WO2018030564A1 - Method for preparing electrolyte ionic liquid containing ether group and having high ion conductivity - Google Patents

Abstract

The objective of the present invention is to provide an ionic liquid comprising an ether group at a cation, wherein the ionic liquids, having a cation comprising a methoxyethyl ether group at methylimidazolium, methylpyrrolidinium, methylpyridinium, methylmorpholinium, and triethylammonium and having, as an anion, tetrafluoroborate, hexafluorophosphate, bisfluorosulfonylimide, and bistrifluoromethanesulfonylimide, have excellent thermal stability of a TGA average of 388°C, an ion conductivity of 40.0 mS/cm or higher, and an electrochemical window of 5.1 V or higher.

Description

[Correction 23.08.2016 by Rule 26] 방법 Method for preparing ionic liquid for electrolyte containing ether group with high ionic conductivity

The present invention relates to a method for preparing an ionic liquid including an ether group having excellent thermal stability by TGA for a secondary battery electrolyte and having high ionic conductivity and an electrochemical window in solution. More specifically, the present invention has a cation in which an ether group is introduced into imidazolium (Imidazolium), pyrrolidinium (Pyrrolidinium), piperidinium (Piperidinium), morphorinium (Morpholinium), ammonium (temonium), and tetra Tetrafluoroborate (BF ₄ ), Hexafluorophosphate (PF ₆ ), Bisfluorosulfonylimide (FSI) and Bistrifluoromethanesulfonylimide (TFSI) The present invention relates to a method for preparing an ionic liquid for an secondary battery energy storage device (ESS) electrolyte comprising an ether group.

The redox flow battery is a secondary battery in which charging and discharging occur due to the redox reaction of the electrolyte. The main difference from the general battery is that the charge and discharge are performed while circulating the electrolyte in which energy is stored. The charging and discharging is carried out in a stack where oxidation and reduction electrochemical reactions occur, and the electricity is stored in the electrolyte in a separate tank. The battery stores power in the electrolyte. Can be discharged.

Currently, the redox flow battery has some commercialized water systems, but has a problem of low energy density of less than 26WH / L and low cell voltage of less than 1.25V. There is a limit.

In order to improve this, a non-aqueous redox flow battery electrolyte having excellent thermal stability and high ionic conductivity and voltage is prepared by preparing an ionic liquid including ether group in a new cation.

As a result of continuous research by the present inventors to solve the problems of the prior art as described above, imidazolium (Imidazolium), Pyrrolididinium (Pyrrolidinium), Piperidinium, Morpholinium (Morpholinium), Ammonium (Ammonium) using 1-bromoethylmethylether (1-Bromoethylmethylether) substituted by a reaction containing a cation containing a methoxyethyl ether group Tetrafluoroborate (BF ₄ ), Hexafluorophosphate (Hexafluorophosphate: PF ₆ ), bisfluorosulfonylimide (FSI) and bistrifluoromethanesulfonylimide (TFSI) in a method for producing an ionic liquid having an anion.

The ionic liquid for electrolytes containing an ether group in the cation has a thermal stability of more than 388 ° C and a high ionic conductivity of more than 40.1 mS / cm in solution phase as a result of differential thermal gravimetric analysis (TGA) analysis. ionic liquid substituted with an alkyl group in cation with a range of 2.0V or more is produced. Non-aqueous redox flow battery, electrolyte for lithium ion secondary battery, ultra capacitor, capacitor, dye-sensitized solar cell The present invention has been completed as the energy storage device electrolyte and electrochromic (EC) material such as electrolyte are expected to be very high.

In order to achieve the object of the present invention,

The cations include 1-bromoethyl methyl in methylimidazolium, methylpyrrolidinium, methylpiperidinium, methylmorpholinium, and triethylammonium. Tetrafluoroborate (BF ₄ ), Hexafluorophosphate (PF ₆ ), Bisflour with a cation containing a methoxyethyl ether group by substitution reaction using 0.8-1.4 equivalents of ether (1-Bromoethylmethylether) An ionic liquid is provided having 1.0-1.2 equivalents of bisfluorosulfonylimide (FSI) and bistrifluoromethanesulfonylimide (TFSI) as anions.

