chemical reaction, and a lubricating oil.
  • the melting point of the ionic liquid provided by the present invention is 120 ° C. or less, preferably 80 ° C. or less, more preferably 50 ° C. or less, further preferably 25 ° C. or less, particularly preferably 0 ° C. or less, and most preferably ⁇ 20 ° C. or less. It is.
  • an ionic liquid of 80 ° C. or lower can be widely used.
  • an energy device such as a solar cell, a lithium battery, or a capacitor
  • an electrochemical device such as an electrochromic device or an electrochemical sensor
  • the melting point of the ionic liquid is preferably room temperature (25 ° C.) or less, more preferably 0 ° C. or less. preferable.
  • the glass transition temperature is ⁇ 70 ° C. or lower, preferably ⁇ 80 ° C. or lower, more preferably ⁇ 90 ° C. or lower, still more preferably. If the temperature is ⁇ 100 ° C. or lower, the ionic liquid can be treated in the same manner as an ionic liquid having the melting point at the same temperature.
  • the present invention uses fluorosulfonyl (trifluoromethylsulfonylamide) (FTA; [(FSO 2 ) (CF 3 SO 2 ) N] ⁇ ) as an anionic component of an ionic liquid.
  • FTA fluorosulfonyl (trifluoromethylsulfonylamide)
  • anionic component of an ionic liquid is a known compound and can be produced, for example, according to Patent Document 3.
  • FTA [(FSO 2 ) (CF 3 SO 2 ) N] -
  • alkali metal ions Na + , K + , Li + , Cs + etc.
  • alkaline earth metal ions Ca 2+ , Mg 2+ , Ba 2+ etc.
  • H + , Bu 3 Sn + and other salt components are mixed with the salt containing the specific cation of the present invention to separate the ionic liquid of the present invention Can be manufactured.
  • a salt of FTA ([(FSO 2 ) (CF 3 SO 2 ) N] ⁇ ) H + obtained by passing through an ion exchange resin and a salt of (any cation of the present invention) + (OH) ⁇
  • an ionic liquid composed of FTA and the cation of the present invention can be preferably obtained.
  • the salt exchange reaction for obtaining the ionic liquid can be performed by a solvent extraction method when a desired molten salt can be extracted.
  • the cation component of the ionic liquid of the present invention is selected from the following cations: Tetramethylammonium (N1111); Ethyltrimethylammonium (N1112); n-propyltrimethylammonium (N1113); Diethyldimethylammonium (N1122); Di-n-propyldimethylammonium (N1133); Triethylmethylammonium (N2221); n-butyldiethylmethylammonium (N1224); N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (DEME); Tetraethylammonium (N2222); Tetra n-propylammonium (N3333); Tetra n-butylammonium (N4444); Tetra n-pentylammonium (N5555); 5-Azonia Spiro [4.4] Nonane (AS44) Dimethylimidazole (DMI) Prop
  • the molecular weight of FTA is intermediate between TFSA ([(CF 3 SO 2 ) 2 N] ⁇ ) and FSA ([(FSO 2 ) 2 N] ⁇ ), which are symmetrical anions. Therefore, viscosity, conductivity, diffusion coefficient, etc. are also expected to have intermediate properties between TFSA and FSA, but with regard to melting point, FTA anion has an asymmetric structure and is expected to decrease more dramatically.
  • the ionic liquid has a thermal stability generally higher than that of FSA.
  • the present inventors have confirmed that the FTA anion used in the present invention has high electrochemical stability comparable to that of conventional anions.
  • the formation of a liquid with a cation (N2222) indicates that the amide salt exhibits the highest oxidative stability to date.
  • 25 kinds of cationic components used in the present invention (N1111, N1112, N1113, N1122, N1133, N2221, N1224, DEME, N2222, N3333, N4444, N5555, AS44, DMI, PMI, BMI, Py11, Py12, Py14, PP11 , PP12, PP13, PP14, P2222, PS44) may be used alone, but by combining two or more cations, the melting point of the ionic liquid can be further lowered and the viscosity can be further lowered. It is.
  • FTA is used as the anion of the ionic liquid, but other anions can be blended as long as FTA is the main component.
  • Viscosity Viscosity was measured using a viscometer (Brookfield model DV-III +) with a 0.6 mL sample at 25 ° C.
  • DSC Differential Scanning Calorimeter
  • the FTA ionic liquid that is unnecessary in the water is extracted with dichloromethane, washed several times with water, and then the dichloromethane is distilled off. Obtained.
  • An ionic liquid composed of a salt of FTA and EMI (1-ethyl-3-methylimidazolium) was prepared in the same manner as described above.
  • N2222 [FSA] MS m / z (%) 130 (100) [N2222] + , 180 (100) [FSA] - ; Anal Calcd. For C 8 H 20 N 2 F 2 O 4 S 2 : C, 31.0; H, 6.5; N, 9.0; F, 12.2; Found: C, 30.8; H, 6.4; N, 9.0; F, 12.2.
  • N1111 [FSA] MS m / z (%) 74 (100) [N1111] + , 180 (100) [FSA] - ; Anal Calcd.
  • N4444 [FSA] MS m / z (%) 242 (100) [N4444] + , 180 (100) [FSA] - ; Anal Calcd. For C 16 H 36 N 2 F 2 O 4 S 2 : C, 45.5; H, 8.6; N, 6.6; F, 9.0; Found: C, 45.2; H, 8.7; N, 6.6; F, 9.1.
  • N3333 [FSA] MS m / z (%) 186 (100) [N3333] + , 180 (100) [FSA] - ; Anal Calcd.
  • N1133 [FSA] MS m / z (%) 130 (100) [N1133] + , 180 (100) [FSA] - ;
  • Anal Calcd.for C 8 H 20 N 2 F 2 O 4 S 2 C, 31.0; H, 6.5; N, 9.0; F, 12.2; Found: C, 30.7; H, 6.2; N, 9.0; F, 12.2 .
  • N1133 [TFSA] MS m / z (%) 130 (100) [N1133] + , 280 (100) [FSA] - ; Anal Calcd.
  • PS44 [FSA] MS m / z (%) 143 (100) [PS44] + , 180 (100) [FSA] - ;
  • Anal Calcd. For C 8 H 16 NPF 2 O 4 S 2 : C, 29.7; H, 5.0; N, 4.4; F, 11.8; Found: C, 29.7; H, 4.8; N, 4.3; F, 11.5.
  • PS44 [TFSA] MS m / z (%) 143 (100) [PS44] + , 280 (100) [TFSA] - ; Anal Calcd.
  • For C 10 H 16 NPF 6 O 4 S 2 C, 28.4; H, 3.8; N, 3.3; F, 26.5; Found: C, 28.5; H, 3.7; N, 3.4; F, 26.9.
  • Tables 1 to 6 show the melting points, electrical conductivity, glass transition point, thermal decomposition temperature, viscosity, and density of the compounds obtained in the above Examples and Comparative Examples.
  • FIG. 1 shows the measurement results of the potential windows of N2222 [FTA], N122.1O2 [FTA], EMI [FTA], and AS44 [FTA].
  • N122.1O2 [FTA] is DEME [FTA].
  • N2222 can be used as the cation species, and the oxidation limit potential is the most positive potential in the conventional amide anion system.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Hybrid Cells (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed is an ionic liquid having a low viscosity, a low melting point, high electrical conductivity and high thermal stability.  The ionic liquid is composed of fluorosulfonyl(trifluoromethylsulfonylamide) (FTA) anions and cations of N1111, N1112, N1113, N1122, N1133, N2221, N1224, DEME, N2222, N3333, N4444, N5555, AS44, DMI, PMI, BMI, Py11, Py12, Py14, PP11, PP12, PP13, PP14, P2222 or PS44.

