WO2015045387A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2015045387A1
WO2015045387A1 PCT/JP2014/004911 JP2014004911W WO2015045387A1 WO 2015045387 A1 WO2015045387 A1 WO 2015045387A1 JP 2014004911 W JP2014004911 W JP 2014004911W WO 2015045387 A1 WO2015045387 A1 WO 2015045387A1
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Prior art keywords
substituent
substituted
group
secondary battery
electrolytic solution
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PCT/JP2014/004911
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English (en)
Japanese (ja)
Inventor
山田　淳夫
裕貴 山田
佳浩 中垣
智之 河合
雄紀 長谷川
浩平 間瀬
合田　信弘
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国立大学法人東京大学
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Priority claimed from JP2014186340A external-priority patent/JP5817003B2/ja
Priority claimed from JP2014186339A external-priority patent/JP5817002B2/ja
Priority claimed from JP2014186338A external-priority patent/JP5817001B2/ja
Priority claimed from JP2014186341A external-priority patent/JP5817004B2/ja
Priority claimed from JP2014186342A external-priority patent/JP5817005B2/ja
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
Priority to KR1020167010615A priority Critical patent/KR101901675B1/ko
Priority to US15/024,415 priority patent/US11011781B2/en
Priority to DE112014004442.3T priority patent/DE112014004442T5/de
Priority to CN201480053195.4A priority patent/CN105580184B/zh
Publication of WO2015045387A1 publication Critical patent/WO2015045387A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery.
  • a lithium ion secondary battery is a secondary battery with high charge / discharge capacity and high output.
  • secondary batteries that are mainly used as power sources for portable electronic devices, notebook computers, and electric vehicles.
  • it is necessary to charge and discharge with a large current, and development of a secondary battery having high rate characteristics capable of high-speed charging and discharging is required.
  • the lithium ion secondary battery has active materials capable of inserting and extracting lithium (Li) in the positive electrode and the negative electrode, respectively. Then, the lithium ion moves through the electrolytic solution sealed between the two electrodes. In order to increase the rate, it is necessary to improve the active material and binder used in the positive electrode and / or the negative electrode, and improve the electrolytic solution.
  • Carbon materials such as graphite are widely used as negative electrode active materials for lithium ion secondary batteries.
  • a non-aqueous carbonate solvent such as a cyclic ester or a chain ester is used for the electrolytic solution.
  • carbonate-based solvent it has been difficult to significantly improve the rate characteristics. That is, as described in Non-Patent Documents 1 to 3 below, carbonate-based solvents such as ethylene carbonate and propylene carbonate have a large activation barrier for electrode reaction. Review of the solvent composition is required.
  • the present invention has been made in view of the above-described circumstances, and a main problem to be solved is to improve battery characteristics by an optimal combination of an electrolytic solution and a negative electrode active material.
  • the organic solvent contains a salt having alkali metal, alkaline earth metal or aluminum as a cation and an organic solvent having a hetero element, and the peak intensity derived from the organic solvent in a vibrational spectroscopic spectrum.
  • the “electrolytic solution with Is> Io” may be referred to as the “electrolytic solution of the present invention”.
  • the feature of the nonaqueous electrolyte secondary battery (1) of the present invention that solves the above problems is that the electrolyte solution of the present invention described above and the G / D ratio, which is the ratio of the peak of G-band and D-band in the Raman spectrum. And a negative electrode having a negative electrode active material layer containing graphite of 3.5 or more.
  • the “G / D ratio is 3.5 or more” in the present invention means that either the area ratio or the height ratio of the G-band and D-band peaks in the Raman spectrum is 3.5 or more. In particular, the height ratio of the peak is 3.5 or more.
  • a feature of the nonaqueous electrolyte secondary battery (3) of the present invention that solves the above problems is that it comprises the above-described electrolytic solution of the present invention and a negative electrode containing a silicon element and / or a tin element in the negative electrode active material. It is in.
  • the characteristics of the nonaqueous electrolyte secondary battery (4) of the present invention that solves the above problems are the above-described electrolytic solution of the present invention, a negative electrode containing a metal oxide capable of inserting and extracting lithium ions as a negative electrode active material, It is in having.
