WO2016111151A1 - Solution electrolytique non-aqueuse et dispositif d'accumulation d'energie utilisant celle-ci - Google Patents

Solution electrolytique non-aqueuse et dispositif d'accumulation d'energie utilisant celle-ci Download PDF

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WO2016111151A1
WO2016111151A1 PCT/JP2015/085636 JP2015085636W WO2016111151A1 WO 2016111151 A1 WO2016111151 A1 WO 2016111151A1 JP 2015085636 W JP2015085636 W JP 2015085636W WO 2016111151 A1 WO2016111151 A1 WO 2016111151A1
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cation
lithium
mol
electrolytic solution
anion
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Japanese (ja)
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永倉　直人
佐藤　誠
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株式会社トクヤマ
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/58—Liquid electrolytes
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • 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
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • 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 a non-aqueous electrolyte and an electricity storage device such as a lithium battery, a lithium ion battery, and a lithium ion capacitor using the nonaqueous electrolyte.
  • an electrolytic solution in which a lithium salt is dissolved in a nonaqueous solvent is used as an electrolytic solution used in an electricity storage device such as a secondary battery.
  • a non-aqueous solvent for example, a mixed solvent such as ethylene carbonate, propylene carbonate, and diethyl carbonate is generally used. LiPF 6 , LiBF 4 or the like is used as the lithium salt.
  • a negative electrode active material of a lithium ion secondary battery a carbonaceous material capable of inserting and extracting lithium ions, and a metal or alloy-based material using silicon or tin etc. aiming at high capacity, etc.
  • carbonaceous materials such as natural graphite, artificial graphite, and amorphous carbon are mainly used.
  • a transition metal composite oxide capable of inserting and extracting lithium ions is used. Typical examples of transition metals are cobalt, nickel, manganese, iron and the like.
  • Patent Documents 1 and 2 describe electrolytes containing cyanoborate anions. However, any of these electrolyte solutions is a mixture of a non-aqueous organic solvent.
  • Patent Document 3 describes an electrolyte composition using an ionic liquid containing a cyanoborate anion.
  • the electrolyte composition is mainly used for photosensitized solar cells and is not shown for lithium ion battery applications.
  • ionic liquids ionic substances
  • ionic liquids are composed of organic cations and anions
  • ionic liquids have attracted attention and are being developed as electrolytic solutions for lithium ion batteries and the like.
  • ionic liquids have higher viscosities than organic solvents and the like, and the temperature range used for battery electrolytes is assumed to be ⁇ 30 to 50 ° C., whereas many become solid at around 0 ° C. .
  • the salt when a metal salt is dissolved as a battery electrolyte, the salt often precipitates at a low temperature.
  • the lithium ion conductivity is lowered at a low temperature and current cannot flow, and there are many problems in the insertion / extraction of lithium ions into / from the electrode, and it has not been put into practical use.
  • Patent Document 4 and Non-Patent Document 1 an ionic substance using (FSO 2 ) 2 N ⁇ (fluorosulfonylimide ion; hereinafter sometimes referred to as “FSI”) as an anion is a lithium secondary battery. It can be used as an electrolyte solution.
  • FSI fluorosulfonylimide ion
  • Patent Document 4 and Non-Patent Document 1 do not disclose an ionic substance that can be used as an electrolyte for a battery other than the ionic substance containing FSI.
  • an electrolytic solution using an ionic substance has a low conductivity at a low temperature and a charging capacity lower than that of a general nonaqueous electrolytic solution (for example, Non-Patent Document 2).
  • a general nonaqueous electrolytic solution for example, Non-Patent Document 2.
  • EMI-FSI 1-ethyl-3-methylimidazolium fluorosulfonylimide
  • the charge / discharge capacity at a low temperature has not been studied, and a method capable of improving the battery performance deterioration at a low temperature is not known.