Description

イオン液体Ionic liquid
　本発明は、イオン液体に関し、詳しくは低粘度及び低融点かつ高い導電性を有するイオン液体に関する。 The present invention relates to an ionic liquid, and particularly relates to an ionic liquid having a low viscosity, a low melting point, and a high conductivity.
　イオン液体は、リチウム二次電池、色素増感太陽電池、アクチュエータ及び電気二重層キャパシタなどの各種電気化学デバイス用の電解質、反応媒体、有機合成の触媒としての応用可能性のためにここ数年特別な注目を集めてきた。従来の有機液体電解質と比較して、イオン液体の電解質としての主な利点は、不燃性、不揮発性及び高い熱安定性である。現在までに報告されているほとんどのイオン液体において、イオン液体のアニオンとしては、ビストリフルオロメチルスルホニルアミド(※従来はビストリフルオロメチルスルホニルイミド、TFSIと呼ばれているものと同じであるが、近年はアミドと呼ぶことがIUPACより推奨されているため本特許ではアミドとする。)([(CF3SO2)2N]-; [TFSA]-と略す。)とテトラフルオロボレート(BF4 -)がその高い電気化学的安定性及び熱安定性のために注目されている（特許文献１，２）。特に[TFSA]-塩は脂肪族四級アンモニウム等の電荷の分散性が低いためイオン液体になりにくいカチオン種においても容易にイオン液体を形成し、かつその電気化学安定性が従来のイミダゾリウム塩にくらべて高い（特許文献３）ため、リチウムの電析が可能となる一方、Li/LiCoO2セル等に適用した場合にあまり高い充放電電流密度での充放電が不可能であった。一方、近年、同じアミド系アニオンである、ビスフルオロメチルスルホニルアミド（[(FSO2)2N]-;[FSA]-）が優れた基礎物性並びに電池特性を示す事が報告されたが、そのリチウム塩（非特許文献１）やイオン液体の熱安定性が低い（非特許文献２）ことから、より熱分解温度が高く優れた電池特性を示すイオン液体が求められている。 Ionic liquids have been special in recent years due to their potential applications as electrolytes, reaction media, and catalysts for organic synthesis for various electrochemical devices such as lithium secondary batteries, dye-sensitized solar cells, actuators and electric double layer capacitors. Has attracted a lot of attention. Compared to conventional organic liquid electrolytes, the main advantages of ionic liquids as electrolytes are non-flammability, non-volatility and high thermal stability. In most ionic liquids reported to date, the anion of the ionic liquid is bistrifluoromethylsulfonylamide (* conventionally the same as what is called bistrifluoromethylsulfonylimide, TFSI, but in recent years, Since it is recommended by IUPAC to call it amide, it is referred to as amide in this patent.) ([(CF 3 SO 2 ) 2 N] − ; [TFSA] − ) and tetrafluoroborate (BF 4 − ) Has attracted attention because of its high electrochemical stability and thermal stability (Patent Documents 1 and 2). In particular [TFSA] - salts also readily form ionic liquids in dispersion is difficult cationic species becomes an ionic liquid for lower charge such as aliphatic quaternary ammonium, and its electrochemical stability is conventional imidazolium salt Since it is higher than that (Patent Document 3), it is possible to deposit lithium. On the other hand, when applied to a Li / LiCoO 2 cell or the like, charging / discharging at a very high charging / discharging current density was impossible. On the other hand, bisfluoromethylsulfonylamide ([(FSO 2 ) 2 N] − ; [FSA] − ), which is the same amide anion, has recently been reported to show excellent basic properties and battery characteristics. Due to the low thermal stability of lithium salts (Non-Patent Document 1) and ionic liquids (Non-Patent Document 2), ionic liquids having higher thermal decomposition temperatures and excellent battery characteristics are required.
　特許文献４には、フルオロスルホニル(トリフルオロメチルスルホニルアミド)(FTA)を含む塩が開示されているが、実施例で得られた塩の融点の開示はなく、この塩がイオン液体であることは実証されていない。 Patent Document 4 discloses a salt containing fluorosulfonyl (trifluoromethylsulfonylamide) (FTA), but there is no disclosure of the melting point of the salt obtained in the examples, and this salt is an ionic liquid. Has not been demonstrated.
特開2002-099001号公報JP 2002-099001 A 特開2003-331918号公報JP 2003-331918 A 特許第2981545号Patent No. 2981545 特開2005-200359号公報JP 2005-200359 A
　本発明は、低粘度及び低融点、高導電性かつ熱安定性の高いイオン液体を提供することを目的とする。 An object of the present invention is to provide an ionic liquid having a low viscosity, a low melting point, high conductivity, and high thermal stability.
　本発明者は、上記課題に鑑み検討を重ねた結果、フルオロスルホニル(トリフルオロメチルスルホニルアミド)(FTA)アニオンと特定のカチオンからなるイオン液体が、低粘度、低融点、低温での高い導電性かつ、比較的高い熱安定性を有することを見出した。 As a result of repeated investigations in view of the above problems, the present inventor has obtained an ionic liquid composed of a fluorosulfonyl (trifluoromethylsulfonylamide) (FTA) anion and a specific cation having a low viscosity, a low melting point, and a high conductivity at a low temperature. And it discovered that it had comparatively high thermal stability.
　即ち、本発明は、以下のイオン液体を提供するものである。
項１．　フルオロスルホニル(トリフルオロメチルスルホニルアミド)(FTA)アニオンと、以下のいずれかのカチオンからなるイオン液体：
テトラメチルアンモニウム（N1111）；
エチルトリメチルアンモニウム（N1112）；
n-プロピルトリメチルアンモニウム（N1113）；
ジエチルジメチルアンモニウム（N1122）；
ジn-プロピルジメチルアンモニウム（N1133）；
トリエチルメチルアンモニウム（N2221）；
n-ブチルジエチルメチルアンモニウム（N1224）；
N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウム(DEME)；
テトラエチルアンモニウム（N2222）；
テトラn-プロピルアンモニウム（N3333）;
テトラn-ブチルアンモニウム（N4444）；
テトラn-ペンチルアンモニウム（N5555）；
5-アゾニアスピロ[4.4]ノナン(AS44)
ジメチルイミダゾール(DMI)
プロピルメチルイミダゾール(PMI)
ブチルメチルイミダゾール(BMI)
N,N-ジメチルピロリジニウム(Py11)
N-メチル-N-エチルピロリジニウム(Py12)
N-メチル-N-ブチルピロリジニウム(Py14)
N,N-ジメチル-ピペリジニウム(PP11)
N-メチル-N-エチル-ピペリジニウム(PP12)
N-メチル-N-プロピル-ピペリジニウム(PP13)
N-メチル-N-ブチル-ピペリジニウム(PP14) 
テトラエチルホスホニウム（Ｐ2222）；または
5-フォスフォニアスピロ[4.4]ノナン(PS44)  
項２．　カチオンがテトラエチルアンモニウム（N2222）またはトリエチルメチルアンモニウム（N2221）である項１に記載のイオン液体。
項３．　カチオンがテトラメチルアンモニウム（N1111）、エチルトリメチルアンモニウム（N1112）、またはn-プロピルトリメチルアンモニウム（N1113）である項１に記載のイオン液体。
項４．　カチオンがN,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウム(DEME)である項１に記載のイオン液体。
項５．　カチオンがテトラエチルホスホニウム（Ｐ2222）である項１に記載のイオン液体。
項６．　カチオンがN-メチル-N-プロピル-ピペリジニウム(PP13)である項１に記載のイオン液体。
項７．　カチオンが5-アゾニアスピロ[4.4]ノナン(AS44)である項１に記載のイオン液体。 That is, the present invention provides the following ionic liquid.
Item 1. An ionic liquid comprising a fluorosulfonyl (trifluoromethylsulfonylamide) (FTA) anion and one of the following cations:
Tetramethylammonium (N1111);
Ethyltrimethylammonium (N1112);
n-propyltrimethylammonium (N1113);
Diethyldimethylammonium (N1122);
Di-n-propyldimethylammonium (N1133);
Triethylmethylammonium (N2221);
n-butyldiethylmethylammonium (N1224);
N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (DEME);
Tetraethylammonium (N2222);
Tetra n-propylammonium (N3333);
Tetra n-butylammonium (N4444);
Tetra n-pentylammonium (N5555);
5-Azonia Spiro [4.4] Nonane (AS44)
Dimethylimidazole (DMI)
Propylmethylimidazole (PMI)
Butylmethylimidazole (BMI)
N, N-dimethylpyrrolidinium (Py11)
N-methyl-N-ethylpyrrolidinium (Py12)
N-methyl-N-butylpyrrolidinium (Py14)
N, N-dimethyl-piperidinium (PP11)
N-methyl-N-ethyl-piperidinium (PP12)
N-methyl-N-propyl-piperidinium (PP13)
N-methyl-N-butyl-piperidinium (PP14)
Tetraethylphosphonium (P2222); or
5-Phosphonia Spiro [4.4] Nonane (PS44)
Item 2. Item 2. The ionic liquid according to Item 1, wherein the cation is tetraethylammonium (N2222) or triethylmethylammonium (N2221).
Item 3. Item 2. The ionic liquid according to Item 1, wherein the cation is tetramethylammonium (N1111), ethyltrimethylammonium (N1112), or n-propyltrimethylammonium (N1113).
Item 4. Item 2. The ionic liquid according to Item 1, wherein the cation is N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (DEME).
Item 5. Item 2. The ionic liquid according to Item 1, wherein the cation is tetraethylphosphonium (P2222).
Item 6. Item 4. The ionic liquid according to Item 1, wherein the cation is N-methyl-N-propyl-piperidinium (PP13).
Item 7. Item 4. The ionic liquid according to Item 1, wherein the cation is 5-azoniaspiro [4.4] nonane (AS44).
　本発明のイオン液体は、リチウム二次電池、燃料電池、色素増感太陽電池、電気二重層キャパシタ等の電気化学デバイス、化学反応の溶剤、潤滑油として適している。 The ionic liquid of the present invention is suitable as an electrochemical device such as a lithium secondary battery, a fuel cell, a dye-sensitized solar cell, and an electric double layer capacitor, a solvent for chemical reaction, and a lubricating oil.
　本発明で使用するカチオンの構造を概略的に以下に示す：  The structure of the cation used in the present invention is schematically shown below:
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　本発明で使用するアニオンと比較対照のアニオンの構造を以下に示す。 The structures of anions used in the present invention and comparative anions are shown below.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　本発明により提供されるイオン液体の融点は、１２０℃以下、好ましくは８０℃以下、より好ましくは５０℃以下、さらに好ましくは２５℃以下、特に好ましくは０℃以下、最も好ましくは－２０℃以下である。例えば燃料電池に使用する場合には８０℃以下のイオン液体を広く使用することができる。一方、太陽電池、リチウム電池、キャパシタなどのエネルギーデバイス、エレクトロクロミックデバイス、電気化学センサーなどの電気化学デバイスではイオン液体の融点は室温（２５℃）以下が好ましく、特に０℃以下であるのがさらに好ましい。 The melting point of the ionic liquid provided by the present invention is 120 ° C. or less, preferably 80 ° C. or less, more preferably 50 ° C. or less, further preferably 25 ° C. or less, particularly preferably 0 ° C. or less, and most preferably −20 ° C. or less. It is. For example, when used for a fuel cell, an ionic liquid of 80 ° C. or lower can be widely used. On the other hand, in an energy device such as a solar cell, a lithium battery, or a capacitor, an electrochemical device such as an electrochromic device or an electrochemical sensor, the melting point of the ionic liquid is preferably room temperature (25 ° C.) or less, more preferably 0 ° C. or less. preferable.
　なお、本発明で使用するイオン液体において、融点を明確に観測できない場合であっても、ガラス転移温度が、－７０℃以下、好ましくは－８０℃以下、より好ましくは－９０℃以下、更に好ましくは－１００℃以下であれば、該イオン液体は同温度の融点を示すイオン液体と同様に扱う事ができるものである。 In the ionic liquid used in the present invention, even when the melting point cannot be clearly observed, the glass transition temperature is −70 ° C. or lower, preferably −80 ° C. or lower, more preferably −90 ° C. or lower, still more preferably. If the temperature is −100 ° C. or lower, the ionic liquid can be treated in the same manner as an ionic liquid having the melting point at the same temperature.
　本発明は、イオン液体のアニオン成分としてフルオロスルホニル(トリフルオロメチルスルホニルアミド)(FTA；[(FSO2)(CF3SO2)N]-)を使用する。該アニオンは公知化合物であり、例えば特許文献３に従い製造することができる。 The present invention uses fluorosulfonyl (trifluoromethylsulfonylamide) (FTA; [(FSO 2 ) (CF 3 SO 2 ) N] − ) as an anionic component of an ionic liquid. The anion is a known compound and can be produced, for example, according to Patent Document 3.
　イオン液体を製造する場合、FTA ([(FSO2)(CF3SO2)N]-）とアルカリ金属イオン（Na+, K+, Li+, Cs+など）、アルカリ土類金属イオン（Ca2+, Mg2+,Ba2+など）、H+, Bu3Sn＋などのカチオン成分との塩を本発明の特定のカチオンを含む塩と混合し、本発明のイオン液体を分離することにより製造できる。例えば、イオン交換樹脂を通すことにより得られるFTA([(FSO2)(CF3SO2)N]-）H+の塩と、(本発明のいずれかのカチオン)＋(OH)－の塩を混合し、水を除くことにより、FTAと本発明のカチオンからなるイオン液体を好ましく得ることができる。イオン液体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る。 When producing ionic liquids, FTA ([(FSO 2 ) (CF 3 SO 2 ) N] - ) and alkali metal ions (Na + , K + , Li + , Cs + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ , Ba 2+ etc.), H + , Bu 3 Sn + and other salt components are mixed with the salt containing the specific cation of the present invention to separate the ionic liquid of the present invention Can be manufactured. For example, a salt of FTA ([(FSO 2 ) (CF 3 SO 2 ) N] − ) H + obtained by passing through an ion exchange resin and a salt of (any cation of the present invention) + (OH) − By mixing and removing water, an ionic liquid composed of FTA and the cation of the present invention can be preferably obtained. The salt exchange reaction for obtaining the ionic liquid can be performed by a solvent extraction method when a desired molten salt can be extracted.
　本発明のイオン液体のカチオン成分は、以下のカチオンから選ばれる：
テトラメチルアンモニウム（N1111）；
エチルトリメチルアンモニウム（N1112）；
n-プロピルトリメチルアンモニウム（N1113）；
ジエチルジメチルアンモニウム（N1122）；
ジn-プロピルジメチルアンモニウム（N1133）；
トリエチルメチルアンモニウム（N2221）；
n-ブチルジエチルメチルアンモニウム（N1224）；
N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウム(DEME)；
テトラエチルアンモニウム（N2222）；
テトラn-プロピルアンモニウム（N3333）;
テトラn-ブチルアンモニウム（N4444）；
テトラn-ペンチルアンモニウム（N5555）；
５-アゾニアスピロ[4.4]ノナン(AS44)
ジメチルイミダゾール(DMI)
プロピルメチルイミダゾール(PMI)
ブチルメチルイミダゾール(BMI)
N,N-ジメチルピロリジニウム(Py11)
N-メチル-N-エチルピロリジニウム(Py12)
N-メチル-N-ブチルピロリジニウム(Py14)
N,N-ジメチル-ピペリジニウム(PP11)
N-メチル-N-エチル-ピペリジニウム(PP12)
N-メチル-N-プロピル-ピペリジニウム(PP13)
N-メチル-N-ブチル-ピペリジニウム(PP14) 
テトラエチルホスホニウム（Ｐ2222）；または
５-フォスフォニアスピロ[4.4]ノナン(PS44)。 The cation component of the ionic liquid of the present invention is selected from the following cations:
Tetramethylammonium (N1111);
Ethyltrimethylammonium (N1112);
n-propyltrimethylammonium (N1113);
Diethyldimethylammonium (N1122);
Di-n-propyldimethylammonium (N1133);
Triethylmethylammonium (N2221);
n-butyldiethylmethylammonium (N1224);
N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (DEME);
Tetraethylammonium (N2222);
Tetra n-propylammonium (N3333);
Tetra n-butylammonium (N4444);
Tetra n-pentylammonium (N5555);
5-Azonia Spiro [4.4] Nonane (AS44)
Dimethylimidazole (DMI)
Propylmethylimidazole (PMI)
Butylmethylimidazole (BMI)
N, N-dimethylpyrrolidinium (Py11)
N-methyl-N-ethylpyrrolidinium (Py12)
N-methyl-N-butylpyrrolidinium (Py14)
N, N-dimethyl-piperidinium (PP11)
N-methyl-N-ethyl-piperidinium (PP12)
N-methyl-N-propyl-piperidinium (PP13)
N-methyl-N-butyl-piperidinium (PP14)
Tetraethylphosphonium (P2222); or 5-phosphonia spiro [4.4] nonane (PS44).
　これらのカチオンは、すべて公知であり、公知の方法によって製造でき、または入手可能である。 These cations are all known and can be produced or obtained by known methods.
　本発明で使用するアニオンであるFTAの分子量は、対称構造を有するアニオンであるTFSA（[(CF3SO2)2N]－）とFSA（[(FSO2)2N]―）の中間であるので、粘度や伝導率、拡散係数等も、TFSAとFSAの中間的な物性を有すると予測されるが、融点に関しては、FTAアニオンは非対称構造を有するためより劇的に低下することが期待され、特に本発明による特定のカチオンと組み合わせた場合では予想以上に低くなり、さらに導電率は、TFSAとFSAの中間よりもFSA塩に近い値となり、さらにFSAの欠点であった熱安定性についても、概ねFSAよりも高い熱安定性を兼ね備えたイオン液体になることが、本発明により見出された。 The molecular weight of FTA, an anion used in the present invention, is intermediate between TFSA ([(CF 3 SO 2 ) 2 N] − ) and FSA ([(FSO 2 ) 2 N] − ), which are symmetrical anions. Therefore, viscosity, conductivity, diffusion coefficient, etc. are also expected to have intermediate properties between TFSA and FSA, but with regard to melting point, FTA anion has an asymmetric structure and is expected to decrease more dramatically. Especially when combined with the specific cation according to the present invention, it is lower than expected, and the conductivity is closer to the FSA salt than the middle of TFSA and FSA, and the thermal stability that was a drawback of FSA However, it has been found by the present invention that the ionic liquid has a thermal stability generally higher than that of FSA.
　本発明で使用するFTAアニオンは従来アニオンに匹敵する高い電気化学安定性を備えている事を、本発明者は確認した。高い対称性を有しその塩が一般的に高い融点を示すN2222,AS44,及びPS44を含むイオン液体は、本発明により初めて得られており、このように従来イオン液体の製造が不可能であったカチオン（N2222）で液体になることは、これまででもっとも高い酸化安定性を示すアミド塩であることを示すものである。 The present inventors have confirmed that the FTA anion used in the present invention has high electrochemical stability comparable to that of conventional anions. An ionic liquid containing N2222, AS44, and PS44, which has a high symmetry and whose salt generally has a high melting point, has been obtained for the first time by the present invention, and thus it has been impossible to produce a conventional ionic liquid. The formation of a liquid with a cation (N2222) indicates that the amide salt exhibits the highest oxidative stability to date.
　本発明で使用する２５種のカチオン成分（N1111、N1112、N1113、N1122、N1133、N2221、N1224、DEME、N2222、N3333、N4444、N5555、AS44、DMI、PMI、BMI、Py11、Py12、Py14、PP11、PP12、PP13、PP14、Ｐ2222、PS44）は、１種のみを使用してもよいが、２種以上のカチオンを組み合わせることで、さらにイオン液体の融点を低下させ、さらに粘度を下げることが可能である。 25 kinds of cationic components used in the present invention (N1111, N1112, N1113, N1122, N1133, N2221, N1224, DEME, N2222, N3333, N4444, N5555, AS44, DMI, PMI, BMI, Py11, Py12, Py14, PP11 , PP12, PP13, PP14, P2222, PS44) may be used alone, but by combining two or more cations, the melting point of the ionic liquid can be further lowered and the viscosity can be further lowered. It is.
　また、イオン液体のアニオンとしては、FTAを使用するが、FTAが主成分である限り、他のアニオンを配合することもできる。 Also, FTA is used as the anion of the ionic liquid, but other anions can be blended as long as FTA is the main component.
　以下、本発明を実施例に基づきより詳細に説明する。 Hereinafter, the present invention will be described in more detail based on examples.
方法
　化合物の同定について、JEOL ECA-500 FT-NMRスペクトロメータを用いて、1H NMR (500.2MHz), 19F NMR (470.6 MHz)及び11B NMR (160.5MHz)スペクトルを測定した。JEOL JMS-HX110/110A  スペクトロメーターを用いて、FAB-MSスペクトルを測定した。
密度: イオン液体の密度は、25℃で1.0 mL のイオン液体の重量を３回測定することにより決定した。
比導電率：ニート(無溶媒)のイオン液体のイオン導電率(κ)は、密閉導電セル中で、導電率計(Radiometer Analytical, model CDM230)を用いて測定した。
粘度：粘度は、25℃で0.6 mLのサンプルを使用して粘度計(Brookfield model DV-III＋)を用いて測定した。 
熱重量分析(TGA): TGAは熱分析システム(Seiko Instruments, TG/DTA 6200)を用いて行った。5mgの平均重量サンプルをプラチナパンに配置し、窒素気流下に10℃/minの割合で約40～600℃に加熱した。分解の開始は、分解温度(Td)として定義した。
示差走査型熱量計(DSC):DSCは熱分析システム（Perkin/Elmer Pyris 1）に液体窒素冷却装置を接続し、-150℃から250℃の範囲内で、ヘリウム気流中10℃/minにて測定し、最も相転移温度を融点とした。室温以上の融点の場合は測定温度近辺での融解現象を目視にて確認した。
合成
　使用するすべての原材料は、市販品であり、さらに精製することなく使用した。化合物の合成は、参考文献１－３に記載の方法に従い行った。
K[CF 3 SO 2 NH]の合成
　無水MeOH (250 ml)中のCF3SO2NH2 (49.3 g, 0.33 mol) の撹拌溶液に、無水MeOH (150 ml)中のKOtBu (36.9 g, 0.33 mol)の溶液を滴下した。反応混合物を50℃で２時間撹拌した。0.02 Torrで24時間エバポレーション後、白色固体を得た(60.53 g, 96.4 ％)。19F NMR (D2O, CFCl3, 470.6 MHz) δ -78.0 (s, 3F); MS m/z (%) 149 (100) [CF3SO2NH]-; Anal Calcd. for CF3O2SNK: C, 6.4; H, 0.5; N, 7.5; Found : C, 6.3; H, 0.7; N, 7.7.
K[CF 3 SO 2 NSO 2 F]の合成
　無水 Et2O (980 ml)中のK[CF3SO2NH] (60.0 g, 0.32 mol)の撹拌溶液に(FSO2)2O1)(69.5 g, 0.38 mol)を-20℃で30分かけて滴下した。
　混合物を-20℃で３時間撹拌を続け、ろ過した。
　粗生成物(21.5 g)をMeOHで洗浄してろ過した。溶媒を真空で除去し、アセトン/CHCl3から再結晶して生成物を得た。19F NMR (CD3OD, CFCl3, 470.6 MHz) δ 56.8 (s, 1F), -78.0 (s, 3F); MS m/z (%) 230 (100) [CF3SO2NSO2F]-; Anal Calcd. for CF4O4S2NK: C,4.5; N, 5.2; Found : C, 4.3; N, 5.4.
　上記のFTAのカリウム塩と、各種のアンモニウムの臭化物を、当モル量混合することにより生じる水に不要なFTAイオン液体をジクロロメタンで抽出、数度の水洗浄の後、ジクロロメタンを留去することによって得た。