  • the feature of the non-aqueous electrolyte secondary battery (5) of the present invention that solves the above problems is that the above-described electrolytic solution of the present invention and the ratio of the major axis to the minor axis (major axis / minor axis) are 1 to 5. And a negative electrode having a negative electrode active material layer containing graphite.
  • nonaqueous electrolyte secondary battery of the present invention battery characteristics are improved.
  • 3 is a graph showing a cyclic voltamentary (CV) of the nonaqueous electrolyte secondary battery of Example 1-1.
  • 3 is a graph showing a cyclic voltamentary (CV) of the nonaqueous electrolyte secondary battery of Example 1-2.
  • 4 is a graph showing a cyclic voltamentary (CV) of the nonaqueous electrolyte secondary battery of Example 1-3.
  • 6 is a graph showing a cyclic voltamentary (CV) of the nonaqueous electrolyte secondary battery of Comparative Example 1-1.
  • 6 is a graph showing a cyclic voltamentary (CV) of the nonaqueous electrolyte secondary battery of Comparative Example 1-2.
  • 6 is a graph showing a cyclic voltamentary (CV) of the nonaqueous electrolyte secondary battery of Comparative Example 1-3.
  • 6 is a graph showing a cyclic voltamentary (CV) of the nonaqueous electrolyte secondary battery of Comparative Example 1-4.
  • 6 is a graph showing a cyclic voltamentary (CV) of the nonaqueous electrolyte secondary battery of Comparative Example 1-5.
  • 7 is a graph showing a cyclic voltamentary (CV) of the nonaqueous electrolyte secondary battery of Comparative Example 1-6.
  • 7 is a graph showing a cyclic voltamentary (CV) of the nonaqueous electrolyte secondary battery of Comparative Example 1-7.
  • 6 is a DSC chart of the nonaqueous electrolyte secondary battery of Example 1-5 and the nonaqueous electrolyte secondary battery of Comparative Example 1-8.
  • 6 is a DSC chart of the nonaqueous electrolyte secondary battery of Example 1-6 and the nonaqueous electrolyte secondary battery of Comparative Example 1-8.
  • 6 is a graph showing the relationship between the number of cycles and the current capacity ratio of the nonaqueous electrolyte secondary battery of Example 1-1 and the nonaqueous electrolyte secondary battery of Comparative Example 1-1.
  • 6 is a charge / discharge curve of the nonaqueous electrolyte secondary battery in Example 1-8.
  • FIG. 6 is a charge / discharge curve of the nonaqueous electrolyte secondary battery of Example 1-9.
  • FIG. 3 is a charge / discharge curve of the nonaqueous electrolyte secondary battery in Example 1-10.
  • 3 is a charge / discharge curve of the nonaqueous electrolyte secondary battery in Example 1-11.
  • 10 is a charge / discharge curve of a nonaqueous electrolyte secondary battery in Comparative Example 1-9.
  • 10 is a graph showing a relationship between a current rate and a voltage curve in the nonaqueous electrolyte secondary battery of Example 1-12.
  • 6 is a graph showing a relationship between a current rate and a voltage curve in the nonaqueous electrolyte secondary battery of Comparative Example 1-4. It is a result of the cycle characteristic of the evaluation example 19.
  • the initial charge / discharge curves of the nonaqueous electrolyte secondary battery of Example 2-1 and the nonaqueous electrolyte secondary battery of Comparative Example 2-1 are shown.
  • 6 is a graph showing the relationship between the number of cycles and the current capacity ratio of the nonaqueous electrolyte secondary battery of Example 2-1 and the nonaqueous electrolyte secondary battery of Comparative Example 2-1.
  • 3 is a charge / discharge curve of the nonaqueous electrolyte secondary battery of Example 3-2 and Comparative Example 3-2. 3 is a charge / discharge curve of the nonaqueous electrolyte secondary battery of Example 3-3. It is a charging / discharging curve of the nonaqueous electrolyte secondary battery of Example 4-1.
  • FIG. It is a STEM analysis result about C of the negative electrode S and O containing film
  • 44 is a graph showing a relationship between a potential (3.1 to 5.1 V) with respect to EB 12 and a response current in Evaluation Example 37.
