WO2015045390A1 - Dispositif de stockage d'électricité - Google Patents

Dispositif de stockage d'électricité Download PDF

Info

Publication number
WO2015045390A1
WO2015045390A1 PCT/JP2014/004914 JP2014004914W WO2015045390A1 WO 2015045390 A1 WO2015045390 A1 WO 2015045390A1 JP 2014004914 W JP2014004914 W JP 2014004914W WO 2015045390 A1 WO2015045390 A1 WO 2015045390A1
Authority
WO
WIPO (PCT)
Prior art keywords
substituted
substituent
group
electrolytic solution
unsaturated
Prior art date
Application number
PCT/JP2014/004914
Other languages
English (en)
Japanese (ja)
Inventor
山田　淳夫
裕貴 山田
雄紀 長谷川
智之 河合
浩平 間瀬
佳浩 中垣
合田　信弘
Original Assignee
国立大学法人東京大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人東京大学 filed Critical 国立大学法人東京大学
Publication of WO2015045390A1 publication Critical patent/WO2015045390A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01M10/052—Li-accumulators
    • 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
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a power storage device.
  • the power storage device refers to all elements and devices having a power storage function.
  • the power storage device includes a secondary battery and a capacitor, and both of them, particularly an electric double layer capacitor and a lithium ion secondary battery, have almost the same structure.
  • a power storage device includes a positive electrode, a negative electrode, a separator, and an electrolytic solution as main components.
  • Lithium ion secondary batteries which are one type of power storage device, are used in various applications such as mobile phones and electric vehicles (EV), and have high energy as characteristics required for lithium ion secondary batteries. Density, cycle characteristics and safety in various operating environments.
  • An appropriate electrolyte is added in an appropriate concentration range to the electrolyte of the lithium ion secondary battery.
  • a lithium salt such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , CF 3 SO 3 Li, or (CF 3 SO 2 ) 2 NLi is added as an electrolyte to the electrolyte solution of a lithium ion secondary battery.
  • the concentration of the lithium salt in the electrolytic solution is generally about 1 mol / L.
  • Patent Document 1 discloses a lithium ion secondary battery using an electrolytic solution containing LiPF 6 at a concentration of 1 mol / L.
  • Patent Document 2 discloses a lithium ion secondary battery using an electrolytic solution containing (CF 3 SO 2 ) 2 NLi at a concentration of 1 mol / L.
  • a microporous membrane made of synthetic resin or a microporous membrane made of ceramic was used as the separator.
  • the electrolytic solution found by the present inventors is higher in viscosity than the conventional electrolytic solution, and the separator used in the conventional power storage device has poor electrolyte permeability, and the performance of the power storage device cannot be exhibited. .
  • An object of the present invention is to provide a power storage device having a novel electrolytic solution found by the present inventors and a separator that can be used in combination with the electrolytic solution.
  • the lithium ion secondary battery can be charged / discharged even using the electrolytic solution found by the present inventors.
  • the electrolytic solution newly found by the present inventors is one in which a metal salt as an electrolyte is added more than usual.
  • the present inventors have analyzed the above electrolytic solution, they have found that an electrolytic solution showing a specific relationship at a peak observed in an IR spectrum or a Raman spectrum is particularly advantageous as an electrolytic solution for a battery.
  • the “water retention ratio” in the present invention refers to the ratio of the actual water retention amount to the reference water retention amount, in other words, the utilization rate of the voids of the separator. The water retention magnification will be described in detail later.
  • the power storage device of the present invention is a power storage device having a positive electrode, a negative electrode, an electrolytic solution, and a separator, and the separator has a water retention ratio of 0.1 or more.
  • the peak intensity derived from the organic solvent in the vibrational spectrum of the electrolyte is Io, and the peak of the organic solvent is shifted.
  • the cation of the salt is preferably lithium.
  • the power storage device of the present invention is preferably a lithium ion secondary battery.
  • the power storage device of the present invention includes a separator having a water retention ratio of 0.1 or more and a newly found electrolyte, the power storage device can exhibit its performance.
  • IR spectrum of the electrolyte solution of the electrolyte solution E11 It is IR spectrum of the electrolyte solution of the electrolyte solution E12. It is IR spectrum of the electrolyte solution of the electrolyte solution E13. It is IR spectrum of the electrolyte solution of the electrolyte solution E14. It is IR spectrum of the electrolyte solution of the electrolyte solution C6. It is IR spectrum of dimethyl carbonate. It is IR spectrum of the electrolyte solution of the electrolyte solution E15. It is IR spectrum of the electrolyte solution of the electrolyte solution E16. It is IR spectrum of the electrolyte solution of the electrolyte solution E17.
  • 10 is a DSC chart of the lithium ion secondary battery of Example 1 in Evaluation Example 11.
  • 10 is a DSC chart of a lithium ion secondary battery of Comparative Example 1 in Evaluation Example 11.
  • 2 is a graph showing a charge / discharge curve of the lithium ion secondary battery of Example 1.
  • FIG. 10 is a graph showing a charge / discharge curve of a lithium ion secondary battery of Comparative Example 2.
  • the charge / discharge curve of the half cell of Reference Example 1-2 is shown.
  • the charging / discharging curve of the half cell of Reference Example 2-2 is shown.
  • the charging / discharging curve of the half cell of the reference example 3 is shown.
  • the charging / discharging curve of the half cell of the reference example 4 is shown.
  • the charging / discharging curve of the half cell of the reference example 5 is shown. It is a graph which shows the relationship between the electric current and electrode potential of the half cell of Reference Example 6 in Evaluation Example 19.
  • 10 is a graph showing the relationship between the potential (3.1 to 4.6 V) and the response current with respect to the half cell of Reference Example 6.
  • 10 is a graph showing the relationship between the potential (3.1 to 5.1 V) and the response current for the half cell of Reference Example 6.
  • 10 is a graph showing a relationship between a potential (3.1 to 4.6 V) and a response current with respect to the half cell of Reference Example 7.
  • 10 is a graph showing the relationship between the potential (3.1 to 5.1 V) and the response current with respect to the half cell of Reference Example 7.
  • 10 is a graph showing the relationship between the potential (3.1 to 4.6 V) and the response current for the half cell of Reference Example 8.
  • 10 is a graph showing the relationship between the potential (3.1 to 5.1 V) and the response current with respect to the half cell of Reference Example 8.
  • 10 is a graph showing the relationship between the potential (3.1 to 4.6 V) and the response current with respect to the half cell of Reference Example 9.
  • 10 is a graph showing the relationship between the potential (3.1 to 5.1 V) and the response current with respect to the half cell of Reference Example 9.
  • 14 is a graph showing the relationship between the potential (3.1 to 4.6 V) and the response current with respect to the half cell of Reference Example 11.
  • 10 is a graph showing the relationship between the potential (3.0 to 4.5 V) and the response current for the half cell of Reference Example 7.
  • 10 is a graph showing the relationship between the potential (3.0 to 5.0 V) and the response current with respect to the half cell of Reference Example 7.
  • 10 is a graph showing the relationship between the potential (3.0 to 4.5 V) and the response current for the half cell of Reference Example 10.
  • 10 is a graph showing the relationship between the potential (3.0 to 5.0 V) and the response current with respect to the half cell of Reference Example 10.
  • 14 is a graph showing the relationship between the potential (3.0 to 4.5 V) and the response current with respect to the half cell of Reference Example 12.
  • 14 is a graph showing the relationship between the potential (3.0 to 5.0 V) and the response current with respect to the half cell of Reference Example 12.
  • FIG. It is a surface analysis result of the aluminum foil in the evaluation example 22 after charging / discharging of the lithium ion secondary battery of Example 1.
  • FIG. It is the surface analysis result of the aluminum foil in the evaluation example 22 after charging / discharging of the lithium ion secondary battery of Example 6.
  • FIG. It is a Raman spectrum of the electrolyte solution E8. It is a Raman spectrum of the electrolyte solution E21. It is a Raman spectrum of the electrolyte solution C4. It is a Raman spectrum of the electrolyte solution E10. It is a Raman spectrum of the electrolyte solution E12. It is a Raman spectrum of the electrolyte solution E14. It is a Raman spectrum of the electrolyte solution C6.
  • the numerical range “a to b” described in this specification includes the lower limit “a” and the upper limit “b”.
  • the numerical range can be configured by arbitrarily combining these upper limit value and lower limit value and the numerical values listed in the examples.
  • numerical values arbitrarily selected from the numerical value range can be used as upper and lower numerical values.
  • the power storage device of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator.
  • Examples of the power storage device of the present invention include a secondary battery and a capacitor.
  • the power storage device of the present invention is preferably a lithium ion secondary battery, an electric double layer capacitor, or a lithium ion capacitor.
  • the power storage device of the present invention is preferably a lithium ion secondary battery.
  • the power storage device of the present invention is characterized by the electrolytic solution and the separator, and the other constituent elements constituting the power storage device may be known ones suitable for each power storage device.
  • the separator and the electrolytic solution will be described in detail.
  • the separator separates the positive electrode and the negative electrode, and allows the electrolyte to pass through while preventing a short circuit of current due to contact between the two electrodes.
  • the water retention magnification of the separator of the present invention is 0.1 or more.
  • the “water retention ratio” in the present invention refers to the ratio of the actual water retention amount to the reference water retention amount, in other words, the utilization rate of the voids of the separator.
  • Water retention ratio in the present invention is determined by the following method.
  • the dry mass Wd of the separator is measured, and the separator is immersed in ultrapure water for 10 minutes. Thereafter, the excess liquid is wiped with a waste cloth, and the wet mass Wh of the separator is measured.
  • Water retention amount We (Wh ⁇ Wd) (1)
  • the reference water retention amount Wt of the separator is calculated according to the equations (2), (3), and (4).
  • the water retention magnification is calculated from equation (5).
  • the water retention ratio is the ratio of the actual water retention amount to the reference water retention amount.
  • Water retention magnification We / Wt (5)
  • Water retention ratio used in the present invention means the utilization factor of the voids of the separator. The higher the “Water Retention Ratio” number, the easier it is for the separator to retain water.
  • the electrolytic solution of the present invention As described later, a cation of a metal salt and a hetero element of an organic solvent (or a preferential coordination solvent) having a hetero element form a coordination bond, and the metal salt and the hetero element are It is presumed that a stable cluster composed of the organic solvent (or preferential coordination solvent) is formed. It is considered that due to the geometric structure of this cluster, the electrolyte solution of the present invention causes a bias in electric charge and develops a polarity that exceeds the polarity of the solvent. Therefore, regarding the polarity, the electrolytic solution of the present invention is expected to exhibit properties close to water, which is a highly polar solvent. As will be described later in Examples, it was found that there is a good relationship between the evaluation result of the separator with water and the permeability of the electrolytic solution of the present invention to the separator.
  • the electrolyte solution of the present invention described later has a higher viscosity than a normal electrolyte solution. Therefore, a separator with good electrolyte permeability is required.
  • the water retention ratio is preferably 0.1 or more, more preferably 0.4 or more, and 0.9 or more. More preferably it is. Most preferable is when the water retention ratio is 1.0 or more, and at this time, all the voids of the separator are filled with water. When the water retention ratio exceeds 1.0, it is considered that the separator material is swollen when water is contained, and the apparent volume is increased. In such a case, it can be judged that the water retention capacity is high.
  • various solvents that do not dissolve the material constituting the separator are water. It may be used instead of.
  • Various solvents having high polarity can be used as such a solvent. Examples thereof include alcohols such as methanol, ethanol, propanol and isopropanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and esters such as methyl acetate and ethyl acetate.
  • the hydrophilicity of the separator material and the continuity of the voids of the separator can be considered.
  • a separator made of a highly hydrophilic material and having a form in which voids are continuously connected is preferable.
  • the separator When the material constituting the separator is a material having low hydrophilicity, the separator has poor wettability with respect to water, and it is difficult for water to enter the gap of the separator. On the other hand, when the material constituting the separator is a highly hydrophilic material, the separator easily attracts water, and the voids of the separator are easily filled with water.
  • the material constituting the separator is preferably a highly hydrophilic material.
  • hydrophilic inorganic materials such as glass, alumina, and silica, cellulose, modified cellulose (for example, carboxymethyl cellulose), polyamide, polyaramid, polyamideimide, polyvinyl alcohol, polycarboxylic acid (for example, polyacrylic acid, polymethacrylic acid) Acid, polyitaconic acid) and other hydrophobic organic materials such as polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polyester, polyacrylonitrile, etc.
  • hydrophilic group such as a group, a sulfo group, a silanol group, an amino group, a hydroxy group, and a phosphoric acid group. A combination of these materials may also be used.
  • the separator may contain a binder for binding the above materials, and may contain various known additives as necessary.
  • additives include antioxidants and removal agents for by-products such as acids.
  • Examples of the form of the separator include a nonwoven fabric and a microporous film.
  • a multilayer structure in which a plurality of non-woven fabrics and / or a plurality of microporous membranes are stacked or combined is also exemplified.
  • the separator is particularly preferably a nonwoven fabric.
  • the non-woven fabric refers to a sheet formed by thermally, mechanically or chemically joining or intertwining fibrous materials. Paper is also a type of non-woven fabric. Since the nonwoven fabric is formed by intertwining or bonding fibrous materials, it is difficult to form voids that cannot be used without being connected to others in the nonwoven fabric. Therefore, in the nonwoven fabric, it is considered that all voids are continuously connected, and the water retention ratio of the nonwoven fabric is estimated to be high.
  • a nonwoven fabric in which a fibrous material having a large diameter and a thin material are appropriately combined may be used.
  • microporous film examples include microporous films.
  • the microporous film may be formed by any existing method, and the structure of the microporous film is not particularly limited.
  • Porous methods can be broadly classified into wet methods and dry methods.
  • the wet method is a method of creating voids in the matrix resin by adding and mixing the extract to be extracted after sheeting into the matrix resin and extracting only the additive using the good solvent of the extract. It is.
  • Various proposals have been made as wet methods.
  • a dry method for example, by adopting low-temperature extrusion and a high draft ratio at the time of melt extrusion, the lamella structure in the film before stretching formed into a sheet is controlled, and this is uniaxially stretched so that at the lamella interface A method (so-called lamellar stretching method) in which cleavage is generated to form voids has been proposed.
  • lamellar stretching method there is a method in which a large amount of inorganic particles or resin incompatible with the matrix resin is added as particles, a sheet is formed and stretched to cause cleavage at the interface between the particles and the matrix resin, thereby forming voids. Proposed.