Ionic liquid according to the present invention thermogravimetric analysis (TGA) is in the range of 290 ~ 430 ℃,

Solution preparation for ionic conductivity measurements ranges from 31.0 to 46.0 mS / cm at 25 ° C in ionic liquid 1 molar (mol / L) acetonitrile, 0.1 mol + vanadium acetoacetonite 0.1 mol + acetonitrile In the acetonitrile solution the electrochemical potential window is between 3.5 and 6.0 V.

Therefore, the ionic liquid of the present invention has a very high ionic conductivity, a high decomposition point and a wide electrochemical potential window due to the improvement of the thermal decomposition temperature, and therefore, an electrolyte and an ultracapacitor for a non-aqueous redox flow battery and a lithium ion secondary battery. High capacity capacitors), capacitors, dye-sensitized solar cell electrolytes such as electrolytes and electrochromic (EC) materials can be widely used.

The ionic liquid containing an ether group in the cation according to the present invention has an excellent thermal stability of 388 ° C. on average, and has a wide electrochemical potential window of at least 40.0 mS / cm and at least 5.1 V. It is thought to be very useful as an electrolyte and electrochromic (EC) material for energy storage devices such as flow batteries, lithium ion secondary batteries, ultra capacitors, capacitors, and dye-sensitized solar cells.

1 is TG / DTA7300, SEICO INST. Differential thermal gravimetric analyzer.

2 is a measurement method of ionic conductivity is Measurement Method: 2 probe, Temperature: 25 ℃, Solution: Ionic Liquid (1mol) in acetonitrile. Biologics VMP3B-8's LSV (Linear Sweep Voltammetry) measuring instrument used in electrochemical potential window.

-Working Electrode: SUS 316 disk 16Φ, Surface area of 2.01Cm ₂

-Reference, Counter Electrode: Lithium

Scan rate (dE / dt): 5 mV / s, potential range:

2.95 ~ 7 V vs. Li / Li + (Anodic scan) @ RT

3.05 ~ 0 V vs. Li / Li + (Cathodic scan)

However, the ionic liquid which does not melt | dissolve in electrolyte solution did not measure the electrochemical potential window.

The present invention is a method for producing an ionic liquid including an ether group having excellent thermal stability by TGA for a secondary battery electrolyte and having a high ionic conductivity and an electrochemical window in solution.

That is, the present invention has a cation in which an ether group is introduced into imidazolium (Imidazolium), pyrrolidinium (Pyrrolidinium), piperidinium (Piperidinium), morpholinium (Morpholinium), and ammonium (Ammonium), and tetrafluoro Tetrafluoroborate (BF ₄ ), Hexafluorophosphate (PF ₆ ), Bisfluorosulfonylimide (FSI) and Bistrifluoromethanesulfonylimide (TFSI) as anions It is a method for preparing an ionic liquid for an energy storage device (ESS) electrolyte for a secondary battery including an ether (Ether) group having.

According to the present invention, a group consisting of methylimidazolium, methylpyrrolidinium, methylpiperidinium, methylpiperidinium, methylmorpholinium, and triethylammonium as cations The anion may be selected from tetrafluoroborate (BF ₄ ), hexafluorophosphate (PF ₆ ), bisfluorosulfonylimide (FSI) and bistrifluoromethanesulfonyl Imide (Bistrifluoromethanesulfonylimide (TFSI)) can be selected from the group consisting of.

According to the present invention, a group consisting of methylimidazolium, methylpyrrolidinium, methylpiperidinium, methylpiperidinium, methylmorpholinium, and triethylammonium as cations The anion may be selected from sodium tetrafluoroborate (NaBF ₄ ), potassium hexafluorofluorophosphate (KPF ₆ ), lithium bisfluorosulfonylimide (LiFSI), and lithium bistrifluorofluoride. Rho methanesulfonylimide (Lithiumbistrifluoromethanesulfonylimide: LiTFSI).

According to the present invention, a group consisting of methylimidazolium, methylpyrrolidinium, methylpiperidinium, methylpiperidinium, methylmorpholinium, and triethylammonium as cations The anion may be selected from hydrotetrafluoroborate (HBF ₄ ), hydrohexafluorophosphate (HPF ₆ ), hydrobisfluorosulfonylimide (HFSI) and hydrobistrifluorofluoro. It can be selected from the group consisting of acid reagents such as mydsulithiumbistrifluoromethanesulfonylimide (HTFSI).