  • 44 is a graph showing a relationship between a potential (3.1 to 4.6 V) with respect to EB 13 and a response current in Evaluation Example 37.
  • 40 is a graph showing a relationship between a potential (3.1 to 5.1 V) with respect to EB 13 and a response current in Evaluation Example 37.
  • 44 is a graph showing a relationship between a potential (3.1 to 4.6 V) with respect to EB 14 and a response current in Evaluation Example 37.
  • 44 is a graph showing a relationship between a potential (3.1 to 5.1 V) with respect to EB 14 and a response current in Evaluation Example 37.
  • 44 is a graph showing a relationship between a potential (3.1 to 4.6 V) with respect to EB 15 and a response current in Evaluation Example 37.
  • 44 is a graph showing a relationship between a potential (3.1 to 5.1 V) with respect to EB 15 and a response current in Evaluation Example 37.
  • 44 is a graph showing a relationship between a potential (3.1 to 4.6 V) with respect to CB6 and a response current in Evaluation Example 37.
  • 44 is a graph showing a relationship between a potential (3.0 to 4.5 V) with respect to EB 13 and a response current in Evaluation Example 37.
  • the scale of the vertical axis in FIG. 93 is changed.
  • 42 is a graph showing a relationship between a potential (3.0 to 5.0 V) with respect to EB 13 and a response current in Evaluation Example 37.
  • the scale of the vertical axis in FIG. 94 is changed.
  • 44 is a graph showing a relationship between a potential (3.0 to 4.5 V) with respect to EB16 and a response current in Evaluation Example 37.
  • 44 is a graph showing a relationship between a potential (3.0 to 5.0 V) with respect to EB16 and a response current in Evaluation Example 37.
  • 44 is a graph showing a relationship between a potential (3.0 to 4.5 V) with respect to CB7 and a response current in Evaluation Example 37.
  • 44 is a graph showing a relationship between a potential (3.0 to 5.0 V) and a response current with respect to CB7 in Evaluation Example 37.
  • 42 is a DSC chart of EB19 in Evaluation Example 39.
  • 42 is a DSC chart of CB10 in Evaluation Example 39.
  • 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 non-aqueous electrolyte secondary battery of the present invention is intended to improve battery characteristics by an optimal combination of an electrolytic solution and a negative electrode active material. Therefore, there are no particular limitations on other battery components, such as the positive electrode.
  • the charge carrier in the nonaqueous electrolyte secondary battery of the present invention is not particularly limited.
  • the nonaqueous electrolyte secondary battery of the present invention may be a nonaqueous electrolyte secondary battery using lithium as a charge carrier (for example, a lithium secondary battery or a lithium ion secondary battery), or sodium as a charge carrier. It may be a non-aqueous electrolyte secondary battery (for example, a sodium secondary battery or a sodium ion secondary battery).
  • the non-aqueous electrolyte secondary battery (1) of the present invention is a main problem that should be solved by improving the rate capacity characteristics and improving the cycle characteristics by an optimal combination of the electrolytic solution and the negative electrode active material. It is.
  • the nonaqueous electrolyte secondary battery (1) of the present invention includes the electrolyte of the present invention and graphite having a G / D ratio of 3.5 or more, which is a ratio of G-band and D-band peaks in the Raman spectrum.
  • a negative electrode having a negative electrode active material layer is a nonaqueous electrolyte secondary battery having improved rate capacity characteristics and cycle characteristics.
  • the nonaqueous electrolyte secondary battery (2) of the present invention is a main problem that should be solved to improve the rate capacity characteristics by an optimal combination of an electrolytic solution and a negative electrode active material.
  • the nonaqueous electrolyte secondary battery (2) of the present invention includes the electrolytic solution of the present invention and a negative electrode having a negative electrode active material layer containing a carbon material having a crystallite size of 20 nm or less.
  • the nonaqueous electrolyte secondary battery (3) of the present invention uses silicon (Si) or tin (Sn) as the negative electrode active material for the nonaqueous electrolyte secondary battery, and improves the battery characteristics of the nonaqueous electrolyte secondary battery. This is the main problem to be solved.
