WO2016084792A1 - Liquide ionique, son procédé de préparation et son utilisation - Google Patents

Liquide ionique, son procédé de préparation et son utilisation Download PDF

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WO2016084792A1
WO2016084792A1 PCT/JP2015/082916 JP2015082916W WO2016084792A1 WO 2016084792 A1 WO2016084792 A1 WO 2016084792A1 JP 2015082916 W JP2015082916 W JP 2015082916W WO 2016084792 A1 WO2016084792 A1 WO 2016084792A1
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ionic liquid
cation
melting point
onium
salt
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PCT/JP2015/082916
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English (en)
Japanese (ja)
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国府英司
高田照久
千葉一美
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カーリットホールディングス株式会社
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Priority to JP2016561891A priority Critical patent/JP6671079B2/ja
Publication of WO2016084792A1 publication Critical patent/WO2016084792A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
    • 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
    • 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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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

Definitions

  • the present invention relates to an ionic liquid obtained by mixing an alkali metal salt and an onium salt, a production method thereof, and an application thereof.
  • Ionic liquids can be used as battery electrolytes with unique characteristics that are different from those of conventional electrolyte systems, and as environmentally friendly solvents for organic / inorganic reactions, catalytic reactions, biochemical reactions, and liquid-liquid extraction separations. Possibilities are being considered.
  • a secondary battery using an electrolytic solution containing an ionic liquid made of a compound having a low melting point made of an onium salt as a solvent and an alkali metal salt dissolved in the solvent is known.
  • Patent Document 1 discloses a lithium secondary battery including a non-aqueous electrolyte containing a lithium salt.
  • This nonaqueous electrolytic solution contains an ionic liquid containing a bis (fluorosulfonyl) imide anion as an anionic component.
  • This ionic liquid is liquid at room temperature and is used as a solvent.
  • Patent Document 2 includes an ionic liquid having a melting point of 50 ° C. or less, a compound that is reduced and decomposed at a noble potential from the ionic liquid, and a lithium salt, A secondary battery using the same is disclosed.
  • an object of the present invention is to provide an ionic liquid having a low melting point obtained by using a molecule having high ion conductivity, a method for producing the ionic liquid, and various uses of the ionic liquid.
  • the production method of the present invention is characterized by mixing an onium salt having a melting point of 50 ° C. or more and an alkali metal salt having a melting point of 50 ° C. or more.
  • the original onium salt and An ionic liquid having a melting point lower than 100 ° C. and lower than the melting point of both alkali metal salts is obtained.
  • the alkali metal salt is preferably a lithium salt.
  • the onium cation in the onium salt is preferably a quaternary ammonium cation, a pyrrolidinium cation, a piperidinium cation or an imidazolium cation.
  • the onium cation is preferably the following formula (1) A quaternary ammonium cation represented by However, the four R 1 are preferably each independently an alkyl group having 1 or 2 carbon atoms.
  • the onium cation is represented by the following formula (2):
  • n is 4 or 5.
  • Two R 2 are preferably each independently an alkyl group having 1 or 2 carbon atoms, or two R 2 are bonded to form an alkylene group having 4 or 5 carbon atoms.
  • the onium cation is represented by the following formula (3): It is an imidazolium cation represented by.
  • Z is preferably a hydrogen atom or a methyl group, and the two R 3 are preferably each independently an alkyl group having 1 or 2 carbon atoms.
  • the ratio of the molar amount of the alkali metal salt (M A ) to the molar amount of the onium salt (M O ) is preferably in the range of M A / M O of 1/9 to 7/3.
  • the ionic liquid obtained by the manufacturing method described above is also an embodiment of the present invention.
  • the ionic liquid of the present invention is composed of a mixture of an onium salt having a melting point of 50 ° C. or higher and an alkali metal salt having a melting point of 50 ° C. or higher, and the melting points of both the original onium salt and the alkali metal salt. And a melting point of 100 ° C. or lower.
  • This ionic liquid preferably contains no solvent.
  • the solvent refers to a compound of the above mixture having a melting point of less than 50 ° C.
  • the ionic liquid of the present invention is useful as a battery electrolyte, an organic reaction solvent or an extraction solvent, and a device having this ionic liquid is also an embodiment of the present invention.
  • an ionic liquid having a melting point lower than the melting point of each component can be obtained by mixing two or more components of the electrolyte.
  • an ionic liquid using an onium salt that does not become an ionic liquid as a single substance can be provided.