  • ionic liquids are expected to be highly safe electrolytes for lithium-ion batteries because of their non-volatility and flame retardancy, but currently they can be charged and discharged and used as non-aqueous electrolytes. Only EMI-FSI can be performed (Non-Patent Document 3), and the appearance of other ionic substances has been demanded.
  • JP2015-103288A Special table 2013-517229 gazette International Publication No. 2012/099259 JP 2009-070636 A
  • the present invention does not contain a volatile organic solvent, is highly safe, is electrochemically stable, and can maintain high electrical conductivity even at low temperatures, a lithium battery using the same, and the like It is an object to provide an electricity storage device.
  • the present inventor has conducted extensive research to solve the above-mentioned problems, and uses a specific cyanofluoroborate organic cation salt as a non-aqueous electrolyte in a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent.
  • a specific cyanofluoroborate organic cation salt as a non-aqueous electrolyte in a non-aqueous electrolyte in which an electrolyte salt is dissolved in a non-aqueous solvent.
  • the present invention includes, for example, the following [1] to [8].
  • a nonaqueous electrolytic solution made of an ionic substance The cation of the ionic substance is composed of 1 to 60 mol% of a lithium cation and an organic onium cation (however, the total of the lithium cation and the organic onium cation is 100 mol%), In 100 mol% of anions contained in the ionic substance, 30 mol% or more of the anions are represented by the following formula (I) BF a (CN) 4-a - (I) (In the formula (I), a is an integer of 1 to 3)
  • An electricity storage device comprising a positive electrode, a negative electrode, and the nonaqueous electrolytic solution according to any one of [1] to [4].
  • the electricity storage device which is a lithium battery, a lithium ion battery, or a lithium ion capacitor.
  • a non-aqueous electrolyte that does not contain a volatile organic solvent, has high safety, is electrochemically stable, and can maintain high electrical conductivity even at low temperatures, and lithium using the same
  • An electricity storage device such as a battery
  • the electrolyte since the vapor pressure is extremely low, there is no risk of ignition, and since the viscosity is low, the electrolyte has sufficient electrical conductivity and can maintain high conductivity even at a low temperature.
  • a power storage device that operates even in a low temperature environment can be obtained.
  • the nonaqueous electrolytic solution of the present invention is a nonaqueous electrolytic solution made of an ionic substance, wherein the cation of the ionic substance is composed of 1 to 60 mol% of a lithium cation and an organic onium cation, and the anion is Of 100 mol% of anions contained in the ionic substance, 30 mol% or more is represented by the following formula (I) BF a (CN) 4-a - (I) (In the formula (I), a is an integer of 1 to 3) It consists of the cyanofluoroborate anion shown by these.
  • the total of the lithium cation and the organic onium cation is 100 mol%.
  • the proportion of the lithium cation in the total of 100 mol% of the lithium cation and the organic onium cation is 1 to 60 mol%.
  • the proportion of the lithium cation is usually 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and usually 60 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less. is there. If it is in the said range, the ratio of the lithium cation which is a medium of an electric current is not too small, the range of the viscosity of electrolyte solution is suitable, and appropriate electrical conductivity can be obtained.
  • the proportion of the lithium cation is preferably 1 to 40 mol%, more preferably 3 to 40 mol%, still more preferably 5 to 30 mol%.
  • the nonaqueous electrolytic solution of the present invention has high lithium salt solubility. Therefore, even when the proportion of the lithium cation is relatively high, precipitation of the lithium salt can be suppressed.
  • the lithium cation mobility estimated value is a value obtained by multiplying the electrical conductivity of the non-aqueous electrolyte by the molar ratio of the lithium cation to the total ions in the non-aqueous electrolyte.
  • the lithium cation mobility estimated value is 0.02 S / m or more at room temperature (23 ° C.), although it depends on the combination of the organic onium cation and the cyanofluoroborate anion. If it is more prepared, it can be 0.07 S / m or more, and if it is further optimized, it can be 0.1 S / m or more.