  • the nonaqueous electrolyte secondary battery (3) of the present invention comprises the electrolytic solution of the present invention and a negative electrode containing a silicon element and / or a tin element in the negative electrode active material.
  • Such a non-aqueous electrolyte secondary battery (3) of the present invention has an effect derived from the negative electrode active material by using a negative electrode active material containing silicon and / or tin and carbon together with the electrolytic solution of the present invention. Excellent battery characteristics are achieved through cooperation with the effects derived from the electrolyte.
  • the non-aqueous electrolyte secondary battery (4) of the present invention is a main problem to be solved by providing a non-aqueous electrolyte secondary battery having a metal oxide as a negative electrode active material and excellent in energy density and charge / discharge efficiency. is there.
  • a technique using a metal oxide capable of inserting and extracting lithium ions as a negative electrode active material for a non-aqueous electrolyte secondary battery is known.
  • this kind of metal oxide for example, lithium titanate is known.
  • non-aqueous electrolyte secondary battery using lithium titanate as a negative electrode it is considered that lithium occlusion and release reactions are performed stably, and as a result, deterioration of the active material is also suppressed. That is, it is known that a non-aqueous electrolyte secondary battery using this type of metal oxide as a negative electrode active material is excellent in cycle characteristics. On the other hand, non-aqueous electrolyte secondary batteries using this type of metal oxide as the negative electrode active material have a lower energy density at the negative electrode than non-aqueous electrolyte secondary batteries using carbon-based negative electrode active materials such as graphite. It has been known.
  • nonaqueous electrolyte secondary battery that uses a metal oxide as a negative electrode active material and has further improved battery characteristics.
  • the nonaqueous electrolyte secondary battery (4) of the present invention uses a metal oxide as a negative electrode active material and is excellent in battery characteristics.
  • the nonaqueous electrolyte secondary battery (5) of the present invention has the negative electrode active material layer containing the electrolyte of the present invention and graphite having a major axis / minor axis ratio (major axis / minor axis) of 1 to 5.
  • a negative electrode is a nonaqueous electrolyte secondary battery having further improved input / output characteristics. That is, when the electrolytic solution of the present invention is used, the input / output characteristics of the nonaqueous electrolyte secondary battery are improved.
  • graphite having a major axis / minor axis ratio (major axis / minor axis) of 1 to 5 is used as the negative electrode active material, so that the non-aqueous electrolyte secondary battery can be inserted. It is possible to further improve the output characteristics.
  • the electrolytic solution of the present invention includes 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 atom,
  • metal salt or simply “salt”
  • organic solvent having a hetero atom With respect to the peak intensity derived from the organic solvent in the vibrational spectrum, if the intensity of the peak inherent to the organic solvent is Io and the intensity of the peak obtained by wave number shifting of the peak inherent to the organic solvent is Is, Is> Io.
  • 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 anion of the salt 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 combine with R 1 or R 2 to form a ring.
  • R 3 X 3 Y General formula (2) (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 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 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 ) C ...
  • R 10 , R 11 , and 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 15 SO 3 ...
  • R 15 is a 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 may be a combination of an appropriate number of cations and anions described above.
  • One kind of metal salt may be adopted, 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.
  • 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
  • Examples of the organic solvent having a hetero element include a chain carbonate 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
  • 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”
  • D 1, 2-dimethoxyethane
  • organic solvents may be used alone or in combination as an electrolyte.
  • the electrolyte solution of the present invention has a peak in which the original peak of the organic solvent is shifted to Io with respect to the peak intensity derived from the organic solvent contained in the electrolyte solution of the present invention in the vibrational spectrum.
  • the intensity of the “shift peak” may be Is, where Is> Io. That is, in the vibrational spectroscopic spectrum chart obtained by subjecting the electrolytic solution of the present invention to vibrational spectroscopic 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 intensity Io of the original peak of the organic solvent and the value of the intensity Is of the shift peak 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 for 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.
  • 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 preferably satisfies the condition of Is> 2 ⁇ Io, more preferably satisfies the condition of Is> 3 ⁇ Io, and particularly preferably satisfies the condition of Is> 5 ⁇ Io.
  • 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.