  • film stretching methods include uniaxial stretching of a film using a roll, sequential biaxial stretching by roll stretching and tenter stretching, and simultaneous biaxial stretching by a simultaneous biaxial tenter. Further, this stretching can be used for either a dry method or a wet method. In the wet method, stretching may be performed while containing a solvent, or may be performed after extracting the solvent.
  • the fine structure of the voids can be controlled by the porous method.
  • the void structure include a direct-hole structure and a three-dimensional network structure.
  • the void structure is a three-dimensional network structure, it is easy to hold the electrolytic solution, but the electrolytic solution is difficult to pass through.
  • the thickness of the separator is preferably 5 ⁇ m or more and 450 ⁇ m or less, and more preferably 10 ⁇ m or more and 100 ⁇ m or less. If the thickness is less than 5 ⁇ m, the strength of the separator is weakened, so that there is a possibility that the electrodes are easily short-circuited due to external force or precipitation of lithium dendrite, leading to self-discharge or heat generation. When the thickness is larger than 450 ⁇ m, the energy density of the power storage device is lowered, the internal resistance is increased, and the output performance of the device is lowered.
  • the separator has a function of isolating the positive electrode and the negative electrode so as not to be short-circuited. Therefore, the diameter of the void formed on the surface of the separator is preferably smaller than the particle size of the positive electrode active material and the particle size of the negative electrode active material. In the lithium ion secondary battery, since the particle diameters of the positive electrode active material and the negative electrode active material are approximately 1 ⁇ m to 10 ⁇ m, the diameter of the void formed on the surface of the separator is preferably less than 10 ⁇ m and less than 1 ⁇ m. More preferably.
  • the electrolytic solution is an electrolytic solution containing a salt having alkali metal, alkaline earth metal or aluminum as a cation (hereinafter sometimes referred to as “metal salt” or simply “salt”) and an organic solvent having a hetero element.
  • metal salt or simply “salt”
  • organic solvent having a hetero element When the peak intensity derived from the organic solvent in the vibrational spectrum of the electrolytic solution is Io, the peak intensity at the peak wavelength of the organic solvent is Io, and the peak intensity at which the peak of the organic solvent is shifted is Is, Is> Io.
  • the electrolyte solution with Is> Io may be referred to as “the electrolyte solution of the present invention”.
  • the metal salt may be a compound that is usually used as an electrolyte, such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiAlCl 4 , etc. contained in the battery electrolyte.
  • the cation of the metal salt include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium, and aluminum.
  • the cation of the metal salt is preferably the same metal ion as the charge carrier of the battery using the electrolytic solution.
  • the metal salt cation is preferably lithium.
  • the chemical structure of the anion of the salt may include at least one element selected from halogen, boron, nitrogen, oxygen, sulfur or carbon.
  • Specific examples of the chemical structure of an anion containing halogen or boron include ClO 4 , PF 6 , AsF 6 , SbF 6 , TaF 6 , BF 4 , SiF 6 , B (C 6 H 5 ) 4 , and B (oxalate). 2 , Cl, Br, and I.
  • the chemical structure of the salt anion is preferably a chemical structure represented by the following general formula (1), general formula (2), or general formula (3).
  • R 1 is hydrogen, halogen, an alkyl group which may be substituted with a substituent, a cycloalkyl group which may be substituted with a substituent, an unsaturated alkyl group which may be substituted with a substituent, or a substituent.
  • An unsaturated alkoxy group that may be substituted with a substituent, a thioalkoxy group that may be substituted with a substituent, an unsaturated thioalkoxy group that may be substituted with a substituent, CN, SCN, or OCN Is done.
  • R 2 represents hydrogen, halogen, an alkyl group which may be substituted with a substituent, a cycloalkyl group which may be substituted with a substituent, an unsaturated alkyl group which may be substituted with a substituent, or a substituent.
  • the R 1 and R 2 may be bonded to each other to form a ring.
  • X 2 is, SO 2
  • R a , R b , R c , and R d are each independently hydrogen, halogen, an alkyl group that may be substituted with a substituent, a cycloalkyl group that may be substituted with a substituent, or a substituent.
  • R a , R b , R c , and R d may be bonded to R 1 or R 2 to form a ring.
  • R 3 is hydrogen, halogen, an alkyl group which may be substituted with a substituent, a cycloalkyl group which may be substituted with a substituent, an unsaturated alkyl group which may be substituted with a substituent, or a substituent.
  • An unsaturated alkoxy group that may be substituted with a substituent, a thioalkoxy group that may be substituted with a substituent, an unsaturated thioalkoxy group that may be substituted with a substituent, CN, SCN, or OCN Is done.
  • R e and R f are each independently hydrogen, halogen, an alkyl group that may be substituted with a substituent, a cycloalkyl group that may be substituted with a substituent, or a group that may be substituted with a substituent.
  • R e and R f may combine with R 3 to form a ring.
  • Y is selected from O and S.
  • R 4 is substituted with hydrogen, halogen, an alkyl group which may be substituted with a substituent, or a substituent.
  • R 5 represents hydrogen, halogen, an alkyl group which may be substituted with a substituent, a cycloalkyl group which may be substituted with a substituent, an unsaturated alkyl group which may be substituted with a substituent, or a substituent.
  • the R 6 is hydrogen, halogen, an alkyl group which may be substituted with a substituent, a cycloalkyl group which may be substituted with a substituent, an unsaturated alkyl group which may be substituted with a substituent, or a substituent.
  • any two or three of R 4 , R 5 and R 6 may be bonded to form a ring.
  • R g , R h , R i , R j , R k , and R l are each independently hydrogen, halogen, an alkyl group that may be substituted with a substituent, or a cycloalkyl that may be substituted with a substituent.
  • an unsaturated alkyl group that may be substituted with a substituent an unsaturated cycloalkyl group that may be substituted with a substituent, an aromatic group that may be substituted with a substituent, or a substituent that is substituted with a substituent
  • R g , R h , R i , R j , R k , and R l may combine with R 4 , R 5, or R 6 to form a ring.
  • substituents in the phrase “may be substituted with a substituent” include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an unsaturated cycloalkyl group, an aromatic group, a heterocyclic group, a halogen, and OH.
  • the chemical structure of the salt anion is more preferably a chemical structure represented by the following general formula (4), general formula (5), or general formula (6).
  • R 7 and R 8 are each independently C n H a F b Cl c Br d I e (CN) f (SCN) g (OCN) h .
  • R m , R n , R o , and R p are each independently substituted with hydrogen, halogen, an alkyl group that may be substituted with a substituent, a cycloalkyl group that may be substituted with a substituent, or a substituent.
  • R m , R n , R o , and R p may combine with R 7 or R 8 to form a ring.
  • R q and R r are each independently hydrogen, halogen, an alkyl group that may be substituted with a substituent, a cycloalkyl group that may be substituted with a substituent, or a group that may be substituted with a substituent.
  • R q and R r may combine with R 9 to form a ring.
  • Y is selected from O and S.
  • R 10 X 10 (R 11 X 11 ) (R 12 X 12 )
  • R 10 , R 11 , R 12 are each independently C n H a F b Cl c Br d I e (CN) f (SCN) g (OCN) h .
  • R s , R t , R u , R v , R w , and R x are each independently hydrogen, halogen, an alkyl group that may be substituted with a substituent, or a cycloalkyl that may be substituted with a substituent.
  • an unsaturated alkyl group that may be substituted with a substituent an unsaturated cycloalkyl group that may be substituted with a substituent, an aromatic group that may be substituted with a substituent, or a substituent that is substituted with a substituent
  • R s , R t , R u , R v , R w , and R x may combine with R 10 , R 11, or R 12 to form a ring.
  • n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2.
  • n is preferably an integer of 1 to 8, more preferably an integer of 1 to 7, and particularly preferably an integer of 1 to 3.
  • the chemical structure of the salt anion is more preferably represented by the following general formula (7), general formula (8) or general formula (9).
  • R 13 SO 2 (R 14 SO 2 ) N
  • R 13 and R 14 are each independently C n H a F b Cl c Br d I e .
  • R 16 SO 2 (R 17 SO 2 ) (R 18 SO 2 ) C General formula (9)
  • R 16 , R 17 , and R 18 are each independently C n H a F b Cl c Br d I e .
  • n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2.
  • n is preferably an integer of 1 to 8, more preferably an integer of 1 to 7, and particularly preferably an integer of 1 to 3.
  • the metal salt is (CF 3 SO 2 ) 2 NLi (hereinafter sometimes referred to as “LiTFSA”), (FSO 2 ) 2 NLi (hereinafter sometimes referred to as “LiFSA”), (C 2 F 5 SO 2 ) 2 NLi, FSO 2 (CF 3 SO 2 ) NLi, (SO 2 CF 2 CF 2 SO 2 ) NLi, (SO 2 CF 2 CF 2 SO 2 ) NLi, FSO 2 (CH 3 SO 2 ) NLi FSO 2 (C 2 F 5 SO 2 ) NLi or FSO 2 (C 2 H 5 SO 2 ) NLi is particularly preferred.
  • the metal salt of the present invention may be a combination of an appropriate number of cations and anions described above.
  • One kind of metal salt in the electrolytic solution of the present invention may be used, or a plurality of kinds may be used in combination.
  • organic solvent having a hetero element an organic solvent in which the hetero element is at least one selected from nitrogen, oxygen, sulfur and halogen is preferable, and an organic solvent in which the hetero element is at least one selected from nitrogen or oxygen Is more preferable.
  • organic solvent having a hetero element an aprotic solvent having no proton donating group such as NH group, NH 2 group, OH group, and SH group is preferable.
  • organic solvent having a hetero element examples include nitriles such as acetonitrile, propionitrile, acrylonitrile, malononitrile, 1,2-dimethoxyethane, 1, 2-diethoxyethane, tetrahydrofuran, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, 2,2-dimethyl-1,3-dioxolane, 2-methyltetrahydropyran, 2-methyltetrahydrofuran, crown Ethers such as ether, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethylmethyl carbonate, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolide Amides such as isopropyl isocyanate, n-propyl isocyanate, chloromethyl
  • Esters glycidyl methyl ether, epoxy butane, epoxy such as 2-ethyloxirane, oxazole, 2-ethyloxazole, oxazoline, oxazole such as 2-methyl-2-oxazoline, ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone Acid anhydrides such as acetic anhydride and propionic anhydride, sulfones such as dimethyl sulfone and sulfolane, sulfoxides such as dimethyl sulfoxide, 1-nitropropane and 2-nitrate Nitros such as propane, furans such as furan and furfural, cyclic esters such as ⁇ -butyrolactone, ⁇ -valerolactone and ⁇ -valerolactone, aromatic heterocycles such as thiophene and pyridine, tetrahydro-4-pyrone, Examples thereof include heterocyclic rings such as 1-methylpyr
  • organic solvent examples include chain carbonates represented by the following general formula (10).
  • n is preferably an integer of 1 to 6, more preferably an integer of 1 to 4, and particularly preferably an integer of 1 to 2.
  • m is preferably an integer of 3 to 8, more preferably an integer of 4 to 7, and particularly preferably an integer of 5 to 6.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethylmethyl Carbonate
  • organic solvents may be used alone or in combination as an electrolyte.
  • a solvent having a relative dielectric constant of 20 or more or a donor ether oxygen is preferable.
  • organic solvent include nitriles such as acetonitrile, propionitrile, acrylonitrile, and malononitrile, 2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, 2,2-dimethyl-1,3-dioxolane, 2-methyltetrahydropyran And ethers such as 2-methyltetrahydrofuran and crown ether, N, N-dimethylformamide, acetone, dimethyl sulfoxide, and sulfolane.
  • acetonitrile hereinafter sometimes referred to as “AN”
  • DM 1, 2-dimethoxyethane
  • the peak intensity derived from the organic solvent contained in the electrolyte solution is denoted by Io, and the peak of the organic solvent inherent peak is shifted (hereinafter, “ If the intensity of “shift peak” is sometimes referred to as “Is”, Is> Io. That is, in the vibrational spectral spectrum chart obtained by subjecting the electrolytic solution of the present invention to vibrational spectral measurement, the relationship between the two peak intensities is Is> Io.
  • the original peak of the organic solvent means a peak observed at the peak position (wave number) when vibration spectroscopy measurement is performed only on the organic solvent.
  • the value of the peak intensity Io inherent in the organic solvent and the value of the shift peak intensity Is are the height or area from the baseline of each peak in the vibrational spectrum.
  • the relationship when there are a plurality of peaks in which the original peak of the organic solvent is shifted, the relationship may be determined based on the peak from which the relationship between Is and Io is most easily determined.
  • an organic solvent that can determine the relationship between Is and Io most easily is selected, an organic solvent that can determine the relationship between Is and Io most easily (the difference between Is and Io is most pronounced) is selected, The relationship between Is and Io may be determined based on the peak intensity. If the peak shift amount is small and the peaks before and after the shift appear to be a gentle mountain, peak separation may be performed using known means to determine the relationship between Is and Io.
  • the peak of an organic solvent that is most easily coordinated with a cation (hereinafter sometimes referred to as “preferred coordination solvent”) is another. Shift in preference to.
  • the mass% of the preferential coordination solvent with respect to the entire organic solvent having a hetero element is preferably 40% or more, more preferably 50% or more, and further preferably 60% or more. 80% or more is particularly preferable.
  • the volume% of the preferential coordination solvent with respect to the entire organic solvent having a hetero element is preferably 40% or more, more preferably 50% or more, and 60% or more. Is more preferable, and 80% or more is particularly preferable.
  • the relationship between the two peak intensities in the vibrational spectrum of the electrolytic solution of the present invention preferably satisfies the condition of Is> 2 ⁇ Io, more preferably satisfies the condition of Is> 3 ⁇ Io, and Is> 5 ⁇ It is more preferable that the condition of Io is satisfied, and it is particularly preferable that the condition of Is> 7 ⁇ Io is satisfied.
  • Most preferred is an electrolytic solution in which the intensity Io of the peak inherent in the organic solvent is not observed and the intensity Is of the shift peak is observed in the vibrational spectrum of the electrolytic solution of the present invention. In the electrolytic solution, it means that all the molecules of the organic solvent contained in the electrolytic solution are completely solvated with the metal salt.
  • the metal salt and the organic solvent (or preferential coordination solvent) having a hetero element have an interaction.
  • a metal salt and a hetero element of an organic solvent (or preferential coordination solvent) having a hetero element form a coordination bond
  • the organic salt (or preferential coordinating solvent) having a metal salt and a hetero element ) Is estimated to form a stable cluster. From the results of evaluation examples described later, this cluster is presumed to be formed by coordination of two molecules of an organic solvent (or preferential coordination solvent) having a hetero element to one molecule of a metal salt.
  • the molar range of the organic solvent having a hetero element (or preferential coordination solvent) with respect to 1 mol of the metal salt in the electrolytic solution of the present invention is preferably 1.4 mol or more and less than 3.5 mol. More preferably, it is 0.5 mol or more and 3.1 mol or less, and 1.6 mol or more and 3 mol or less are still more preferable.
  • the electrolytic solution of the present invention it is presumed that clusters are generally formed by coordination of two molecules of an organic solvent (or preferential coordination solvent) having a hetero element to one molecule of a metal salt.
  • concentration (mol / L) of the electrolytic solution of the invention depends on the molecular weight of each of the metal salt and the organic solvent and the density when the solution is used. Therefore, it is not appropriate to prescribe the concentration of the electrolytic solution of the present invention.
  • the concentration c (mol / L) of the electrolytic solution of the present invention is individually exemplified in Table 1.
  • the organic solvent that forms the cluster and the organic solvent that is not involved in the formation of the cluster have different environments. Therefore, in vibrational spectroscopy measurement, the peak derived from the organic solvent forming the cluster is higher than the observed wave number of the peak derived from the organic solvent not involved in the cluster formation (original peak of the organic solvent). Or it is observed shifted to the low wavenumber side. That is, the shift peak corresponds to the peak of the organic solvent forming the cluster.