  • the concentration of the lithium cation is preferably 0.03 to 3 mol / L, more preferably 0.05 to 3 mol / L, still more preferably 0.05 to 2 mol / L, particularly preferably. 0.1 to 2 mol / L.
  • concentration of the lithium cation is within the above range, the viscosity of the nonaqueous electrolytic solution is likely to be within an appropriate range, and the electrical conductivity can be increased.
  • organic onium cation known organic onium cations can be used without particular limitation, and examples thereof include organic ammonium cations and aromatic heterocyclic compound cations.
  • organic ammonium cation examples include trimethylpropylammonium cation, trimethylisopropylammonium cation, butyltrimethylammonium cation, hexyltrimethylammonium cation, octyltrimethylammonium cation, dodecyltrimethylammonium cation, dimethyldipropylammonium cation, tetraethylammonium cation, N- Examples include methyl-N-propylpyrrolidinium cation, N, N-tetramethylenepyrrolidinium cation, 5-azonia- [4,4] spirononane cation, and 5-azonia- [4,5] spirodecane cation.
  • a trimethylpropylammonium cation, a tetraethylammonium cation, a diethylmethylmethoxyethylammonium cation, and the like are preferable because of high electrochemical stability, relatively low viscosity, and easy synthesis.
  • aromatic heterocyclic compound cations include imidazolium cations, pyridinium cations, pyridazinium cations, pyrimidinium cations, pyrazinium cations, pyrazolium cations, thiazonium cations Oxozolium cations, triazonium cations, pyrrolidinium cations.
  • Imidazolium cations such as 1-tert-butyl-3-isopropylimidazolium cation; pyridinium cations such as N-ethylpyridinium cation and N-butylpyridinium cation are preferable.
  • organic onium cations may be used alone or in combination of two or more.
  • 1-ethyl-3-ethyl cation is particularly suitable as a particularly suitable organic onium cation used in a nonaqueous electrolytic solution for an electricity storage device.
  • examples thereof include a methyl imidazolium cation and a diethylmethylmethoxyethylammonium cation.
  • an anion is represented by the following formula (I) in 100 mol% of the anion contained in the ionic substance.
  • BF a (CN) 4-a - (I) (In the formula (I), a is an integer of 1 to 3) It consists of the cyanofluoroborate anion shown by these.
  • the proportion of the cyanofluoroborate anion is 30 mol% or more, preferably 60 mol% or more, particularly preferably 90 mol% or more, and most preferably 100 mol% in 100 mol% of anions contained in the ionic substance. is there.
  • the electrolytic solution containing the cyanofluoroborate anion has the advantages of high electrochemical stability and high conductivity. Further, by including the cyanofluoroborate anion, the ionic substance can have a low viscosity and a low melting point.
  • the nonaqueous electrolytic solution of the present invention contains at least one selected from the group consisting of BF (CN) 3 ⁇ , BF 2 (CN) 2 ⁇ and BF 3 (CN) ⁇ as the cyanofluoroborate anion.
  • cyanofluoroborate anions may be used alone or in combination of two or more.
  • tricyanofluoroborate anion BF (CN) 3 ⁇
  • dicyanodifluoroborate anion BF 2 (CN) 2 ⁇
  • All the anions contained in the non-aqueous electrolyte of the present invention may be the cyanofluoroborate anion, but other anions may be contained.
  • an existing anion can be used without particular limitation.
  • other anions for example, CF 3 SO 3 ⁇ , N (FSO 2 ) 2 ⁇ , N (FSO 2 ) (CF 3 SO 2 ) ⁇ , N (CF 3 SO 2 ) 2 ⁇ , N (C 2 F 5 SO 2 ) 2 ⁇ , cyclic 1,2-perfluoroethanedisulfonylimide anion, cyclic 1,3-perfluoropropane disulfonylimide anion, C (FSO 2 ) 3 ⁇ , C (CF 3 SO 2 ) 3 ⁇ , C (C 2 F 5 SO 2 ) 3 ⁇ , bisoxalatoborate anion, difluorooxalatoborate anion, tetrafluorooxala
  • BF 4 ⁇ , PF 6 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (FSO 2 ) 2 N ⁇ and the like are particularly preferably used because an electrolytic solution having high electrochemical stability and high conductivity can be obtained. I can do things.