DEME[FTA](0.65 g, 80.3 ％) 
1H NMR (CD3OD, TMS, 500.2 MHz) δ 1.33 (m, 6H), 3.04 (s, 3H), 3.38 (s, 3H), 3.43(q, J = 7.3 Hz, 4H), 3.51 (t, J = 4.5 Hz, 2H), 3.78 (m, 2H); 19F NMR (CD3OD, CFCl3, 470.6 MHz) δ 56.6 (s, F), -78.2 (s, 3F); MS m/z (%) 146 (100) [DEME]+, 230(100) [FTA]-; Anal Calcd. for C9H20N2F4O5S2: C, 28.7; H, 5.4; N, 7.4; F, 20.2; Found : C, 28.8; H, 5.1; N, 7.5; F, 20.2; 

PP13[FTA] (2.30 g, 88.2 ％) 
1H NMR (CD3OD, TMS, 500.2 MHz) δ 1.02 (t, J= 7.3 Hz, 3H), 1.62-1.76 (m 2H), 1.77-1.84 (m 2H), 1.90 (m, 4H), 3.04 (s, 3H), 3.27-3.31(m, 2H), 3.35 (t, J = 5.8 Hz, 4H); 19F NMR (CD3OD, CFCl3, 470.6 MHz) δ 56.9 (s, F), -78.1 (s, 3F); MS m/z (%) 142 (100) [PP13]+, 230 (100) [FTA]-; Anal Calcd. for C10H20N2F4O4S2: C, 32.3; H, 5.4; N, 7.5; F, 20.4; Found : C, 32.4; H, 5.2; N, 7.6; F, 20.4

N1111[FTA] 
　CH3CN(10 ml)中のK[CF3SO2NSO2F](0.94 g, 3.5 mmol)の撹拌溶液にN1111Br (0.54 g,3.5 mmol)を室温で加えた。混合物をさらに3時間撹拌した。溶媒を留去後、白色固体をCH2Cl2に溶かし、濾別した。溶媒を真空下で除去した。得られた液体を80℃、0.02 Torrで24時間乾燥した。(1.06 g, 99.5 ％) 
1H NMR (CD3OD, TMS, 500.2 MHz) δ 3.19 (s, 12H); 19F NMR (CD3OD, CFCl3, 470.6 MHz) δ 56.6 (s, F), -78.2 (s, 3F); MS m/z (%) 74 (100) [N1111]+,230 (100) [FTA]-;Anal Calcd. for C5H12N2F4O4S2: C, 19.7; H, 4.0; N, 9.2; F, 25.0; Found : C, 19.9; H, 3.9; N, 9.3; F, 24.8.

N2221[FTA] 
MS m/z (%) 116 (100) [N2221]+,230 (100) [FTA]- Anal Calcd. for C8H18N2F4O4S2: C,27.7; H, 5.2; N, 8.1; F, 21.9; Found : C, 27.8; H, 5.2; N, 8.2; F, 21.9.

N1112[FTA] (0.51 g, 22.3 ％) 
1H NMR (CD3OD, TMS, 500.2 MHz) δ 1.39 (t, J = 7.5 Hz, 3H), 3.10 (s, 9H), 3.41 (q, J = 7.2 Hz, 2H); 19F NMR (CD3OD, CFCl3, 470.6 MHz) δ 56.6 (s, F), -78.1 (s, 3F); MS m/z (%) 88 (100) [N1112]+, 230 (100) [FTA]-; Anal Calcd. for C6H14N2F4O4S2: C, 22.6; H, 4.4; N, 8.8; F, 23.9; Found : C, 22.4; H, 4.4; N, 8.9; F, 24.0

N1113[FTA] (1.46 g, 62.9 ％) 
1H NMR (CD3OD, TMS, 500.2 MHz) δ1.02 (t, J = 7.3 Hz, 3H), 1.78-1.86 (m, 2H), 3.12 (s, 9H), 3.26-3.32 (m, 2H); 19F NMR (CD3OD, CFCl3, 470.6 MHz) δ 56.8 (s, F), -78.1 (s, 3F); MS m/z (%) 102 (100) [N1113]+, 230 (100) [CF3SO2NSO2F]-; Anal Calcd. for C7H16N2F4O4S2: C, 25.3; H, 4.9; N, 8.4; F, 22.9; Found : C, 25.5; H, 4.8; N, 8.5; F, 22.7.

N2222[FTA] (2.13 g, 84.4 ％) 
1H NMR (CD3OD, TMS, 500.2 MHz) δ 1.29 (t, J = 7.5 Hz, 12H), 3.29 (q, J = 7.2 Hz, 8H); 19F NMR (CD3OD, CFCl3, 470.6 MHz) δ 56.7 (s, F), -78.1 (s, 3F); MS m/z (%) 130 (100) [N2222]+,230 (100) [FTA]-; Anal Calcd. for C9H20N2F4O4S2: C, 30.0;H, 5.6; N, 7.8; F, 21.1; Found : C, 29.8; H, 5.5; N, 7.8; F, 21.1.