  • onium salts with a high melting point have low molecular weight, good molecular symmetry, excellent crystallinity, and excellent ionic conductivity when dissolved in a solvent. It was difficult to make an ionic liquid by itself.
  • onium salts having a high melting point are difficult to dissolve alkali metal salts at room temperature, it has been considered difficult to use them as secondary batteries that can be driven at room temperature.
  • an ionic liquid having a low melting point can be obtained even if the onium salt itself used as a raw material has a high melting point.
  • the ionic liquid thus obtained tends to have a low viscosity due to the low molecular weight of the cation used, and is a molten salt with a low melting point, so that, for example, high ionic conductivity exceeding 1 mS / cm at room temperature is achieved. Can do.
  • the molten salt obtained by the present invention can be kept in a liquid state even at a low temperature of 0 ° C. or lower depending on the mixed composition.
  • the secondary battery using the ionic liquid obtained by the present invention as an electrolytic solution has good rate characteristics even at room temperature because the electrolytic solution exhibits low viscosity and high ionic conductivity, and no solvent is used. Therefore, it is non-volatile, flame retardant, and excellent in safety.
  • an onium salt and an alkali metal salt are mixed.
  • an onium salt having a melting point of 50 ° C. or higher is used, and an alkali metal salt having a melting point of 50 ° C. or higher is used.
  • An ionic liquid is a liquid salt composed of ions (anions and cations).
  • an ionic liquid having a melting point of 100 ° C. or lower is called an ionic liquid.
  • the melting point of the ionic liquid is preferably 65 ° C. or lower, more preferably 30 ° C. or lower.
  • the ionic liquid obtained by the present invention has a melting point lower than the melting point of the used onium salt and lower than the melting point of the used alkali metal.
  • an onium salt having a melting point of 50 ° C. or higher is used.
  • the molecular weight (formula) of the onium cation moiety is 150 or less.
  • small molecules tend to have low viscosity and high conductivity, but small molecules and high molecular structure symmetry tend to increase crystallinity when solidified. Therefore, the melting point with a single onium salt is high. Therefore, mixing an onium salt with a small molecular weight to make an ionic liquid is effective for lowering the viscosity of the obtained ionic liquid, improving conductivity, and the like.
  • the melting point of the onium salt is 50 ° C. or higher, preferably 55 ° C.
  • the upper limit of the melting point of the onium salt is not particularly limited, and examples thereof include 400 ° C.
  • the molecular weight (formula) of the onium cation moiety is preferably 150 or less, more preferably 120 or less.
  • the lower limit of the molecular weight (formula) is not particularly limited, and is, for example, 70.
  • the cation in the onium salt is preferably a quaternary ammonium cation, a pyrrolidinium cation, a piperidinium cation or an imidazolium cation.
  • the quaternary ammonium cation is preferably a cation represented by the above formula (1).
  • four R 1 s are each independently an alkyl group having 1 or 2 carbon atoms, and preferably all four R 1 s are the same alkyl group because of the high symmetry of the molecular structure.
  • the pyrrolidinium cation and the piperidinium cation are preferably cations represented by the above formula (2).
  • Two R 2 s in the formula (2) are each independently an alkyl group having 1 or 2 carbon atoms, or two R 2 are bonded to form an alkylene group having 4 or 5 carbon atoms.
  • the two R 2 are preferably the same alkyl group because of the high symmetry of the molecular structure.
  • the imidazolium cation is preferably a cation represented by the above formula (3).
  • Z in Formula (3) is a hydrogen atom or a methyl group.
  • R 3 in the formula (3) are each independently an alkyl group having 1 or 2 carbon atoms. Preferably two R 3 are the same alkyl group because of the high symmetry of the molecular structure.
  • these suitable onium cations include, but are not limited to, tetramethylammonium cation, ethyltrimethylammonium cation, diethyldimethylammonium cation, triethylmethylammonium cation, tetraethylammonium cation, dimethylpyrrolidinium cation, ethylmethyl Pyrrolidinium cation, diethyl pyrrolidinium cation, dimethyl piperidinium cation, ethyl methyl piperidinium cation, diethyl piperidinium cation, dimethyl imidazolium cation, trimethyl imidazolium cation, azonia spiro [4.4] cation, azonia spiro [4 .5] cations, azonia spiro [5,5] cations, and the like.