  • vibrational spectrum examples include an IR spectrum and a Raman spectrum.
  • measurement method for IR measurement examples include transmission measurement methods such as Nujol method and liquid film method, and reflection measurement methods such as ATR method.
  • transmission measurement methods such as Nujol method and liquid film method
  • reflection measurement methods such as ATR method.
  • IR measurement may be performed under low humidity or no humidity conditions such as a dry room or a glove box, or Raman measurement may be performed with the electrolyte solution in a sealed container.
  • LiTFSA is dissolved in an acetonitrile solvent at a concentration of 1 mol / L to obtain an electrolytic solution according to conventional technical common sense. Since 1 L of acetonitrile corresponds to about 19 mol, 1 L of conventional electrolyte includes 1 mol of LiTFSA and 19 mol of acetonitrile. Then, in the conventional electrolyte, there are many acetonitriles that are not solvated with LiTFSA (not coordinated with Li) simultaneously with acetonitrile that is solvated with LiTFSA (coordinated with Li). .
  • the acetonitrile molecule is different between the LiTFSA solvated acetonitrile molecule and the LiTFSA non-solvated acetonitrile molecule, in the IR spectrum, the acetonitrile peaks of both are distinguished and observed. Is done. More specifically, the peak of acetonitrile that is not solvated with LiTFSA is observed at the same position (wave number) as in the case of IR measurement of only acetonitrile, but the peak of acetonitrile that is solvated with LiTFSA. Is observed with the peak position (wave number) shifted to the high wave number side.
  • the electrolytic solution of the present invention has a higher LiTFSA concentration than the conventional electrolytic solution, and the number of acetonitrile molecules solvated with LiTFSA (forming clusters) in the electrolytic solution is different from that of LiTFSA. More than the number of unsolvated acetonitrile molecules. Then, the relation between the intensity Io of the original peak of the acetonitrile and the intensity Is of the peak obtained by shifting the original peak of acetonitrile in the vibrational spectrum of the electrolytic solution of the present invention is Is> Io.
  • Table 2 exemplifies wave numbers of organic solvents that are considered useful for the calculation of Io and Is in the vibrational spectrum of the electrolytic solution of the present invention, and their attribution. It should be added that the wave number of the observed peak may be different from the following wave numbers depending on the measurement apparatus, measurement environment, and measurement conditions of the vibrational spectrum.
  • the electrolytic solution of the present invention is different from the conventional electrolytic solution in that the presence environment of the metal salt and the organic solvent is different and the concentration of the metal salt is high, so that the metal ion transport rate in the electrolytic solution is improved (especially metal When Li is lithium, the lithium transport number is improved), the reaction rate between the electrode and the electrolyte solution is improved, the uneven distribution of the salt concentration of the electrolyte solution that occurs during high-rate charge / discharge of the battery, and the electric double layer capacity can be expected to increase . Furthermore, in the electrolytic solution of the present invention, since most of the organic solvent having a hetero element forms a cluster with a metal salt, the vapor pressure of the organic solvent contained in the electrolytic solution is lowered. As a result, volatilization of the organic solvent from the electrolytic solution of the present invention can be reduced.
  • the electrolyte of the present invention has a higher viscosity than the conventional battery electrolyte. Therefore, if it is a battery using the electrolyte solution of this invention, even if a battery is damaged, electrolyte solution leakage is suppressed. Moreover, the capacity
  • the capacity of the secondary battery using the electrolytic solution of the present invention is suitably maintained during high-speed charge / discharge. It is considered that the uneven distribution of Li concentration in the electrolytic solution could be suppressed due to the physical properties of the electrolytic solution of the present invention with high viscosity.
  • the high viscosity of the electrolyte solution of the present invention due to the high viscosity of the electrolyte solution of the present invention, the liquid retention of the electrolyte solution at the electrode interface is improved, and the state where the electrolyte solution is insufficient at the electrode interface (so-called liquid withdrawn state) can also be suppressed. This is considered to be one of the reasons that the capacity decrease during the charge / discharge cycle is suppressed.
  • a range of 10 ⁇ ⁇ 500 is preferable, a range of 12 ⁇ ⁇ 400 is more preferable, a range of 15 ⁇ ⁇ 300 is further preferable, and 18 A range of ⁇ ⁇ 150 is particularly preferable, and a range of 20 ⁇ ⁇ 140 is most preferable.
  • the ion conductivity ⁇ (mS / cm) of the electrolytic solution of the present invention is preferably 1 ⁇ ⁇ .
  • a suitable range including the upper limit when a suitable range including the upper limit is shown, a range of 2 ⁇ ⁇ 200 is preferable, and a range of 3 ⁇ ⁇ 100 is more preferable.
  • the range of 4 ⁇ ⁇ 50 is more preferable, and the range of 5 ⁇ ⁇ 35 is particularly preferable.
  • the electrolytic solution of the present invention contains a metal salt cation in a high concentration.
  • the distance between adjacent cations is extremely short.
  • a cation such as lithium ion moves between the positive electrode and the negative electrode during charge / discharge of the secondary battery
  • the cation closest to the destination electrode is first supplied to the electrode.
  • the other cation adjacent to the said cation moves to the place with the said supplied cation.
  • the density d (g / cm 3 ) in the electrolytic solution of the present invention is preferably d ⁇ 1.2 or d ⁇ 2.2, more preferably 1.2 ⁇ d ⁇ 2.2.
  • a range of 24 ⁇ d ⁇ 2.0 is more preferable, a range of 1.26 ⁇ d ⁇ 1.8 is more preferable, and a range of 1.27 ⁇ d ⁇ 1.6 is particularly preferable.
  • the density d (g / cm 3 ) in the electrolytic solution of the present invention means the density at 20 ° C.
  • D / c obtained by dividing the density d (g / cm 3 ) of the electrolytic solution in the electrolytic solution of the present invention by the concentration c (mol / L) of the electrolytic solution is in the range of 0.15 ⁇ d / c ⁇ 0.71.
  • 0.15 ⁇ d / c ⁇ 0.56 more preferably in the range of 0.25 ⁇ d / c ⁇ 0.56, and 0.26 ⁇ d / c ⁇ 0.50.
  • Within the range is more preferable, and within the range of 0.27 ⁇ d / c ⁇ 0.47 is particularly preferable.
  • D / c in the electrolytic solution of the present invention can be defined even when a metal salt and an organic solvent are specified.
  • d / c is preferably within the range of 0.42 ⁇ d / c ⁇ 0.56, and 0.44 ⁇ d / c ⁇ 0.52 The range of is more preferable.
  • d / c is preferably in the range of 0.35 ⁇ d / c ⁇ 0.41, and 0.36 ⁇ d / c ⁇ 0.39. The inside is more preferable.
  • d / c is preferably in the range of 0.32 ⁇ d / c ⁇ 0.46, and in the range of 0.34 ⁇ d / c ⁇ 0.42. The inside is more preferable.
  • d / c is preferably in the range of 0.25 ⁇ d / c ⁇ 0.31, and in the range of 0.26 ⁇ d / c ⁇ 0.29. The inside is more preferable.
  • d / c is preferably in the range of 0.32 ⁇ d / c ⁇ 0.48, and in the range of 0.32 ⁇ d / c ⁇ 0.46.
  • the inside is preferable, and the inside of the range of 0.34 ⁇ d / c ⁇ 0.42 is more preferable.
  • d / c is preferably in the range of 0.34 ⁇ d / c ⁇ 0.50, and in the range of 0.37 ⁇ d / c ⁇ 0.45. The inside is more preferable.
  • d / c is preferably in the range of 0.36 ⁇ d / c ⁇ 0.54, and in the range of 0.39 ⁇ d / c ⁇ 0.48.
  • the inside is more preferable.
  • the method for producing the electrolytic solution of the present invention will be described. Since the electrolytic solution of the present invention has a higher metal salt content than the conventional electrolytic solution, the production method in which an organic solvent is added to a solid (powder) metal salt results in the formation of aggregates. It is difficult to produce an electrolytic solution. Therefore, in the manufacturing method of the electrolyte solution of this invention, it is preferable to manufacture, adding a metal salt gradually with respect to an organic solvent, and maintaining the solution state of electrolyte solution.
  • the electrolytic solution of the present invention includes a liquid in which the metal salt is dissolved in the organic solvent beyond the conventionally considered saturation solubility.
  • a method for producing an electrolytic solution of the present invention includes a first dissolution step of preparing a first electrolytic solution by mixing an organic solvent having a hetero element and a metal salt, dissolving the metal salt, stirring and / or Alternatively, a metal salt is added to the first electrolytic solution under heating conditions to dissolve the metal salt to prepare a supersaturated second electrolytic solution, and a second electrolysis under stirring and / or heating conditions. A metal salt is added to the solution to dissolve the metal salt, and a third dissolution step of preparing a third electrolytic solution is included.
  • the “supersaturated state” means a state in which metal salt crystals are precipitated from the electrolyte when the stirring and / or heating conditions are canceled or when crystal nucleation energy such as vibration is applied. Means.
  • the second electrolytic solution is “supersaturated”, and the first electrolytic solution and the third electrolytic solution are not “supersaturated”.
  • the above-described method for producing the electrolytic solution of the present invention is a thermodynamically stable liquid state, and passes through the first electrolytic solution containing the conventional metal salt concentration, and then the thermodynamically unstable liquid state.
  • the second electrolytic solution passes through the two electrolytic solutions and becomes a thermodynamically stable new electrolytic third solution, that is, the electrolytic solution of the present invention.
  • the third electrolyte solution is composed of, for example, two molecules of an organic solvent for one lithium salt molecule, and a strong distribution between these molecules. It is presumed that the cluster stabilized by the coordinate bond inhibits the crystallization of the lithium salt.
  • the first dissolution step is a step of preparing a first electrolytic solution by mixing an organic solvent having a hetero atom and a metal salt to dissolve the metal salt.
  • a metal salt may be added to the organic solvent having a heteroatom, or an organic solvent having a heteroatom may be added to the metal salt.
  • the first dissolution step is preferably performed under stirring and / or heating conditions. What is necessary is just to set suitably about stirring speed. About heating conditions, it is preferable to control suitably with thermostats, such as a water bath or an oil bath. Since heat of dissolution is generated when the metal salt is dissolved, it is preferable to strictly control the temperature condition when using a metal salt that is unstable to heat. In addition, the organic solvent may be cooled in advance, or the first dissolution step may be performed under cooling conditions.
  • the first dissolution step and the second dissolution step may be performed continuously, or the first electrolytic solution obtained in the first dissolution step is temporarily stored (standing), and after a certain time has passed, You may implement a melt
  • the second dissolution step is a step of preparing a supersaturated second electrolyte solution by adding a metal salt to the first electrolyte solution under stirring and / or heating conditions to dissolve the metal salt.
  • the stirring condition may be achieved, or the second dissolution step is performed using a stirrer and a device (stirrer) that operates the stirrer.
  • the stirring condition may be used.
  • Heating conditions it is preferable to control suitably with thermostats, such as a water bath or an oil bath.
  • thermostats such as a water bath or an oil bath.
  • the warming said by the manufacturing method of electrolyte solution refers to warming a target object to the temperature more than normal temperature (25 degreeC).
  • the heating temperature is more preferably 30 ° C. or higher, and further preferably 35 ° C. or higher. Further, the heating temperature is preferably lower than the boiling point of the organic solvent.
  • the added metal salt is not sufficiently dissolved, increase the stirring speed and / or further heating.
  • a small amount of an organic solvent having a hetero atom may be added to the electrolytic solution in the second dissolution step.
  • the second dissolution step and the third dissolution step are preferably carried out continuously.
  • the third dissolution step is a step of preparing a third electrolyte solution by adding a metal salt to the second electrolyte solution under stirring and / or heating conditions to dissolve the metal salt.
  • it is necessary to add a metal salt to the supersaturated second electrolytic solution and dissolve it. Therefore, it is essential to perform the stirring and / or heating conditions as in the second dissolution step. Specific stirring and / or heating conditions are the same as those in the second dissolution step.
  • the third electrolytic solution (the electrolytic solution of the present invention) can be manufactured. finish. Even when the stirring and / or heating conditions are canceled, the metal salt crystals are not precipitated from the electrolytic solution of the present invention.
  • the electrolytic solution of the present invention is composed of, for example, two molecules of an organic solvent for one molecule of a lithium salt, and is presumed to form a cluster stabilized by a strong coordinate bond between these molecules. Is done.
  • the first to third dissolving steps can be performed even if the supersaturated state is not passed at the treatment temperature in each dissolving step.
  • the electrolytic solution of the present invention can be appropriately produced using the specific dissolution means described in 1.
  • a vibrational spectroscopic measurement step of performing vibrational spectroscopic measurement of the electrolytic solution being manufactured for example, a method of sampling a part of each electrolytic solution in the middle of production and using it for vibration spectroscopic measurement, or a method of performing spectroscopic spectroscopic measurement of each electrolytic solution in situ (situ) But it ’s okay.
  • a method for in-vitro vibrational spectroscopic measurement of an electrolytic solution a method of introducing an electrolytic solution in the middle of production into a transparent flow cell and performing vibrational spectroscopic measurement, or a method of performing Raman measurement from outside the container using a transparent production vessel can be mentioned. Since the relationship between Is and Io in the electrolytic solution can be confirmed during the production by including the vibrational spectroscopic measurement step in the method for producing the electrolytic solution of the present invention, whether the electrolytic solution during the production reaches the electrolytic solution of the present invention. It is possible to determine whether or not the amount of metal salt added to reach the electrolytic solution of the present invention when the electrolytic solution being manufactured does not reach the electrolytic solution of the present invention. can do.
  • the solvent in addition to the organic solvent having a hetero element, the solvent has a low polarity (low dielectric constant) or a low donor number and does not exhibit a special interaction with a metal salt, that is, the present invention.
  • a solvent that does not affect the formation and maintenance of the clusters in the electrolyte can be added.
  • the solvent that does not exhibit a special interaction with the metal salt include benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, 1-methylnaphthalene, hexane, heptane, and cyclohexane. it can.
  • a flame retardant solvent can be added to the electrolytic solution of the present invention.
  • a flame retardant solvent include halogen solvents such as carbon tetrachloride, tetrachloroethane, and hydrofluoroether, and phosphoric acid derivatives such as trimethyl phosphate and triethyl phosphate.
  • the electrolytic solution of the present invention when the electrolytic solution of the present invention is mixed with a polymer or an inorganic filler to form a mixture, the mixture contains the electrolytic solution and becomes a pseudo solid electrolyte.
  • the pseudo-solid electrolyte As the battery electrolyte, leakage of the electrolyte in the battery can be suppressed.
  • a polymer used for a battery such as a lithium ion secondary battery or a general chemically crosslinked polymer can be employed.
  • a polymer that can absorb an electrolyte such as polyvinylidene fluoride and polyhexafluoropropylene and gel can be used, and a polymer such as polyethylene oxide in which an ion conductive group is introduced.