P2222[FTA] (2.38 g, 90.1 ％) 
1H NMR (CD3OD, TMS, 500.2 MHz) δ 1.22-1.28 (m, 12H), 2.21-2.28 (m 8H); 19F NMR (CD3OD, CFCl3, 470.6 MHz) δ 56.6 (s, F), -78.1 (s, 3F); MS m/z (%) 147 (100) [P2222]+,230 (100) [FTA]-; Anal Calcd. for C9H20NPF4O4S2: C, 28.7; H, 5.3; N, 3.7; F, 20.1; Found : C, 28.7; H, 5.2; N, 3.7; F, 19.7. For identification of the method compounds, 1 H NMR (500.2 MHz), 19 F NMR (470.6 MHz) and 11 B NMR (160.5 MHz) spectra were measured using a JEOL ECA-500 FT-NMR spectrometer. FAB-MS spectra were measured using a JEOL JMS-HX110 / 110A spectrometer.
Density: The density of the ionic liquid was determined by measuring 1.0 mL of ionic liquid three times at 25 ° C.
Specific conductivity : The ionic conductivity (κ) of neat (solvent-free) ionic liquid was measured using a conductivity meter (Radiometer Analytical, model CDM230) in a closed conductive cell.
Viscosity: Viscosity was measured using a viscometer (Brookfield model DV-III +) with a 0.6 mL sample at 25 ° C.
Thermogravimetric analysis (TGA): TGA was performed using a thermal analysis system (Seiko Instruments, TG / DTA 6200). A 5 mg average weight sample was placed in a platinum pan and heated to about 40-600 ° C. at a rate of 10 ° C./min under a nitrogen stream. The onset of decomposition was defined as the decomposition temperature (T d ).
Differential Scanning Calorimeter (DSC): DSC is connected to a thermal analysis system (Perkin / Elmer Pyris 1) with a liquid nitrogen cooler at -150 ° C to 250 ° C in a helium stream at 10 ° C / min. Measurement was made and the phase transition temperature was taken as the melting point. In the case of a melting point above room temperature, the melting phenomenon near the measurement temperature was visually confirmed.
All raw materials used for synthesis were commercial products and were used without further purification. The compound was synthesized according to the method described in Reference 1-3.
Synthesis of K [CF 3 SO 2 NH] A stirred solution of CF 3 SO 2 NH 2 (49.3 g, 0.33 mol) in anhydrous MeOH (250 ml) was added to KO t Bu (36.9 g in anhydrous MeOH (150 ml)). , 0.33 mol) was added dropwise. The reaction mixture was stirred at 50 ° C. for 2 hours. After evaporation at 0.02 Torr for 24 hours, a white solid was obtained (60.53 g, 96.4%). 19 F NMR (D 2 O, CFCl 3 , 470.6 MHz) δ -78.0 (s, 3F); MS m / z (%) 149 (100) [CF 3 SO 2 NH] - ; Anal Calcd. For CF 3 O 2 SNK: C, 6.4; H, 0.5; N, 7.5; Found: C, 6.3; H, 0.7; N, 7.7.
Synthesis of K [CF 3 SO 2 NSO 2 F] To a stirred solution of K [CF 3 SO 2 NH] (60.0 g, 0.32 mol) in anhydrous Et 2 O (980 ml) (FSO 2 ) 2 O 1) ( 69.5 g, 0.38 mol) was added dropwise at -20 ° C over 30 minutes.
The mixture was kept stirring at −20 ° C. for 3 hours and filtered.
The crude product (21.5 g) was washed with MeOH and filtered. The solvent was removed in vacuo and recrystallized from acetone / CHCl 3 to give the product. 19 F NMR (CD 3 OD, CFCl 3 , 470.6 MHz) δ 56.8 (s, 1F), -78.0 (s, 3F); MS m / z (%) 230 (100) [CF 3 SO 2 NSO 2 F] - ; Anal Calcd.for CF 4 O 4 S 2 NK: C, 4.5; N, 5.2; Found: C, 4.3; N, 5.4.
By extracting equimolar amounts of the above FTA potassium salt and various ammonium bromides, the FTA ionic liquid that is unnecessary in the water is extracted with dichloromethane, washed several times with water, and then the dichloromethane is distilled off. Obtained.

DEME [FTA] (0.65 g, 80.3%)
1 H NMR (CD 3 OD, TMS, 500.2 MHz) δ 1.33 (m, 6H), 3.04 (s, 3H), 3.38 (s, 3H), 3.43 (q, J = 7.3 Hz, 4H), 3.51 (t , J = 4.5 Hz, 2H), 3.78 (m, 2H); 19 F NMR (CD 3 OD, CFCl 3 , 470.6 MHz) δ 56.6 (s, F), -78.2 (s, 3F); MS m / z (%) 146 (100) [DEME] + , 230 (100) [FTA] - ; Anal Calcd. For C 9 H 20 N 2 F 4 O 5 S 2 : C, 28.7; H, 5.4; N, 7.4; F, 20.2; Found: C, 28.8; H, 5.1; N, 7.5; F, 20.2;

PP13 [FTA] (2.30 g, 88.2%)
1 H NMR (CD 3 OD, TMS, 500.2 MHz) δ 1.02 (t, J = 7.3 Hz, 3H), 1.62-1.76 (m 2H), 1.77-1.84 (m 2H), 1.90 (m, 4H), 3.04 (s, 3H), 3.27-3.31 (m, 2H), 3.35 (t, J = 5.8 Hz, 4H); 19 F NMR (CD 3 OD, CFCl 3 , 470.6 MHz) δ 56.9 (s, F),- 78.1 (s, 3F); MS m / z (%) 142 (100) [PP13] + ,   230 (100) [FTA] - ; Anal Calcd. For C 10 H 20 N 2 F 4 O 4 S 2 : C, 32.3; H, 5.4; N, 7.5; F, 20.4; Found: C, 32.4; H, 5.2; N, 7.6; F, 20.4

N1111 [FTA]
To a stirred solution of K [CF 3 SO 2 NSO 2 F] (0.94 g, 3.5 mmol) in CH 3 CN (10 ml) was added N1111Br (0.54 g, 3.5 mmol) at room temperature. The mixture was stirred for an additional 3 hours. After distilling off the solvent, the white solid was dissolved in CH 2 Cl 2 and filtered off. The solvent was removed under vacuum. The obtained liquid was dried at 80 ° C. and 0.02 Torr for 24 hours. (1.06 g, 99.5%)
1 H NMR (CD 3 OD, TMS, 500.2 MHz) δ 3.19 (s, 12H); 19 F NMR (CD 3 OD, CFCl 3 , 470.6 MHz) δ 56.6 (s, F), -78.2 (s, 3F) ; MS m / z (%) 74 (100) [N1111] + , 230 (100) [FTA] - ; Anal Calcd. For C 5 H 12 N 2 F 4 O 4 S 2 : C, 19.7; H, 4.0 ; N, 9.2; F, 25.0; Found: C, 19.9; H, 3.9; N, 9.3; F, 24.8.

N2221 [FTA]
. MS m / z (%) 116 (100) [N2221] +, 230 (100) [FTA] - Anal Calcd for C 8 H 18 N 2 F 4 O 4 S 2: C, 27.7; H, 5.2; N , 8.1; F, 21.9; Found: C, 27.8; H, 5.2; N, 8.2; F, 21.9.

N1112 [FTA] (0.51 g, 22.3%)
1 H NMR (CD 3 OD, TMS, 500.2 MHz) δ 1.39 (t, J = 7.5 Hz, 3H), 3.10 (s, 9H), 3.41 (q, J = 7.2 Hz, 2H); 19 F NMR (CD 3 OD, CFCl 3 , 470.6 MHz) δ 56.6 (s, F), -78.1 (s, 3F); MS m / z (%) 88 (100) [N1112] + ,   230 (100) [FTA] - ; Anal Calcd. For C 6 H 14 N 2 F 4 O 4 S 2 : C, 22.6; H, 4.4; N, 8.8; F, 23.9; Found: C, 22.4; H, 4.4; N, 8.9; F, 24.0

N1113 [FTA] (1.46 g, 62.9%)
1 H NMR (CD 3 OD, TMS, 500.2 MHz) δ1.02 (t, J = 7.3 Hz, 3H), 1.78-1.86 (m, 2H), 3.12 (s, 9H), 3.26-3.32 (m, 2H ); 19 F NMR (CD 3 OD, CFCl 3 , 470.6 MHz) δ 56.8 (s, F), -78.1 (s, 3F); MS m / z (%) 102 (100) [N1113] + ,   230 (100) [CF 3 SO 2 NSO 2 F] - ; Anal Calcd. For C 7 H 16 N 2 F 4 O 4 S 2 : C, 25.3; H, 4.9; N, 8.4; F, 22.9; Found: C, 25.5; H, 4.8; N, 8.5; F, 22.7.

N2222 [FTA] (2.13 g, 84.4%)
1 H NMR (CD 3 OD, TMS, 500.2 MHz) δ 1.29 (t, J = 7.5 Hz, 12H), 3.29 (q, J = 7.2 Hz, 8H); 19 F NMR (CD 3 OD, CFCl 3 , 470.6 MHz) δ 56.7 (s, F), -78.1 (s, 3F); MS m / z (%) 130 (100) [N2222] + , 230 (100) [FTA] - ; Anal Calcd. For C 9 H 20 N 2 F 4 O 4 S 2 : C, 30.0; H, 5.6; N, 7.8; F, 21.1; Found: C, 29.8; H, 5.5; N, 7.8; F, 21.1.

P2222 [FTA] (2.38 g, 90.1%)
1 H NMR (CD 3 OD, TMS, 500.2 MHz) δ 1.22-1.28 (m, 12H), 2.21-2.28 (m 8H); 19 F NMR (CD 3 OD, CFCl 3 , 470.6 MHz) δ 56.6 (s, F), -78.1 (s, 3F); MS m / z (%) 147 (100) [P2222] + , 230 (100) [FTA] - ; Anal Calcd. For C 9 H 20 NPF 4 O 4 S 2 : C, 28.7; H, 5.3; N, 3.7; F, 20.1; Found: C, 28.7; H, 5.2; N, 3.7; F, 19.7.
比較例１Comparative Example 1
　FTAに代えてTFSAまたはFSAを用いた他は上記と同様にして、対応する化合物を合成した。 The corresponding compound was synthesized in the same manner as above except that TFSA or FSA was used instead of FTA.
比較例２Comparative Example 2
　FTAとEMI（1-エチル-3-メチルイミダゾリウム）の塩からなるイオン液体を上記と同様にして作製した。 An ionic liquid composed of a salt of FTA and EMI (1-ethyl-3-methylimidazolium) was prepared in the same manner as described above.
　以下のイオン液体を製造した。使用した全ての原材料は市販されており、さらに精製することなく用いた。化合物の合成は、参考文献1-7に記載の方法に準じて行った。
Py13[FTA] (2.17 g, 86.5 ％) 
1H NMR (CD3OD, TMS, 500.2 MHz) δ 1.02 (t, J = 7.3 Hz, 3H), 1.80-1.87 (m 2H), 2.22 (s 4H), 3.05 (s, 3H), 3.28-3.32 (m, 2H), 3.47-3.56 (m, 4H); 19F NMR (CD3OD, CFCl3, 470.6 MHz) δ 56.8 (s, F), -78.1 (s, 3F); MS m/z (%) 128 (100) [Py13]+, 230 (100) [CF3SO2NSO2F]-; Anal Calcd. for C9H18N2F4O4S2: C, 30.2; H, 5.1; N, 7.8; F, 21.2; Found : C, 30.1; H, 4.9; N, 7.7; F, 21.2

DEME[FSA] 
MS m/z (%) 146 (100) [DEME]+,180 (100) [FSA]-; Anal Calcd. for C8H20N2F2O5S2: C, 29.4; H, 6.2; N, 8.6; F, 11.6; Found : C, 29.4; H, 6.2; N, 8.5; F, 11.6.

N2221[FSA] 
MS m/z (%) 116 (100) [N2221]+,180 (100) [FSA]-; Anal Calcd. for C7H18N2F2O4S2:C, 28.4; H, 6.1; N, 9.5; F, 12.8; Found : C, 28.2; H, 6.0; N, 9.4; F, 12.7.

N1113[FSA] 
MS m/z (%) 102 (100) [N1113]+,180 (100) [FSA]-; Anal Calcd. for C6H16N2F2O4S2: C, 25.5; H, 5.7; N, 9.9; F, 13.5; Found : C, 25.5; H, 5.6; N, 10.0; F, 13.5.

N1112[FSA] 
MS m/z (%) 88 (100) [N1112]+,180 (100) [FSA]-; Anal Calcd. for C5H14N2F2O4S2: C, 22.4; H, 5.3; N, 10.4; F, 14.2; Found : C, 22.3; H, 5.2; N, 10.4; F, 14.0.

N2222[FSA] 
MS m/z (%) 130 (100) [N2222]+,180 (100) [FSA]-; Anal Calcd. for C8H20N2F2O4S2: C, 31.0; H, 6.5; N, 9.0; F, 12.2; Found : C, 30.8; H, 6.4; N, 9.0; F, 12.2.

N1111[FSA] 
MS m/z (%) 74 (100) [N1111]+,180 (100) [FSA]-; Anal Calcd. for C4H12N2F2O4S2: C, 18.9; H, 4.8; N, 11.0; F, 14.9; Found : C, 18.8; H,4.7; N,11.0; F, 14.9.
P2222[TFSA] 
MS m/z (%) 147 (100) [P2222]+,280 (100) [TFSA]-; Anal Calcd. for C10H20NPF6O4S2: C, 28.1; H, 4.7; N, 3.3; F, 26.7; Found : C, 28.0; H, 4.6; N, 3.2; F, 25.6

P2222[FSA] 
MS m/z (%) 147 (100) [P2222]+,180 (100) [FSA]-; Anal Calcd. for C8H20NPF2O4S2: C, 29.4; H, 6.2; N, 4.3; F, 11.6; Found : C, 29.2; H, 6.1; N, 4.1; F, 11.4.