  • the anion in the onium salt is not particularly limited, and is not limited to F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , N (FSO 2 ) 2 ⁇ , N (FSO 2 ) (CF 3 SO 2 ) ⁇ , N ( CF 3 SO 2 ) 2 ⁇ , N (CF 3 CF 2 SO 2 ) 2 ⁇ , N (C 2 H 5 SO 2 ) 2 ⁇ , CF 3 SO 3 ⁇ , CF 3 CF 2 SO 3 ⁇ , PF 6 ⁇ , BF 4 ⁇ , ClO 4 ⁇ , AsF 6 ⁇ and the like can be mentioned.
  • the onium salt For obtaining the onium salt, a commercially available product may be used, or a conventionally known production method may be appropriately referred to.
  • a desired onium cation halide as described in Examples below, etc. May be mixed with an alkali metal salt of a desired anion under an aqueous solution, and then the desired onium salt may be extracted with an organic solvent.
  • an onium salt When an onium salt is obtained by synthesis, it may be purified by a recrystallization method or the like, or dried under reduced pressure.
  • Alkali metal salt examples of the alkali metal cation in the alkali metal salt include a lithium cation, a sodium cation, and a potassium cation.
  • an alkali metal salt having a melting point of 50 ° C. or higher is used.
  • the melting point of ordinary alkali metal salts is 50 ° C. or higher, and these can be used without any particular limitation.
  • N (FSO 2 ) 2 ⁇ , N (CF 3 SO 2 ) 2 ⁇ , and BF 4 ⁇ are preferable because they can further reduce the viscosity of the molten salt.
  • alkali metal salt a commercially available product or the like may be used as it is, or it may be produced by appropriately referring to conventional techniques.
  • the above-described onium salt and alkali metal salt are mixed to obtain an ionic liquid.
  • the onium salt and the metal salt may be chemically brought into contact with each other, and for example, dry mixing or wet mixing using an appropriate solvent may be used.
  • the solvent is preferably distilled off after mixing.
  • a mixture having a lower melting point than the original onium salt, a lower melting point than the original alkali metal salt, and a melting point of 100 ° C. or less is obtained.
  • Non-limiting examples of specific mixing steps are described in the examples below.
  • the preferred range for the ratio of both salts in obtaining a low melting point ionic liquid by mixing an onium salt and an alkali metal salt is as follows.
  • the ratio of the molar amount (M A ) of the alkali metal salt to the molar amount (M O ) of the onium salt is preferably such that M A / M O is in the range of 1/9 to 7/3.
  • two or more onium salts and / or alkali metal salts may be mixed.
  • a “ternary” ionic liquid can be obtained by mixing two kinds of onium salts and one kind of alkali metal salt.
  • the ionic liquid of the present invention is composed of a mixture of an onium salt having a melting point of 50 ° C. or higher and an alkali metal salt having a melting point of 50 ° C. or higher, and the melting points of both the original onium salt and the alkali metal salt. And a melting point of 100 ° C. or lower.
  • the ionic liquid of the present invention preferably does not contain a solvent.
  • the “solvent” refers to a substance other than the above mixture and having a melting point of less than 50 ° C. By not containing a solvent, the advantages of the ionic liquid itself can be more effectively demonstrated.
  • the ionic liquid of the present invention may contain other components in addition to the above-mentioned mixture of onium salt and alkali metal, though not necessarily preferable.
  • examples of such other components include, but are not limited to, acetonitrile, ethylene carbonate, sulfolane, tetraethylene glycol dimethyl ether, and vinylene carbonate.
  • the proportion of the salt formed by mixing the onium salt and the alkali metal salt in the ionic liquid of the present invention is preferably 80% by mass or more, and more preferably 90% by mass or more. Most preferably, the ionic liquid consists only of a mixture of the above-described onium salt and alkali metal salt.
  • the ionic liquid is preferably used alone or mixed with a solvent as the battery electrolyte or electrolyte.
  • the battery may be a primary battery or a secondary battery, for example, a lithium ion battery.
  • the solvent that can be used is not particularly limited, and examples thereof include known nonaqueous organic solvents such as ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, ⁇ -butyrolactone, dimethoxyethane, methyl acetate, and methyl formate. Non-limiting examples.
  • the ionic liquid described above may be used as the electrolyte, or a gel electrolyte in which this is fixed with a polymer matrix.
  • the battery such as a lithium ion secondary battery
  • the prior art can be referred to as appropriate.
  • the positive electrode, the negative electrode, the separator, etc. of the battery may be used as they are, or the battery
  • the shape include a cylindrical shape, a square shape, a coin shape, and a film shape.