  • polymers include polymethyl acrylate, polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyethylene glycol dimethacrylate, polyethylene glycol acrylate, polyglycidol, polytetrafluoroethylene, polyhexafluoropropylene, Polycarboxylic acid such as polysiloxane, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyitaconic acid, polyfumaric acid, polycrotonic acid, polyangelic acid, carboxymethylcellulose, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene , Polycarbonate, unsaturated polyester copolymerized with maleic anhydride and glycols, Polyethylene oxide derivative having a group, a copolymer of vinylidene fluoride and hexafluoropropylene can be exempl
  • Polysaccharides are also suitable as the polymer.
  • Specific examples of the polysaccharide include glycogen, cellulose, chitin, agarose, carrageenan, heparin, hyaluronic acid, pectin, amylopectin, xyloglucan, and amylose.
  • adopt the material containing these polysaccharides as said polymer The agar containing polysaccharides, such as agarose, can be illustrated as the said material.
  • the inorganic filler is preferably an inorganic ceramic such as oxide or nitride.
  • Inorganic ceramics have hydrophilic and hydrophobic functional groups on the surface. Therefore, when the functional group attracts the electrolytic solution, a conductive path can be formed in the inorganic ceramic. Furthermore, the inorganic ceramics dispersed in the electrolytic solution can form a network between the inorganic ceramics by the functional groups and serve to contain the electrolytic solution. With such a function of the inorganic ceramics, it is possible to more suitably suppress the leakage of the electrolytic solution in the battery. In order to suitably exhibit the above functions of the inorganic ceramics, the inorganic ceramics preferably have a particle shape, and particularly preferably have a particle size of nano level.
  • the inorganic ceramics include general alumina, silica, titania, zirconia, and lithium phosphate. Further, the inorganic ceramic itself may be lithium conductive, and specifically, Li 3 N, LiI, LiI—Li 3 N—LiOH, LiI—Li 2 S—P 2 O 5 , LiI—Li 2 S —P 2 S 5 , LiI—Li 2 S—B 2 S 3 , Li 2 O—B 2 S 3 , Li 2 O—V 2 O 3 —SiO 2 , Li 2 O—B 2 O 3 —P 2 O 5 , Li 2 O—B 2 O 3 —ZnO, Li 2 O—Al 2 O 3 —TiO 2 —SiO 2 —P 2 O 5 , LiTi 2 (PO 4 ) 3 , Li— ⁇ Al 2 O 3 , LiTaO 3 Can be illustrated.
  • Li 3 N LiI, LiI—Li 3 N—LiOH, LiI—Li 2 S—
  • Glass ceramics may be employed as the inorganic filler. Since glass ceramics can contain an ionic liquid, the same effect can be expected for the electrolytic solution of the present invention. Glass ceramics include a compound represented by xLi 2 S- (1-x) P 2 S 5 , a compound obtained by substituting a part of S of the compound with another element, and a P of the compound. An example in which the part is replaced with germanium can be exemplified.
  • the electrolytic solution of the present invention described above exhibits excellent ionic conductivity, it is suitably used as an electrolytic solution for a power storage device.
  • it is preferably used as an electrolyte solution for a secondary battery, and particularly preferably used as an electrolyte solution for a lithium ion secondary battery.
  • the lithium ion secondary battery of the present invention employs a negative electrode having a negative electrode active material capable of occluding and releasing lithium ions, a positive electrode having a positive electrode active material capable of occluding and releasing lithium ions, and a lithium salt as a metal salt.
  • the electrolytic solution of the present invention and a separator are provided.
  • the negative electrode has a current collector and a negative electrode active material layer bound to the surface of the current collector.
  • the current collector refers to a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharge or charging of a lithium ion secondary battery.
  • As the current collector at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, and stainless steel Metal materials can be exemplified.
  • the current collector may be covered with a known protective layer.
  • the current collector can take the form of a foil, a sheet, a film, a linear shape, a rod shape, a mesh, or the like. Therefore, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.
  • a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.
  • the thickness is preferably in the range of 1 ⁇ m to 100 ⁇ m.
  • the negative electrode active material layer contains a negative electrode active material and, if necessary, a binder and / or a conductive aid.
  • the negative electrode active material a material capable of inserting and extracting lithium ions can be used. Accordingly, there is no particular limitation as long as it is a simple substance, alloy, or compound that can occlude and release lithium ions.
  • a negative electrode active material Li, group 14 elements such as carbon, silicon, germanium and tin, group 13 elements such as aluminum and indium, group 12 elements such as zinc and cadmium, group 15 elements such as antimony and bismuth, magnesium , Alkaline earth metals such as calcium, and group 11 elements such as silver and gold may be employed alone.
  • silicon or the like is used for the negative electrode active material, a silicon atom reacts with a plurality of lithiums, so that it becomes a high-capacity active material.
  • an alloy or compound in which another element such as a transition metal is combined with a simple substance such as silicon as the negative electrode active material.
  • the alloy or compound include tin-based materials such as Ag—Sn alloy, Cu—Sn alloy and Co—Sn alloy, carbon-based materials such as various graphites, SiO x (disproportionated into silicon simple substance and silicon dioxide). Examples thereof include silicon-based materials such as 0.3 ⁇ x ⁇ 1.6), silicon alone, or composites obtained by combining silicon-based materials and carbon-based materials.
  • the binder plays a role of connecting the active material and the conductive auxiliary agent to the surface of the current collector.
  • binder examples include fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene, and fluororubber, thermoplastic resins such as polypropylene and polyethylene, imide resins such as polyimide and polyamideimide, and alkoxysilyl group-containing resins. be able to.
  • fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene, and fluororubber
  • thermoplastic resins such as polypropylene and polyethylene
  • imide resins such as polyimide and polyamideimide
  • alkoxysilyl group-containing resins alkoxysilyl group-containing resins.
  • a polymer having a hydrophilic group may be employed as the binder.
  • the hydrophilic group of the polymer having a hydrophilic group include a phosphate group such as a carboxyl group, a sulfo group, a silanol group, an amino group, a hydroxyl group, and a phosphate group.
  • a polymer containing a carboxyl group in the molecule such as polyacrylic acid (PAA), carboxymethyl cellulose (CMC), or polymethacrylic acid, or a polymer containing a sulfo group such as poly (p-styrenesulfonic acid) is preferable.
  • Polymers containing a large amount of carboxyl groups and / or sulfo groups such as polyacrylic acid or a copolymer of acrylic acid and vinyl sulfonic acid, are water-soluble. Therefore, the polymer having a hydrophilic group is preferably a water-soluble polymer, and a polymer containing a plurality of carboxyl groups and / or sulfo groups in one molecule is preferable.
  • the polymer containing a carboxyl group in the molecule can be produced by, for example, a method of polymerizing an acid monomer or adding a carboxyl group to the polymer.
  • Acid monomers include acrylic acid, methacrylic acid, vinyl benzoic acid, crotonic acid, pentenoic acid, angelic acid, tiglic acid, etc., acid monomers having one carboxyl group in the molecule, itaconic acid, mesaconic acid, citraconic acid, fumaric acid
  • Examples include maleic acid, 2-pentenedioic acid, methylene succinic acid, allyl malonic acid, isopropylidene succinic acid, 2,4-hexadiene diacid, acetylenedicarboxylic acid, and other acid monomers having two or more carboxyl groups in the molecule. Is done. A copolymer obtained by polymerizing two or more kinds of monomers selected from these may be used.
  • a polymer composed of a copolymer of acrylic acid and itaconic acid as described in JP2013-065493A, and containing an acid anhydride group formed by condensation of carboxyl groups in the molecule It is also preferable to use as a binder.
  • the structure derived from a highly acidic monomer having two or more carboxyl groups in one molecule is considered to facilitate trapping of lithium ions and the like before the electrolytic solution decomposition reaction occurs during charging.
  • the acidity is not excessively increased because there are more carboxyl groups and the acidity is higher than polyacrylic acid and polymethacrylic acid, and a predetermined amount of the carboxyl groups are changed to acid anhydride groups. Therefore, a secondary battery having an electrode formed using this binder has improved initial efficiency and improved input / output characteristics.
  • Conductive aid is added to increase the conductivity of the electrode. Therefore, the conductive auxiliary agent may be added arbitrarily when the electrode conductivity is insufficient, and may not be added when the electrode conductivity is sufficiently excellent.
  • the conductive auxiliary agent may be any chemically inert electronic high conductor, such as carbon black, graphite, acetylene black, ketjen black (registered trademark), or vapor grown carbon fiber (Vapor Grown Carbon). Fiber: VGCF) and various metal particles are exemplified. These conductive assistants can be added to the active material layer alone or in combination of two or more.
  • the positive electrode used for the lithium ion secondary battery has a positive electrode active material capable of inserting and extracting lithium ions.
  • the positive electrode has a current collector and a positive electrode active material layer bound to the surface of the current collector.
  • the positive electrode active material layer includes a positive electrode active material and, if necessary, a binder and / or a conductive aid.
  • the positive electrode current collector is not particularly limited as long as it is a metal that can withstand a voltage suitable for the active material to be used. For example, the one described for the negative electrode current collector can be adopted. When the potential of the positive electrode is 4 V or more on the basis of lithium, it is preferable to employ aluminum as the current collector for the positive electrode.
  • the positive electrode current collector is preferably made of aluminum or an aluminum alloy.
  • aluminum refers to pure aluminum, and aluminum having a purity of 99.0% or more is referred to as pure aluminum.
  • An alloy obtained by adding various elements to pure aluminum is referred to as an aluminum alloy. Examples of the aluminum alloy include Al—Cu, Al—Mn, Al—Fe, Al—Si, Al—Mg, AL—Mg—Si, and Al—Zn—Mg.
  • A1000 series alloys pure aluminum series
  • A3000 series alloys Al-Mn series
  • A8000-based alloy Al-Fe-based
  • the current collector may be covered with a known protective layer. What collected the surface of the electrical power collector by the well-known method may be used as an electrical power collector.
  • the binder and conductive additive for the positive electrode are the same as those described for the negative electrode.
  • a positive electrode active material a solid solution composed of a spinel such as LiMn 2 O 4 and a mixture of a spinel and a layered compound, LiMPO 4 , LiMVO 4 or Li 2 MSiO 4 (wherein M is Co, Ni, Mn, And a polyanionic compound represented by (selected from at least one of Fe).
  • tavorite compound the M a transition metal
  • LiMPO 4 F such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (M is a transition metal
  • Limbo 3 such LiFeBO 3 (M is a transition metal
  • M is a transition metal
  • any metal oxide used as the positive electrode active material may have the above composition formula as a basic composition, and a metal element contained in the basic composition may be substituted with another metal element.
  • a charge carrier for example, lithium ion which contributes to charging / discharging.
  • sulfur alone (S) a compound in which sulfur and carbon are compounded
  • a metal sulfide such as TiS 2
  • an oxide such as V 2 O 5 and MnO 2
  • conjugated materials such as conjugated diacetate-based organic substances and other known materials can also be used.
  • a compound having a stable radical such as nitroxide, nitronyl nitroxide, galvinoxyl, phenoxyl, etc. may be adopted as the positive electrode active material.
  • a positive electrode active material that does not contain a charge carrier such as lithium it is necessary to add a charge carrier to the positive electrode and / or the negative electrode in advance by a known method.
  • the charge carrier may be added in an ionic state or in a non-ionic state such as a metal.
  • the charge carrier when the charge carrier is lithium, it may be integrated by attaching a lithium foil to the positive electrode and / or the negative electrode.
  • an active material layer on the surface of the current collector As a method for forming the active material layer on the surface of the current collector, a conventionally known method such as a roll coating method, a die coating method, a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method is used.
  • An active material may be applied to the surface of the electric body. Specifically, an active material layer-forming composition containing an active material and, if necessary, a binder and a conductive aid is prepared, and an appropriate solvent is added to the composition to make a paste, and then the collection is performed. After applying to the surface of the electric body, it is dried. Examples of the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water. In order to increase the electrode density, the dried product may be compressed.
  • a separator is sandwiched between the positive and negative electrodes to form an electrode body.
  • the electrode body may be either a stacked type in which the positive electrode, the separator and the negative electrode are stacked, or a wound type in which the positive electrode, the separator and the negative electrode are sandwiched.
  • the electrolyte solution of the present invention is added to the electrode body and lithium ions are added.
  • a secondary battery may be used.
  • the lithium ion secondary battery of this invention should just be charged / discharged in the voltage range suitable for the kind of active material contained in an electrode.
  • the shape of the lithium ion secondary battery of the present invention is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a laminate shape can be adopted.
  • An electric double layer capacitor has a structure in which a positive electrode and a negative electrode are arranged facing each other with a separator interposed between them, placed in a container, and filled with an electrolytic solution.
  • An electric double layer capacitor can store electric charge between electrodes by applying a voltage between the electrodes.
  • the electric double layer is a phenomenon in which positive charges and negative charges face each other at very short intervals at the interface between the electrode and the electrolyte.
  • the positive and negative electrodes of the electric double layer capacitor are obtained by arranging a conductor with a large surface area on a current collector.
  • Examples of the conductor having a large surface area include activated carbon and polyacene compounds.
  • Each electrode may contain a binder in order to bind such a conductor having a large surface area, and may further contain a conductive additive.
  • Other components can be the same as those described for the lithium ion secondary battery.
  • the lithium ion capacitor is a combination of a negative electrode of a lithium ion secondary battery and a positive electrode of an electric double layer capacitor.
  • the positive electrode of the lithium ion capacitor is charged and discharged by forming an electric double layer, and the negative electrode is charged and discharged by a lithium chemical reaction.
  • the description of the positive electrode is the same as the description of the electric double layer capacitor, and the description of the negative electrode is the same as the description of the lithium ion secondary battery.
  • the power storage device of the present invention may be mounted on a vehicle.
  • the vehicle may be a vehicle that uses electric energy from the power storage device for all or part of its power source, and may be, for example, an electric vehicle, a hybrid vehicle, or the like.
  • a lithium ion secondary battery When a lithium ion secondary battery is mounted on a vehicle, a plurality of lithium ion secondary batteries may be connected in series to form an assembled battery.
  • Examples of devices equipped with the power storage device include various home appliances driven by batteries such as personal computers and portable communication devices, office devices, and industrial devices in addition to vehicles.
  • the power storage device of the present invention includes wind power generation, solar power generation, hydroelectric power generation, and other power system power storage devices and power smoothing devices, power for power sources such as ships, and / or power supply sources for auxiliary equipment, aircraft, spacecrafts, and the like.
  • Power source for power and / or auxiliary equipment, auxiliary power source for vehicles not using electricity as a power source power source for mobile home robots, power source for system backup, power source for uninterruptible power supply, for electric vehicles You may use for the electrical storage apparatus which stores temporarily the electric power required for charge in a charging station.