  • 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 solvent (or preferential coordinating solvent) having a metal salt and a hetero element ) Is estimated to form a stable cluster. From the results of 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 with 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 viscosity ⁇ (mPa ⁇ s) of the electrolytic solution of the present invention is preferably in the range of 10 ⁇ ⁇ 500, more preferably in the range of 12 ⁇ ⁇ 400, further preferably in the range of 15 ⁇ ⁇ 300, and 18 ⁇ .
  • a range of ⁇ 150 is particularly preferred, and a range of 20 ⁇ ⁇ 140 is most preferred.
  • the electrolytic solution of the present invention exhibits excellent ionic conductivity. For this reason, the nonaqueous electrolyte secondary battery of this invention is excellent in a battery characteristic.
  • the ionic 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 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 described below is a value obtained by dividing the above d by the salt concentration c (mol / L).
  • d / c is 0.15 ⁇ d / c ⁇ 0.71, preferably 0.15 ⁇ d / c ⁇ 0.56, and 0.25 ⁇ d / c ⁇ 0. Within the range of .56, more preferably within the range of 0.26 ⁇ d / c ⁇ 0.50, and particularly preferably within the range of 0.27 ⁇ d / c ⁇ 0.47.
  • 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 ⁇ 0.48, and in the range of 0.25 ⁇ d / c ⁇ 0.38.
  • the range of 0.25 ⁇ d / c ⁇ 0.31 is still more preferable, and the range of 0.26 ⁇ d / c ⁇ 0.29 is still 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 0.34 ⁇ 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 electrolyte solution of the present invention is different in the environment in which the metal salt and the organic solvent are present, and has a high density. , Improvement in lithium transport number), improvement in the reaction rate between the electrode and the electrolyte solution, relaxation of uneven distribution of the salt concentration of the electrolyte that occurs during high-rate charge / discharge of the battery, and increase in the electric double layer capacity can be expected. Furthermore, in the electrolytic solution of the present invention, since the density is high, 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 electrolytic solution of the present invention it is presumed that a cluster is formed by coordination of two molecules of an organic solvent (or a preferential coordination solvent) having a hetero element with 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.
  • Table 1 individually illustrates the concentration (mol / L) of the electrolytic solution of the present invention.
  • 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.
  • an IR spectrum or a Raman spectrum can be exemplified.
  • the measurement method for IR measurement 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.
  • the vibrational spectroscopic measurement is preferably performed under conditions that can reduce or ignore the influence of moisture in the atmosphere.
  • IR measurement may be performed under low or no humidity conditions such as a dry room or a glove box, or Raman measurement may be performed with the electrolytic solution of the present invention 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 the wave numbers of organic solvents that are considered useful for the calculation of Io and Is and their attribution in the vibrational spectrum of the electrolytic solution of the present invention. 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.
  • the preferable Li concentration of the electrolytic solution of the present invention is about 2 to 5 times the Li concentration of a general electrolytic solution. 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 uneven distribution of Li concentration in the liquid can be considered. However, it has become clear that 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. In addition, due to the high viscosity of the electrolyte solution of the present invention, the liquid retention of the electrolyte solution at the electrode interface has been improved, and the state where the electrolyte solution is insufficient at the electrode interface (so-called liquid withdrawn state) has been suppressed. The reason is considered.
  • the electrolytic solution of the present invention contains a metal salt cation in a high concentration.
  • the distance between adjacent cations is extremely short.
  • cations such as lithium ions move between the positive electrode and the negative electrode during charge / discharge of the nonaqueous electrolyte secondary battery
  • the cations closest to the destination electrode are first supplied to the electrode.
  • the other cation adjacent to the said cation moves to the place with the said supplied cation.
  • the nonaqueous electrolyte secondary battery of the present invention has an S, O-containing film on the electrode (that is, the negative electrode and / or the positive electrode), and the S, O-containing film has an S ⁇ O structure. It is thought to contain many cations. It is considered that cations contained in the S, O-containing film are preferentially supplied to the electrode.
  • the cation transport rate is further improved by having an abundant cation source (that is, an S, O-containing film) in the vicinity of the electrode. Therefore, in the nonaqueous electrolyte secondary battery of the present invention, it is considered that excellent battery characteristics are exhibited by the cooperation of the electrolytic solution of the present invention and the S, O-containing film.
