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WO2005042466A1 - Sel d'ammonium quaternaire, electrolyte, solution d'electrolyte et dispositif electrochimique - Google Patents

Sel d'ammonium quaternaire, electrolyte, solution d'electrolyte et dispositif electrochimique Download PDF

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Publication number
WO2005042466A1
WO2005042466A1 PCT/JP2004/016018 JP2004016018W WO2005042466A1 WO 2005042466 A1 WO2005042466 A1 WO 2005042466A1 JP 2004016018 W JP2004016018 W JP 2004016018W WO 2005042466 A1 WO2005042466 A1 WO 2005042466A1
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WIPO (PCT)
Prior art keywords
quaternary ammonium
ammonium salt
electrolyte
bonded
methoxymethyl
Prior art date
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English (en)
Japanese (ja)
Inventor
Akihiro Nabeshima
Hiroaki Tokuda
Tetsuo Nishida
Megumi Tomisaki
Kazutaka Hirano
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Otsuka Chemical Co Ltd
Stella Chemifa Corp
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Otsuka Chemical Co Ltd
Stella Chemifa Corp
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Priority to JP2005515146A priority Critical patent/JP4836578B2/ja
Publication of WO2005042466A1 publication Critical patent/WO2005042466A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
    • 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

  • Quaternary ammonium salts electrolytes, electrolytes and electrochemical devices
  • the present invention relates to a quaternary ammonium salt, an electrolyte, an electrolytic solution, and an electrochemical device.
  • room temperature molten salts examples include, for example, those represented by the general formula
  • R 1A , R 2A , R 3A and are the same or different and are each an alkyl group having 115 carbon atoms or R, 1 O— (CH 2) — (R ′ is a methyl group or ethyl Group, n is an integer of 1 to 4)
  • W represents a nitrogen atom or a phosphorus atom, and Y represents a monovalent aion. ] Is known (Patent Document 1).
  • Patent Document 1 The aliphatic ammonium salt disclosed in Patent Document 1 has excellent solubility in non-aqueous organic solvents and has a property that salt precipitation hardly occurs at low temperatures.
  • Patent document l WO 02/076924 A1
  • An object of the present invention is to provide a quaternary ammonium salt having a melting point of 10 ° C. or less, high electric conductivity, and excellent solubility in a non-aqueous organic solvent. It is.
  • the present inventors have intensively studied to develop a quaternary ammonium salt capable of solving the above problems.
  • the specific quaternary ammonium salt represented by the following general formula (1) which has neither a specific description nor suggestion in Patent Document 1, has a low melting point of 10 ° C or less, It has been found that it has excellent solubility in organic organic solvents, has remarkably high electric conductivity, and can be suitably used as an electrolyte.
  • the present invention has been completed based on such knowledge.
  • the present invention provides the following quaternary ammonium salts, electrolytes, electrolytes, and electrochemical devices.
  • R 1 and R 2 are the same or different and each represent a C alkyl group.
  • R 1 and R 2 are the same or different and each represent a C alkyl group.
  • R 3 and R 4 are the same or different and represent a methyl group or an ethyl group.
  • X— represents an anion.
  • R 1 and R 2 are the same or different and each represents a C alkyl group.
  • R 1 and R 2 are the same or different and each represents a C alkyl group.
  • R 3 and R 4 are the same or different and represent a methyl group or an ethyl group.
  • X— represents an anion.
  • X— is BF—, A1C1-—, Al C1-—, PF—, AsF—, N (CF SO) —, N (CF SO)
  • Electrode containing one or more of the electrolytes described in any of 7-12 above 14.
  • organic solvent is at least one selected from the group consisting of cyclic carbonates, chain carbonates, nitrile compounds, and sulfonate compounds.
  • organic solvent is at least one selected from the group consisting of propylene carbonate, ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate.
  • An electrochemical device comprising the electrolytic solution according to 13 above.
  • examples of the C alkyl group represented by R 1 and R 2 include methyl
  • the C alkyl group is a methyl group.
  • saturated heterocyclic ring formed combine with each other together with the nitrogen atom R 1 and the R 2 is bonded, for example, a saturated heterocyclic ring of 3-5 members.
  • Preferred saturated heterocycles are pyrrolidine rings.
  • Specific quaternary ammonium cations include bis (methoxymethyl) dimethylammonium cation, N, N- (dimethoxymethyl) N-ethyl-N-methylammonium-dimethylcation, and N, N- (dimethoxymethyl).
  • anion represented by X— for example, BF—, A1C1-, Al C1-, PF—, AsF—, N
  • Preferred anions are BF— and N (CF SO)
  • Preferred quaternary ammonium salts include, for example, bis (methoxymethyl) dimethylammoniumtetrafluoroborate, N, N— (dimethoxymethyl) N-ethyl-N-methylammonium N-N- (dimethoxymethyl) N-propyl N-methyltetrafluoroborate, N, N- (dimethoxymethyl) N-butyl-N-methyl-tetrafluoroborate Tetrafluoroborate, bis (methoxymethyl) getyl-ammonium-tetrafluoroborate, N— (ethoxymethyl) N— (methoxymethyl) N, N—dimethylammonium-dimethyltetrafluoroborate, N— (Ethoxymethyl) -N- (methoxymethyl) N-ethyl-N-methylammonium-dimethyltetrafluoroborate, bis (ethoxymethyl) dimethylammonium-dimethyltetrafluoroborate , N, N
  • the quaternary ammonium salt of the present invention is produced by various methods. A typical method will be described using the following reaction formula.
  • R 2 , R 3 , R 4 and X— are the same as above.
  • X 1 represents a halogen atom.
  • M represents a hydrogen atom or a metal atom.
  • a quaternary ammonium salt represented by the general formula (4) is produced.
  • the salt exchange reaction between the quaternary ammonium salt represented by the general formula (4) and the general formula (5) the compound represented by the general formula (1) Grade ammonium salt can be produced.
  • M is H or an alkali metal atom such as Na, K, and Li; an alkaline earth metal atom such as Ca, Mg, and Ba; and a metal atom such as Ag. including.
  • the tertiary amine of the general formula (2) is synthesized according to a known method. Such methods are described, for example, in C.M.McLeod und G.M.Robinson, J.Chem.Soc, 119, 1470 (1921),
  • the tertiary amine represented by the general formula (2) is generally a secondary amine or formaldehyde.
  • the reaction temperature is suitably -5 to 25 ° C when an aqueous formaldehyde solution is used, and 60 to 100 ° C when paraformaldehyde is used.
  • the reaction is generally completed within several hours to 24 hours.