In the present invention, in order to include an ether group in the cation, it is preferable to use a reagent such as 2-Bromoethyl methyl ether, 2-Chloroethyl methyl ether, 2-Iodoethyl ether or more.

According to the present invention, methylimidazolium (Methylimidazolium), methylpyrrolidinium (Methylpyrrolidinium), methylpiperidinium (Methylpiperidinium), methylmorpholinium (Methylmorpholinium) and triethylammonium (Triethylammonium) is 1.0 ~ 10mol Sodium tetrafluoroborate (NaBF ₄ ), potassium hexafluorophosphate (KPF ₆ ), lithium bisfluorosulfonylimide (LiFSI) and lithium bistrifluoromethanesulfonyl 0.8-10 mol of imide (Lithiumbistrifluoromethanesulfonylimide: LiTFSI) is added to the reaction, followed by synthesis of an organic layer to prepare an ionic liquid for electrolyte.

According to the present invention, methylimidazolium (Methylimidazolium), methylpyrrolidinium (Methylpyrrolidinium), methylpiperidinium (Methylpiperidinium), methylmorpholinium (Methylmorpholinium) and triethylammonium (Triethylammonium) is 1.0 ~ 10mol Hydrotetrafluoroborate (HBF ₄ ), Hydrohexafluorofluorophosphate (HPF ₆ ), Hydrobisfluorosulfonylimide (HFSI), Hydrobistrifluoromethanesulfonyl Reaction and synthesis are performed by adding 0.8-10 mol of mead (Hydrolithiumbistrifluoromethanesulfonylimide: HTFSI) to prepare an ionic liquid for electrolyte.

According to the present invention, an electrolyte or a conductive solvent of ACN (Acetonitrile), EC (Ethylene carbonate), PC (Propylene carbonate), and DMC (Dimethyl) are mixed with an ionic liquid + Vanadium (III) Acetylacetonate + Acetonitrile. Ether used for electrolyte composition such as carbonate), DEC (Diethyl carbonate), EMC (Ethyl methyl carbonate), EA (Ethylene acetate), and DMM (Dipropylene glycol dimethyl ether), DME (Dimethyl ether), DEE (Diethyl ether) A mixed composition of an ionic liquid containing an (Ether) group and a conductive solvent may be used.

The ionic liquid according to the present invention is a non-aqueous redox flow battery, a lithium ion secondary battery, an ultracapacitor (ultra capacitor), an energy storage device electrolyte such as a capacitor, a dye-sensitized solar cell electrolyte, and electrochromic (EC). ) Can be used as a material.

In the ionic liquid according to the present invention, the components of the product as described above may be used as composition additives, regulators or promoters or main raw materials.

In the following examples, the present invention will be described in more detail, but the examples are only illustrative of the present invention and the present invention is not limited thereto.

[Measurement of properties]

The structural information of the ionic liquid synthesized according to the following preparation was measured by ¹ H-, ¹⁹ F-NMR, and the basis of thermal stability was determined by TGA, and the ion conductivity (mS / cm) and electricity by LSV. The chemical potential window (V) was measured and the result is described in each Example.

[Production example]

Example 1:

Preparation of 1- (2-methoxyethyl) -3-methylimidazolium bis (trifluoromethylsulfonyl) -imide (MeoMIM-TFSI)

Add 40 g (0.181 mol) of MeoMIM-Br to a round flask, add distilled water, add 62.3 g (0.217 mol) of LiTFSI, and stir at room temperature for 12 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain 71.62 g of MeoMIM-TFSI.

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 8.74 (1H, NCHN, s), 7.39 (1H, NCHCN, s), 7.24 (1H, NCHCN, s), 4.53 (2H, NCCH ₂ O, t ), 3.95 (3H, OCH ₃ , s), 3.71 (2H, NCH ₂ CO, t), 3.37 (3H, NCH ₃ , s), TGA: 430.65 ° C, ion conductivity: 41.2 mS / cm at 25 ° C, electrical Chemical potential window: 4.5 V.