  • the method for producing the ionic substance constituting the nonaqueous electrolytic solution of the present invention is not particularly limited.
  • the lithium cation is 1 to 60 mol% in 100 mol% of all cations.
  • the organic onium cation A + in the above formula (II) is an organic onium cation constituting the cation of the ionic substance described above, and is not particularly limited, but is an organic ammonium cation, an aromatic heterocyclic compound cation. Is preferred.
  • the cyanofluoroborate salt represented by the above formula (II) is represented by the following formula (IV) M + ⁇ BF a (CN) 4-a - (IV) (In the formula (IV), a is an integer of 1 to 3, and M + is a metal ion.)
  • a is an integer of 1 to 3
  • M + is a metal ion.
  • the salt exchange method is preferably used because of the ease of reaction.
  • the metal (M in the formula (IV)) preferably used is an alkali metal such as lithium, sodium or potassium; an alkaline earth such as magnesium or calcium A metal etc. can be mentioned.
  • alkali metals such as lithium, sodium and potassium are preferably used because of easy ion exchange.
  • potassium is particularly preferably used because of the low hygroscopicity of the metal salt as a raw material.
  • the non-aqueous electrolyte of the present invention is used for a lithium ion battery (such as a lithium battery, a lithium ion battery, or a lithium ion capacitor), lithium is preferable in that contamination of other alkali metals can be reduced. Used for.
  • a lithium ion battery such as a lithium battery, a lithium ion battery, or a lithium ion capacitor
  • lithium salt represented by the formula (III) a known lithium salt can be used, and an industrial grade or reagent grade one can be used.
  • the non-aqueous electrolyte preferably has 100 mol% of the anion represented by the formula (I) in 100 mol% of the anion contained in the ionic substance, and X ⁇ represented by the formula (III) is cyano.
  • a fluoroborate anion is preferred.
  • a lithium salt in which X ⁇ is a cyanofluoroborate anion can be synthesized by a known method.
  • lithium metal cyanide is dissolved in an organic solvent such as acetonitrile and acetone.
  • the above BF 3 gas is blown into a solution obtained by dissolving an alkali metal or alkaline earth metal cyanide other than lithium, such as potassium, sodium, magnesium, calcium, etc. in an organic solvent
  • a BF 3 addition compound such as boron trifluoride ether BF 3 ⁇ OEt 2 is allowed to act in the presence of an aprotic solvent to synthesize a corresponding alkali metal or alkaline earth metal salt of cyanofluoroborate
  • the nonaqueous electrolytic solution of the present invention when used as an electrolyte for an electricity storage device, it is preferable to sufficiently remove impurities. It is preferable that the water concentration in the non-aqueous electrolyte is 1000 ppm or less, and the metal concentration other than Li is 20 ppm or less for Na, 10 ppm or less for K, 10 ppm or less for Ca, 3 ppm or less for Fe, and 10 ppm or less for Pb. Non-aqueous electrolyte is 100% by mass).
  • the nonaqueous electrolytic solution of the present invention preferably contains an ionic substance as a main component and does not substantially contain an organic solvent.
  • the organic solvent content of the nonaqueous electrolytic solution of the present invention is usually 10% by mass or less, preferably 5% by mass or less, and more preferably 1% by mass or less.
  • the non-aqueous electrolyte of the present invention By applying the non-aqueous electrolyte of the present invention to an electricity storage device, a battery that is not flammable and operates even at low temperatures can be provided.
  • nonaqueous electrolytic solution of the present invention has a low melting point and high conductivity is not necessarily clear, but is considered as follows.
  • the nonaqueous electrolytic solution of the present invention contains cyanofluoroborate anion in an amount of 30 mol% or more, preferably 60 mol% or more in the total anion contained in the ionic substance.