  • the tertiary amine represented by the general formula (2) is easily isolated from the reaction mixture by a conventional isolation means, for example, extraction, rectification and the like.
  • Examples of the compound represented by the general formula (3) include chloromethyl methyl ether, bromomethylinolemethynoateate, odomethinolemethynoateate, chloromethineleetinoateate, and Lomomethylethyl ether, eodomethylethyl ether and the like are included.
  • solvents can be used as long as they can dissolve the tertiary amine represented by the general formula (2) and the compound represented by the general formula (3) and do not adversely affect the reaction. Can be used widely.
  • solvents include, for example, benzene, toluene, xylene and the like.
  • Aromatic hydrocarbons Halogenated hydrocarbons such as dichloromethane, chloroform, tetrachlorosilane, etc .; Lower alcohols such as methanol, ethanol, isopropanol, n-butanol and tert-butanol; Ketones such as acetone and methyl ethyl ketone ; Jefferies chill ether, ethers such as diisopropyl ether; n - hexane, aliphatic hydrocarbons such as n- heptane; alicyclic hydrocarbons such as cyclohexane and the like cycloalkyl and the like.
  • aromatic hydrocarbons such as toluene, halogenated hydrocarbons such as dichloromethane, and ketones such as acetone are preferred.
  • solvents can be used alone or in combination of two or more. These solvents are preferably non-aqueous solvents.
  • the compound represented by the general formula (3) is generally used in an amount of 0.3 to 5 mol, preferably 0.6 to 1.2 mol, per 1 mol of the tertiary amine (2).
  • the reaction is usually performed at ⁇ 10 to 25 ° C., and is generally completed in several hours to about 24 hours.
  • the compound represented by the general formula (5) used as a raw material is a known compound, for example,
  • This salt exchange reaction is performed in an appropriate solvent.
  • the solvent used is a solvent capable of dissolving the quaternary ammonium salt represented by the general formula (4) and the compound represented by the general formula (5) and having no adverse effect on the reaction. As long as it is publicly known, it can be widely used.
  • solvents examples include water; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, etc .; lower alcohols such as methanol, ethanol, isopropanol, n-butanol, tert-butanol; acetone, methyl Ketones such as ethyl ketone; Esters such as tyl; and aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide. Of these, lower alcohols such as methanol; halogenated hydrocarbons such as chloroform, and water are preferred. These solvents can be used alone or in combination of two or more.
  • Salt exchange can also be performed using ion exchange resin.
  • An ion exchange resin is usually used as the ion exchange resin.
  • solvent used here known solvents can be widely used as long as they can dissolve the general formula (4) and do not adversely affect the salt exchange reaction.
  • solvents are generally water, alcohols and the like.
  • the use ratio of the quaternary ammonium salt represented by the general formula (4) and the compound represented by the general formula (5) is usually 0.5 mol per 1 mol of the former. It is good to be 5 mol, preferably 0.9 to 1.2 mol. Since the reaction usually proceeds rapidly, for example, the temperature of a solution in which both are dissolved in a solvent should be maintained near room temperature. Generally, the salt exchange reaction is completed in about 10 minutes to 12 hours.
  • the target compound obtained in each of the above reactions can be easily separated from the reaction mixture by a conventional separation means, for example, a conventional isolation and purification means such as concentration, washing, organic solvent extraction, chromatography, and recrystallization. It is isolated and purified.
  • a conventional isolation and purification means such as concentration, washing, organic solvent extraction, chromatography, and recrystallization. It is isolated and purified.
  • reaction conditions for producing a quaternary ammonium salt are as follows.
  • a quaternary ammonium salt represented by the general formula (4) is dissolved in the lower alcohol, and a predetermined amount is added to this solution.
  • Borofluoric acid, silver borofluoride or the like and react at about room temperature for about 30 minutes.
  • the target compound can be isolated by distilling off hydrogen halide formed by the reaction, filtering off halogen salts such as silver halide, and concentrating the filtrate under reduced pressure and drying.
  • a known method for example, N
  • a quaternary ammonium represented by the general formula (4) is dissolved in water, and a predetermined amount of an alkali metal salt of pistrifluoromethanesulfonimide (a lithium salt of bistrifluoromethanesulfonimide, sodium Salt, potassium salt, etc.) and react at 0-25 ° C for 30 minutes. Extract the desired product with an appropriate solvent (e.g., dichloromethane, chloroform, ethyl acetate, etc.), wash the extract with water, concentrate under reduced pressure, and dry to isolate the desired compound. Can be.
  • an appropriate solvent e.g., dichloromethane, chloroform, ethyl acetate, etc.
  • the quaternary ammonium salt of the present invention is a room temperature molten salt that is liquid at room temperature, has excellent solubility in non-aqueous organic solvents, and has high electric conductivity. Therefore, the quaternary ammonium salt of the present invention can be suitably used as an electrolyte.
  • the electrolyte itself that also forms the quaternary ammonium salt of the present invention can be used as the electrolytic solution. Further, the electrolyte which also forms the quaternary ammonium salt of the present invention can be used by mixing with an appropriate solvent.
  • examples of the solvent include cyclic carbonates, chain carbonates, ester phosphates, cyclic ethers, chain ethers, ratatonyi conjugates, chain esters, nitrile compounds, amide compounds, and sulfone imides. And the like. These solvents are used alone or as a mixture of two or more.
  • cyclic carbonate examples include ethylene carbonate, propylene carbonate, butylene carbonate and the like.
  • chain carbonate examples include dimethyl carbonate, ethyl methyl carbonate, getyl carbonate and the like.
  • phosphate ester examples include trimethyl phosphate, triethyl phosphate, ethyl dimethyl phosphate, and getyl methyl phosphate.
  • cyclic ether examples include tetrahydrofuran, 2-methyltetrahydrofuran and the like.
  • chain ether examples include dimethoxyethane.
  • ratatonyi ligated products include ⁇ -petit mouth ratatones and the like.
  • chain ester examples include methyl propionate, methyl acetate and ethyl acetate. Ruacetate, methyl formate and the like can be mentioned.
  • nitrile conjugate examples include acetonitrile and the like.
  • amido conjugate examples include dimethylformamide and the like.
  • sulfone conjugate examples include sulfolane and methyl sulfolane.
  • the concentration of the electrolyte is preferably 0.1 M or more, more preferably 0.5 M or more, and still more preferably 1 M or more. It is better to do the above.
  • electrolyte of the present invention can be used in combination with a known electrolyte.
  • Examples of known electrolytes to be used by mixing with the electrolyte of the present invention include alkali metal salts, quaternary ammonium salts, quaternary phosphonium salts, and the like.