  • examples of the negative electrode material include lithium metal and alloys thereof, carbon materials and polymer materials that can be doped / undoped with lithium, lithium intercalation compounds such as metal oxides, and the like.
  • Examples thereof include composite oxides of lithium and transition metals such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , and LiMnO 2 , polymer materials, and the like.
  • Examples of the separator include a porous film made of a polymer material such as polyethylene and polypropylene.
  • a material of the current collector for example, copper, aluminum, stainless steel, titanium, nickel, tungsten steel, carbon material and the like are used, and the shape thereof includes foil, net, nonwoven fabric, punched metal and the like. In the examples described later, examples of manufacturing coin-type batteries are given.
  • the ionic liquid can be used as a solvent for various organic synthesis reactions.
  • the above-mentioned ionic liquid has low solubility in water.
  • a two-phase reaction field composed of an aqueous phase and an ionic liquid can be constructed.
  • the ionic liquid described above may be used for the construction of a three-phase reaction field composed of a low polarity organic solvent / water / room temperature molten salt. This is because the ionic liquid is hardly soluble in an organic solvent having low polarity such as toluene, ethyl acetate, diethyl ether and the like.
  • an ionic liquid may be used as a reaction solvent and then used as an extraction solvent for separation and purification.
  • the above-described ionic liquid may be used as an extraction solvent for separation and purification in an organic synthesis reaction.
  • the reaction solvent is distilled off from the reaction mixture using a metal catalyst, and ether and ionic liquid are added to the resulting residue, the reaction product is held in the ether phase, and the metal catalyst is held in the ionic liquid. be able to.
  • the above ionic liquid may be used as an electrolytic solution for plating.
  • the ionic liquid obtained in the present invention is suitable because it has high heat resistance, a wide temperature range in the liquid state, and high ionic conductivity.
  • the ionic liquid may be used as a capacitor electrolyte such as an electric double layer capacitor, an electrorheological fluid, a heat storage medium, a catalyst, or the like.
  • LiFSI lithium bis (fluorosulfonyl) imide
  • LiTFSI lithium bis (fluoromethanesulfonyl) imide
  • SBP-FSI 5-azoniaspiro [4,4] nonanebis (fluorosulfonyl) imide
  • SBP-BF4 5-azoniaspiro [4,4] nonane Tetrafluoroborate
  • SBP-TFSI 5-azoniaspiro [4,4] nonanebis (trifluoromethanesulfonyl) imide
  • TMA-FSI tetramethylammonium bis (fluorosulfonyl) imide
  • DMI-FSI dimethylimidazolium bis (fluorosulfonyl) imide
  • DEDMA- FSI diethyldimethylammonium bis (fluorosulfonyl) imide
  • DEDMA-TFSI diethyldimethylammonium bis (fluorosulfon
  • Example 1 an ionic liquid obtained by mixing LiFSI and SBP-FSI was produced as follows (molar ratio, 3: 7).
  • SBP-FSI 1 H-NMR (CD3OD, TMS, 300.4MHz) ⁇ 2.22 (m, 8H), ⁇ 3.55 (m, 8H) 19 F-NMR (CD3CN, CFCl3,470.6 MHz): ⁇ 56.6 (s, 2F)
  • ⁇ Viscosity measurement> An E-type viscometer manufactured by Tokimec Co., Ltd. was used. First, the viscometer was calibrated with JS50 standard solution. Then, the thermostat was set to 25 ° C., 1 ml of the sample was injected into the apparatus, and the viscosity of the sample at 25 ° C. was measured.
  • FIG. 1 shows an output example from the DSC apparatus.
  • the liquid at 30 ° C. or lower is kept in a ⁇ 20 ° C. constant temperature bath for 24 hours, and when the liquid is held, it is judged that it is lower than ⁇ 20 ° C. (denoted as “ ⁇ 20” in the table below) When the liquid state was not retained, it was determined that the temperature was ⁇ 20 ° C. to 30 ° C. (denoted as “ ⁇ 30” in the table below).
  • Example 2 to 18 As in Example 1, ionic liquids were produced and evaluated using other compounds. In addition, the viscosity measurement was not performed about what is solid at 25 degreeC. Even such an ionic liquid can enjoy the effects of the present invention depending on the temperature range to be used, and therefore is within the scope of the present invention.
  • the raw materials used in the production of each ionic liquid are as follows. In addition, what was manufactured by the well-known method was used for the halide of onium cation. LiTFSI: Nippon Solvay Co., Ltd. KTFSI: Mitsubishi Materials Electronics Chemical Co., Ltd.