PP14[FTA]
MS m/z (%) 156 (100) [PP14]+,230 (100) [CF3SO2NSO2F]-; Anal Calcd. for C11H22N2F4O4S2: C, 34.2; H, 5.7; N, 7.3; F, 19.7; Found : C, 33.9; H, 5.7; N, 7.1; F, 19.7. 

PP14[FSA]
MS m/z (%) 156 (100) [PP14]+,180 (100) [FSA]-; Anal Calcd. for C10H22N2F2O4S2: C, 35.7; H, 6.6; N, 8.3; F, 11.3; Found : C, 35.6; H, 6.6; N, 8.3; F, 11.4. 

PP14[TFSA]
MS m/z (%) 156 (100) [PP14]+,280 (100) [TFSA]-; Anal Calcd. for C12H22N2F6O4S2: C, 33.02; H, 5.08; N, 6.42; F, 26.12; Found : C, 32.7; H, 5.0; N, 6.2; F, 26.3.

PP11[FTA]
MS m/z (%) 114 (100) [PP11]+,230 (100) [FTA]-; Anal Calcd. for C8H16N2F4O4S2: C, 27.9; H, 4.7; N, 8.1; F, 22.1; Found : C, 27.7; H, 4.5; N, 8.2; F, 22.1. 
PP11[FSA]
MS m/z (%) 114 (100) [PP11]+,180 (100) [FSA]-; Anal Calcd. for C7H16N2F2O4S2: C, 28.6; H, 5.5; N, 9.5; F, 12.9; Found : C, 28.4; H, 5.3; N, 9.6; F, 12.9. 

N5555[FSA] 
MS m/z (%) 298 (100) [N5555]+,180 (100) [FSA]-; Anal Calcd. for C20H44N2F2O4S2: C, 50.2; H, 9.3; N, 5.9; F, 7.9; Found : C, 50.0; H, 9.3; N, 5.8; F, 7.9.

N4444[FSA] 
MS m/z (%) 242 (100) [N4444]+,180 (100) [FSA]-; Anal Calcd. for C16H36N2F2O4S2: C, 45.5; H, 8.6; N, 6.6; F, 9.0; Found : C, 45.2; H, 8.7; N, 6.6; F, 9.1.

N3333[FSA] 
MS m/z (%) 186 (100) [N3333]+,180 (100) [FSA]-; Anal Calcd. for C12H28N2F2O4S2: C, 39.3; H, 7.7; N, 7.6; F,10.4; Found : C, 39.2; H, 7.5; N, 7.8; F, 10.4.

PMI[FSA] 
MS m/z (%) 125 (100) [PMI]+,180 (100) [FSA]-; Anal Calcd. for C7H13N3F2O4S2: C, 27.5; H, 4.3; N, 13.8; F, 12.4; Found : C, 27.7; H, 4.2; N, 13.7; F, 12.5.

PMI[TFSA] 
MS m/z (%) 125 (100) [PMI]+,280 (100) [TFSA]-; Anal Calcd. for C9H13N3F6O4S2: C, 26.7; H, 3.3; N, 10.4; F, 28.1; Found : C, 26.7; H, 3.2; N, 10.5; F, 27.9.

N1224[TFSA] 
MS m/z (%) 144 (100) [N1224]+,280 (100) [TFSA]-; Anal Calcd. for C11H22N2F6O4S2: C, 31.1; H, 5.2; N, 6.6; F, 26.9; Found : C, 31.0; H, 5.0; N, 6.6; F, 26.9.

DMI[TFSA] 
MS m/z (%) 97 (100) [DMI]+,280 (100) [TFSA]-; Anal Calcd. for C7H9N3F6O4S2: C, 22.3; H, 2.4; N, 11.1; F, 30.2; Found : C, 22.1; H, 2.5; N, 11.4; F, 30.0.

DMI[FSA] 
MS m/z (%) 97 (100) [DMI]+,180 (100) [FSA]-; Anal Calcd. for C5H9N3F2O4S2: C, 21.7; H, 3.3; N, 15.2; F, 13.7; Found : C, 21.7; H, 3.3; N, 15.2; F, 13.7.

N1224[FSA] 
MS m/z (%) 144 (100) [N1224]+,280 (100) [TFSA]-; Anal Calcd. for C9H22N2F2O4S2: C, 33.3; H, 6.8; N, 8.6; F, 11.7; Found : C, 33.3; H, 6.6; N, 8.8; F, 11.9.

N1133[FSA] 
MS m/z (%) 130 (100) [N1133]+,180 (100) [FSA]-; Anal Calcd. for C8H20N2F2O4S2: C, 31.0; H, 6.5; N, 9.0; F, 12.2; Found : C, 30.7; H, 6.2; N, 9.0; F, 12.2.

N1133[TFSA] 
MS m/z (%) 130 (100) [N1133]+,280 (100) [FSA]-; Anal Calcd. for C10H20N2F6O4S2: C, 29.3; H, 4.9; N, 6.8; F, 27.8; Found : C, 29.1; H, 4.6; N, 6.8; F, 27.6.

N1224[FTA]
MS m/z (%) 144 (100) [N1224]+,230 (100) [FTA]-; Anal Calcd. for C10H22N2F4O4S2: C, 32.1; H, 5.9; N, 7.5; F, 20.3; Found : C, 32.2; H, 5.7; N, 7.6; F, 20.3.

N3333[FTA] 
MS m/z (%) 186 (100) [N3333]+,230 (100) [FTA]-; Anal Calcd. for C13H28N2F4O4S2: C, 37.5; H, 6.8; N, 6.7; F,18.3; Found : C, 37.4; H, 6.5; N, 6.8; F, 18.3.

N4444[FTA] 
MS m/z (%) 242 (100) [N4444]+,230 (100) [FTA]-; Anal Calcd. for C17H36N2F4O4S2: C, 43.2; H, 7.7; N, 5.9; F, 16.1; Found : C, 43.3; H,7.5; N, 6.0; F, 15.9.

N5555[FTA] 
MS m/z (%) 296 (100) [N5555]+,230 (100) [FTA]-; Anal Calcd. for C21H44N2F4O4S2: C, 47.7; H, 8.4; N, 5.3; F, 14.4; Found : C, 47.3; H, 8.5; N, 5.3; F, 14.2.

PP12[FSA]
MS m/z (%) 128 (100) [PP12]+,180 (100) [FSA]-; Anal Calcd. for C8H18N2F2O4S2: C, 31.2; H, 5.9; N, 9.1; F, 12.3; Found : C, 30.9; H, 5.6; N, 9.1; F, 12.3. 

Py12[FTA]
MS m/z (%) 114 (100) [Py12]+,230 (100) [FTA]-; Anal Calcd. for C8H16N2F4O4S2: C, 27.9; H, 4.7; N, 8.1; F, 22.1; Found : C, 27.9; H, 4.7; N, 8.3; F, 21.9. 

Py14[FTA]
MS m/z (%) 142 (100) [Py14]+,230 (100) [FTA]-; Anal Calcd. for C10H20N2F4O4S2: C, 32.25; H, 5.41; N, 7.52; F, 20.41; Found : C, 32.11; H, 5.16; N, 7.61; F, 20.43. 

Py14[FSA]
MS m/z (%) 142 (100) [Py14]+,180 (100) [FSA]-; Anal Calcd. for C9H20N2F2O4S2: C, 33.53; H, 6.25; N, 8.69; F, 11.79; Found : C, 33.29; H, 6.00; N, 8.80; F, 11.78. 

BMI[FTA] 
MS m/z (%) 139 (100) [BMI]+,230 (100) [FTA]-; Anal Calcd. for C9H15N3F4O4S2: C, 29.3; H, 4.1; N, 11.4; F, 20.6; Found : C, 29.1; H, 4.1; N, 11.4; F, 20.4.

PMI[FTA] 
MS m/z (%) 125 (100) [PMI]+,230 (100) [FTA]-; Anal Calcd. for C8H13N3F4O4S2: C, 27.0; H, 3.7; N, 11.8 F, 21.4; Found : C, 27.1; H, 3.6; N, 11.9; F, 21.3.

DMI[FTA] 
MS m/z (%) 97 (100) [DMI]+,230 (100) [FTA]-; Anal Calcd. for C6H9N3F4O4S2: C, 22.0; H, 2.8; N, 12.8 F, 22.3; Found : C, 22.1; H, 2.8; N, 13.1; F, 23.3.

BMI[FTA] 
MS m/z (%) 139 (100) [BMI]+,230 (100) [FTA]-; Anal Calcd. for C9H15N3F4O4S2: C, 29.3; H, 4.1; N, 11.4; F, 20.6; Found : C, 29.1; H, 4.1; N, 11.4; F, 20.4.

Py12[FSA] MS m/z (%) 114 (100) [Py12]+,180 (100) [FSA]-; Anal Calcd. for C7H16N2F2O4S2: C, 28.6; H, 5.5; N, 9.5; F, 12.9; Found : C, 28.4; H, 5.3; N, 9.6; F, 12.9. 

AS44[FTA]
MS m/z (%) 126 (100) [AS44]+,230 (100) [FTA]-; Anal Calcd. for C9H16N2F4O4S2: C, 30.3; H, 4.5; N, 7.9; F, 21.3; Found : C,30.1 ; H,4.5 ; N,7.7 ; F,21.2 . 

AS44[TFSA]
MS m/z (%) 126 (100) [AS44]+,280 (100) [TFSA]-; Anal Calcd. for C10H16N2F6O4S2: C, 29.6; H, 4.0; N, 6.9; F, 28.1; Found : C,29.1 ; H,3.9 ; N,6.8 ; F,28.1 . 
 
AS44[FSA]
MS m/z (%) 126 (100) [AS44]+,180 (100) [FSA]-; Anal Calcd. for C8H16N2F2O4S2: C, 31.4; H, 5.3; N, 9.1; F, 12.4; Found : C,31.0 ; H,9.2 ; N,12.4; F,31.1. 

PS44[FTA]
MS m/z (%) 143 (100) [PS44]+,230 (100) [FTA]-; Anal Calcd. for C9H16NPF4O4S2: C, 29.0; H, 4.3; N, 3.8; F, 20.0; Found : C,39.2 ; H,4.1 ; N,3.9; F,19.6. 
PS44[FSA]
MS m/z (%) 143 (100) [PS44]+,180 (100) [FSA]-; Anal Calcd. for C8H16NPF2O4S2: C, 29.7; H, 5.0; N, 4.4; F, 11.8; Found : C,29.7 ; H,4.8 ; N,4.3; F,11.5. 
PS44[TFSA]
MS m/z (%) 143 (100) [PS44]+,280 (100) [TFSA]-; Anal Calcd. for C10H16NPF6O4S2: C, 28.4; H, 3.8; N, 3.3; F, 26.5; Found : C, 28.5; H, 3.7; N, 3.4; F, 26.9.  The following ionic liquids were produced. All raw materials used were commercially available and were used without further purification. The compound was synthesized according to the method described in References 1-7.
Py13 [FTA] (2.17 g, 86.5%)
1 H NMR (CD 3 OD, TMS, 500.2 MHz) δ 1.02 (t, J = 7.3 Hz, 3H), 1.80-1.87 (m 2H), 2.22 (s 4H), 3.05 (s, 3H), 3.28-3.32 (m, 2H), 3.47-3.56 (m, 4H); 19 F NMR (CD 3 OD, CFCl 3 , 470.6 MHz) δ 56.8 (s, F), -78.1 (s, 3F); MS m / z ( %) 128 (100) [Py13] + ,   230 (100) [CF 3 SO 2 NSO 2 F] - ; Anal Calcd. For C 9 H 18 N 2 F 4 O 4 S 2 : C, 30.2; H, 5.1; N, 7.8; F, 21.2; Found: C, 30.1; H, 4.9; N, 7.7; F, 21.2

DEME [FSA]
MS m / z (%) 146 (100) [DEME] + , 180 (100) [FSA] - ;   Anal Calcd.for C 8 H 20 N 2 F 2 O 5 S 2 : C, 29.4; H, 6.2; N, 8.6; F, 11.6; Found: C, 29.4; H, 6.2; N, 8.5; F, 11.6 .

N2221 [FSA]
MS m / z (%) 116 (100) [N2221] + , 180 (100) [FSA] - ; Anal Calcd. For C 7 H 18 N 2 F 2 O 4 S 2 : C, 28.4; H, 6.1; N, 9.5; F, 12.8; Found: C, 28.2; H, 6.0; N, 9.4; F, 12.7.

N1113 [FSA]
MS m / z (%) 102 (100) [N1113] + , 180 (100) [FSA] - ; Anal Calcd. For C 6 H 16 N 2 F 2 O 4 S 2 : C, 25.5; H, 5.7; N, 9.9; F, 13.5; Found: C, 25.5; H, 5.6; N, 10.0; F, 13.5.