  • Examples of the alkali metal salt include a lithium salt, a sodium salt, and a potassium salt. More specifically, lithium salts include lithium hexafluorophosphate, lithium borofluoride, lithium perchlorate, lithium trifluoromethanesulfonate, lithium sulfolimide, lithium lithium sulfolmethide, and the like. More specifically, examples of the sodium salt include sodium hexafluorophosphate, sodium borofluoride, sodium perchlorate, sodium trifluoromethanesulfonate, sodium sulfolimide, sodium sulfolmethide, and the like.
  • potassium salts include potassium hexafluorophosphate, potassium borofluoride, potassium perchlorate, potassium trifluorosulfonate, potassium sulfolimide, potassium sulfolmethide, and the like.
  • Examples of the quaternary ammonium salts include tetraalkylammonium salts, imidazole salts, virazolym salts, pyridium salts, triazolium salts, and pyridazim salts. It is. More specifically, tetraalkylammonium salts include, for example, tetraethylammoniumtetrafluoroborate, tetramethylammoniumtetrafluoroborate, and tetramethylammonium-tetrafluoroborate.
  • Tetrabutylammonium-tetrafluoroborate triethylmethylammonium-tetrafluoroborate, trimethylethylammonium-tetrafluoroborate, dimethylgethylammonium-tetrafluoroborate , Trimethylpropylammonium tetrafluoroborate, trimethylbutylammonium Tetrafluoroborate, dimethylethylpropylammonium-tetrafluoroborate, methylethylpropylbutylammonium-tetrafluoroborate, N, N-dimethylpi-oligo-dimethyltetrafluoroborate , N-ethyl-N-methylpyrrolidi-dimethyltetrafluoroborate, N-methyl-N-propylpyrrolidiniumtetrafluoroborate, N-ethynole-N-propylpyrrolidi-dimethyltetrafluoroborate
  • examples of the imidazolyl salt include 1,3 dimethylimidazolymtetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, and 1,3 ethylimidazolyltetrafluoroborate.
  • Roborate 1,2-dimethyl-3-ethylimidazolium tetrafluoroborate, 1,2 dimethyl-3 propylimidazolidium tetrafluoroborate and the like.
  • virazolidium salt there are 1,2-dimethylpyrazolidium tetrafluoroborate, 1-methyl-2-ethylpyrazolidium tetrafluoroborate, 1-propyl 2-methylbirazoli Dumtetrafluoroborate, 1-methyl-2-butylbiazolidiumtetrafluoroborate and the like can be mentioned.
  • examples of the pyridi-pium salts include N-methylpyridi-p-tetrafluoroborate, N-ethylpyridi-p-tetrafluoroborate, N-propylpyridi-p-tetrafluoroborate, and N-butylpyridi-p-tetratetraborate Fluoroborate and the like.
  • triazolyl salts include 1-methyltriazolyltetrafluoroborate, 1-ethyltriazolyltetrafluoroborate, and 1-propyltriazolyltetrafluoroborate. And 1-butyltriazolyltetrafluoroborate.
  • pyridazim-dum salts include 1-methylpyridazim-dumtetrafluoroborate, 1-ethylpyridazi-dumtetrafluoroborate, 1-propylpyridazi-dumtetrafluoroborate, 1-butylpyridazi-dimethyltetrafluoroborate and the like.
  • Examples of the quaternary phospho-dimethyl salt include, for example, tetraethyl phospho-dimethyl tetrafluoroborate Rate, tetramethylphospho-dimethyltetrafluoroborate, tetrapropylphospho-dimethyltetrafluroborate, tetrabutylphospho-dimethyltetrafluoroborate, triethylmethionolephosphonium tetraphlenololoborate, trimethinole Ethynolephosphonium tetrafluorolenoborolate, dimethyl getyl phosphonium tetrafluoroborate, trimethylpropyl phosphonetetrafluoroborate, trimethylbutyl phospho-dimethyltetrafluoroborate, dimethyl ester Tylpropylphosphoniumtetrafluoroborate, methylethylpropylbutylphospho-dimethyltetrafluoroborate and the like can be mentioned
  • these known electrolytes are used alone or as a mixture of two or more.
  • Examples of the electrochemical device include an electric double layer capacitor, a secondary battery, and the like.
  • the electrolyte or electrolyte of the present invention is used for known electric double layer capacitors and secondary batteries, and can be used in the same manner as the electrolyte or electrolyte.
  • the quaternary ammonium salt of the present invention a solution in which the salt is dissolved in an organic solvent can be used as an electrolyte for an electrochemical device.
  • the electrolyte concentration is preferably 0.1 M or more, more preferably 0.5 M or more, particularly Preferably it is 1M or more. If the electrolyte concentration is less than 0.1 M, the electrical conductivity will be low, and the performance of the electrochemical device will be reduced.
  • the upper limit of the electrolyte concentration is the concentration at which quaternary ammonium salts which are liquid at room temperature are separated from the organic solvent, and 100% if they are not separated from the organic solvent. For quaternary ammonium salts which are solid at room temperature, the upper limit is the concentration at which the salts are saturated with an organic solvent.
  • An electrolyte for an electrochemical device can be prepared using the quaternary ammonium salt of the present invention.
  • the electrolytic solution obtained by the present invention can be used for an electrochemical device capable of storing electric energy by physical action or chemical action, and can be suitably used for, for example, an electric double layer capacitor and a lithium battery.
  • a method for preparing an electrolytic solution for an electric double layer capacitor using the quaternary ammonium salt of the present invention will be described below.
  • the quaternary ammonium salt of the present invention is a liquid, it is itself.
  • the atmosphere is not mixed with air, for example, in a glove box in an inert atmosphere such as argon gas or nitrogen gas. It is preferable to carry out the preparation work.
  • the moisture in the working environment can be managed with a dew point meter.
  • the dew point is 60 ° C or less. If the dew point is 60 ° C. or higher, it is not preferable that the working time is long because the electrolyte absorbs the moisture in the atmosphere and the water in the electrolyte rises.
  • the water content in the electrolyte can be measured with a Karl Fischer meter.
  • the electrolyte concentration is determined from the viewpoint of the electrical conductivity of the electrolyte as described above.
  • the concentration is preferably 0.1 M or more, more preferably 0.5 M or more, and particularly preferably 1 M or more.
  • the upper limit of the electrolyte concentration is not limited as long as precipitation and separation of the electrolyte do not occur.
  • the organic solvent the various solvents described above can be used.
  • the type of the organic solvent used and the present invention are not limited. It is preferable to determine the mixing ratio of these according to the type of the quaternary ammonium salt.