  • Table 1 shows the measurement results of the melting point of a single electrolyte before mixing.
  • Tables 2 to 6 show the measurement results of LiFSI-onium FSI ionic liquid.
  • Table 7 shows the measurement results of LiTFSI-onium FSI ionic liquid.
  • Table 8 shows the measurement results of LiTFSI-onium TFSI ionic liquid.
  • Table 9 shows the measurement results of LiFSI-onium BF4 ionic liquid.
  • Tables 10 to 11 show the measurement results of the ternary ionic liquid.
  • the ionic liquid of the present invention was electrochemically stable, with no decomposition observed over a wide range of potentials.
  • This coating solution was coated on an aluminum foil having a thickness of 20 ⁇ m with a coating machine, dried at 80 ° C., and then subjected to a roll press treatment to obtain a positive electrode having a positive electrode active material weight of 7.4 mg / cm 2 .
  • This coating solution was coated on a copper foil having a thickness of 18 ⁇ m with a coating machine, dried at 80 ° C., and then subjected to a roll press treatment to obtain a negative electrode having a negative electrode active material weight of 3.4 mg / cm 2 .
  • the battery was evaluated using a 2032 standard stainless steel coin cell manufactured by Hosen Co., Ltd.
  • a cross-sectional view of the manufactured coin-type battery 10 is shown in FIG.
  • the positive electrode 1 a positive electrode prepared in a dry room controlled at a dew point of ⁇ 40 ° C. or lower was punched to ⁇ 14.
  • the prepared negative electrode 2 was punched into ⁇ 16.
  • the positive electrode 1 has a positive electrode current collector 1a
  • the negative electrode 2 has a negative electrode current collector 2a.
  • a polyethylene separator 7 was punched into ⁇ 19, and a negative electrode 2, a separator 7, a gasket 6, a positive electrode 1, and a stainless steel spacer (1 mm) leaf spring were combined in this order.
  • the electrolytic solution was impregnated under reduced pressure at ⁇ 0.09 MPa for 1 hour.
  • These power generation elements were housed in a stainless steel case (consisting of a positive electrode case 4 and a negative electrode case 5).
  • the positive electrode case 4 and the negative electrode case 5 serve as a positive electrode terminal and a negative electrode terminal.
  • a gasket 6 made of polypropylene is interposed between the positive electrode case 4 and the negative electrode case 5 to ensure sealing and insulation between the positive electrode case 4 and the negative electrode case 5. Thereafter, the cell was sealed with a caulking machine to obtain a secondary battery cell for evaluation.
  • discharge rate test Using a charge / discharge test apparatus, the upper limit voltage is regulated to 4.2V, the lower limit voltage is regulated to 2.7V, the charge is regulated to a 0.1C time rate, and the discharge rate is 0.1C, 0.2C, 0.5C. 1C, 2C, 3C, 5C, and 10C were specified, and the expression capacity at the time of rapid discharge was confirmed.
  • Example 17 The ionic liquid used in the secondary battery of each example is as follows. Secondary battery Ionic liquid Example 19 Example 1 Example 20 Example 2 Example 21 Example 3 Example 22 Example 6 Example 23 Example 7 Example 24 Example 8 Example 25 Example 9 Example 26 Example 11 Example 27 Example 12 Example 28 Example 13 Example 29 Example 14 Example 30 Example 15 Example 31 Example 17
  • Table 12 shows the charge / discharge cycle test results.
  • the lithium ion secondary battery using the ionic liquid of the present invention can obtain a cycle capacity retention rate and a better discharge capacity equivalent to those at 20 ° C. driving at a battery driving temperature of 60 ° C.
  • FIG. 4 shows the discharge rate test results at 20 ° C. for the secondary batteries of Examples 19-21.
  • the lithium ion secondary battery using the ionic liquid of the present invention can exhibit a good discharge capacity in 1C rate discharge at 20 ° C. In comparison between Examples 19, 20, and 21, the best rate characteristics are obtained with the battery of Example 21.
  • the rate characteristics of the ionic liquid of Example 3 having a high molar ratio of the Li salt having a high viscosity can be obtained.
  • the ionic liquid of the present invention is useful as an electrolytic solution for a secondary battery that is driven with good durability and rate characteristics in a wide temperature range from room temperature to medium temperature.