Example 2:

Preparation of 1- (2-methoxyethyl) -3-methylimidazoliumtetrafluoroborate ((MeoMIM-BF ₄ )

Add 40 g (0.181 mol) of MeoMIM-Br to a round flask, add 23.8 g (0.217 mol) of acetone and NaBF ₄ , and stir at room temperature for 12 hours. After the reaction was completed, the solvent was removed using distillation under reduced pressure to obtain 40.06 g of MeoMIM-BF ₄ .

¹ H-NMR (400 MHz, CDCl ₃ ): δH = 8.83 (1H, NCHN, s), 7.33 (1H, NCHCN, s), 7.20 (1H, NCHCN, s), 4.31 (2H, NCCH ₂ O, t ), 3.89 (3H, OCH ₃ , s), 3.66 (2H, NCH ₂ CO, t), 3.29 (3H, NCH ₃ , s), ¹⁹ F-NMR (300 MHz, CDCl ₃ ): δF = 151.546 (4F , BF ₄ ), TGA: 399.64 ° C., ion conductivity: 41.8 mS / cm at 25 ° C., Electrochemical window: 3.5 V.

Example 3:

Of 1- (2-methoxyethyl) -3-methylimidazolium hexafluorophosphate (MeoMIM-PF ₄ ) Produce

40 g (0.181 mol) of MeoMIM-Br is added to a round flask, and 50 ml of CH ₂ Cl ₂ and 39.9 g (0.217 mol) of KPF ₆ are added thereto, followed by stirring at room temperature for 12 hours. After the reaction was completed, the solvent was distilled under reduced pressure to obtain 49.20 g of MeoMIM-PF ₆ .

¹ H-NMR (400 MHz, DMSO): δH = 8.98 (1H, NCHN, s), 7.66 (1H, NCHCN, s), 7.62 (1H, NCHCN, s), 4.31 (2H, NCCH ₂ O, t) , 3.83 (3H, OCH ₃ , s), 3.66 (2H, NCH ₂ CO, t), 3.25 (3H, NCH ₃ , s), Thermal decomposition temperature (TGA): 400 ° C, ion conductivity: 35.7 mS / cm at 25 ° C., Electrochemical window: 5.0 V.

Example 4:

Preparation of 1- (2-methoxyethyl) -1-methylpyrrolidinium bis (trifluoromethylsulfonyl) -imide (MeoMPyr-TFSI)

41.85 g (0.186 mol) of MeoMPyr-Br is added to a round flask, distilled water is added, and 49.12 g (0.224 mol) of LiTFSI is added thereto, followed by stirring at room temperature for 12 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain 55.8 g of MeoMPyr-TFSI.

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 3.72 (2H, NCCH ₂ O, t), 3.51 (4H, CCH ₂ NCH ₂ C, m), 3.49 (2H, NCH ₂ CO, t), 3.31 (3H, OCH ₃ , s), 3.04 (3H, NCH ₃ , s), 2.19 (4H, CCH ₂ CH ₂ C, m), TGA: 417.37 ° C, Ion Conductivity: 40.4 mS / cm at 25 ° C, Electrochemical window : 6.0 V.

Example 5:

Preparation of 1- (2-methoxyethyl) -1-methylpyrrolidiniumtetrafluoroborate (MeoMPyr-BF4)

58.98 g (0.263 mol) of MeoMPyr-Br is added to a round flask, and acetone and 34.67 g (0.315 mol) of NaBF ₄ are added thereto, followed by stirring at room temperature for 12 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain 58.2 g of MeoMPyr-BF ₄ .

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 3.74 (2H, NCCH ₂ O, t), 3.60 (4H, CCH ₂ NCH ₂ C, m), 3.53 (2H, NCH ₂ CO, t), 3.31 (3H, OCH ₃ , s), 3.08 (3H, NCH ₃ , s), 2.18 (4H, CCH ₂ CH ₂ C, m), ¹⁹ F-NMR (300 MHz, CDCl ₃ ), δ F = 151.333 (4F, BF ₄ ), TGA: 406.55 ° C., ion conductivity: 42.9 mS / cm at 25 ° C., Electrochemical window: 4.5.