  • N (ethoxymethyl) N (methoxymethyl) pyrrolidi-dimethyltetrafluoroborate in the electrolyte is The proportion is preferably 10-80% by weight, more preferably 15-70% by weight, even more preferably 20-60% by weight.
  • N (ethoxymethyl) N— (methoxymethyl) pyrrolidium in the electrolyte is preferably 20-90% by weight, more preferably 30-80% by weight.
  • N (ethoxymethyl) N (methoxymethyl) pyrrolidi-dimethyltetrafluoroborate in the electrolyte ratio is preferably 30 to 90 weight 0/0, more preferably 40- 80 weight 0/0.
  • the quaternary ammonium salt of the present invention can also be used for an electrolyte for a lithium battery.
  • the working environment in which the preparation is performed is preferably in a glove box in which the dew point is controlled.
  • an electrolytic solution can be obtained by dissolving a lithium salt in the quaternary ammonium salt. Further, the quaternary ammonium salt of the present invention is mixed with an appropriate organic solvent, and the lithium salt is dissolved in the mixture to obtain an electrolyte solution.
  • lithium salt various salts can be used as described above.
  • the type is not particularly limited as long as no lithium salt is precipitated.
  • the lithium salt concentration is usually 0.1 M or more and 2.0 M or less, preferably 0.15 M or more, 1.5 M or less, preferably 0.2 M or more, 1.2 M or less, particularly preferably 0.3 M or more, and 1.0 M or less.
  • the lithium salt concentration is less than 0.1 M, when the charge / discharge rate is high, the lithium ions are depleted in the vicinity of the electrode, and the charge / discharge characteristics tend to deteriorate.
  • the lithium ion concentration exceeds 2.0 M, the viscosity of the electrolyte increases, and the electric conductivity tends to decrease.
  • one of the quaternary ammonium salt of the present invention and the ion forming the lithium salt contains BF-. The reason is certain
  • the amount is preferable to adjust the amount to be at least 0.8%, and it is more preferable to adjust the amount to be 0.8% or more.
  • the upper limit concentration is that the number of BF-containing ions is 100% of the total number of ions in the electrolyte.
  • the electrolytic solution may be used after being diluted with an organic solvent.
  • organic solvents include cyclic carbonates, chain carbonates, cyclic ethers and chain ethers. , Nitrile compounds, sulfonated compounds and the like.
  • Specific examples of the cyclic carbonate include ethylene carbonate and propylene carbonate.
  • Specific examples of the chain carbonate include dimethyl carbonate, ethyl methyl carbonate and the like.
  • Specific examples of the cyclic ether include tetrahydrofuran, hexahydropyran and the like.
  • Specific examples of the chain ether include 1,2-dimethoxyethane.
  • As a specific example of the nitrile conjugate, acetonitrile and the like can be mentioned.
  • Specific examples of the sulfone compound include sulfolane.
  • organic solvents can be used as a mixture.
  • examples of the combination include ethylene carbonate and dimethinole carbonate, ethylene carbonate and ethynolemethinole carbonate, ethylene carbonate and propylene carbonate, and ethylene carbonate and tetrahydrofuran.
  • the electrolytic solution used in the present invention preferably contains a specific organic additive.
  • organic additives include, for example, ethylene carbonate, bi-lene carbonate, butylene carbonate, ethylene trithio carbonate, vinylene trithio carbonate, ethylene sulfide and the like. Of these, ethylene carbonate and vinylene carbonate are preferred. These organic additives are used alone or in combination of two or more.
  • a lithium ion selective permeable membrane known as Electrolyte Interface is formed, which can suppress the decomposition and insertion of the ammonium cation forming the molten salt at room temperature into the anode material, and as a result, provide stable charge and discharge characteristics of the lithium battery. Can be.
  • the organic additive includes a substance that also functions as a diluent.
  • the content of these organic additives is preferably such that the ratio of the organic additives to the total weight of the electrolyte is 1% by weight or more and 40% by weight or less, more preferably 1% by weight or more and 30% by weight or less. More preferably, it is 1% by weight or more and 20% by weight or less, most preferably 1% by weight or more and 10% by weight or less.
  • the content of the organic additive is 1% by weight or less, a sufficient film is not formed on the negative electrode surface, and there is a tendency that the decomposition of the ammonium cation forming the room temperature molten salt and the insertion into the negative electrode material cannot be suppressed. Occurs.
  • An electric double layer capacitor can be suitably produced using the electrolytic solution of the present invention obtained as described above.
  • this electric double layer capacitor for example, the one shown in FIG. 1 can be mentioned.
  • the shape of the electric double layer capacitor is not limited to the coin type as shown in Fig. 1, but it is a stacked type in which the electrodes are stacked and stored in a can body, and a wound type in which the electrodes are wound and stored. Or a laminate type packaged in an aluminum laminate.
  • the structure of a coin-type electric double layer capacitor will be described as an example.
  • FIG. 1 is a drawing showing a cross section of a coin-type electric double layer capacitor. Electrodes 1 and 2 are arranged to face each other with a separator 3 interposed therebetween, and housed in containers 4 and 5.
  • the electrode includes a polarizable electrode portion made of a carbon material such as activated carbon and a current collector portion.
  • the container bodies 4 and 5 are made of, for example, stainless steel, aluminum or the like which is not corroded by the electrolyte.
  • the container bodies 4 and 5 are electrically insulated by an insulating gasket 6, and at the same time, seal the inside of the metal can body so that moisture and air from the outside of the can body do not enter.
  • the current collector and the container body 4 of the electrode 1 and the current collector of the electrode 2 and the metal spacer 7 are in contact with each other at an appropriate pressure due to the presence of the metal spring 8, respectively. Keep in touch.
  • the current collector may be bonded using a conductive paste such as a carbon paste.
  • the polarizable electrode material has a large specific surface area, a high electric conductivity, and is preferably a material, and is electrochemically stable to the electrolytic solution within the range of applied voltage to be used. It is necessary. Examples of such a material include a carbon material, a metal oxide material, and a conductive polymer material. Considering cost, the polarizable electrode material is preferably a carbon material.
  • activated carbon materials are preferred. Specific examples thereof include sawdust activated carbon, coconut activated carbon, pitch'cotas-based activated carbon, phenol-based activated carbon, polyacrylonitrile-based activated carbon, and cellulose-based activated carbon. Forces are not limited to these.
  • Examples of the metal oxide-based material include, but are not limited to, ruthenium oxide, manganese oxide, manganese oxide, and the like.
  • Examples of the conductive polymer material include polyaline, polypyrrole film, and polythiophene. Force, such as a film and a poly (3,4-ethylenedioxythiophene) film. The present invention is not limited to these.