  • Electrolytic solution E1 The electrolytic solution used in the present invention was produced as follows.
  • the obtained electrolytic solution had a volume of 20 mL, and (CF 3 SO 2 ) 2 NLi contained in this electrolytic solution was 18.38 g.
  • the concentration of (CF 3 SO 2 ) 2 NLi in the electrolytic solution E1 was 3.2 mol / L.
  • 1.6 molecules of 1,2-dimethoxyethane are contained with respect to (CF 3 SO 2 ) 2 NLi1 molecules.
  • the above production was carried out in a glove box under an inert gas atmosphere.
  • Electrolytic solution E2 Using 16.08 g of (CF 3 SO 2 ) 2 NLi, an electrolytic solution E2 having a concentration of (CF 3 SO 2 ) 2 NLi of 2.8 mol / L was produced in the same manner as the electrolytic solution E1. In the electrolytic solution E2, 2.1 molecules of 1,2-dimethoxyethane are contained per molecule of (CF 3 SO 2 ) 2 NLi.
  • Electrolytic solution E3 About 5 mL of acetonitrile, which is an organic solvent, was placed in a flask equipped with a stir bar. Under stirring conditions, (CF 3 SO 2 ) 2 NLi, which is a lithium salt, was gradually added to and dissolved in acetonitrile in the flask. When 19.52 g of (CF 3 SO 2 ) 2 NLi was added in total, the mixture was stirred overnight. The resulting electrolyte was transferred to a 20 mL volumetric flask and acetonitrile was added until the volume was 20 mL. This was designated as an electrolytic solution E3. The production was performed in a glove box under an inert gas atmosphere. In the electrolytic solution E3, 3 molecules of acetonitrile are contained with respect to 1 molecule of (CF 3 SO 2 ) 2 NLi.
  • Electrolytic solution E4 Using 24.11 g of (CF 3 SO 2 ) 2 NLi, an electrolytic solution E4 having a concentration of (CF 3 SO 2 ) 2 NLi of 4.2 mol / L was produced in the same manner as the electrolytic solution E3. In the electrolytic solution E4, 1.9 molecules of acetonitrile are contained with respect to (CF 3 SO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E5 Using (FSO 2) 2 NLi of 13.47g lithium salt, except for using 1,2-dimethoxyethane as the organic solvent, in the same manner as the electrolyte solution E3, (FSO 2) concentration of 2 NLi 3 An electrolytic solution E5 having a concentration of 6 mol / L was produced. In the electrolytic solution E5, 1.9 molecules of 1,2-dimethoxyethane are contained per 1 molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E6 (Electrolytic solution E6) Using 14.97 g of (FSO 2 ) 2 NLi, an electrolytic solution E6 having a concentration of (FSO 2 ) 2 NLi of 4.0 mol / L was produced in the same manner as the electrolytic solution E5. In the electrolytic solution E6, 1.5 molecules of 1,2-dimethoxyethane are contained per 1 molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E7 having a concentration of 4.2 mol / L of (FSO 2 ) 2 NLi was produced in the same manner as the electrolytic solution E3 except that 15.72 g of (FSO 2 ) 2 NLi was used as the lithium salt. .
  • electrolytic solution E7 3 molecules of acetonitrile are contained with respect to 1 molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E8 having a concentration of (FSO 2 ) 2 NLi of 4.5 mol / L was produced in the same manner as the electrolytic solution E7 using 16.83 g of (FSO 2 ) 2 NLi.
  • electrolytic solution E8 2.4 molecules of acetonitrile are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E9 Using 20.21 g of (FSO 2 ) 2 NLi, an electrolytic solution E9 having a concentration of (FSO 2 ) 2 NLi of 5.4 mol / L was produced in the same manner as the electrolytic solution E7. In the electrolytic solution E9, 2 molecules of acetonitrile are contained with respect to 1 molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E10 About 5 mL of dimethyl carbonate, which is an organic solvent, was placed in a flask equipped with a stir bar. Under stirring conditions, (FSO 2 ) 2 NLi, which is a lithium salt, was gradually added to dimethyl carbonate in the flask and dissolved. When (FSO 2 ) 2 NLi was added in a total amount of 14.64 g, the mixture was stirred overnight. The resulting electrolyte was transferred to a 20 mL volumetric flask and dimethyl carbonate was added until the volume was 20 mL. This was designated as an electrolytic solution E10. The production was performed in a glove box under an inert gas atmosphere.
  • the concentration of (FSO 2 ) 2 NLi in the electrolytic solution E10 was 3.9 mol / L.
  • two molecules of dimethyl carbonate are contained with respect to one molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E11 Dimethyl carbonate was added to the electrolytic solution E10 for dilution to obtain an electrolytic solution E11 having a (FSO 2 ) 2 NLi concentration of 3.4 mol / L. In the electrolytic solution E11, 2.5 molecules of dimethyl carbonate are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E12 Dimethyl carbonate was added to the electrolytic solution E10 for dilution to obtain an electrolytic solution E12 having a (FSO 2 ) 2 NLi concentration of 2.9 mol / L. In the electrolytic solution E12, 3 molecules of dimethyl carbonate are contained with respect to 1 molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E13 Dimethyl carbonate was added to the electrolytic solution E10 for dilution to obtain an electrolytic solution E13 having a concentration of (FSO 2 ) 2 NLi of 2.6 mol / L. In the electrolytic solution E13, 3.5 molecules of dimethyl carbonate are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E14 Dimethyl carbonate was added to the electrolytic solution E10 for dilution to obtain an electrolytic solution E14 having a (FSO 2 ) 2 NLi concentration of 2.0 mol / L. In the electrolytic solution E14, 5 molecules of dimethyl carbonate are contained with respect to 1 molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E15 About 5 mL of ethyl methyl carbonate, which is an organic solvent, was placed in a flask equipped with a stir bar. Under stirring conditions, (FSO 2 ) 2 NLi, which is a lithium salt, was gradually added to and dissolved in ethyl methyl carbonate in the flask. When 12.81 g of (FSO 2 ) 2 NLi was added in total, the mixture was stirred overnight. The obtained electrolytic solution was transferred to a 20 mL volumetric flask, and ethyl methyl carbonate was added until the volume became 20 mL. This was designated as an electrolytic solution E15. The production was performed in a glove box under an inert gas atmosphere.
  • the concentration of (FSO 2 ) 2 NLi in the electrolytic solution E15 was 3.4 mol / L.
  • two molecules of ethyl methyl carbonate are contained with respect to one molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E16 The electrolyte solution E15 was diluted by adding ethyl methyl carbonate to obtain an electrolyte solution E16 having a (FSO 2 ) 2 NLi concentration of 2.9 mol / L. In the electrolytic solution E16, 2.5 molecules of ethyl methyl carbonate are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E17 The electrolyte solution E15 was diluted by adding ethyl methyl carbonate to obtain an electrolyte solution E17 having a (FSO 2 ) 2 NLi concentration of 2.2 mol / L. In the electrolytic solution E17, 3.5 molecules of ethyl methyl carbonate are contained per 1 molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E18 About 5 mL of diethyl carbonate, which is an organic solvent, was placed in a flask equipped with a stirring bar. Under stirring conditions, (FSO 2 ) 2 NLi, which is a lithium salt, was gradually added to and dissolved in diethyl carbonate in the flask. When 11.37 g of the total amount of (FSO 2 ) 2 NLi was added, the mixture was stirred overnight. The resulting electrolyte was transferred to a 20 mL volumetric flask and diethyl carbonate was added until the volume was 20 mL. This was designated as an electrolytic solution E18. The production was performed in a glove box under an inert gas atmosphere.
  • the concentration of (FSO 2 ) 2 NLi in the electrolytic solution E18 was 3.0 mol / L.
  • two molecules of diethyl carbonate are included with respect to one molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E19 Diethyl carbonate was added to the electrolytic solution E18 for dilution to obtain an electrolytic solution E19 having a (FSO 2 ) 2 NLi concentration of 2.6 mol / L. In the electrolytic solution E19, 2.5 molecules of diethyl carbonate are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E20 Diethyl carbonate was added to the electrolytic solution E18 for dilution to obtain an electrolytic solution E20 having a (FSO 2 ) 2 NLi concentration of 2.0 mol / L. In the electrolytic solution E20, 3.5 molecules of diethyl carbonate are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • electrolyte E21 (Electrolytic solution E21) Using (FSO 2) 2 NLi in 18.71G, in the same manner as the electrolyte solution E7, was prepared electrolyte E21 is (FSO 2) concentration of 2 NLi is 5.0 mol / L. In the electrolytic solution E21, 2.1 molecules of acetonitrile are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution C1 (Electrolytic solution C1) Using (CF 3 SO 2) 2 NLi of 5.74 g, as except for using 1,2-dimethoxyethane organic solvents, in the same manner as the electrolyte solution E3, is (CF 3 SO 2) concentration of 2 NLi Electrolyte C1 which is 1.0 mol / L was manufactured. In the electrolytic solution C1, 8.3 molecules of 1,2-dimethoxyethane are contained with respect to (CF 3 SO 2 ) 2 NLi1 molecules.
  • Electrolytic solution C2 (Electrolytic solution C2) Using 5.74 g of (CF 3 SO 2 ) 2 NLi, an electrolytic solution C2 having a concentration of (CF 3 SO 2 ) 2 NLi of 1.0 mol / L was produced in the same manner as the electrolytic solution E3. In the electrolytic solution C2, 16 molecules of acetonitrile are contained with respect to (CF 3 SO 2 ) 2 NLi1 molecule.
  • Electrolytic solution C3 Using 3.74 g of (FSO 2 ) 2 NLi, an electrolytic solution C3 having a concentration of (FSO 2 ) 2 NLi of 1.0 mol / L was produced in the same manner as the electrolytic solution E5. In the electrolytic solution C3, 8.8 molecules of 1,2-dimethoxyethane are contained per molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution C4 Using 3.74 g of (FSO 2 ) 2 NLi, an electrolytic solution C4 having a concentration of (FSO 2 ) 2 NLi of 1.0 mol / L was produced in the same manner as the electrolytic solution E7. In the electrolyte solution C4, 17 molecules of acetonitrile are contained with respect to (FSO 2 ) 2 NLi1 molecule.
  • Electrolytic solution C5 (Electrolytic solution C5) Except that a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 3: 7, hereinafter referred to as “EC / DEC”) is used as the organic solvent, and 3.04 g of LiPF 6 is used as the lithium salt.
  • Electrolytic solution C6 Dimethyl carbonate was added to the electrolytic solution E10 for dilution to obtain an electrolytic solution C6 having a (FSO 2 ) 2 NLi concentration of 1.1 mol / L. In the electrolytic solution C6, 10 molecules of dimethyl carbonate are contained per 1 molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution C7 The electrolyte solution E15 was diluted by adding ethyl methyl carbonate to obtain an electrolyte solution C7 having a (FSO 2 ) 2 NLi concentration of 1.1 mol / L.
  • electrolytic solution C7 8 molecules of ethyl methyl carbonate are contained with respect to (FSO 2 ) 2 NLi1 molecule.
  • Electrolytic solution C8 Diethyl carbonate was added to the electrolytic solution E18 for dilution to obtain an electrolytic solution C8 having a (FSO 2 ) 2 NLi concentration of 1.1 mol / L. In the electrolytic solution C8, 7 molecules of diethyl carbonate are contained per 1 molecule of (FSO 2 ) 2 NLi.
  • Table 3 shows a list of the electrolytic solutions E1 to E21 and the electrolytic solutions C1 to C8.
  • Electrolytic solution E3, electrolytic solution E4, electrolytic solution E7, electrolytic solution E8, electrolytic solution E9, electrolytic solution C2, electrolytic solution C4, and acetonitrile, (CF 3 SO 2 ) 2 NLi, (FSO 2 ) 2 NLi are as follows: The IR measurement was performed under the following conditions. IR spectra in the range of 2100 cm ⁇ 1 to 2400 cm ⁇ 1 are shown in FIGS. 1 to 10, respectively. Further, IR measurement was performed on the electrolytic solutions E10 to E20, the electrolytic solutions C6 to C8, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate under the following conditions.
  • FIGS. 11 to 27 show IR spectra in the range of 1900 to 1600 cm ⁇ 1 in FIGS. 11 to 27, respectively.
  • FIG. 28 shows an IR spectrum in the range of 1900 to 1600 cm ⁇ 1 for (FSO 2 ) 2 NLi.
  • the horizontal axis in the figure is the wave number (cm ⁇ 1 ), and the vertical axis is the absorbance (reflection absorbance).
  • IR measurement conditions Device FT-IR (Bruker Optics) Measurement conditions: ATR method (using diamond) Measurement atmosphere: Inert gas atmosphere
  • FIG. IR spectrum of the electrolyte E9 represented by 5 is not a peak derived from acetonitrile observed around 2250 cm -1, inter 2250 cm from the vicinity -1 shifted acetonitrile 2280cm around -1 to the high frequency side C and N
  • the relationship between the peak intensities of Is and Io was Is> Io.
  • Ionic conductivity measurement conditions In an Ar atmosphere, an electrolytic solution was sealed in a glass cell with a platinum constant and a known cell constant, and impedance at 30 ° C. and 1 kHz was measured. The ion conductivity was calculated from the impedance measurement result.
  • Solartron 147055BEC Solartron
  • Electrolytic solution E1, electrolytic solution E2, electrolytic solutions E4 to E6, electrolytic solution E8, electrolytic solution E10, electrolytic solution E12, electrolytic solution E15, electrolytic solution E18, and electrolytic solution E21 all exhibited ionic conductivity. Therefore, it can be understood that the electrolytic solution of the present invention can function as an electrolytic solution for various batteries.
  • Electrolytic solution E1 electrolytic solution E2, electrolytic solutions E4 to E6, electrolytic solution E8, electrolytic solution E10, electrolytic solution E12, electrolytic solution E15, electrolytic solution E18, electrolytic solution E21, and electrolytic solutions C1 to C4, electrolytic solutions C6 to C8
  • the viscosity of was measured under the following conditions. The results are shown in Table 5.
  • Viscosity measurement conditions Using a falling ball viscometer (Lovis 2000 M manufactured by Anton Paar GmbH (Anton Paar)), an electrolytic solution was sealed in a test cell under an Ar atmosphere, and the viscosity was measured at 30 ° C.
  • Electrolytic solution E1, electrolytic solution E2, electrolytic solutions E4 to E6, electrolytic solution E8, electrolytic solution E10, electrolytic solution E12, electrolytic solution E15, electrolytic solution E18, and electrolytic solution E21 have a viscosity of electrolytic solutions C1 to C4 and electrolytic solution C6. It was significantly higher than the viscosity of ⁇ C8. Therefore, if the battery uses the electrolytic solution of the present invention, leakage of the electrolytic solution is suppressed even if the battery is damaged.
  • the maximum volatilization rates of the electrolytic solutions E2, E4, E8, E10, and E12 were significantly smaller than the maximum volatilization rates of the electrolytic solutions C1, C2, C4, and C6. Therefore, even if the battery using the electrolytic solution of the present invention is damaged, the volatilization rate of the electrolytic solution is small, so that rapid volatilization of the organic solvent to the outside of the battery is suppressed.
  • Electrolyte E4 did not ignite even after 15 seconds of indirect flame. On the other hand, the electrolytic solution C2 burned out in about 5 seconds.
  • the counter electrode was metal Li.
  • Reference Example 2-1 A half cell of Reference Example 2-1 was produced in the same manner as in Reference Example 1-1 except that the electrolyte C5 was used as the electrolyte.
  • the half cell is charged at a rate of 0.1 C, 0.2 C, 0.5 C, 1 C, and 2 C (1 C means a current value required to fully charge or discharge the battery in one hour at a constant current).
  • discharge was performed, and the capacity (discharge capacity) of the working electrode at each speed was measured.
  • the counter electrode is regarded as a negative electrode and the working electrode is regarded as a positive electrode.
  • the ratio (rate characteristic) of the capacity at other rates to the capacity of the working electrode at the 0.1 C rate was calculated. The results are shown in Table 7.
  • the half cell of Reference Example 1-1 was excellent in that the decrease in capacity was suppressed compared to the half cell of Reference Example 2-1 at any rate of 0.2C, 0.5C, 1C, and 2C. The rate characteristics are shown. It was confirmed that the secondary battery using the electrolytic solution of the present invention exhibits excellent rate characteristics.
  • the half cell of Reference Example 2-1 has a tendency to increase the polarization when a current is passed at a rate of 1 C with repeated charging and discharging, and the capacity obtained by reaching from 2 V to 0.01 V rapidly decreases. .
  • the half cell of Reference Example 1-1 even when charging / discharging was repeated, there was almost no increase or decrease in polarization, as can be confirmed from the fact that the three curves overlapped in FIG.
  • the reason why the polarization increased in the half cell of Reference Example 2-1 was that a sufficient amount of Li was added to the reaction interface with the electrode due to uneven Li concentration generated in the electrolyte when rapidly charging and discharging was repeated. Can no longer be supplied, that is, the Li concentration of the electrolyte is unevenly distributed.
  • the Li transport number of the electrolytic solution E2 and the electrolytic solution E8 was significantly higher than the Li transport number of the electrolytic solution C4 and the electrolytic solution C5.
  • the Li ion conductivity of the electrolytic solution can be calculated by multiplying the ionic conductivity (total ionic conductivity) contained in the electrolytic solution by the Li transport number. If it does so, it can be said that the electrolyte solution of this invention has the high transport rate of lithium ion (cation) compared with the conventional electrolyte solution which shows comparable ionic conductivity.