Example 6:

Preparation of 1- (2-methoxyethyl) -1-methylpyrrolidium hexafluorophosphate (MeoMPyr-PF ₆ )

46.99 g (0.209 mol) of MeoMPyr-Br is added to a round flask, and 50 ml of CH ₂ Cl ₂ and 46.31 g (0.251 mol) of KPF ₆ are added thereto, followed by stirring at room temperature for 12 hours. After the reaction was completed, the mixture was extracted and distilled under reduced pressure to obtain 57.6 g of MeoMPyr-PF ₆ .

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 3.74 (2H, NCCH ₂ O, t), 3.55 (2H, CCH ₁ NCH ₁ C, m), 3.51 (2H, NCH ₂ CO, t), 3.39 (2H, CCH ₁ NCH ₁ C, m), 3.32 (3H, OCH ₃ , s), 3.05 (3H, NCH ₃ , s), 2.18 (4H, CCH ₂ CH ₂ C, m), ¹⁹ F-NMR ( 300 MHz, CDCl ₃ ): δF = 70.909 (3F, PF ₃ ), 73.909 (3F, PF ₃ ), TGA: 401.25 ° C., ion conductivity: 45.6 mS / cm at 25 ° C.

Example 7:

Preparation of 1- (2-methoxyethyl) -1-methylpiperidiniumbis (trifluoromethylsulfonyl) -imide (MeoMPip-TFSI)

32.83 g (0.14 mol) of MeoMPip-Br is added to a round flask, distilled water is added, 47.48 g (0.17 mol) of LiTFSI is added, and the mixture is stirred at room temperature for 12 hours. After the reaction is completed, the mixture is extracted and the organic layer is removed by distillation under reduced pressure to obtain 58.8 g of MeoMPip-TFSI.

¹ H-NMR (400 MHz, DMSO): δH = 3.72 (2H, NCCH ₂ O, t), 3.66 (2H, NCH ₂ CO, t), 3.51 (2H, CCH ₁ NCH ₁ C, m), 3.32 ( 2H, CCH ₁ NCH ₁ C, m), 3.27 (3H, OCH ₃ , s), 3.01 (3H, NCH ₃ , s), 1.81 (4H, CCH ₂ CCH ₂ C, m), 1.52 (2H, CCCH ₂ CC, m), ¹⁹ F-NMR (300 MHz, CDCl ₃ ): δF = 78.902 (6F, N (SCF ₃ ) ₂ ), TGA: 411.97 ° C, ion conductivity: 36.9 mS / cm at 25 ° C, Electrochemical window: 4.5 V.

Example 8:

Preparation of 1- (2-methoxyethyl) -1-methylpiperidiumtetrafluoroborate (MeoMPip-BF ₄ )

Add 59.06 g (0.25 mol) of MeoMPip-Br to a round flask, add acetone and 32.67 g (0.30 mol) of NaBF ₄ and stir at room temperature for 12 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain 48 g of MeoMPip-BF ₄ .

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 3.76 (2H, NCCH ₂ O, t), 3.58 (2H, NCH ₂ CO, t), 3.48 (2H, CCH ₁ NCH ₁ C, m), 3.34 (2H, CCH ₁ NCH ₁ C, m), 3.30 (3H, OCH ₃ , s), 3.11 (3H, NCH ₃ , s), 1.84 (4H, CCH ₂ CCH ₂ CCH, m), 1.67 (2H, CCCH ₂ CC, m), ¹⁹ F-NMR (300 MHz, CDCl ₃ ): δF = 150.922 (4F, BF ₄ ), TGA: 397.71 ° C., ion conductivity: 40.8 mS / cm at 25 ° C.

Example 9:

Preparation of 1- (2-methoxyethyl) -1-methylpiperidium hexafluorophosphate (MeoMPip-PF ₆ )

47.61 g (0.2 mol) of MeoMPip-Br was added to a round flask, and 50 ml of CH ₂ Cl ₂ and 44.15 g (0.24 mol) of KPF ₆ were added thereto, followed by stirring at room temperature for 12 hours. After the reaction was completed, the mixture was extracted and distilled under reduced pressure to obtain 57.6 g of MeoMPip-PF ₆ .