  • the electrode is formed by pressing the above-mentioned polarizable electrode material with a binder under pressure, or mixing the above-mentioned polarizable electrode material with a binder together with an organic solvent such as pyrrolidone to form a paste into an aluminum foil. Etc., and then dried after coating.
  • the separator As the separator, a separator having high electronic insulation and excellent wettability of the electrolytic solution and high ion permeability is preferable, and it is necessary that the separator be electrochemically stable within an applied voltage range.
  • the material of the separator is not particularly limited, but paper making which is strong such as rayon and manila hemp; polyolefin-based porous film; polyethylene nonwoven fabric; polypropylene nonwoven fabric and the like are preferably used.
  • a lithium secondary battery can be suitably prepared using the electrolyte solution of the present invention obtained as described above.
  • Examples of the shape of the lithium secondary battery of the present invention include a coin shape, a cylindrical shape, a square shape, and a laminate, but the shape is not limited to these shapes.
  • a coin-type cell shown in FIG. 2 can be mentioned.
  • a stacked body in which the positive electrode 11, the separator 13, the negative electrode 12, and the spacer 17 are stacked in this order from the positive electrode can 14 side is housed.
  • the electrolyte is impregnated between the positive electrode 11, the separator 13, and the negative electrode 12.
  • the gasket 16 interposed between the positive electrode can 14 and the negative electrode can 15 are crimped to join the two, thereby sealing the laminate.
  • Examples of the positive electrode active material include LiCoO, LiNiO, LiNiCoO, and LiNiCoM.
  • Composite oxides with metals oxides such as TiO and V O; sulfides such as TiS and FeS;
  • the power of the battery capacity and the energy density The composite oxide of lithium and a transition metal is preferable.
  • the positive electrode is formed by press-molding these positive electrode active materials together with a known conductive auxiliary and a binder, or by mixing the positive electrode active material together with a known conductive auxiliary and a binder with an organic solvent such as pyrrolidone.
  • the paste can be obtained by applying a paste into a current collector, such as an aluminum foil, followed by drying.
  • lithium metal As the negative electrode active material, lithium metal, an alloy of lithium metal and another metal, and a material into which lithium ions are inserted and desorbed are used.
  • alloys of lithium metal and other metals include LiAl, Li—Sn, LiZn, and LiSi.
  • the material into which lithium ions are inserted and desorbed include carbon materials obtained by firing resins and pitches, carbon materials obtained by adding a boron compound to these carbon materials, and natural graphite. These negative electrode active materials are used alone or as a mixture of two or more.
  • the negative electrode is formed by pressure-forming these negative electrode active materials together with a known conductive auxiliary and a binder, or by forming the negative electrode active material together with a known conductive auxiliary and a binder together with an organic solvent such as pyrrolidone. To a paste, and then apply it to a current collector such as a copper foil and then dry it.
  • the separator is not particularly limited as long as it is an insulator and a chemically stable material immediately after the passage of the electrolytic solution.
  • the quaternary ammonium salt of the present invention and an electrolytic solution containing the same are suitable as an electrolytic solution for an electrochemical device having high electric conductivity and high solubility in an organic solvent.
  • Examples of the electrochemical device include, but are not limited to, electric double-layer capacitors, secondary batteries, dye-sensitized solar cells, electocole chromic elements, capacitors, and the like. Particularly suitable electrochemical devices are electric double layer capacitors and secondary batteries.
  • the quaternary ammonium salt of the present invention has a melting point of 10 ° C or less, it can maintain a liquid form at room temperature (25 ° C). Further, the quaternary ammonium salt of the present invention is remarkably excellent in solubility in organic solvents and has high electric conductivity.
  • the quaternary ammonium salt of the present invention which is itself liquid at room temperature (25 ° C), can be used as an electrolyte as it is. This electrolyte can prevent electrolyte deposition even at low temperatures. Stable electrical conductivity can be achieved. Further, since this quaternary ammonium salt can be used as an electrolyte as it is, it is possible to increase the ion concentration of the electrolyte, and to exhibit high electrical conductivity.
  • the quaternary ammonium salt of the present invention which is excellent in solubility in an organic solvent, can be dissolved in an organic solvent to form an electrolyte.
  • the quaternary ammonium salt of the present invention does not precipitate, and there is no fear that the electric conductivity of the electrolytic solution is reduced.
  • the quaternary ammonium salt of the present invention is excellent in fluidity due to its low viscosity, and therefore, is suitable for use in an electrolytic solution of an electric device using a porous electrode that requires permeability. Can also be suitably used.
  • FIG. 1 is a partial cross-sectional view of an electric double layer capacitor produced in Example 10 of the present invention.
  • FIG. 2 is a partial sectional view of a lithium secondary battery prepared in Example 12 of the present invention.
  • FIG. 3 is a graph showing the electrical conductivity of mixed solutions of various concentrations obtained in Example 6, Example 7, and Comparative Example 3 of the present invention.
  • Dimethylmethoxymethylamine 30 Og was dissolved in 120 g of toluene, and the atmosphere was replaced with nitrogen. To this solution, 16.3 g of chloromethyl methyl ether (reagent: manufactured by Tokyo Chemical Industry) was added dropwise at 5 ° C over 1 hour. The solution was stirred at 5 ° C for 10 hours to complete the reaction. The lower layer separated from the two layers was separated, washed three times with 150 g of toluene, further three times with 150 g of methyl ethyl ketone, dried under reduced pressure, and dried with 25 g of dimethyldimethoxymethylammonium. -Pemuchloride (colorless liquid) was obtained.
  • dimethyldimethoxymethylammonium chloride was dissolved in 50 g of methanol, and 45.3 g of a 30% HBF methanol solution was added. Hydrogen chloride and excess under reduced pressure
  • the melting point of the quaternary ammonium salt (bis (methoxymethyl) dimethylammonium-tetrafluoroborate) obtained above was measured using a differential thermal analyzer (RIGAKU, DSC8230B) manufactured by Rigaku Corporation. Was performed using Specifically, the sample weight was 20 mg, and the sample was quenched to 150 ° C with liquid argon, and then heated at a rate of 5 ° CZ. The melting point was also determined by the intersection force between the baseline tangent and the tangent to the peak slope. The melting point of the quaternary ammonium salt obtained in Example 1 was 4 ° C.
  • the melting point of the quaternary ammonium salt (bis (methoxymethyl) pyrrolidi-dimethylbistrifluoromethanesulfonylimide) obtained above was measured in the same manner as in Example 1.
  • the melting point of the quaternary ammonium salt obtained in Example 2 could not be clearly determined.
  • the glass transition temperature (Tg) was -90 ° C.