  • the cyanofluoroborate anion is relatively smaller in anion diameter and molecular weight than known anions (for example, (CF 3 SO 2 ) N ⁇ , (FSO 2 ) 2 N ⁇ ), and has a small polarity and interaction between compounds. Is small, the viscosity is low and ions easily move. For this reason, it is thought that the non-aqueous electrolyte of the present invention containing a cyanofluoroborate anion has high conductivity.
  • hexafluorophosphate anion, tetrafluoroborate anion and tetracyanoborate anion have high symmetry and are easy to aggregate and crystallize, whereas cyanofluoroborate anion is more symmetric than these anions. Is low, it is difficult to crystallize, and the melting point of the nonaqueous electrolytic solution of the present invention is considered to be low.
  • the non-aqueous electrolyte of the present invention may contain additives used for existing batteries or electric double layer capacitors.
  • the nonaqueous electrolytic solution of the present invention can be used for power storage devices such as lithium batteries (lithium primary batteries), lithium ion batteries (lithium secondary batteries), and lithium ion capacitors. Among these, it is preferable to use for a lithium battery and a lithium ion battery, and it is more preferable to use for a lithium ion battery. Further, the non-aqueous electrolyte may be used in a gel form as well as a liquid form. Furthermore, the non-aqueous electrolyte of the present invention can be used for a solid polymer electrolyte. The non-aqueous electrolyte of the present invention is suitably used for an electricity storage device because it has an extremely low vapor pressure, has no danger of ignition, is electrochemically stable, and can maintain high electrical conductivity even at low temperatures. be able to.
  • the lithium battery includes a negative electrode, a positive electrode, a separator disposed between the positive electrode and the negative electrode, and the nonaqueous electrolytic solution of the present invention.
  • the lithium battery has the same configuration as the known lithium battery except for the non-aqueous electrolyte.
  • the positive electrode and the negative electrode are laminated through a porous film impregnated with the non-aqueous electrolyte, and these are the cases. It has the form stored in. Therefore, the shape of the lithium battery is not particularly limited, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.
  • At least one selected from the group consisting of lithium and lithium alloys is used as an active material.
  • the positive electrode contains a positive electrode active material, and preferably further contains a conductive material and a binder.
  • a positive electrode active material materials commonly used in the field of lithium batteries can be used as they are, and among them, metal oxides such as manganese dioxide, graphite fluoride, thionyl chloride and the like can be preferably used.
  • Manganese dioxide is particularly preferable because of its good discharge characteristics.
  • the non-aqueous electrolyte lithium ion battery of the present invention comprises a negative electrode and a positive electrode that can occlude and release lithium ions, and the non-aqueous electrolyte of the present invention.
  • the configuration of the lithium ion battery is the same as that of a known lithium ion battery except for the non-aqueous electrolyte.
  • the positive electrode and the negative electrode are laminated through the porous film impregnated with the non-aqueous electrolyte of the present invention. These have a form housed in a case. Therefore, the shape of the lithium ion battery is not particularly limited, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.
  • the negative electrode used in the lithium ion battery preferably has a negative electrode active material layer on the current collector.
  • the negative electrode active material is not particularly limited as long as it can electrochemically occlude and release lithium ions. Specific examples thereof include carbonaceous materials, alloy-based materials, lithium-containing metal composite oxide materials, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the positive electrode active material is preferably a material containing lithium and at least one transition metal. Specific examples include lithium transition metal composite oxides and lithium-containing transition metal phosphate compounds. These positive electrode active materials may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the lithium secondary battery has excellent electrochemical characteristics at high temperatures even when the end-of-charge voltage is 4.2 V or higher, particularly 4.3 V or higher.
  • the lithium battery in the present invention can be charged / discharged at ⁇ 40 to 100 ° C.
  • a lithium ion capacitor is a power storage device that uses a carbon material such as graphite as a negative electrode and stores energy using lithium ion intercalation thereto.