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 3.74 (2H, NCCH ₂ O, t), 3.40 (2H, NCH ₂ CO, t), 3.34 (2H, CCH ₁ NCH ₁ C, m), 3.63 (2H, CCH ₁ NCH ₁ C, m), 3.06 (3H, OCH ₃ , s), 3.06 (3H, NCH ₃ , s), 1.83 (4H, CCH ₂ CCH ₂ C, m), 1.65 (2H, CCCH ₂ CC, m), ¹⁹ F-NMR (300 MHz, CDCl ₃ ): δF = 70.587 (3F, PF ₃ ), 73.110 (3F, PF ₃ ), TGA: 290 ° C, ion conductivity: 43.6 mS / cm at 25 ℃.

Example 10:

Preparation of 4- (2-methoxyethyl) -4-methylmorpholin-4-niumbis (trifluoromethyl-sulfonyl) imide (MeoMMor-TFSI)

Put 32.72g (0.14 mol) of MeoMMor-Br in a round flask, add distilled water, add 46.94g (0.163 mol) of LiTFSI, and stir at room temperature for 12 hours. After the reaction was completed, the mixture was extracted, and the organic layer was removed by distillation under reduced pressure to obtain 58.8 g of MeoMMor-TFSI.

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 3.93 (4H, CCH ₂ OCH ₂ C, t), 3.77 (2H, NCCH ₂ O, t), 3.65 (2H, NCH ₃ CO, t), 3.54 (2H, CCH ₁ NCH ₁ C, m), 3.39 (2H, CCH ₁ NCH ₁ C, m) 3.31 (3H, OCH ₃ , s), 3.21 (3H, NCH ₃ , s), ¹⁹ F-NMR (300 MHz, CDCl ₃ ): δF = 78.887 (6F, N (SCF ₃ ) ₂ ), TGA: 385.41 ° C., ionic conductivity: 34.4 mS / cm at 25 ° C., Electrochemical window: 4.5 V.

Example 11:

Preparation of 4- (2-methoxyethyl) -4-methylpololli-4niumtetrafluoroborate (MeoMMor-BF ₄ )

Add 59.06 g (0.25 mol) of MeoMMor-Br to a round flask, add 32.67 g (0.30 mol) of acetone and NaBF ₄ , and stir at room temperature for 12 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure to obtain 58.2 g of MeoMMor-BF ₄ .

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 4.11 (2H, NCCH ₂ O, t), 4.02 (4H, CCH ₂ OCH ₂ C, m), 3.92 (2H, NCCH ₃ CO, t), 3.81 (2H, CCH ₁ NCH ₁ C, m), 3.68 (2H, CCH ₁ NCH ₁ C, m) 3.53 (3H, OCH ₃ , s), 3.39 (3H, NCH ₃ , s), ¹⁹ F-NMR (300 MHz, CDCl ₃ ): δ F = 150.543 (4F, BF ₄ ), TGA: 376.52 ° C., ion conductivity: 31.0 mS / cm at 25 ° C.

Example 12:

Preparation of 4- (2-methoxyethyl) -4-methylmorpholin-4-nium hexafluorophosphate (MeoMMor-PF ₆ )

47.6 g (0.20 mol) of MeoMMor-Br is added to a round flask, and 50 ml of CH ₂ Cl ₂ and 44.15 g (0.24 mol) of KPF ₆ are added thereto, followed by stirring at room temperature for 12 hours. After the reaction was completed, the solvent was distilled under reduced pressure to obtain 7.2 g of MeoMMor-PF ₆ .

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 3.95 (2H, NCCH ₂ O, t), 3.81 (4H, CCH ₂ OCH ₂ C, m), 3.67 (2H, NCCH ₃ CO, t), 3.55 (2H, CCH ₁ NCH ₁ C, m), 3.38 (2H, CCH ₁ NCH ₁ C, m) 3.32 (3H, OCH ₃ , s), 3.23 (3H, NCH ₃ , s), ¹⁹ F-NMR (300 MHz, CDCl ₃ ): δF = 70.725 (3F, PF ₃ ), 73.249 (3F, PF ₃ ), TGA: 369.86 ° C., ion conductivity: 39.7 mS / cm at 25 ° C.