  • N (methoxyethyl) N-methylpyrrolidium-dimethiodide 10.00 was dissolved in 67 ml of ultrapure water, 4.27 g of silver oxide was added, and the mixture was stirred for 3 hours. The reaction solution was filtered to completely remove the precipitate. After removal, 42% tetrafluoroboric acid was added in small portions until the pH reached 5-6. The reaction solution was freeze-dried and further dried under reduced pressure to obtain 8.26 g of N (methoxyethyl) N-methylpyrrolidi-dimethyltetrafluoroborate, which was the target substance.
  • N (methoxyethyl) N, N getyl-N-methylammonium tetrafluoroborate was synthesized according to WO 02/076924 A 1 (Patent Document 1).
  • N (Methoxyethyl) N, N Jethyl-N-methylammonium (9.20 g) was dissolved in tetrahydrofuran (11 ml), and methyl iodide (10.18 g) was added at 0 ° C. The temperature was gradually raised, and the reaction was carried out at room temperature for 24 hours. After completion of the reaction, tetrahydrofuran was distilled off under reduced pressure, and the residue was recrystallized with a mixed solvent of tetrahydrofuran / ethanol to obtain 17.52 g of N (methoxyethyl) N, N getyl-N-methylammonium iodide.
  • N (Methoxyethyl) N, N Jethyl-N-methylammonium iodide 10.OOg was dissolved in 67 ml of ultrapure water, 4.25 g of silver oxide was added, and the mixture was stirred for 3 hours. After the reaction solution was filtered to completely remove the precipitate, 42% tetrafluoroboric acid was added little by little until the pH reached 5-6. The reaction solution was freeze-dried and further dried under reduced pressure to obtain 8.20 g of N (methoxyethyl) N, N getyl-N-methylammonium tetrafluoroborate, which was the target substance.
  • Paraformaldehyde (reagent: manufactured by MERK) 101.2 g, potassium carbonate (reagent: manufactured by Wako Pure Chemical) 234. Og and ethyl alcohol (reagent: manufactured by Wako Pure Chemical) 971.3 g were charged, and pyrrolidine (reagent: Tokyo Chemical Industry) Og was dropped at 10 ° C or lower. It took 2 hours for the dripping. After completion of the dropwise addition, the mixture was reacted under reflux for 7 hours. Ethyl alcohol was distilled off, and the residue was distilled under reduced pressure (70 mmHg) to obtain 148.4 g of ethoxymethylpyrrolidine.
  • the organic layer was washed three times with a small amount of water and concentrated.
  • the concentrate was dissolved in ethyl alcohol and recrystallized at 50 ° C. Recrystallization was repeated 5 times.
  • the obtained crystals were dried under reduced pressure to obtain the desired product, 83. Og.
  • N (Ethoxymethyl) N (methoxymethyl) pyrrolidi-pampark Molerate 30 Og prepared in Synthesis Example 2 was dissolved in 250 ml of methyl alcohol, and ion-exchange resin was used. Replaced with fluoroborate). Confirmation of the ion exchange was performed by ion chromatography (TOSOH CM-8020). After confirming the ion exchange, the methyl alcohol solution was concentrated and dried under reduced pressure to obtain 26.lg of the desired product. — NMR (d— CH OH) S ppm:
  • Radiometer CDC641T was used for the measurement cell at 25 ° C.
  • N (ethoxymethyl) N (methoxymethyl) pyrrolidi-dimethyltetrafluoroborate and propylene carbonate (PC) (reagent: manufactured by Kishidai-Dogaku Co., Ltd., lithium nottery grade) produced in Example 4 were added to various concentrations.
  • Mixing was carried out in a dry box under a nitrogen atmosphere with a dew point of 60 ° C or less.
  • the water content of the mixed solution was measured with a Karl Fischer moisture meter (Hiranuma Sangyo Co., Ltd., Hiranuma Trace Moisture Analyzer AQ-7) and found to be 30 ppm or less.
  • the concentration of N (ethoxymethyl) N (methoxymethyl) pyrrolidinium tetrafluoroborate in the mixed solution was as shown in Table 2.
  • PC propylene carbonate
  • mixing was performed in a dry bot- tom in a nitrogen atmosphere having a dew point of 60 ° C or less.
  • the water content of the mixed solution was measured with a Karl Fischer moisture meter (Hiranuma Sangyo Co., Ltd., Hiranuma Trace Moisture Analyzer AQ-7) and confirmed to be 30 ppm or less.
  • the concentration of bis (methoxymethyl) dimethylammonium-tetrafluoroborate in the mixed solution was as shown in Table 3.
  • the mixed solutions having various concentrations were transferred to a glass container provided with a screw stopper in a dry box in an amount of 4 ml each and taken out of the dry box.
  • the glass containers containing the various solutions were immersed in a thermostat and kept at 25 ° C for 5 hours.
  • N- (methoxyethyl) N, N getyl-N-methylammonium-tetrafluoroborate and propylene carbonate (PC) (Liquid nottery grade, manufactured by Kishidai Tangaku Co., Ltd.) produced in Comparative Example 2 was mixed in a dry box in a nitrogen atmosphere with a dew point of 60 ° C or less.
  • the water content of the mixed solution was measured with a Karl Fischer moisture meter (Hiranuma Sangyo Co., Ltd., Hiranuma Trace Moisture Analyzer AQ-7) and found to be 30 ppm or less.
  • the concentration of N (methoxyethyl) N, N getyl-N-methylammonium-tetrafluoroborate in the mixed solution was as shown in Table 4.
  • the mixed solutions having various concentrations were transferred to a glass container equipped with a screw stopper in a dry box in an amount of 4 ml, and taken out of the dry box.
  • the glass containers containing the various solutions were immersed in a thermostat and kept at 25 ° C for 5 hours each.
  • N (ethoxymethyl) N (methoxymethyl) pyrrolidinium tetrafluoroborate and ethyl methyl carbonate (EMC) (reagent: manufactured by Kishida Chemical Co., Ltd., lithium battery grade) produced in Example 4 were prepared at various concentrations. The dew point is 60 ° C or less.
  • the mixture was mixed in a dry box under an atmosphere. The water content of the mixed solution was measured with a Karl Fischer water meter (manufactured by Hiranuma Sangyo Co., Ltd., Hiranuma Trace Moisture Analyzer AQ-7) and found to be 30 ppm or less.
  • the concentration of N (ethoxymethyl) N (methoxymethyl) piperidiniumtetrafluoroborate in the mixed solution was as shown in Table 5.
  • Each mixed solution was transferred to a glass container provided with a screw stopper in an amount of 4 ml each in a dry box, and was taken out of the dry box.