  • 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 dissolving 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, under heating conditions, the metal salt is added to the first electrolyte solution, the metal salt is dissolved, and a second electrolyte solution in a supersaturated state is prepared; and stirring and / or heating conditions, A third dissolving step of adding the metal salt to the second electrolytic solution, dissolving the metal salt, and preparing a third electrolytic solution;
  • the “supersaturated state” refers to 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.
  • heating here refers to warming a target object to 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 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.
  • 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, polymethacrylate, polymethyl methacrylate, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyethylene glycol dimethacrylate, polyethylene glycol acrylate, polyglycidol, polytetrafluoroethylene, polyhexa Fluoropropylene, polysiloxane, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, polyitaconic acid, polyfumaric acid, polycrotonic acid, polyangelic acid, polycarboxylic acids such as carboxymethylcellulose, styrene-butadiene rubber, nitrile-butadiene Rubber, polystyrene, polycarbonate, maleic anhydride and glycols copolymerized Sum polyesters, polyethylene oxide derivative having a substituent, a copolymer of vinylidene fluoride and hexafluoropropylene can be
  • 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.
  • 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 compounds represented by xLi 2 S- (1-x) P 2 S 5 , those obtained by substituting part of S of the compound with other elements, and compounds of 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 power storage devices such as batteries.
  • 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.
  • nonaqueous electrolyte secondary battery of the present invention using the electrolytic solution of the present invention will be described. Unless otherwise specified, it is considered that the nonaqueous electrolyte secondary batteries (1) to (5) of the present invention described above are all explained.
  • the nonaqueous electrolyte secondary battery includes a negative electrode having a negative electrode active material capable of occluding and releasing charge carriers such as lithium ions, a positive electrode having a positive electrode active material capable of occluding and releasing the charge carriers, and the electrolytic solution of the present invention With. Since the electrolytic solution of the present invention employs a lithium salt as a metal salt, it is particularly suitable as an electrolytic solution for a lithium ion secondary battery.
  • the negative electrode has a current collector and a negative electrode active material layer bound to the current collector surface.
  • 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 nonaqueous electrolyte 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. What collected the surface of the electrical power collector by the well-known method may be used as an electrical power collector.
  • 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, metal foils, such as copper foil, nickel foil, stainless steel foil, can be used suitably as a collector, for example.
  • the thickness is preferably in the range of 1 ⁇ m to 100 ⁇ m.
  • the negative electrode active material layer includes a negative electrode active material and generally a binder. Furthermore, you may contain a conductive support agent as needed.
  • the negative electrode active material in the nonaqueous electrolyte secondary battery (1) contains graphite having a G / D ratio of 3.5 or more.
  • the G / D ratio is the ratio of the G-band and D-band peaks in the Raman spectrum.
  • each peak appears in the G-band (1590cm -1 vicinity) and D-band (1350cm around -1), G-band 'is derived from the graphite structure, D-band' is to be attributed to a defect . Therefore, the higher the G / D ratio, which is the ratio of G-band to D-band, means that the graphite has fewer defects and higher crystallinity.
  • graphite having a G / D ratio of 3.5 or more may be referred to as high crystalline graphite
  • graphite having a G / D ratio of less than 3.5 may be referred to as low crystalline graphite.
  • graphite either natural graphite or artificial graphite can be used.
  • scaly graphite spherical graphite, massive graphite, earthy graphite, and the like can be used.
  • coated graphite whose surface is coated with a carbon material or the like can be used.
  • the negative electrode active material may be mainly high crystalline graphite having a G / D ratio of 3.5 or more, and may contain low crystalline graphite or amorphous carbon.
  • the negative electrode active material in the nonaqueous electrolyte secondary battery (2) includes a carbon material having a crystallite size of 20 nm or less.
  • a larger crystallite size means that the atoms are arranged periodically and accurately according to a certain rule.
  • a carbon material having a crystallite size of 20 nm or less has poor periodicity and accuracy.
  • the size of the graphite crystal is 20 nm or less, or due to the influence of strain, defects, impurities, etc., the regularity of the arrangement of the atoms constituting the graphite becomes poor.
  • the size is 20 nm or less.