Example 13:

Preparation of Triethyl-2-methoxyethanaminiumbis (trifluoromethylsulfonyl) amide (MeoTEA-TFSI)

Add 32.72g (0.14 mol) of MeoTEA-Br to a round flask, add distilled water, add 46.93g (0.16 mol) of LiTFSI, and stir at room temperature for 12 hours. After the reaction was completed, the mixture was extracted and the organic layer was removed by distillation under reduced pressure to obtain 57.6 g of MeoTEA-TFSI.

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 3.73 (2H, NCCH ₂ O, t), 3.42 (2H, NCH ₂ CO, t), 3.36 (3H, OCH ₃ , s), 3.34 (6H, N (CH ₂ C) ₃ , m), 1.32 (9H, N (CCH ₃ ) ₃ , t), ¹⁹ F-NMR (300 MHz, CDCl ₃ ): δF = 78.847 (6F, N (SCF ₃ ) ₂ ) , TGA: 393.58 ° C., ion conductivity: 37.9 mS / cm at 25 ° C., Electrochemical window: 6.0 V.

Example 14:

Preparation of Triethyl-2- = methoxyethanaminitetrafluoroborate (MeoTEA-BF ₄ )

Add 58.32 g (0.24 mol) of MeoTEA-Br to a round flask, add 31.99 g (0.29 mol) of acetone and NaBF ₄ , and stir at room temperature for 12 hours. After the reaction was completed, 55.8 g of MeoTEA-BF ₄ was obtained by removing the solvent using distillation under reduced pressure.

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 3.76 (2H, NCCH ₂ O, t), 3.48 (2H, NCH ₂ CO, t), 3.39 (6H, N (CH ₂ C) ₃ , m) , 3.35 (3H, OCH ₃ , s), 1.32 (9H, N (CCH ₃ ) ₃ , t), ¹⁹ F-NMR (300 MHz, CDCl ₃ ): δF = 152.242 (4F, BF ₄ ), TGA: 379.87 ℃, ion conductivity: 46.0 mS / cm at 25 ℃.

Example 15:

Preparation of Triethyl-2-methoxyethanaminium hexafluorophosphate (MeoTEA-PF ₆ )

47.21 g (0.20 mol) of MeoMIM-Br is added to a round flask, and 50 ml of CH ₂ Cl ₂ and 43.42 g (0.24 mol) of KPF ₆ are added thereto, followed by stirring at room temperature for 12 hours. After the reaction was completed, the mixture was extracted and distilled under reduced pressure to obtain 56.4 g of MeoTEA-PF ₆ .

¹ H-NMR (400 MHz, CDCl ₃ ): δ H = 3.74 (2H, NCCH ₂ O, t), 3.42 (2H, NCH ₂ CO, t), 3.36 (3H, OCH ₃ , s), 3.35 (6H, N (CH ₂ C) ₃ , m), 1.32 (9H, N (CCH ₃ ) ₃ , t), ¹⁹ F-NMR (300 MHz, CDCl ₃ ): δF = 71.390 (3F, PF ₃ ), 73.912 (3F , PF ₃ ), TGA: 373.27 ° C., ion conductivity: 45.5 mS / cm at 25 ° C.

Claims (10)