N1112 [FSA]
MS m / z (%) 88 (100) [N1112] + , 180 (100) [FSA] - ; Anal Calcd. For C 5 H 14 N 2 F 2 O 4 S 2 : C, 22.4; H, 5.3; N, 10.4; F, 14.2; Found: C, 22.3; H, 5.2; N, 10.4; F, 14.0.

N2222 [FSA]
MS m / z (%) 130 (100) [N2222] + , 180 (100) [FSA] - ; Anal Calcd. For C 8 H 20 N 2 F 2 O 4 S 2 : C, 31.0; H, 6.5; N, 9.0; F, 12.2; Found: C, 30.8; H, 6.4; N, 9.0; F, 12.2.

N1111 [FSA]
MS m / z (%) 74 (100) [N1111] + , 180 (100) [FSA] - ; Anal Calcd. For C 4 H 12 N 2 F 2 O 4 S 2 : C, 18.9; H, 4.8; N, 11.0; F, 14.9; Found: C, 18.8; H, 4.7; N, 11.0; F, 14.9.
P2222 [TFSA]
MS m / z (%) 147 (100) [P2222] + , 280 (100) [TFSA] - ; Anal Calcd. For C 10 H 20 NPF 6 O 4 S 2 : C, 28.1; H, 4.7; N, 3.3; F, 26.7; Found: C, 28.0; H, 4.6; N, 3.2; F, 25.6

P2222 [FSA]
MS m / z (%) 147 (100) [P2222] + , 180 (100) [FSA] - ; Anal Calcd. For C 8 H 20 NPF 2 O 4 S 2 : C, 29.4; H, 6.2; N, 4.3; F, 11.6; Found: C, 29.2; H, 6.1; N, 4.1; F, 11.4.

PP14 [FTA]
MS m / z (%) 156 (100) [PP14] + , 230 (100) [CF 3 SO 2 NSO 2 F] - ; Anal Calcd. For C 11 H 22 N 2 F 4 O 4 S 2 : C, 34.2; H, 5.7; N, 7.3; F, 19.7; Found: C, 33.9; H, 5.7; N, 7.1; F, 19.7.

PP14 [FSA]
MS m / z (%) 156 (100) [PP14] + , 180 (100) [FSA] - ; Anal Calcd. For C 10 H 22 N 2 F 2 O 4 S 2 : C, 35.7; H, 6.6; N, 8.3; F, 11.3; Found: C, 35.6; H, 6.6; N, 8.3; F, 11.4.

PP14 [TFSA]
MS m / z (%) 156 (100) [PP14] + , 280 (100) [TFSA] - ; Anal Calcd. For C 12 H 22 N 2 F 6 O 4 S 2 : C, 33.02; H, 5.08; N, 6.42; F, 26.12; Found: C, 32.7; H, 5.0; N, 6.2; F, 26.3.

PP11 [FTA]
MS m / z (%) 114 (100) [PP11] + , 230 (100) [FTA] - ; Anal Calcd. For C 8 H 16 N 2 F 4 O 4 S 2 : C, 27.9; H, 4.7; N, 8.1; F, 22.1; Found: C, 27.7; H, 4.5; N, 8.2; F, 22.1.
PP11 [FSA]
MS m / z (%) 114 (100) [PP11] + , 180 (100) [FSA] - ; Anal Calcd. For C 7 H 16 N 2 F 2 O 4 S 2 : C, 28.6; H, 5.5; N, 9.5; F, 12.9; Found: C, 28.4; H, 5.3; N, 9.6; F, 12.9.

N5555 [FSA]
MS m / z (%) 298 (100) [N5555] + , 180 (100) [FSA] - ; Anal Calcd. For C 20 H 44 N 2 F 2 O 4 S 2 : C, 50.2; H, 9.3; N, 5.9; F, 7.9; Found: C, 50.0; H, 9.3; N, 5.8; F, 7.9.

N4444 [FSA]
MS m / z (%) 242 (100) [N4444] + , 180 (100) [FSA] - ; Anal Calcd. For C 16 H 36 N 2 F 2 O 4 S 2 : C, 45.5; H, 8.6; N, 6.6; F, 9.0; Found: C, 45.2; H, 8.7; N, 6.6; F, 9.1.

N3333 [FSA]
MS m / z (%) 186 (100) [N3333] + , 180 (100) [FSA] - ; Anal Calcd. For C 12 H 28 N 2 F 2 O 4 S 2 : C, 39.3; H, 7.7; N, 7.6; F, 10.4; Found: C, 39.2; H, 7.5; N, 7.8; F, 10.4.

PMI [FSA]
MS m / z (%) 125 (100) [PMI] + , 180 (100) [FSA] - ; Anal Calcd. For C 7 H 13 N 3 F 2 O 4 S 2 : C, 27.5; H, 4.3; N, 13.8; F, 12.4; Found: C, 27.7; H, 4.2; N, 13.7; F, 12.5.

PMI [TFSA]
MS m / z (%) 125 (100) [PMI] + , 280 (100) [TFSA] - ; Anal Calcd. For C 9 H 13 N 3 F 6 O 4 S 2 : C, 26.7; H, 3.3; N, 10.4; F, 28.1; Found: C, 26.7; H, 3.2; N, 10.5; F, 27.9.

N1224 [TFSA]
MS m / z (%) 144 (100) [N1224] + , 280 (100) [TFSA] - ; Anal Calcd. For C 11 H 22 N 2 F 6 O 4 S 2 : C, 31.1; H, 5.2; N, 6.6; F, 26.9; Found: C, 31.0; H, 5.0; N, 6.6; F, 26.9.

DMI [TFSA]
MS m / z (%) 97 (100) [DMI] + , 280 (100) [TFSA] - ; Anal Calcd. For C 7 H 9 N 3 F 6 O 4 S 2 : C, 22.3; H, 2.4; N, 11.1; F, 30.2; Found: C, 22.1; H, 2.5; N, 11.4; F, 30.0.

DMI [FSA]
MS m / z (%) 97 (100) [DMI] + , 180 (100) [FSA] - ;   Anal Calcd.for C 5 H 9 N 3 F 2 O 4 S 2 : C, 21.7; H, 3.3; N, 15.2; F, 13.7; Found: C, 21.7; H, 3.3; N, 15.2; F, 13.7 .

N1224 [FSA]
MS m / z (%) 144 (100) [N1224] + , 280 (100) [TFSA] - ;   Anal Calcd.for C 9 H 22 N 2 F 2 O 4 S 2 : C, 33.3; H, 6.8; N, 8.6; F, 11.7; Found: C, 33.3; H, 6.6; N, 8.8; F, 11.9 .

N1133 [FSA]
MS m / z (%) 130 (100) [N1133] + , 180 (100) [FSA] - ;   Anal Calcd.for C 8 H 20 N 2 F 2 O 4 S 2 : C, 31.0; H, 6.5; N, 9.0; F, 12.2; Found: C, 30.7; H, 6.2; N, 9.0; F, 12.2 .

N1133 [TFSA]
MS m / z (%) 130 (100) [N1133] + , 280 (100) [FSA] - ;   Anal Calcd. For C 10 H 20 N 2 F 6 O 4 S 2 : C, 29.3; H, 4.9; N, 6.8; F, 27.8; Found: C, 29.1; H, 4.6; N, 6.8; F, 27.6 .

N1224 [FTA]
MS m / z (%) 144 (100) [N1224] + , 230 (100) [FTA] - ;   Anal Calcd.for C 10 H 22 N 2 F 4 O 4 S 2 : C, 32.1; H, 5.9; N, 7.5; F, 20.3; Found: C, 32.2; H, 5.7; N, 7.6; F, 20.3 .

N3333 [FTA]
MS m / z (%) 186 (100) [N3333] + , 230 (100) [FTA] - ; Anal Calcd. For C 13 H 28 N 2 F 4 O 4 S 2 : C, 37.5; H, 6.8; N, 6.7; F, 18.3; Found: C, 37.4; H, 6.5; N, 6.8; F, 18.3.

N4444 [FTA]
MS m / z (%) 242 (100) [N4444] + , 230 (100) [FTA] - ;   Anal Calcd.for C 17 H 36 N 2 F 4 O 4 S 2 : C, 43.2; H, 7.7; N, 5.9; F, 16.1; Found: C, 43.3; H, 7.5; N, 6.0; F, 15.9 .

N5555 [FTA]
MS m / z (%) 296 (100) [N5555] + , 230 (100) [FTA] - ;   Anal Calcd.for C 21 H 44 N 2 F 4 O 4 S 2 : C, 47.7; H, 8.4; N, 5.3; F, 14.4; Found: C, 47.3; H, 8.5; N, 5.3; F, 14.2 .

PP12 [FSA]
MS m / z (%) 128 (100) [PP12] + , 180 (100) [FSA] - ; Anal Calcd. For C 8 H 18 N 2 F 2 O 4 S 2 : C, 31.2; H, 5.9; N, 9.1; F, 12.3; Found: C, 30.9; H, 5.6; N, 9.1; F, 12.3.

Py12 [FTA]
MS m / z (%) 114 (100) [Py12] + , 230 (100) [FTA] - ; Anal Calcd. For C 8 H 16 N 2 F 4 O 4 S 2 : C, 27.9; H, 4.7; N, 8.1; F, 22.1; Found: C, 27.9; H, 4.7; N, 8.3; F, 21.9.

Py14 [FTA]
MS m / z (%) 142 (100) [Py14] + , 230 (100) [FTA] - ; Anal Calcd. For C 10 H 20 N 2 F 4 O 4 S 2 : C, 32.25; H, 5.41; N, 7.52; F, 20.41; Found: C, 32.11; H, 5.16; N, 7.61; F, 20.43.

Py14 [FSA]
MS m / z (%) 142 (100) [Py14] + , 180 (100) [FSA] - ; Anal Calcd. For C 9 H 20 N 2 F 2 O 4 S 2 : C, 33.53; H, 6.25; N, 8.69; F, 11.79; Found: C, 33.29; H, 6.00; N, 8.80; F, 11.78.

BMI [FTA]
MS m / z (%) 139 (100) [BMI] + , 230 (100) [FTA] - ;   Anal Calcd.for C 9 H 15 N 3 F 4 O 4 S 2 : C, 29.3; H, 4.1; N, 11.4; F, 20.6; Found: C, 29.1; H, 4.1; N, 11.4; F, 20.4 .

PMI [FTA]
MS m / z (%) 125 (100) [PMI] + , 230 (100) [FTA] - ;   Anal Calcd.for C 8 H 13 N 3 F 4 O 4 S 2 : C, 27.0; H, 3.7; N, 11.8 F, 21.4; Found: C, 27.1; H, 3.6; N, 11.9; F, 21.3.

DMI [FTA]
MS m / z (%) 97 (100) [DMI] + , 230 (100) [FTA] - ;   Anal Calcd.for C 6 H 9 N 3 F 4 O 4 S 2 : C, 22.0; H, 2.8; N, 12.8 F, 22.3; Found: C, 22.1; H, 2.8; N, 13.1; F, 23.3.

BMI [FTA]
MS m / z (%) 139 (100) [BMI] + , 230 (100) [FTA] - ;   Anal Calcd.for C 9 H 15 N 3 F 4 O 4 S 2 : C, 29.3; H, 4.1; N, 11.4; F, 20.6; Found: C, 29.1; H, 4.1; N, 11.4; F, 20.4 .

Py12 [FSA] MS m / z (%) 114 (100) [Py12] + , 180 (100) [FSA] - ; Anal Calcd. For C 7 H 16 N 2 F 2 O 4 S 2 : C, 28.6; H, 5.5; N, 9.5; F, 12.9; Found: C, 28.4; H, 5.3; N, 9.6; F, 12.9.

AS44 [FTA]
MS m / z (%) 126 (100) [AS44] + , 230 (100) [FTA] - ; Anal Calcd. For C 9 H 16 N 2 F 4 O 4 S 2 : C, 30.3; H, 4.5; N, 7.9; F, 21.3; Found: C, 30.1; H, 4.5; N, 7.7; F, 21.2.

AS44 [TFSA]
MS m / z (%) 126 (100) [AS44] + , 280 (100) [TFSA] - ; Anal Calcd. For C 10 H 16 N 2 F 6 O 4 S 2 : C, 29.6; H, 4.0; N, 6.9; F, 28.1; Found: C, 29.1; H, 3.9; N, 6.8; F, 28.1.

AS44 [FSA]
MS m / z (%) 126 (100) [AS44] + , 180 (100) [FSA] - ; Anal Calcd. For C 8 H 16 N 2 F 2 O 4 S 2 : C, 31.4; H, 5.3; N, 9.1; F, 12.4; Found: C, 31.0; H, 9.2; N, 12.4; F, 31.1.