  • the positive electrode include those using an electric double layer between an activated carbon electrode and an electrolytic solution, those using a ⁇ -conjugated polymer electrode doping / dedoping reaction, and the like.
  • the present invention since it does not contain a volatile organic solvent, it is highly safe, electrochemically stable, and can maintain electric conductivity even at low temperatures, such as a non-aqueous electrolyte and a lithium battery using the same.
  • An electricity storage device can be provided.
  • the above electrolytic solution can be obtained by using an electrolytic solution in which a cyanofluoroborate lithium salt is dissolved in a cyanofluoroborate / organic cation salt.
  • the electrolytic solution of the present invention is used as a non-aqueous electrolytic solution for a vehicle-mounted power storage device or a large battery for storing natural energy, a power storage device that operates even in a low temperature environment can be obtained.
  • Electrochemical measurement Place an appropriate amount of sample solution (2 ml or less) into a cell for VC-4 voltammetry manufactured by BAS, and measure cyclic voltammetry with a potentiostat manufactured by Autolab using a glassy carbon electrode, a platinum electrode, and an Ag / Ag + type reference electrode. And electrochemical stability (potential window) was evaluated.
  • Electrolyte Resistance Component The electrolyte resistance component measured at room temperature (23 ° C.) and 0 ° C. was measured with VersaSTAT4 manufactured by Toyo Technica.
  • Table 1 shows that the ionic substance containing cyanofluoroborate anion has a lower viscosity than other ionic substances. For this reason, it has the advantage that handling is easy. In addition, an ionic substance containing a cyanofluoroborate anion has an equivalent or superior potential window as compared with other ionic substances.
  • Example 1 19.6 g of EMIM bromide and 10.8 g of dicyanodifluoroborate lithium salt were dissolved in 10 ml of ion-exchanged water, respectively.
  • the EMIM bromide aqueous solution prepared above was placed in a flask, and a dicyanodifluoroborate lithium aqueous solution was added dropwise. After the addition, the solution separated into two layers. 20 ml of methylene chloride was added thereto, and the methylene chloride layer was separated.
  • the ratio of organic cation to lithium cation in the whole solution was 0.9 (90 mol%): 0.1 (10 mol%) (concentration of lithium cation) 0.63 g of dicyanodifluoroborate lithium salt and 11.15 g of EMIM dicyanodifluoroborate were dissolved so as to be 0.55 mol / L).
  • the electrical conductivity at 10 ° C. of the solution (non-aqueous electrolyte; hereinafter sometimes referred to as “EMIM 0.9 Li 0.1 dicyanodifluoroborate”) was measured and found to be 0.80 S / m.
  • the measurement result of the cyclic voltammogram is shown in FIG.
  • the electrochemical stability was -2.5 to 2.4 (V vs Ag / Ag +).
  • the electrical conductivity of the non-aqueous electrolyte solution of EMIM 0.9 Li 0.1 dicyanodifluoroborate prepared above was measured at ⁇ 10, ⁇ 20, and ⁇ 30 ° C.
  • Table 2 shows the results of the composition ratio, electrical conductivity, and electrochemical stability of the nonaqueous electrolytic solution.
  • Table 2 shows values that the lithium cation contributes to electric conduction (“estimated value of lithium cation mobility”).
  • Example 2 An organic cation and lithium were used in the same manner as in Example 1 except that the commercially available EMIM ⁇ BF 4 was used instead of the EMIM dicyanodifluoroborate of Example 1 and LiBF 4 was used instead of the dicyanodifluoroborate lithium salt.
  • a non-aqueous electrolyte having a cation ratio of 0.9 (90 mol%): 0.1 (10 mol%) was prepared, and the electrical conductivity and electrochemical stability were measured, and the lithium cation mobility estimated value was obtained. It was.
  • Table 2 shows the composition, electrical conductivity, electrochemical stability, and estimated lithium cation mobility of the non-aqueous electrolyte.