The cation has one selected from the group consisting of imidazolium, pyrrolididinium, piperidinium, morpholinium, and ammonium. Tetrafluoroborate (BF ₄ ), Hexafluorophosphate (PF ₆ ), Bisfluorosulfonylimide (FSI), Bistrifluoromethanesulfonylimide (TFSI) Method for producing an ionic liquid for an electrolyte comprising an ether group having a high ion conductivity, characterized in that using a combination group of. The method of claim 1, wherein the cation comprises methylimidazolium, methylpyrrolidinium, methylpiperidinium, methylpiperidinium, methylmorpholinium, and triethylammonium. Selected from the group, an anion as tetrafluoroborate (BF ₄ ), hexafluorophosphate (PF ₆ ), bisfluorosulfonylimide (FSI) and bistrifluoromethanesulfonyl Imid (Bistrifluoromethanesulfonylimide: TFSI) A method for producing an ionic liquid for an electrolyte, characterized in that selected from the group consisting of. The method of claim 1, wherein the cation comprises methylimidazolium, methylpyrrolidinium, methylpiperidinium, methylpiperidinium, methylmorpholinium, and triethylammonium. Selected from the group, and anions include sodium tetrafluoroborate (NaBF ₄ ), potassium hexafluorofluorophosphate (KPF ₆ ), lithium bisfluorosulfonylimide (LiFSI) and lithium bistrifluorofluoride; Process for producing an ionic liquid for an electrolyte, characterized in that selected from the group consisting of methanesulfonylimide (Lithiumbistrifluoromethanesulfonylimide: LiTFSI). The method of claim 1, wherein the cation comprises methylimidazolium, methylpyrrolidinium, methylpiperidinium, methylpiperidinium, methylmorpholinium, and triethylammonium. Selected from the group, anion, hydrotetrafluoroborate (HBF ₄ ), hydrohexafluorophosphate (HPF ₆ ), hydrobisfluorosulfonylimide (HFSI) and hydrobistrifluorofluoro; A method for producing an ionic liquid for an electrolyte, characterized in that it is selected from the group consisting of acid reagents such as rho methanesulfonylimide (Hydrolithium bistrifluoromethanesulfonylimide: HTFSI). The method according to claim 1, characterized in that a reagent such as 2-Bromoethyl methyl ether, 2-Chloroethyl methyl ether, 2-Iodoethyl ether or the like is used in order to include an ether group in the cation. Method for producing an ionic liquid for an electrolyte. According to claim 1, Methylimidazolium (Methylimidazolium), Methylpyrrolidinium (Methylpyrrolidinium), Methylpiperidinium (Methylpiperidinium), Methylmorpholinium (Methylmorpholinium) and Triethylammonium (Triethylammonium) is 1.0-10 mol Sodiumtetrafluoroborate (NaBF ₄ ), Potassium hexafluorophosphate (KPF ₆ ), Lithiumbisfluorosulfonylimide (LIFSI) and lithium bistrifluoromethanesulfonyl Method of producing an ionic liquid for an electrolyte, characterized in that the reaction is added to 0.8 ~ 10 mol of imide (Lithiumbistrifluoromethanesulfonylimide: LiTFSI), taking the organic layer and synthesized. According to claim 1, Methylimidazolium (Methylimidazolium), Methylpyrrolidinium (Methylpyrrolidinium), Methylpiperidinium (Methylpiperidinium), Methylmorpholinium (Methylmorpholinium) and Triethylammonium (Triethylammonium) is 1.0-10 mol Hydrotetrafluoroborate (HBF ₄ ), Hydrohexafluorofluorophosphate (HPF ₆ ), Hydrobisfluorosulfonylimide (HFSI), Hydrobistrifluoromethanesulfonyl Method for producing an ionic liquid for an electrolyte, characterized in that the synthesis after the reaction by adding an imide (Hydrolithiumbistrifluoromethanesulfonylimide: HTFSI) 0.8 ~ 10mol. The method of claim 1, wherein the ionic liquid + Vanadium (III) Acetylacetonate + Acetonitrile solvent is mixed with an electrolyte or a conductive solvent of ACN (Acetonitrile), EC (Ethylene carbonate), PC (Propylene carbonate), DMC ( Dimethyl carbonate (DEC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), ethylene acetate (EA), etc. and dipropylene glycol dimethyl ether (DMM), dimethyl ether (DME), and diethyl ether (DEE) A method for producing an electrolyte ionic liquid, characterized in that the composition consisting of a mixture of an ionic liquid containing an ether group and a conductive solvent. The energy storage device according to any one of claims 1 to 8, wherein the non-aqueous redox flow battery, the lithium ion secondary battery, the ultracapacitor, the capacitor, and the dye-sensitized solar cell electrolyte are used. Method for producing an electrolyte ionic liquid, characterized in that used as an electrolyte and electrochromic (EC) material. An ionic liquid for an electrolyte, which is used as a composition additive, a regulator or an accelerator, or a main raw material of a component of a product as in claim 9 using the manufacturing method according to any one of claims 1 to 8.

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