  • the glass containers containing the various solutions were immersed in a thermostat and kept at 25 ° C for 5 hours.
  • N- (methoxyethyl) N, N getyl-N-methylammonium tetrafluoroborate and ethyl methyl carbonate (EMC) (reagent: manufactured by Kishidai-Dogaku Co., Ltd., lithium nottery grade) produced in Comparative Example 2 were Mixing was performed in a nitrogen atmosphere dry box with a dew point of 60 ° C or less to obtain various concentrations.
  • the water content of the mixed solution was measured with a Karl Fischer moisture meter (Hiranuma Sangyo Co., Ltd., Hiranuma Trace Moisture Analyzer AQ-7) and confirmed to be 30 ppm or less.
  • the concentration of N (methoxyethyl) N, N getyl-N-methylammonium tetrafluoroborate in the mixed solution was as shown in Table 6.
  • N (methoxyethyl) N methylpyrrolidi-dimethyltetrafluoroborate and ethyl methyl carbonate (EMC) (reagent: manufactured by Kishida Chemical Co., Ltd., lithium nottery grade) produced in Comparative Example 1 were prepared at various concentrations. Mixing was performed in a nitrogen atmosphere dry box with a dew point of 60 ° C or less. The water content of the mixed solution was measured with a Karl Fischer moisture meter (Hiranuma Sangyo Co., Ltd., Hiranuma Trace Moisture Analyzer AQ-7) and confirmed to be 30 ppm or less. The concentration of N (methoxyethyl) N methylpyrrolidi-dimethyltetrafluoroborate in the mixed solution was as shown in Table 7.
  • Each mixed solution was transferred to a glass container provided with a screw stopper in an amount of 4 ml in a dry box and taken out of the dry box.
  • the glass containers containing the various solutions were immersed in a thermostat and kept at 25 ° C for 5 hours.
  • N (ethoxymethyl) N (methoxymethyl) pyrrolidi-dimethylbis (trifluoromethanesulfol) imide obtained in Example 5 lithium bis (trifluoromethanesulfol) imide (LiTFSI) was added at 0.5 M or 1.
  • LiTFSI lithium bis (trifluoromethanesulfol) imide
  • N (Methoxyethyl) N, N Jethyl-N-methylammonium-dimethylbis (trifluoromethylsulfonyl) imide (reagent: Kanto-Danigaku Co., Ltd. for material research) is dried under reduced pressure (water content: 20 ppm or less), and lithium bis (trifluoromethyl) Lomethanesulfol) imide (LiTFSI) was added to a concentration of 0.5M or 1.OM, and mixed in a nitrogen atmosphere dry box with a dew point of 60 ° C or less.
  • the water content of the mixed solution was measured with a Karl Fischer moisture meter (Hiranuma Sangyo Co., Ltd., Hiranuma Trace Moisture Analyzer AQ-7) and confirmed to be 30 ppm or less.
  • Example 6 From the mixed solution (electrolyte solution) produced in Example 6, the following electric double layer capacitor was prepared using a mixed solution of N (ethoxymethyl) N (methoxymethyl) pyrrolidi-dimethyltetrafluoroborate at a concentration of 2M. did.
  • Electrode 1 and electrode 2 are made of a conductive material mainly composed of activated carbon, a binder, and N-methylbiphenyl. A paste obtained by kneading with mouth lidone was coated on an aluminum foil to a thickness of 150 ⁇ m, and then dried, and the obtained sheet electrode was cut into a disk shape.
  • the container body 4, the container body 5, the spacer 7, and the spring 8 are all made of stainless steel, and the separator 7 is a polypropylene non-woven fabric.
  • the electric double layer capacitor was assembled in a glove box filled with argon gas.
  • the electrode 1, the electrode 2, the container 4, the container 5, the spring 8, and the spacer 7 were vacuum-dried under heating at 120 ° C. for 24 hours, and then taken into a glove box.
  • Electrode 1, electrode 2 and separator 3 were impregnated with the mixed solution (electrolyte solution for electric double layer capacitor) obtained in Example 6.
  • the electrode separator 3, the electrode 2, the spacer 7, and the spring 8 are placed in this order on the container 4 so that the configuration shown in FIG. 1 is obtained, and the gasket 6 is inserted.
  • the container body 5 was placed on the top.
  • the opening of the container body 4 was sealed by bending inward to form an electric double layer capacitor.
  • LiTFSI lithium bistrifluoromethanesulfonimide
  • a coin-type nonaqueous electrolyte lithium secondary battery as shown in FIG. 2 was produced.
  • 11 is a positive electrode
  • 12 is a negative electrode
  • 13 is a porous separator
  • 14 is a positive electrode can
  • 15 is a negative electrode can
  • 16 is a gasket
  • 17 is a spacer
  • 18 is a spring.
  • Natural graphite and polyvinylidene fluoride (PVdF) as a binder were mixed at a weight ratio of 9: 1, and N-methylpyrrolidone was added thereto to obtain a paste.
  • This paste was uniformly applied on a 22-m-thick copper foil using an applicator for electrode application. This was vacuum-dried at 120 ° C. for 8 hours, and a negative electrode 12 having a diameter of 16 mm was obtained using an electrode punching machine.
  • N-methylpyrrolidone was added to the mixture to obtain a paste.
  • This paste was vacuum dried at 120 ° C. for 8 hours, and a positive electrode 11 having a diameter of 16 mm was obtained with an electrode punching machine.
  • the positive electrode 11 was placed on the bottom surface of the positive electrode can 14, and the porous separator 13 was placed thereon. Then, the non-aqueous electrolyte prepared in Example 11 was injected, and the gasket 16 was inserted. Thereafter, the negative electrode 12, the spacer 17, the spring 18, and the negative electrode can 15 are sequentially placed on the separator 13, and the positive electrode can 14 is removed using a coin crimper machine. The opening was closed by bending inward to form a non-aqueous electrolyte lithium secondary battery.
  • the battery prepared as described above was evaluated as follows. The battery was charged at a constant current of 0.4 mA, and when the voltage reached 4. IV, the battery was charged at a constant voltage of 4. IV for 1 hour. Discharging was performed at a constant current of 1. OmA until the voltage reached 3V. When the voltage reached 3V, it was held at 3V for 1 hour, and the charge / discharge characteristics were examined. As a result, the secondary battery of the present invention prepared in Example 11 showed good cycle characteristics.