  • Example 3 Except that Example of commercially available butyl methylpyrrolidin instead of 1 of EMIM dicyano-difluoro borate pyridinium ⁇ (FSO 2) using 2 N, were also used in place of the dicyano-difluoro borate lithium salt (FSO 2) 2, As in Example 1, a non-aqueous electrolyte having an organic cation / lithium cation ratio of 0.9 (90 mol%): 0.1 (10 mol%) was prepared, and the electrical conductivity and electrochemical stability were measured. In addition, an estimated value of lithium cation mobility was obtained. Table 2 shows the composition, electrical conductivity, electrochemical stability, and estimated lithium cation mobility of the non-aqueous electrolyte.
  • FSO 2 dicyano-difluoro borate lithium salt
  • the non-aqueous electrolyte of the present invention has a higher electrical conductivity than known ionic liquids, and is particularly suitable for use at low temperatures.
  • it has a wide electrochemical stability and is suitable as an electrolytic solution for power storage devices such as lithium batteries, lithium ion batteries, and lithium ion capacitors.
  • Examples 6 to 9, Comparative Examples 6 and 7 The same procedure as in Example 2 was performed, except that 8.04 g of EMIM chloride was changed to 19.4 g, and 12.5 g of tricyanofluoroborate lithium salt was used instead of 11.4 g of dicyanodifluoroborate lithium salt, and 23.7 g Of EMIM tricyanofluoroborate (liquid) (yield 87.3%).
  • Comparative Example 8 (ratio of lithium cation 0.00 mol%), Comparative Example 9 (ratio of lithium cation 0.79 mol%), Example 10 (ratio of lithium cation 2.88 mol%), Example 11 (lithium) Cation ratio 13.23 mol%), Example 12 (lithium cation ratio 24.52 mol%), Example 13 (lithium cation ratio 33.64 mol%), room temperature (23 ° C) electrical conductivity
  • the lithium cation mobility estimated value was calculated
  • Examples 14 to 18, Comparative Examples 10 and 11 22.5 g of diethylmethylmethoxyethylammonium bromide (hereinafter sometimes referred to as “DEME”) bromide is used instead of 8.04 g of EMIM chloride, and tricyanofluoroborate is used instead of 11.4 g of dicyanodifluoroborate lithium salt.
  • DEME diethylmethylmethoxyethylammonium bromide
  • Example 19 15 ml of dried EMIM tricyanofluoroborate produced in Example 6 and the like was collected, and 1.84 g of tricyanofluoroborate lithium salt was dissolved therein. In addition, EMIM tricyanofluoroborate was added so that the total amount was 20 ml, and a non-aqueous electrolyte with a lithium cation ratio of 14.5 mol% and a dicyanofluoroborate anion ratio of 100 mol% in the anion was prepared. did.
  • the negative electrode was produced in the same process as the positive electrode, using 82 parts by mass of LTO (Li 4 Ti 5 O 12 ) as an active material, 8 parts by mass of acetylene black as a conductive material, and 10 parts by mass of polyvinylidene fluoride as a binder.
  • LTO Li 4 Ti 5 O 12
  • the separator used was a polyethylene microporous membrane (thickness 20 ⁇ m, porosity 40%).
  • the positive electrode and negative electrode prepared above were punched out to 14 ⁇ 20 mm 2 and dried at 170 ° C. for 10 hours, respectively, faced through a separator and inserted into an aluminum laminate, and the electrolyte was poured and impregnated under reduced pressure. Thereafter, vacuum sealing was performed to produce a single-layer laminate cell (battery) for battery performance evaluation.
  • the measurement results of the charge / discharge characteristics measured by the methods described in (3) Charge capacity and discharge capacity and (4) Electrolytic solution resistance component are shown in FIG.
  • the room temperature is 23 ° C.