PS44 [FTA]
MS m / z (%) 143 (100) [PS44] + , 230 (100) [FTA] - ; Anal Calcd. For C 9 H 16 NPF 4 O 4 S 2 : C, 29.0; H, 4.3; N, 3.8; F, 20.0; Found: C, 39.2; H, 4.1; N, 3.9; F, 19.6.
PS44 [FSA]
MS m / z (%) 143 (100) [PS44] + , 180 (100) [FSA] - ; Anal Calcd. For C 8 H 16 NPF 2 O 4 S 2 : C, 29.7; H, 5.0; N, 4.4; F, 11.8; Found: C, 29.7; H, 4.8; N, 4.3; F, 11.5.
PS44 [TFSA]
MS m / z (%) 143 (100) [PS44] + , 280 (100) [TFSA] - ; Anal Calcd. For C 10 H 16 NPF 6 O 4 S 2 : C, 28.4; H, 3.8; N, 3.3; F, 26.5; Found: C, 28.5; H, 3.7; N, 3.4; F, 26.9.
試験例１Test example 1
　上記実施例、比較例で得られた化合物の融点、導電率、ガラス転移点、熱分解温度、粘度、密度を表１～表６に示す。 Tables 1 to 6 show the melting points, electrical conductivity, glass transition point, thermal decomposition temperature, viscosity, and density of the compounds obtained in the above Examples and Comparative Examples.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
試験例２Test example 2
　実施例及び比較例の各種イオン液体について、還元リミット電位、酸化リミット電位、電位窓を測定し、表７及び図１に示した。なお、表７の「＊」で示されている値は、引用文献＊に記載された値をそのまま記載した。
引用文献 ＊　松本一ら、Journal of Power Sources, 160巻,2号,2006年，1308-1313頁、
電位窓測定結果
２５℃
走査速度：50mV/s
作用電極：グラッシーカーボン電極
対極：白金
参照電極：EMI[TFSA]に60mMテトラプロピルアンモニウムヨウ化物と15mMのヨウ素を含有させたヨウ素レドックスを先端をポーラスバイコールガラスで閉じたガラス管に入れ、白金線を含浸させたもの。
（各イオン液体中でのフェロセンの酸化還元電位を測定し内部標準とした）
　N2222[FTA]、N122.1O2 [FTA]、EMI[FTA]、AS44[FTA]の電位窓の測定結果を図１に示す。 With respect to various ionic liquids of Examples and Comparative Examples, the reduction limit potential, the oxidation limit potential, and the potential window were measured and are shown in Table 7 and FIG. In addition, the value shown by "*" of Table 7 described the value described in cited reference * as it was.
Citations * Matsumoto Kazu et al., Journal of Power Sources, 160, 2, 2006, 1308-1313,
Potential window measurement result 25 ° C
Scanning speed: 50mV / s
Working electrode: Glassy carbon electrode Counter electrode: Platinum Reference electrode: Put EMI [TFSA] iodine redox containing 60 mM tetrapropylammonium iodide and 15 mM iodine into a glass tube whose tip is closed with porous Vycor glass, and put the platinum wire Impregnated.
(The ferrocene redox potential in each ionic liquid was measured and used as an internal standard.)
FIG. 1 shows the measurement results of the potential windows of N2222 [FTA], N122.1O2 [FTA], EMI [FTA], and AS44 [FTA].
　なお、N122.1O2[FTA]は、DEME[FTA]のことである。 N122.1O2 [FTA] is DEME [FTA].
　また、表７の還元リミット電位、酸化リミット電位は、1mA/cm2における電位とした。 In addition, the reduction limit potential and the oxidation limit potential in Table 7 were set at 1 mA / cm 2 .
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　これらの結果から、FTAアニオンは、従来のTFSAやFSAに匹敵する高い電気化学安定性を有する事が明らかである。 From these results, it is clear that FTA anion has high electrochemical stability comparable to conventional TFSA and FSA.
　特に、カチオン種にN2222を用いる事が可能であり、酸化リミット電位は、従来のアミドアニオン系ではもっとも正電位である。 Especially, N2222 can be used as the cation species, and the oxidation limit potential is the most positive potential in the conventional amide anion system.
試験例３Test example 3
　EMI[FTA]、AS44[FTA]及び濃度１MのLi-PF6を含むエチレンカーボネート＋ジメチルカーボネート（EC＋DMC）溶液それぞれを用いて、Li/LiCoO2セルを参考文献８と同じ方法にて作製し、レート試験後に4.2Vで充電したときの交流インピーダンスを測定した。 Using each of EMI [FTA], AS44 [FTA] and an ethylene carbonate + dimethyl carbonate (EC + DMC) solution containing Li-PF 6 at a concentration of 1M, a Li / LiCoO 2 cell was prepared by the same method as in Reference 8. The AC impedance when charged at 4.2 V after the rate test was measured.
　また、AS44[FTA]、EMI[FTA]、EMI[FSA]、EMI[TFSA]、Py13[TFSA]及びPy13 [FSA]それぞれのLi/LiCoO2セルの放電容量とCレートとの関係を測定した。各測定結果を図２及び図３に示す。なお、リチウム電解液は、各イオン液体にリチウム塩Li-TFSA（0.5M）を溶解させて調製した。セル構成は、参考文献９を参照して作成した。 We also measured the relationship between the discharge capacity and C rate of each Li / LiCoO 2 cell in AS44 [FTA], EMI [FTA], EMI [FSA], EMI [TFSA], Py13 [TFSA] and Py13 [FSA]. . Each measurement result is shown in FIGS. The lithium electrolyte was prepared by dissolving lithium salt Li-TFSA (0.5M) in each ionic liquid. The cell configuration was created with reference to Reference 9.
　図２の測定結果より、EMI-FTAの界面抵抗はEC+DMCと比べてもそれほど大きくなく、界面抵抗は比較的小さいことがわかった。また、図３の測定結果より、EMI[FTA]を用いたセルではEMI[FSA]とほぼ同等、AS44[FTA]を用いたセルでは、より粘性が低いPy13[FSA]と同等の性能を示し、TFSAでは如何に粘性の低い系を用いても不可能であった1C(0.2mA/cm2)以上での充放電が可能になることが分かった。交流インピーダンス測定による見かけの界面電荷移動抵抗は、FTA系はFSA 系に近い低い値を示すことからアニオン中での-FSO2基の存在が界面抵抗の低下の原因であることが示唆され、これが高いレート特性を示す原因と考えられる。 From the measurement results in FIG. 2, it was found that the interface resistance of EMI-FTA is not so large compared to EC + DMC, and the interface resistance is relatively small. In addition, from the measurement results in Fig. 3, the cell using EMI [FTA] shows almost the same performance as EMI [FSA], and the cell using AS44 [FTA] shows the same performance as Py13 [FSA], which has lower viscosity. In TFSA, it was found that charging and discharging at 1 C (0.2 mA / cm 2 ) or more, which was impossible even with a low viscosity system, became possible. The apparent interfacial charge transfer resistance by AC impedance measurement shows that the FTA system shows a low value close to that of the FSA system, suggesting that the presence of -FSO 2 groups in the anion is the cause of the decrease in interfacial resistance. This is considered to be a cause of high rate characteristics.
　AS44[FTA]を用いたLi/LiCoO2セルの充放電レート特性（25℃）に及ぼすセパレータ厚みおよびLi塩濃度による影響を検討し、最適化を行った結果図４に示すように、従来の有機溶媒電解液並みの高い充放電レート特性を発揮することが分かった。リチウム塩濃度を高くすることで、正負電極界面電荷移動抵抗がより小さくなる一方、従来のTFSAイオン液体では1M程度のリチウム塩添加によって粘度が七倍以上と著しく高くなるのにたいし、図５に示すようにFTAでは、FSAと同様に粘度があまり変化しないことも相まってこのような高い性能が発揮されたものと考えられる。
参考文献1) S. Kongpricha, W. C. Preusse, R. Schwarer, J. K. Ruff, Inorganic Syntheses 8, 151-155.
参考文献2) Z. B. Zhou, M. Takeda, M. Ue, J Fluorine Chem. 2003, 123, 127-131.
参考文献3) Z. B. Zhou, H. Matsumoto, K. Tatsumi, Chem.Eur. J.2004, 10, 6581-6591.
参考文献4) Zhi-bin Zhou, Hajime Matsumoto, Kuniaki Tatsumi, Chem. Eur. J., 2005, 11, 752-766.
参考文献5) Zhi-bin Zhou, Hajime Matsumoto, Kuniaki Tatsumi, Chem. Eur. J., 2006, 12, 2196-2212.
参考文献6) V .Ｂraun, Chemische Berichte, 1916, 49, 970.
参考文献7) N. Ya Derkach, A. V. Kirsanov, Zhurnal Obshchei Khimii 1968, 38(2), 331-7. 
参考文献8) H. Sakaebe et al., Electrochim. Acta 53 (2007) 1048.
参考文献9) H. Sakaebe, H. Matsumoto, Electrochem. Commun., 5(7),594 (2003). As a result of investigating and optimizing the effect of separator thickness and Li salt concentration on the charge / discharge rate characteristics (25 ° C) of Li / LiCoO 2 cells using AS 44 [FTA] It was found that the charge / discharge rate characteristics as high as those of organic solvent electrolytes were exhibited. By increasing the lithium salt concentration, the positive and negative electrode interfacial charge transfer resistance becomes smaller. On the other hand, in the conventional TFSA ionic liquid, when the lithium salt of about 1M is added, the viscosity becomes significantly higher than 7 times. As shown in Fig. 5, FTA is considered to have exhibited such high performance in combination with the fact that the viscosity does not change much like FSA.
(Reference 1) S. Kongpricha, W. C. Preusse, R. Schwarer, J. K. Ruff, Inorganic Syntheses 8, 151-155.
(Reference 2) Z. B. Zhou, M. Takeda, M. Ue, J Fluorine Chem. 2003, 123, 127-131.
(Reference 3) Z. B. Zhou, H. Matsumoto, K. Tatsumi, Chem. Eur. J. 2004, 10, 6581-6591.
(Reference 4) Zhi-bin Zhou, Hajime Matsumoto, Kuniaki Tatsumi, Chem. Eur. J., 2005, 11, 752-766.
(Reference 5) Zhi-bin Zhou, Hajime Matsumoto, Kuniaki Tatsumi, Chem. Eur. J., 2006, 12, 2196-2212.
(Reference 6) V. Braun, Chemische Berichte, 1916, 49, 970.
(Reference 7) N. Ya Derkach, A. V. Kirsanov, Zhurnal Obshchei Khimii 1968, 38 (2), 331-7.
(Reference 8) H. Sakaebe et al., Electrochim. Acta 53 (2007) 1048.
(Reference 9) H. Sakaebe, H. Matsumoto, Electrochem. Commun., 5 (7), 594 (2003).
N2222[FTA]、DEME[FTA]、EMI[FTA]およびAS44[FTA]の２５℃でのリニアスイープボルタモグラムの測定結果を示す。The measurement result of the linear sweep voltammogram at 25 degrees C of N2222 [FTA], DEME [FTA], EMI [FTA], and AS44 [FTA] is shown. 電解液として、EMI[FTA]、AS44[FTA]におよそ0.5MのLi[TFSA]を添加したもの、1 M Li-PF6を含むEC＋DMC(1:1)溶液を用いた場合のLi/LiCoO2セルのレート試験後、4.2Vで充電後のセルの交流インピーダンス測定結果（Cole-Cole plot）を示す。Li / LiCoO in the case of using EMI [FTA], AS44 [FTA] with approximately 0.5M Li [TFSA] added, and EC + DMC (1: 1) solution containing 1 M Li-PF 6 The result of AC impedance measurement (Cole-Cole plot) of the cell after charging at 4.2V after the rate test of 2 cells is shown. EMI[FTA]、AS44[FTA]、EMI[FSA]及びEMI[TFSA]のLi/LiCoO2セルの放電容量とCレートとの関係を示す。The relationship between the discharge capacity and C rate of Li / LiCoO 2 cells of EMI [FTA], AS44 [FTA], EMI [FSA], and EMI [TFSA] is shown. AS44[FTA]を電解質に用いたLi/LiCoO2セルのレート特性に及ぼすLi塩濃度とセパレータ厚みの効果。Effect of Li salt concentration and separator thickness on rate characteristics of Li / LiCoO 2 cells using AS44 [FTA] as electrolyte. イオン液体の粘度に及ぼす共存Li塩濃度依存性。Coexistence of Li salt concentration on the viscosity of ionic liquids.