  • Li transport number was measured by changing the measurement temperature of the electrolytic solution E8.
  • the measurement temperatures were 30 ° C., 10 ° C., ⁇ 10 ° C., and ⁇ 30 ° C.
  • the results are shown in Table 8B.
  • Electrolytic solution E10, electrolytic solution E12, electrolytic solution E15, and electrolytic solution E18 were each put in a container, filled with an inert gas, and sealed. These were stored in a freezer at ⁇ 30 ° C. for 2 days. Each electrolyte was observed after storage. None of the electrolytes were solidified and maintained in a liquid state, and no salt deposition was observed.
  • Separators A to H were prepared. Separator A is manufactured by GE Healthcare Japan Co., Ltd., model number 1825-055 Whatman glass fiber filter paper has a thickness of 400 ⁇ m, and separator B is manufactured by Toyo Filter Paper Co., Ltd., model number: qualitative filter paper NO. 2.
  • separator C is cellulose nonwoven fabric, thickness 20 ⁇ m
  • separator D is manufactured by Merck Co., Ltd., model number: JAWP-047-00, microporous made of hydrophilic polytetrafluoroethylene (hydrophilic PTFE)
  • the membrane is 85 ⁇ m thick
  • the separator E is a polyethylene (PE) non-woven fabric, 20 ⁇ m thick
  • the separator F is a polypropylene (PP) microporous membrane, 25 ⁇ m thick
  • the separator G is manufactured by Toyo Roshi Kaisha, Ltd.
  • Electrolytic permeability test Each separator was fixed on a black plate, and 200 ⁇ l of electrolytic solution E8 was dropped. After 10 seconds, the surface of the separator was observed, and it was judged that the electrolyte had permeated when the electrolyte soaked in and the black color of the plate placed under the separator was seen through. The case where the electrolyte solution permeated was judged as ⁇ , and the case where the electrolyte solution did not permeate was judged as ⁇ .
  • Each separator was immersed in ultrapure water for 10 minutes, and then the excess liquid was wiped with a waste cloth, and the wet mass Wh of the separator was measured.
  • Water retention amount We (Wh ⁇ Wd) (1)
  • the calculation of the water retention magnification of the separator A was as follows.
  • the dry weight Wd of the cut sample was 8.41 mg.
  • the wet weight Wh after being immersed in water for 10 minutes was 62.0 mg.
  • the amount of water retained was 53.59 mg from the formula (1).
  • the electrolytic solution of the present invention does not penetrate when the water retention ratio is less than 0.1. Accordingly, the water retention ratio needs to be 0.1 or more, and the water retention ratio is preferably 0.4 or more.
  • the water retention ratio of the separators A, B, and C was 1.0 or more, and the water retention was extremely high, and the electrolyte permeability was also high. This is presumably because the separators A, B, and C are made of a highly hydrophilic glass or cellulose, and the separator is a nonwoven fabric in which all voids are considered to be connected continuously.
  • Separator D is a microporous membrane, but by using highly hydrophilic hydrophilic PTFE, the water retention ratio was as high as 0.95, and the permeability of the electrolytic solution of the present invention was also high.
  • the material of the separator E is polyethylene having a low hydrophilicity, but the form is a nonwoven fabric. It was found that a separator in the form of a nonwoven fabric has a high water retention ratio even when the hydrophilicity of the material is small, and the electrolyte solution penetrates.
  • the water retention ratio of separators F, G, and H was less than 0.1, and the electrolyte did not penetrate.
  • the reason can be considered as follows. It is considered that the separators F, G, and H did not attract water due to the low hydrophilicity of the separator material. Moreover, since the separators F, G, and H are microporous membranes, it is presumed that voids that are not connected to others are formed in the separators. Therefore, even if a lot of voids are included in the separator, it is estimated that the voids did not contribute to the permeability of the electrolytic solution of the present invention.
  • the separator B was prepared as a separator.
  • a separator was sandwiched between the positive electrode and the negative electrode to form an electrode plate group.
  • the electrode plate group was covered with a set of two laminated films, and the three sides were sealed, and then the electrolyte solution E8 was injected into the laminated film in a bag shape. Thereafter, the remaining one side was sealed to obtain a lithium ion secondary battery in which the four sides were hermetically sealed and the electrode plate group and the electrolyte were sealed. This battery was used as the lithium ion secondary battery of Example 1.
  • Lithium ion secondary battery of Comparative Example 1 A lithium ion secondary battery of Comparative Example 1 was prepared in the same manner as the lithium ion secondary battery of Example 1 except that the electrolytic solution C5 was used instead of the electrolytic solution E8.
  • the thermal stability of the lithium ion secondary batteries of Example 1 and Comparative Example 1 was evaluated by the following method.
  • the lithium ion secondary battery was fully charged under a potential difference of 4.2 V and a constant current and constant voltage condition.
  • the fully charged lithium ion secondary battery was disassembled and the positive electrode was taken out.
  • 3 mg of the positive electrode and 1.8 ⁇ L of the electrolytic solution were placed in a stainless steel pan, and the pan was sealed. Using a sealed pan, under a nitrogen atmosphere, the heating rate was 20 ° C / min.
  • the differential scanning calorimetry was performed under the conditions described above, and the DSC curve was observed.
  • FIG. 30 shows a DSC chart of the lithium ion secondary battery of Example 1
  • FIG. 31 shows a DSC chart of the lithium ion secondary battery of Comparative Example 1.
  • the lithium ion secondary battery using the electrolytic solution of the present invention has a lower reactivity between the positive electrode active material and the electrolytic solution than the lithium ion secondary battery using the conventional electrolytic solution, It was found to be excellent in thermal stability.
  • a charge / discharge test was performed using the lithium ion secondary battery of Example 1 and the lithium ion secondary battery of Comparative Example 2.
  • the charge / discharge conditions were set to CC charge / discharge at 0.1C.
  • Changes in voltage with respect to time of the lithium ion secondary battery of Example 1 and the lithium ion secondary battery of Comparative Example 2 were graphed and shown in FIGS. 32 and 33.
  • 32 is a graph showing a charge / discharge curve of the lithium ion secondary battery of Example 1
  • FIG. 33 is a graph showing a charge / discharge curve of the lithium ion secondary battery of Comparative Example 2.
  • the lithium ion secondary battery of Example 1 was able to charge / discharge well, but the lithium ion secondary battery of Comparative Example 2 was hardly charged / discharged.
  • the viscosity of the electrolyte used in the lithium ion secondary batteries of Example 1 and Comparative Example 2 was very high at 23.8 (mPa ⁇ s). Due to the high viscosity of the electrolyte used, the lithium ion secondary battery of Comparative Example 2 cannot pass through the separator G used, and the lithium ion secondary battery of Comparative Example 2 can be charged and discharged. It is estimated that there was not.
  • the discharge capacity per mass of the positive electrode active material of each lithium ion secondary battery is calculated from this charge / discharge curve, the discharge capacity per mass of the positive electrode active material of the lithium ion secondary battery of Example 1 is 158 mAh / g.
  • the discharge capacity per positive electrode active material mass of the lithium ion secondary battery of Comparative Example 2 was 0.58 mAh / g.
  • the discharge capacity of the lithium ion secondary battery of Example 1 uses the same positive electrode and negative electrode, uses an EC-based general electrolyte, and discharge capacity of a lithium ion secondary battery using a general separator It was equivalent.
  • Lithium ion secondary battery of Example 3 A lithium ion secondary battery of Example 3 was made in the same manner as the lithium ion secondary battery of Example 2 except that the negative electrode produced as described below was used.
  • Lithium ion secondary battery of Comparative Example 3 A lithium ion secondary battery of Comparative Example 3 was produced in the same manner as the lithium ion secondary battery of Example 2 except that the electrolyte solution C5 was used instead of the electrolyte solution E8.
  • Lithium ion secondary battery of Comparative Example 4 A lithium ion secondary battery of Comparative Example 4 was prepared in the same manner as the lithium ion secondary battery of Example 3 except that the electrolyte solution C5 was used instead of the electrolyte solution E8.
  • the battery output density (W / L) at 25 ° C. for 2 seconds was calculated.
  • Table 10 shows the evaluation results of the input characteristics.
  • “2 seconds input” means an input 2 seconds after the start of charging
  • “5 seconds input” means an input 5 seconds after the start of charging.
  • the input of the lithium ion secondary battery of Example 2 was significantly higher than the input of the lithium ion secondary battery of Comparative Example 3 regardless of the difference in temperature.
  • the input of the lithium ion secondary battery of Example 3 was significantly higher than the input of the lithium ion secondary battery of Comparative Example 4.
  • the battery input density of the lithium ion secondary battery of Example 2 was significantly higher than the battery input density of the lithium ion secondary battery of Comparative Example 3.
  • the battery input density of the lithium ion secondary battery of Example 3 was significantly higher than the battery input density of the lithium ion secondary battery of Comparative Example 4.
  • Evaluation of output characteristics at 0 ° C. or 25 ° C. and SOC 20% Evaluation conditions were a state of charge (SOC) 20%, 0 ° C. or 25 ° C., operating voltage range 3V-4.2V, and capacity 13.5 mAh.
  • SOC 20%, 0 ° C. is a region where output characteristics are difficult to be obtained, for example, when used in a refrigerator room.
  • the output characteristics were evaluated three times for each battery for the 2-second output and 5-second output.
  • the battery output density (W / L) at 25 ° C. for 2 seconds output was calculated.
  • Table 10 shows the evaluation results of the output characteristics.
  • “2 seconds output” means an output 2 seconds after the start of discharge
  • “5 seconds output” means an output 5 seconds after the start of discharge.
  • the output of the lithium ion secondary battery of Example 2 was significantly higher than the output of the lithium ion secondary battery of Comparative Example 3 regardless of the difference in temperature.
  • the output of the lithium ion secondary battery of Example 3 was significantly higher than the output of the lithium ion secondary battery of Comparative Example 4.
  • the battery output density of the lithium ion secondary battery of Example 2 was significantly higher than the battery output density of the lithium ion secondary battery of Comparative Example 3.
  • the battery output density of the lithium ion secondary battery of Example 3 was significantly higher than the battery output density of the lithium ion secondary battery of Comparative Example 4.
  • the counter electrode was metal Li.
  • Reference Example 2-2 A half cell of Reference Example 2-2 was manufactured in the same manner as Reference Example 1-2, except that Electrolytic Solution C5 was used as the electrolytic solution.
  • Reference Example 3 A half cell of Reference Example 3 was produced in the same manner as in Reference Example 1-2, except that Electrolyte E10 was used as the electrolyte.
  • Reference Example 4 A half cell of Reference Example 4 was produced in the same manner as in Reference Example 1-2 except that Electrolyte E15 was used as the electrolyte.
  • Reference Example 5 A half cell of Reference Example 5 was produced in the same manner as in Reference Example 1-2, except that Electrolyte E18 was used as the electrolyte.
  • the half cells of Reference Examples 1-2, 3, 4, and 5 using the electrolytic solution of the present invention are reversibly charged and discharged similarly to the half cells of Reference Example 2-2 using the conventional electrolytic solution. I understood it.
  • Reference Examples 1-2, 3, 4, and 5 are the rates of 0.2C, 0.5C, and 1C
  • Reference Examples 1-2 and 3 are the half cells of Reference Example 2-2 at the rate of 2C. In comparison, it was confirmed that the capacity decrease was suppressed and an excellent rate characteristic was exhibited.
  • Lithium ion secondary battery of Example 2 The lithium ion secondary battery of Example 2 described above was used.
  • Lithium ion secondary battery of Comparative Example 3 The lithium ion secondary battery of Comparative Example 3 described above was used.
  • the discharge capacity retention rate at the 500th cycle was measured, and the results are shown in Table 11.
  • the discharge capacity retention ratio is a value obtained as a percentage of the value obtained by dividing the discharge capacity at the 500th cycle by the initial discharge capacity ((discharge capacity at the 500th cycle) / (initial discharge capacity) ⁇ 100).
  • the lithium secondary batteries of Examples 2 and 4 have low resistance even after cycling. Further, the lithium secondary battery of Example 4 has a particularly high capacity retention rate, and the resistance is greatly reduced after the cycle test.
  • Aluminum foil with a thickness of 20 ⁇ m (JIS A1000 series) was used as the working electrode, and the counter electrode was metal Li.
  • the separator was Whatman glass fiber filter paper having a thickness of 400 ⁇ m and a product number of 1825-055 manufactured by GE Healthcare Japan.
  • the power storage device using the electrolytic solution of the present invention and using the aluminum current collector is unlikely to elute Al even at a high potential.
  • the electrolytic solution of the present invention is different from the conventional electrolytic solution in the types of metal salt and organic solvent, the existing environment and the metal salt concentration. In comparison with this, it is presumed that the solubility of Al in the electrolytic solution of the present invention is low.
  • Reference Example 8 A half cell of Reference Example 8 was prepared in the same manner as the half cell of Reference Example 6 except that the electrolyte solution E15 was used instead of the electrolyte solution E8.
  • Reference Example 9 A half cell of Reference Example 9 was prepared in the same manner as the half cell of Reference Example 6 except that the electrolyte solution E18 was used instead of the electrolyte solution E8.
  • Reference Example 10 A half cell of Reference Example 10 was prepared in the same manner as the half cell of Reference Example 6 except that the electrolyte solution E12 was used instead of the electrolyte solution E8.
  • Reference Example 11 A half cell of Reference Example 11 was prepared in the same manner as the half cell of Reference Example 6 except that the electrolyte solution C5 was used instead of the electrolyte solution E8.
  • Reference Example 12 A half cell of Reference Example 12 was prepared in the same manner as the half cell of Reference Example 6, except that the electrolyte solution C6 was used instead of the electrolyte solution E8.
  • FIGS. 1 and FIGS. 2 Graphs showing the relationship between the potential and response current for the half cells of Reference Examples 6 to 9 and Reference Example 11 are shown in FIGS. Further, graphs showing the relationship between the potential and the response current for the half cells of Reference Example 7, Reference Example 10, and Reference Example 12 are shown in FIGS.
  • the electrolytic solution E8 the electrolytic solution E10, the electrolytic solution E12, the electrolytic solution E15, and the electrolytic solution E18 to aluminum is low even under a high potential condition exceeding 5V. That is, the electrolytic solution E8, the electrolytic solution E10, the electrolytic solution E12, the electrolytic solution E15, and the electrolytic solution E18 can be said to be suitable electrolytic solutions for a battery using aluminum as a current collector.
  • the lithium ion secondary batteries of Example 1, Example 6 and Comparative Example 1 were set to a working voltage range of 3 V to 4.2 V, and charging / discharging was repeated 100 times at a rate of 1C. I took it out.
  • the amount of Al eluted from the positive electrode into the electrolyte and deposited on the surface of the negative electrode was measured with an ICP (high frequency inductively coupled plasma) emission spectrometer.
  • Table 15 shows the measurement results.
  • the amount of Al (%) in Table 15 indicates the mass of Al per gram of the negative electrode active material layer in%, and the amount of Al ( ⁇ g / sheet) represents the mass of Al ( ⁇ g per negative electrode active material layer).
  • Al amount (%) ⁇ 100 ⁇ mass of each negative electrode active material layer Al amount ( ⁇ g / sheet).