  • Positive electrode 1a Positive electrode current collector 2: Negative electrode 2a: Negative electrode current collector 3: Electrolyte solution 4: Positive electrode case 5: Negative electrode case 6: Gasket 7: Separator 10: Coin type battery 11: Reduction-side linear sweep voltammetry Measurement result 12: Measurement result of linear sweep voltammetry on the oxidation side

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Abstract

[Problème] L'invention vise à fournir : un liquide ionique possèdant un bas point de fusion, le liquide ionique étant obtenu à l'aide d'un polymère hautement conducteur d'ions ; son procédé de production ; et diverses utilisations de ce liquide ionique. [Solution] L'invention concerne un procédé de production d'un liquide ionique possédant un point de fusion qui est inférieur ou égal à 100 °C et inférieur aux points de fusion à la fois d'un sel d'onium naturel et d'un sel de métal alcalin, caractérisé en ce que le sel d'onium possédant un point de fusion supérieur ou égal à 50 °C et le sel de métal alcalin possédant un point de fusion supérieur ou égal à 50 °C sont mélangés. Le liquide ionique résultant de ce procédé de production peut être utilisé de manière appropriée dans la solution électrolytique de piles secondaires et dans d'autres applications similaires.
PCT/JP2015/082916 2014-11-28 2015-11-24 Liquide ionique, son procédé de préparation et son utilisation WO2016084792A1 (fr)

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Cited By (8)

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JP2017091813A (ja) * 2015-11-10 2017-05-25 日産自動車株式会社 イオン伝導性を有する固体電解質およびこれを用いた電気化学デバイス
JP2018116840A (ja) * 2017-01-18 2018-07-26 Tdk株式会社 リチウム二次電池
JP2019008958A (ja) * 2017-06-23 2019-01-17 住友電気工業株式会社 溶融塩電解質およびカリウム溶融塩電池
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JP2020057523A (ja) * 2018-10-02 2020-04-09 エリーパワー株式会社 リチウムイオン電池の製造方法及びリチウムイオン電池
KR20200059924A (ko) * 2018-11-22 2020-05-29 건국대학교 글로컬산학협력단 이미다졸륨 기반 리튬 염, 이의 제조방법 및 이를 포함하는 전해질 조성물
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JP2018116840A (ja) * 2017-01-18 2018-07-26 Tdk株式会社 リチウム二次電池
JP2019008958A (ja) * 2017-06-23 2019-01-17 住友電気工業株式会社 溶融塩電解質およびカリウム溶融塩電池
US20190173131A1 (en) * 2017-12-05 2019-06-06 Toyota Motor Engineering & Manufacturing North America, Inc. Aqueous electrolytes with bis(fluorosulfonyl)imide salt electrolyte and ionic liquid system and batteries using the electrolyte system
US10868339B2 (en) * 2017-12-05 2020-12-15 Toyota Motor Engineering & Manufacturing North America, Inc. Aqueous electrolytes with bis(fluorosulfonyl)imide salt electrolyte and ionic liquid system and batteries using the electrolyte system
JP7231188B2 (ja) 2018-10-02 2023-03-01 エリーパワー株式会社 リチウムイオン電池の製造方法
JP2020057523A (ja) * 2018-10-02 2020-04-09 エリーパワー株式会社 リチウムイオン電池の製造方法及びリチウムイオン電池
JP7461677B2 (ja) 2018-10-02 2024-04-04 エリーパワー株式会社 リチウムイオン電池の製造方法
KR20200059924A (ko) * 2018-11-22 2020-05-29 건국대학교 글로컬산학협력단 이미다졸륨 기반 리튬 염, 이의 제조방법 및 이를 포함하는 전해질 조성물
KR102195257B1 (ko) * 2018-11-22 2020-12-24 건국대학교 글로컬산학협력단 이미다졸륨 기반 리튬 염, 이의 제조방법 및 이를 포함하는 전해질 조성물
KR20200133450A (ko) * 2019-05-20 2020-11-30 건국대학교 글로컬산학협력단 이미다졸륨 기능화된 이미드 기반 리튬 염, 이의 제조방법 및 이를 포함하는 리튬 이온 배터리용 전해질 조성물
KR102240799B1 (ko) 2019-05-20 2021-04-16 이피캠텍 주식회사 이미다졸륨 기능화된 이미드 기반 리튬 염, 이의 제조방법 및 이를 포함하는 리튬 이온 배터리용 전해질 조성물
WO2021138370A1 (fr) * 2019-12-30 2021-07-08 The Board Of Trustees Of The Leland Stanford Junior University Batteries au lithium-métal à haute sécurité et haute capacité dans un électrolyte liquide ionique avec additif de sodium

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