Claims (7)

  1. フルオロスルホニル(トリフルオロメチルスルホニルアミド)(FTA)アニオンと、以下のいずれかのカチオンからなるイオン液体：
    テトラメチルアンモニウム（N1111）；
    エチルトリメチルアンモニウム（N1112）；
    n-プロピルトリメチルアンモニウム（N1113）；
    ジエチルジメチルアンモニウム（N1122）；
    ジn-プロピルジメチルアンモニウム（N1133）；
    トリエチルメチルアンモニウム（N2221）；
    n-ブチルジエチルメチルアンモニウム（N1224）；
    N,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウム(DEME)；
    テトラエチルアンモニウム（N2222）；
    テトラn-プロピルアンモニウム（N3333）;
    テトラn-ブチルアンモニウム（N4444）；
    テトラn-ペンチルアンモニウム（N5555）；
    5-アゾニアスピロ[4.4]ノナン(AS44)
    ジメチルイミダゾール(DMI)
    プロピルメチルイミダゾール(PMI)
    ブチルメチルイミダゾール(BMI)
    N,N-ジメチルピロリジニウム(Py11)
    N-メチル-N-エチルピロリジニウム(Py12)
    N-メチル-N-ブチルピロリジニウム(Py14)
    N,N-ジメチル-ピペリジニウム(PP11)
    N-メチル-N-エチル-ピペリジニウム(PP12)
    N-メチル-N-プロピル-ピペリジニウム(PP13)
    N-メチル-N-ブチル-ピペリジニウム(PP14)
    テトラエチルホスホニウム（Ｐ2222）；または
    5-フォスフォニアスピロ[4.4]ノナン(PS44)。     An ionic liquid comprising a fluorosulfonyl (trifluoromethylsulfonylamide) (FTA) anion and one of the following cations:
    Tetramethylammonium (N1111);
    Ethyltrimethylammonium (N1112);
    n-propyltrimethylammonium (N1113);
    Diethyldimethylammonium (N1122);
    Di-n-propyldimethylammonium (N1133);
    Triethylmethylammonium (N2221);
    n-butyldiethylmethylammonium (N1224);
    N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (DEME);
    Tetraethylammonium (N2222);
    Tetra n-propylammonium (N3333);
    Tetra n-butylammonium (N4444);
    Tetra n-pentylammonium (N5555);
    5-Azonia Spiro [4.4] Nonane (AS44)
    Dimethylimidazole (DMI)
    Propylmethylimidazole (PMI)
    Butylmethylimidazole (BMI)
    N, N-dimethylpyrrolidinium (Py11)
    N-methyl-N-ethylpyrrolidinium (Py12)
    N-methyl-N-butylpyrrolidinium (Py14)
    N, N-dimethyl-piperidinium (PP11)
    N-methyl-N-ethyl-piperidinium (PP12)
    N-methyl-N-propyl-piperidinium (PP13)
    N-methyl-N-butyl-piperidinium (PP14)
    Tetraethylphosphonium (P2222); or
    5-Phosphonia spiro [4.4] nonane (PS44).
  2. カチオンがテトラエチルアンモニウム（N2222）またはトリエチルメチルアンモニウム（N2221）である請求項１に記載のイオン液体。 The ionic liquid according to claim 1, wherein the cation is tetraethylammonium (N2222) or triethylmethylammonium (N2221).
  3. カチオンがテトラメチルアンモニウム（N1111）、エチルトリメチルアンモニウム（N1112）、またはn-プロピルトリメチルアンモニウム（N1113）である請求項１に記載のイオン液体。 The ionic liquid according to claim 1, wherein the cation is tetramethylammonium (N1111), ethyltrimethylammonium (N1112), or n-propyltrimethylammonium (N1113).
  4. カチオンがN,N-ジエチル-N-メチル-N-(2-メトキシエチル)アンモニウム(DEME)である請求項１に記載のイオン液体。 The ionic liquid according to claim 1, wherein the cation is N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (DEME).
  5. カチオンがテトラエチルホスホニウム（Ｐ2222）である請求項１に記載のイオン液体。 The ionic liquid according to claim 1, wherein the cation is tetraethylphosphonium (P2222).
  6. カチオンがN-メチル-N-プロピル-ピペリジニウム(PP13)である請求項１に記載のイオン液体。 The ionic liquid according to claim 1, wherein the cation is N-methyl-N-propyl-piperidinium (PP13).
  7. カチオンが5-アゾニアスピロ[4.4]ノナン(AS44)である請求項１に記載のイオン液体。  The ionic liquid according to claim 1, wherein the cation is 5-azoniaspiro [4.4] nonane (AS44).
PCT/JP2009/058579 2008-05-09 2009-05-01 Ionic liquid WO2009136608A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2010511070A JP5339542B2 (en) 2008-05-09 2009-05-01 Ionic liquid
US12/991,817 US20110070486A1 (en) 2008-09-10 2009-05-01 Ionic liquid

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2008123623 2008-05-09
JP2008-123623 2008-05-09
JP2008-231764 2008-09-10
JP2008231764 2008-09-10

Publications (1)

Publication Number Publication Date
WO2009136608A1 true WO2009136608A1 (en) 2009-11-12

Family

ID=41264664

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/058579 WO2009136608A1 (en) 2008-05-09 2009-05-01 Ionic liquid

Country Status (2)

Country Link
JP (1) JP5339542B2 (en)
WO (1) WO2009136608A1 (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010532071A (en) * 2007-06-29 2010-09-30 コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガニゼイション Lithium energy storage device
JP2011100777A (en) * 2009-11-04 2011-05-19 Sanyo Chem Ind Ltd Electrolyte and electrochemical element using the same
WO2012014938A1 (en) * 2010-07-30 2012-02-02 出光興産株式会社 Lubricant base oil and lubricant composition
WO2012042005A1 (en) * 2010-09-30 2012-04-05 Basf Se Additive for electrolytes
JP2012126846A (en) * 2010-12-16 2012-07-05 Mitsubishi Materials Corp Adhesive composition
JP2012204133A (en) * 2011-03-25 2012-10-22 National Institute Of Advanced Industrial & Technology Nonaqueous electrolyte lithium ion battery having carbonaceous negative electrode
JP2013177324A (en) * 2012-02-28 2013-09-09 National Institute Of Advanced Industrial Science & Technology Ionic liquid
JP2013196922A (en) * 2012-03-21 2013-09-30 National Institute Of Advanced Industrial & Technology Electrolyte for lithium ion battery
JP2014165110A (en) * 2013-02-27 2014-09-08 National Institute Of Advanced Industrial & Technology Lithium secondary battery using lithium molten salt for electrolyte
WO2016031961A1 (en) * 2014-08-29 2016-03-03 国立研究開発法人産業技術総合研究所 Ionic liquid and plastic crystal
JP2016033117A (en) * 2014-07-31 2016-03-10 国立大学法人鳥取大学 Ionic liquid, electrolyte for redox flow secondary battery, redox flow secondary battery and salt
JP2017091813A (en) * 2015-11-10 2017-05-25 日産自動車株式会社 Solid electrolyte having ion conductivity and electrochemical device using the same
US10049825B2 (en) 2012-04-27 2018-08-14 Semiconductor Energy Laboratory Co., Ltd. Cyclic quaternary ammonium salt, nonaqueous solvent, nonaqueous electrolyte, and power storage device
JP2020500159A (en) * 2016-10-19 2020-01-09 ハイドロ−ケベック Sulfamic acid derivatives and process for their preparation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101752638B1 (en) * 2015-08-12 2017-07-03 상명대학교산학협력단 Flame resistant electrolyte for lithium secondary battery and manufacturing method of the same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005200359A (en) * 2004-01-16 2005-07-28 Tosoh Corp Ionic compound

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005200359A (en) * 2004-01-16 2005-07-28 Tosoh Corp Ionic compound

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010532071A (en) * 2007-06-29 2010-09-30 コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガニゼイション Lithium energy storage device
JP2011100777A (en) * 2009-11-04 2011-05-19 Sanyo Chem Ind Ltd Electrolyte and electrochemical element using the same
WO2012014938A1 (en) * 2010-07-30 2012-02-02 出光興産株式会社 Lubricant base oil and lubricant composition
JP2012031275A (en) * 2010-07-30 2012-02-16 Idemitsu Kosan Co Ltd Lubricant base oil and lubricant composition
CN103201891A (en) * 2010-09-30 2013-07-10 巴斯夫欧洲公司 Additive for electrolytes
WO2012042005A1 (en) * 2010-09-30 2012-04-05 Basf Se Additive for electrolytes
JP2013542562A (en) * 2010-09-30 2013-11-21 ビーエーエスエフ ソシエタス・ヨーロピア Additive for electrolyte
JP2012126846A (en) * 2010-12-16 2012-07-05 Mitsubishi Materials Corp Adhesive composition
JP2012204133A (en) * 2011-03-25 2012-10-22 National Institute Of Advanced Industrial & Technology Nonaqueous electrolyte lithium ion battery having carbonaceous negative electrode
JP2013177324A (en) * 2012-02-28 2013-09-09 National Institute Of Advanced Industrial Science & Technology Ionic liquid
JP2013196922A (en) * 2012-03-21 2013-09-30 National Institute Of Advanced Industrial & Technology Electrolyte for lithium ion battery
US10049825B2 (en) 2012-04-27 2018-08-14 Semiconductor Energy Laboratory Co., Ltd. Cyclic quaternary ammonium salt, nonaqueous solvent, nonaqueous electrolyte, and power storage device
JP2014165110A (en) * 2013-02-27 2014-09-08 National Institute Of Advanced Industrial & Technology Lithium secondary battery using lithium molten salt for electrolyte
JP2016033117A (en) * 2014-07-31 2016-03-10 国立大学法人鳥取大学 Ionic liquid, electrolyte for redox flow secondary battery, redox flow secondary battery and salt
WO2016031961A1 (en) * 2014-08-29 2016-03-03 国立研究開発法人産業技術総合研究所 Ionic liquid and plastic crystal
JPWO2016031961A1 (en) * 2014-08-29 2017-06-08 国立研究開発法人産業技術総合研究所 Ionic liquids and plastic crystals
JP2017091813A (en) * 2015-11-10 2017-05-25 日産自動車株式会社 Solid electrolyte having ion conductivity and electrochemical device using the same
JP2020500159A (en) * 2016-10-19 2020-01-09 ハイドロ−ケベック Sulfamic acid derivatives and process for their preparation
US11345657B2 (en) 2016-10-19 2022-05-31 Hydro-Quebec Sulfamic acid derivatives and processes for their preparation
JP7171555B2 (en) 2016-10-19 2022-11-15 ハイドロ－ケベック Sulfamic acid derivatives and processes for their preparation

Also Published As

Publication number Publication date
JP5339542B2 (en) 2013-11-13
JPWO2009136608A1 (en) 2011-09-08

Similar Documents

Publication Publication Date Title
JP5339542B2 (en) Ionic liquid
US20110070486A1 (en) Ionic liquid
US8871974B2 (en) Ionic liquid containing phosphonium cation having P—N bond and method for producing same
EP2090565B1 (en) Ionic liquids of quaternary ammonium salts
Lee et al. Ionic liquids containing an ester group as potential electrolytes
Sanghi et al. Physicochemical properties of 1, 2, 3-triazolium ionic liquids
JP5950916B2 (en) Electrolyte formulation comprising cyano-alkoxy-borate anion
JP5674390B2 (en) Sulfone compound and non-aqueous electrolyte using the same
JP6145449B2 (en) Electrolytic solution for electrochemical devices, aluminum electrolytic capacitor and electric double layer capacitor
US20010033964A1 (en) Alkylspiroborate salts for use in electrochemical cells
JP2005139100A (en) Ordinary temperature melted salt
JP4322004B2 (en) Onium salt
KR102285191B1 (en) Silicon-containing sulfuric acid ester salt
JP4127788B2 (en) Onium salt
Wang et al. Physicochemical properties of functionalized 1, 3-dialkylimidazolium ionic liquids based on the bis (fluorosulfonyl) imide anion
JP2005104846A (en) Quaternary ammonium ambient-temperature molten salt and its manufacturing method
JP5227524B2 (en) Ionic liquid having sulfonium cation containing SN bond and method for producing the same
US8859800B2 (en) Compounds containing alkyl-alkoxy-cyano-borate anions
Koželj et al. Silylated quaternary ammonium salts–ionic liquids with hydrophobic cations
JP2005112733A (en) Onium salt
JP2012529450A (en) Novel imidazolium salts with liquid crystal properties useful as electrolytes
JP5703009B2 (en) Sulfone compound, method for producing sulfone compound, and electrolytic solution for electrochemical device
JP2000016983A (en) Salt, electrolysis solution and electrochemical device using the same
US8765296B2 (en) Ionic liquid
JP2023036567A (en) Ionic liquid, and composite electrolyte

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09742732

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010511070

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 12991817

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09742732

Country of ref document: EP

Kind code of ref document: A1