  • the amount of Al deposited on the negative electrode surface was significantly less than that of the lithium ion secondary battery of Comparative Example 1. Therefore, in the lithium ion secondary batteries of Example 1 and Example 6 using the electrolytic solution of the present invention, the positive electrode current collector is more than the lithium ion secondary battery of Comparative Example 1 using the conventional electrolytic solution. It was found that the elution of Al from was suppressed.
  • Example 22 Surface analysis of Al current collector
  • the lithium ion secondary batteries of Example 1 and Example 6 were set to a working voltage range of 3 V to 4.2 V, and were repeatedly charged and discharged 100 times at a rate of 1 C, and disassembled after 100 times of charging and discharging to provide a positive electrode current collector.
  • Each aluminum foil was taken out, and the surface of the aluminum foil was washed with dimethyl carbonate.
  • the surface of the aluminum foil of the lithium ion secondary batteries of Example 1 and Example 6 after washing was subjected to surface analysis by X-ray photoelectron spectroscopy (XPS) while etching by Ar sputtering.
  • 55 and 56 show the surface analysis results of the aluminum foil after charge and discharge of the lithium ion secondary batteries of Example 1 and Example 6.
  • the surface analysis results of the aluminum foil which is the current collector for the positive electrode after charging and discharging of the lithium ion secondary batteries of Examples 1 and 6, are almost the same. I can say that.
  • the chemical state of Al on the outermost surface was AlF 3 .
  • Al, O, and F peaks were detected. It was found that the portion etched once to three times from the surface was a composite state of Al—F bond and Al—O bond. As the etching was further continued, the O and F peaks disappeared from the fourth etching (depth about 25 nm in terms of SiO 2 ), and only the Al peak was observed.
  • AlF 3 is observed at the Al peak position 76.3 eV
  • pure Al is observed at the Al peak position 73 eV
  • Al peak position is observed.
  • the broken lines shown in FIGS. 55 and 56 show typical peak positions of AlF 3 , Al, and Al 2 O 3, respectively.
  • the surface of the aluminum foil of the lithium ion secondary battery after charging and discharging according to the present invention has an Al—F bond (presumed to be AlF 3 ) layer with a thickness of about 25 nm in the depth direction. It was confirmed that a layer in which Al—F bonds (presumed to be AlF 3 ) and Al—O bonds (presumed to be Al 2 O 3 ) were mixed was formed.
  • a passive film composed of an Al—F bond (presumed to be AlF 3 ) is formed on the outermost surface of the aluminum foil after charging and discharging. It was found that it was formed.
  • Example 7 Evaluation of lithium ion secondary battery output characteristics (Examination of low weight) (Example 7)
  • a lithium ion secondary battery of Example 7 was made in the same manner as the lithium ion secondary battery of Example 2 except that the basis weight of the positive electrode was 5.5 mg / cm 2 and the basis weight of the negative electrode was 4 mg / cm 2 .
  • Comparative Example 5 A lithium ion secondary battery of Comparative Example 5 was produced in the same manner as the lithium ion secondary battery of Comparative Example 3 except that the basis weight of the positive electrode was 5.5 mg / cm 2 and the basis weight of the negative electrode was 4 mg / cm 2 .
  • the evaluation conditions are: state of charge (SOC) 80%, 25 ° C., use voltage range 3V-4.2V, capacity 13.5 mAh, 5 seconds input, state of charge (SOC) 30%, ⁇ 10 ° C. or ⁇ 30 ° C.,
  • the operating voltage range was 3V-4.2V
  • the capacity was 13.5 mAh
  • the output was 2 seconds.
  • ⁇ 10 ° C. and ⁇ 30 ° C. are regions where output characteristics are difficult to be obtained as in the case of use in a low temperature environment.
  • Table 16 shows the input / output characteristics evaluation results.
  • 5 seconds input means an input after 5 seconds from the start of charging
  • 2 seconds output means an output after 2 seconds from the start of discharging.
  • the input / output of the lithium ion secondary battery of Example 7 is the same as that of the lithium ion secondary battery of Comparative Example 5 even in the low-weight lithium ion secondary battery regardless of the temperature difference. It was significantly higher than the output.
  • FIGS. 57 to 63 show Raman spectra in which peaks derived from the anion portion of the metal salt of each electrolytic solution were observed.
  • the horizontal axis represents the wave number (cm ⁇ 1 )
  • the vertical axis represents the scattering intensity.
  • the electrolyte was sealed in a quartz cell under an inert gas atmosphere and used for measurement.
  • the Raman spectra 700 to 800 cm ⁇ 1 of the electrolytic solutions E10, E12, E14, and C6 shown in FIGS. 60 to 63 are derived from (FSO 2 ) 2 N of LiFSA dissolved in dimethyl carbonate. A characteristic peak was observed. Here, it can be seen from FIGS. 60 to 63 that the peak shifts to the higher wavenumber side as the LiFSA concentration increases. This phenomenon is similar to that discussed in the previous paragraph. As the electrolyte concentration increases, (FSO 2 ) 2 N corresponding to the anion of the salt interacts with Li, and this state It can be considered that the change was observed as a peak shift of the Raman spectrum.
  • Example 8 A lithium ion secondary battery of Example 8 was created in the same manner as the lithium ion secondary battery of Example 1 except that the electrolytic solution E10 was used as the electrolyte of the lithium ion secondary battery.
  • each battery was charged to 4.1 V under the conditions of a temperature of 25 ° C. and a CC charge of 1 C, and rested for 1 minute.
  • a cycle test was conducted by repeating 500 cycles of discharging to 3.0 V and resting for 1 minute.
  • the discharge capacity retention ratio in each cycle was measured, and the results are shown in FIG. Table 17 shows the discharge capacity retention ratio at the 500th cycle.
  • the discharge capacity maintenance ratio is a value obtained by a percentage ((discharge capacity of each cycle) / (initial discharge capacity) ⁇ 100) obtained by dividing the discharge capacity of each cycle by the initial discharge capacity.
  • Reference Example 14 A half cell of Reference Example 14 was obtained in the same manner as the half cell of Reference Example 13, except that the electrolyte C5 was used as the electrolyte.
  • the voltage curve of the half cell of Reference Example 13 at each current rate shows a higher voltage than the voltage curve of the half cell of Reference Example 14. It was confirmed that the lithium ion secondary battery using the electrolytic solution of the present invention exhibits excellent rate characteristics even in a low temperature environment.
  • Example 9 A lithium ion secondary battery of Example 9 using the electrolytic solution E8 was produced as follows.
  • a lithium-containing metal oxide having a layered rock salt structure represented by LiNi 5/10 Co 2/10 Mn 3/10 O 2 as a positive electrode active material, 8 parts by mass of acetylene black as a conductive auxiliary agent, and a binder 2 parts by mass of polyvinylidene fluoride as an agent was mixed. This mixture was dispersed in an appropriate amount of N-methyl-2-pyrrolidone to prepare a slurry. An aluminum foil having a thickness of 20 ⁇ m was prepared as a positive electrode current collector. The slurry was applied to the surface of the aluminum foil using a doctor blade so as to form a film. The aluminum foil coated with the slurry was dried at 80 ° C.
  • a cellulose nonwoven fabric having a thickness of 20 ⁇ m was prepared as a separator.
  • a separator was sandwiched between the positive electrode and the negative electrode to form an electrode plate group.
  • the electrode plate group was covered with a set of two laminated films, and the three sides were sealed, and then the electrolyte solution E8 was injected into the laminated film in a bag shape. Thereafter, the remaining one side was sealed to obtain a lithium ion secondary battery in which the four sides were hermetically sealed and the electrode plate group and the electrolyte were sealed.
  • This battery was a lithium ion secondary battery of Example 9.
  • Example 10 A lithium ion secondary battery of Example 10 was obtained in the same manner as in Example 9, except that the electrolytic solution E10 was used as the electrolytic solution.
  • Example 11 A lithium ion secondary battery of Example 11 was obtained in the same manner as in Example 9, except that the electrolytic solution E12 was used as the electrolytic solution.
  • Comparative Example 6 A lithium ion secondary battery of Comparative Example 6 was obtained in the same manner as in Example 9, except that the electrolytic solution C5 was used as the electrolytic solution.
  • the lithium ion secondary batteries of Examples 9 to 11 and Comparative Example 6 were prepared, and the internal resistance of the batteries was evaluated.
  • CC charging / discharging that is, constant current charging / discharging was repeated at room temperature in the range of 3.0 V to 4.1 V (vs. Li standard).
  • alternating current impedance after the first charge / discharge and the alternating current impedance after 100 cycles progress were measured.
  • the reaction resistances of the electrolytic solution, the negative electrode, and the positive electrode were each analyzed.
  • FIG. 67 two arcs were seen in the complex impedance plane plot.
  • the arc on the left side of the figure that is, the side where the real part of the complex impedance is small
  • the arc on the right side in the figure is called the second arc.
  • the reaction resistance of the negative electrode was analyzed based on the size of the first arc
  • the reaction resistance of the positive electrode was analyzed based on the size of the second arc.
  • the resistance of the electrolytic solution was analyzed based on the leftmost plot in FIG. 67 continuous with the first arc.
  • Table 19 shows the resistance of the electrolytic solution after the first charge / discharge (so-called solution resistance), the reaction resistance of the negative electrode, and the reaction resistance of the positive electrode
  • Table 20 shows each resistance after 100 cycles.
  • the negative electrode reaction resistance and the positive electrode reaction resistance after 100 cycles tended to be lower than the respective resistances after the first charge / discharge.
  • the negative electrode reaction resistance and the positive electrode reaction resistance of the lithium ion secondary batteries of Examples 9 to 11 were the negative electrode reaction resistance and the positive electrode reaction resistance of the lithium ion secondary battery of Comparative Example 6. It was low compared to.
  • the solution resistance of the electrolyte solution in the lithium ion secondary batteries of Examples 9 and 11 and Comparative Example 6 was almost the same.
  • the solution resistance of the electrolytic solution in the lithium ion secondary battery of Example 10 was higher than that of Examples 9 and 11 and Comparative Example 6.
  • the solution resistance of each electrolyte solution in each lithium ion secondary battery was the same after the first charge / discharge and after 100 cycles. For this reason, it is thought that durability deterioration of each electrolyte solution has not arisen.
  • the difference between the negative electrode reaction resistance and the positive electrode reaction resistance generated in the comparative examples and examples described above is considered not to be related to the durability deterioration of the electrolytic solution but to the electrode itself.
  • the internal resistance of the lithium ion secondary battery can be comprehensively determined from the solution resistance of the electrolytic solution, the reaction resistance of the negative electrode, and the reaction resistance of the positive electrode. Based on the results of Table 19 and Table 20, from the viewpoint of suppressing the increase in the internal resistance of the lithium ion secondary battery, the lithium ion secondary batteries of Examples 10 and 11 have the most excellent durability, and then Example 9 It can be said that the lithium ion secondary battery is excellent in durability.
  • the lithium ion secondary batteries of Examples 9 to 11 had 100 equivalent to the lithium ion secondary battery of Comparative Example 6 containing EC even though it did not contain EC as a material for SEI.
  • the capacity retention rate during the cycle was shown. This is presumably because the positive electrode and the negative electrode in the lithium ion secondary batteries of Examples 9 to 11 have films derived from the electrolytic solution of the present invention.
  • capacitance maintenance factor was shown also after 500 cycles progress, and it was excellent in durability especially. From this result, it can be said that when DMC is selected as the organic solvent of the electrolytic solution, durability is further improved as compared with the case where AN is selected.
  • Specific examples of the electrolytic solution of the present invention include the following electrolytic solutions. The following electrolytes include those already described.
  • Electrolytic solution A The electrolytic solution of the present invention was produced as follows.
  • the obtained electrolytic solution had a volume of 20 mL, and (CF 3 SO 2 ) 2 NLi contained in this electrolytic solution was 18.38 g. This was designated as an electrolytic solution A.
  • the concentration of (CF 3 SO 2 ) 2 NLi in the electrolytic solution A was 3.2 mol / L, and the density was 1.39 g / cm 3 . The density was measured at 20 ° C.
  • the above production was carried out in a glove box under an inert gas atmosphere.
  • Electrolytic solution B By a method similar to that for the electrolytic solution A, an electrolytic solution B having a (CF 3 SO 2 ) 2 NLi concentration of 2.8 mol / L and a density of 1.36 g / cm 3 was produced.
  • Electrolytic solution C About 5 mL of acetonitrile, which is an organic solvent, was placed in a flask equipped with a stir bar. Under stirring conditions, (CF 3 SO 2 ) 2 NLi, which is a lithium salt, was gradually added to and dissolved in acetonitrile in the flask. The mixture was stirred overnight when the prescribed (CF 3 SO 2 ) 2 NLi was added. The resulting electrolyte was transferred to a 20 mL volumetric flask and acetonitrile was added until the volume was 20 mL. This was designated as an electrolytic solution C. The production was performed in a glove box under an inert gas atmosphere.
  • the electrolytic solution C had a (CF 3 SO 2 ) 2 NLi concentration of 4.2 mol / L and a density of 1.52 g / cm 3 .
  • Electrolytic solution D By a method similar to that of the electrolytic solution C, an electrolytic solution D having a concentration of (CF 3 SO 2 ) 2 NLi of 3.0 mol / L and a density of 1.31 g / cm 3 was produced.
  • Electrolytic solution F The concentration of (CF 3 SO 2 ) 2 NLi is 3.2 mol / L and the density is 1.49 g / cm 3 except that dimethyl sulfoxide is used as the organic solvent. Electrolytic solution F was produced.
  • Electrolytic solution J (Electrolytic solution J) Except that acetonitrile was used as the organic solvent, an electrolytic solution J having a concentration of (FSO 2 ) 2 NLi of 5.0 mol / L and a density of 1.40 g / cm 3 in the same manner as the electrolytic solution G Manufactured.
  • Electrolytic solution K In the same manner as the electrolytic solution J, an electrolytic solution K having a concentration of (FSO 2 ) 2 NLi of 4.5 mol / L and a density of 1.34 g / cm 3 was produced.
  • Electrolytic solution L About 5 mL of dimethyl carbonate, which is an organic solvent, was placed in a flask equipped with a stir bar. Under stirring conditions, (FSO 2 ) 2 NLi, which is a lithium salt, was gradually added to dimethyl carbonate in the flask and dissolved. When (FSO 2 ) 2 NLi was added in a total amount of 14.64 g, the mixture was stirred overnight. The resulting electrolyte was transferred to a 20 mL volumetric flask and dimethyl carbonate was added until the volume was 20 mL. This was designated as an electrolytic solution L. The production was performed in a glove box under an inert gas atmosphere.
  • the concentration of (FSO 2 ) 2 NLi in the electrolytic solution L was 3.9 mol / L, and the density of the electrolytic solution L was 1.44 g / cm 3 .
  • Electrolytic solution N About 5 mL of ethyl methyl carbonate, which is an organic solvent, was placed in a flask equipped with a stir bar. Under stirring conditions, (FSO 2 ) 2 NLi, which is a lithium salt, was gradually added to and dissolved in ethyl methyl carbonate in the flask. When 12.81 g of (FSO 2 ) 2 NLi was added in total, the mixture was stirred overnight. The obtained electrolytic solution was transferred to a 20 mL volumetric flask, and ethyl methyl carbonate was added until the volume became 20 mL. This was designated as an electrolytic solution N. The production was performed in a glove box under an inert gas atmosphere.
  • the concentration of (FSO 2 ) 2 NLi in the electrolytic solution N was 3.4 mol / L, and the density of the electrolytic solution N was 1.35 g / cm 3 .
  • Electrolytic solution O About 5 mL of diethyl carbonate, which is an organic solvent, was placed in a flask equipped with a stirring bar. Under stirring conditions, (FSO 2 ) 2 NLi, which is a lithium salt, was gradually added to and dissolved in diethyl carbonate in the flask. When 11.37 g of the total amount of (FSO 2 ) 2 NLi was added, the mixture was stirred overnight. The resulting electrolyte was transferred to a 20 mL volumetric flask and diethyl carbonate was added until the volume was 20 mL. This was designated as an electrolytic solution O. The production was performed in a glove box under an inert gas atmosphere.
  • the concentration of (FSO 2 ) 2 NLi in the electrolytic solution O was 3.0 mol / L, and the density of the electrolytic solution O was 1.29 g / cm 3 .
  • Table 22 shows a list of the electrolyte solutions.