  • Example 19 battery grade EMIM. (FSO 2 ) 2 N was used instead of EMIM dicyanodifluoroborate, and 2.99 g Li. (FSO 2) instead of 1.72 g dicyanodifluoroborate lithium salt. )
  • a non-aqueous electrolyte in which the ratio of lithium cation in the cation was 14.5 mol% and the ratio of (FSO 2 ) 2 N anion in the anion was 100 mol% was prepared in the same manner except that 2 N salt was used.
  • a cell (battery) was produced in the same manner as in Example 19 except for the above.
  • Example 19 the measurement results of the charge / discharge characteristics are shown in FIG.
  • the lithium ion battery using the non-aqueous electrolyte of the present invention has substantially the same charge / discharge capacity as that of the battery prepared in Reference Example 1, which is a known electrolyte, and the resistance of the electrolyte is room temperature and 0. Both the temperatures were low, and lithium ions could be conducted more. Further, in the lithium ion battery using the non-aqueous electrolyte of the present invention, the decrease rate of the discharge capacity at 0 ° C. from the discharge capacity at room temperature is 14%, which is the decrease rate of the battery manufactured in Reference Example 1. It can be seen that 73% can be greatly suppressed, and the discharge characteristics at a lower temperature are excellent.

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Abstract

Le problème est de fournir une solution électrolytique non aqueuse qui ne contienne pas de solvant organique volatile, et qui soit donc très sûre, qui soit électro-chimiquement stable, et qui soit capable de maintenir sa conductivité électrique même à basse température, ainsi que de fournir un dispositif d'accumulation d'énergie utilisant cette solution de la même manière qu'une batterie au lithium. La solution que présente l'invention concerne une solution électrolytique non aqueuse qui contient une substance ionique, dans laquelle: les cations dans la substance ionique contiennent un cation de lithium par 1 à 60% en moles et un cation d'onium organique (où le total de cation de lithium et de cation d'onium organique est de 100% en moles); et les anions contiennent l'anion de cyano-fluoroborate représenté par la formule (I) à une concentration d'au moins 30% en moles sur les 100% en moles des anions contenus dans la substance ionique. BFa(CN)4-a - (I) (Dans la formule (I), a est un entier de 1-3.)
PCT/JP2015/085636 2015-01-06 2015-12-21 Solution electrolytique non-aqueuse et dispositif d'accumulation d'energie utilisant celle-ci WO2016111151A1 (fr)

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Cited By (2)

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JPWO2018020669A1 (ja) * 2016-07-29 2019-02-28 株式会社東芝 非水電解質電池及び電池パック
WO2021176920A1 (fr) * 2020-03-02 2021-09-10 日清紡ホールディングス株式会社 Solution électrolytique pour dispositif de stockage d'énergie, et liquide ionique

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WO2023188395A1 (fr) * 2022-03-31 2023-10-05 ビークルエナジージャパン株式会社 Batterie secondaire au lithium-ion
CN116470144B (zh) * 2023-03-29 2024-05-14 中国科学院青岛生物能源与过程研究所 一种碱金属电池使用的电解质及其制备和应用

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JP2014529895A (ja) * 2011-08-25 2014-11-13 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ 色素増感太陽電池のための添加剤
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JP2004175667A (ja) * 2002-11-22 2004-06-24 Tokuyama Corp オニウム塩
JP2009170431A (ja) * 2009-04-28 2009-07-30 Gs Yuasa Corporation 非水電解質電池
JP2012028311A (ja) * 2010-06-22 2012-02-09 Nippon Synthetic Chem Ind Co Ltd:The 電解質材料、リチウム二次電池用電解質、及び、それを用いたリチウム二次電池、並びに新規なリチウム塩
JP2014529895A (ja) * 2011-08-25 2014-11-13 メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ 色素増感太陽電池のための添加剤
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2018020669A1 (ja) * 2016-07-29 2019-02-28 株式会社東芝 非水電解質電池及び電池パック
WO2021176920A1 (fr) * 2020-03-02 2021-09-10 日清紡ホールディングス株式会社 Solution électrolytique pour dispositif de stockage d'énergie, et liquide ionique

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