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Abstract

L'invention concerne un sel d'ammonium quaternaire représenté par la formule générale (1) dans laquelle R1 et R2 peuvent être identiques ou différents et représentent un groupe alkyle C1-4, R1 et R2 peuvent former un hétérocycle saturé avec des atomes d'azote auxquels ils se lient respectivement, R3 et R4 peuvent être identiques ou différents et représentent un groupe méthyle ou un groupe éthyle, et X- représente un anion. Un tel sel d'ammonium quaternaire possède un point de fusion égal ou inférieur à 10 °C, présente une excellente solubilité dans des solvants organiques non aqueux et possède une conductivité électrique exceptionnellement élevée. Ce sel d'ammonium quaternaire est de préférence utilisé en tant qu'électrolyte.
PCT/JP2004/016018 2003-10-31 2004-10-28 Sel d'ammonium quaternaire, electrolyte, solution d'electrolyte et dispositif electrochimique Ceased WO2005042466A1 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007109698A (ja) * 2005-10-11 2007-04-26 Kaneka Corp イオン性液体と有機溶媒を含む電解液
JP2007141489A (ja) * 2005-11-15 2007-06-07 Gs Yuasa Corporation:Kk 非水電解質電池
GB2436469A (en) * 2006-03-25 2007-09-26 Ionic Polymer Solutions Ltd Method of conduction using a quaternary ammonium compound
JP2008034256A (ja) * 2006-07-28 2008-02-14 Gs Yuasa Corporation:Kk 非水電解質電池
WO2008032688A1 (fr) * 2006-09-12 2008-03-20 Nippon Chemical Industrial Co., Ltd Électrolyte, solution électrolytique pour pile secondaire à ions lithium comprenant l'électrolyte, et pile secondaire à ions lithium dans laquelle est utilisée la solution électrolytique
CN101747213A (zh) * 2008-12-19 2010-06-23 中国科学院兰州化学物理研究所 以双醚基季铵为阳离子的离子液体及其合成方法
WO2012023534A1 (fr) * 2010-08-17 2012-02-23 セントラル硝子株式会社 Procédé de fabrication d'un liquide concentré d'hexafluorophosphate de lithium
JP2012116802A (ja) * 2010-12-02 2012-06-21 Nitto Boseki Co Ltd イオン液体及びその製造方法
WO2012133174A1 (fr) * 2011-03-25 2012-10-04 昭栄化学工業株式会社 Solvant électrolytique pour un matériau actif d'électrode positive composé de sel d'oxoacide de lithium, solution électrolytique pour un matériau actif d'électrode positive composé de sel d'oxoacide de lithium, et batterie secondaire au lithium-ion
JP2014197454A (ja) * 2013-03-29 2014-10-16 トヨタ自動車株式会社 リチウム空気電池用の電解液
CN104737256A (zh) * 2012-10-16 2015-06-24 日清纺控股株式会社 蓄电器件用电解质盐和电解液以及蓄电器件
CN115295882A (zh) * 2022-08-29 2022-11-04 珠海中科先进技术研究院有限公司 一种锂离子电池电解液及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG10201604045YA (en) * 2012-04-13 2016-07-28 Arkema Inc Battery based on organosulfur species

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002076924A1 (fr) * 2001-03-26 2002-10-03 Nisshinbo Industries, Inc., Liquide ionique, sel electrolytique et solution electrolytique pour dispositif de stockage, condensateur electrique a double couche et pile secondaire

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002076924A1 (fr) * 2001-03-26 2002-10-03 Nisshinbo Industries, Inc., Liquide ionique, sel electrolytique et solution electrolytique pour dispositif de stockage, condensateur electrique a double couche et pile secondaire

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BOEHME H. ET AL.: "Zur acylspaltung von formaldehyd-N,O-acetalen", CHEMISCHE BERICHTE, vol. 110, no. 1, 1977, pages 208 - 216, XP002984485 *
CHEMICAL ABSTRACTS, vol. 74, no. 11, 1971, Columbus, Ohio, US; abstract no. 52950G, BOEHME H. ET AL.: "Alpha-halo amines. XXVII. Reactions of alpha-halo ethers, alpha-halo thioethers, and halo amines with N,O-,N,S-, and N,N-acetals" page 292; XP002984484 *
CHEMISCHE BERICHTE, vol. 103, no. 12, 1970, pages 3918 - 3922 *

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JP2007141489A (ja) * 2005-11-15 2007-06-07 Gs Yuasa Corporation:Kk 非水電解質電池
GB2436469B (en) * 2006-03-25 2010-10-06 Ionic Polymer Solutions Ltd Quaternary ammonium compounds and their uses
GB2436469A (en) * 2006-03-25 2007-09-26 Ionic Polymer Solutions Ltd Method of conduction using a quaternary ammonium compound
JP2008034256A (ja) * 2006-07-28 2008-02-14 Gs Yuasa Corporation:Kk 非水電解質電池
US8247112B2 (en) 2006-09-12 2012-08-21 Nippon Chemical Industrial Co., Ltd. Electrolyte, electrolyte solution for lithium-ion secondary battery comprising the electrolyte, and lithium-ion secondary battery using the electrolyte solution
WO2008032688A1 (fr) * 2006-09-12 2008-03-20 Nippon Chemical Industrial Co., Ltd Électrolyte, solution électrolytique pour pile secondaire à ions lithium comprenant l'électrolyte, et pile secondaire à ions lithium dans laquelle est utilisée la solution électrolytique
JP2008071499A (ja) * 2006-09-12 2008-03-27 Nippon Chem Ind Co Ltd 電解質、それを含有するリチウムイオン二次電池用電解液およびこれを用いたリチウムイオン二次電池
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US9343774B2 (en) 2010-08-17 2016-05-17 Central Glass Company, Limited Method for producing a lithium hexafluorophosphate concentrated liquid
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WO2012023534A1 (fr) * 2010-08-17 2012-02-23 セントラル硝子株式会社 Procédé de fabrication d'un liquide concentré d'hexafluorophosphate de lithium
JP2012116802A (ja) * 2010-12-02 2012-06-21 Nitto Boseki Co Ltd イオン液体及びその製造方法
WO2012133174A1 (fr) * 2011-03-25 2012-10-04 昭栄化学工業株式会社 Solvant électrolytique pour un matériau actif d'électrode positive composé de sel d'oxoacide de lithium, solution électrolytique pour un matériau actif d'électrode positive composé de sel d'oxoacide de lithium, et batterie secondaire au lithium-ion
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US9379413B2 (en) 2011-03-25 2016-06-28 Shoei Chemical Inc. Electrolyte solvent for cathode active material composed of lithium oxo acid salt, electrolyte solution for cathode active material composed of lithium oxo acid salt, and lithium ion secondary battery
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JP4836578B2 (ja) 2011-12-14
TWI359127B (fr) 2012-03-01

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