Abstract

L'invention concerne un dispositif de stockage d'électricité qui comprend une nouvelle solution d'électrolyte inventée par les inventeurs de la présente invention, et un séparateur qui peut être utilisé en association avec la solution d'électrolyte. Ce dispositif de stockage d'électricité comprend une électrode positive, une électrode négative, une solution d'électrolyte et un séparateur, et est caractérisé en ce que le séparateur a un rapport de rétention d'eau de 0,1 ou plus; en ce que la solution d'électrolyte contient un solvant organique ayant un hétéro-élément et un sel; un métal alcalin, un métal alcalino-terreux ou de l'aluminium étant utilisé sous forme de cations; et en ce que, par rapport à l'intensité de crête attribuée au solvant organique dans un spectre vibratoire de la solution d'électrolyte, si Io est l'intensité de crête d'origine du solvant organique et Is est l'intensité d'une crête décalée du solvant organique, Io et Is satisfont la relation Is > Io.
PCT/JP2014/004914 2013-09-25 2014-09-25 Dispositif de stockage d'électricité WO2015045390A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2013198594 2013-09-25
JP2013-198594 2013-09-25
JP2014-065840 2014-03-27
JP2014065840 2014-03-27
JP2014186393A JP5965446B2 (ja) 2013-09-25 2014-09-12 蓄電装置
JP2014-186393 2014-09-12

Publications (1)

Publication Number Publication Date
WO2015045390A1 true WO2015045390A1 (fr) 2015-04-02

Family

ID=52742559

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/004914 WO2015045390A1 (fr) 2013-09-25 2014-09-25 Dispositif de stockage d'électricité

Country Status (2)

Country Link
JP (1) JP5965446B2 (fr)
WO (1) WO2015045390A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7387671B2 (ja) * 2021-03-30 2023-11-28 ソフトバンク株式会社 準固体電解質および二次電池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006115023A1 (fr) * 2005-04-19 2006-11-02 Matsushita Electric Industrial Co., Ltd. Solution d'electrolyte non aqueux, dispositif de stockage d'energie electrochimique utilisant cette solution et accumulateur auxiliaire a electrolyte non aqueux
WO2007125682A1 (fr) * 2006-04-28 2007-11-08 Panasonic Corporation Dispositif de stockage d'energie electrochimique
JP2008047479A (ja) * 2006-08-21 2008-02-28 Matsushita Electric Ind Co Ltd 非水電解液およびそれを具備した電気化学エネルギー蓄積デバイス

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006115023A1 (fr) * 2005-04-19 2006-11-02 Matsushita Electric Industrial Co., Ltd. Solution d'electrolyte non aqueux, dispositif de stockage d'energie electrochimique utilisant cette solution et accumulateur auxiliaire a electrolyte non aqueux
WO2007125682A1 (fr) * 2006-04-28 2007-11-08 Panasonic Corporation Dispositif de stockage d'energie electrochimique
JP2008047479A (ja) * 2006-08-21 2008-02-28 Matsushita Electric Ind Co Ltd 非水電解液およびそれを具備した電気化学エネルギー蓄積デバイス

Also Published As

Publication number Publication date
JP5965446B2 (ja) 2016-08-03
JP2015195166A (ja) 2015-11-05

Similar Documents

Publication Publication Date Title
JP5965445B2 (ja) 非水電解質二次電池
KR101967677B1 (ko) 비수계 2차 전지
JP5967781B2 (ja) 非水電解質二次電池
JP5816997B2 (ja) アルカリ金属、アルカリ土類金属又はアルミニウムをカチオンとする塩と、ヘテロ元素を有する有機溶媒とを含む高粘度電解液
JP5817009B1 (ja) 非水系二次電池
WO2015045389A1 (fr) Solution d'électrolyte pour dispositifs de stockage d'électricité tels que des batteries et des condensateurs contenant du sel, un métal alcalin, un métal terreux alcalin ou de l'aluminium servant de cations, et un solvant organique possédant un hétéro-élément, procédé de production de celle-ci, et condensateur muni de ladite solution d'électrolyte.
JP6575022B2 (ja) アルカリ金属、アルカリ土類金属又はアルミニウムをカチオンとする塩と、ヘテロ元素を有する有機溶媒とを含む電解液
WO2015045387A1 (fr) Batterie secondaire à électrolyte non aqueux
JP5965444B2 (ja) 非水系二次電池
WO2015045386A1 (fr) Batterie rechargeable non aqueuse
JP5816999B2 (ja) アルカリ金属、アルカリ土類金属又はアルミニウムをカチオンとする塩と、ヘテロ元素を有する有機溶媒とを含む電解液の製造方法
JP5817004B2 (ja) リチウムイオン二次電池
JP5817001B2 (ja) 非水系二次電池
JP5965446B2 (ja) 蓄電装置
JP5817003B2 (ja) 非水電解質二次電池
JP6423330B2 (ja) アルカリ金属、アルカリ土類金属又はアルミニウムをカチオンとする塩と、ヘテロ元素を有する有機溶媒とを含む電解液群
JP2015088474A (ja) 非水系二次電池
JP5817006B1 (ja) 非水系二次電池
JP2016189340A (ja) 非水電解質二次電池
WO2015045393A1 (fr) Batterie secondaire à électrolyte non aqueux
JP5817007B1 (ja) 非水系二次電池
JP5817008B1 (ja) 非水系二次電池

Legal Events

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

Ref document number: 14848375

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14848375

Country of ref document: EP

Kind code of ref document: A1