  • the carbon material having a crystallite size of 20 nm or less is typically hard carbon or soft carbon, but the “carbon material having a crystallite size of 20 nm or less” in the nonaqueous electrolyte secondary battery (2) of the present invention is It is not limited to.
  • an X-ray diffraction method using CuK ⁇ rays as an X-ray source may be used.
  • L 0.94 ⁇ / ( ⁇ cos ⁇ ) here, L: Crystallite size ⁇ : Incident X-ray wavelength (1.54 mm) ⁇ : half width of peak (radian) ⁇ : Diffraction angle
  • Nonaqueous electrolyte secondary battery (3) contains a silicon element and / or a tin element. Silicon and tin are known to be negative electrode active materials that can greatly improve the capacity of the nonaqueous electrolyte secondary battery. Silicon and tin belong to group 14 elements. Since these simple substances can occlude and release a large number of charge carriers (lithium ions, etc.) per unit volume (mass), they become high-capacity negative electrode active materials. However, on the other hand, non-aqueous electrolyte secondary batteries using these as negative electrode active materials have relatively poor rate characteristics.
  • a non-aqueous electrolyte secondary battery using carbon as a negative electrode active material has excellent rate characteristics. Therefore, by using both of them as the negative electrode active material, the nonaqueous electrolyte secondary battery can have a high capacity, and excellent rate characteristics can be imparted to the nonaqueous electrolyte secondary battery.
  • Silicon has a large theoretical capacity when used as a negative electrode active material, but has a large volume change during charge and discharge. Therefore, as the negative electrode active material containing silicon element, it is particularly preferable to use SiO x (0.3 ⁇ x ⁇ 1.6) disproportionated into two phases of a Si phase and a silicon oxide phase.
  • the Si phase in SiO x can occlude and release lithium ions. This Si phase undergoes volume change (that is, expansion and contraction) as lithium ions are occluded and released.
  • Silicon oxide phase consists of SiO 2 or the like, the volume change due to charging and discharging as compared with Si phase is small.
  • SiO x as the negative electrode active material realizes a high capacity by the Si phase and suppresses the volume change of the entire negative electrode active material (or the negative electrode) by having the silicon oxide phase. If x is less than the lower limit, the Si ratio becomes excessive, so that the volume change at the time of charging / discharging becomes too large and the cycle characteristics deteriorate. On the other hand, when x exceeds the upper limit value, the Si ratio becomes too small and the energy density decreases.
  • the range of x is more preferably 0.5 ⁇ x ⁇ 1.5, and further preferably 0.7 ⁇ x ⁇ 1.2.
  • the alloying reaction by the silicon element contained in the lithium element and Si phase is believed to occur during charge and discharge of a nonaqueous electrolyte secondary battery. And it is thought that this alloying reaction contributes to charging / discharging of a nonaqueous electrolyte secondary battery (in this case, a lithium ion secondary battery). Similarly, it is considered that a negative electrode active material containing a tin element described later can be charged and discharged by an alloying reaction between a tin element and a lithium element.
  • Examples of the negative electrode active material containing tin element include Sn alone, tin alloy (Cu—Sn alloy, Co—Sn alloy), amorphous tin oxide, tin silicon oxide, and the like. Among them, the amorphous tin oxide SnB 0.4 P 0.6 O 3.1 is exemplified. The Suzukei containing oxide SnSiO 3 is illustrated.
  • the negative electrode active material containing silicon element and the negative electrode active material containing tin element can be combined with a material containing carbon element (carbon material).
  • a carbon material such as graphite is a material with less volume change at the time of charging / discharging as compared with a silicon simple substance or a tin simple substance. Therefore, by combining a negative electrode active material containing silicon element and a negative electrode active material containing tin element with such a carbon material, damage of the negative electrode due to volume change during charging and discharging can be suppressed. Durability is improved. As a result, the cycle characteristics of the nonaqueous electrolyte secondary battery are improved.
  • the composite of the negative electrode active material containing silicon element and / or the negative electrode active material containing tin element and the carbon material may be performed by a known method.
  • the carbon material to be combined with the negative electrode active material containing silicon element and / or the negative electrode active material containing tin element graphite, hard carbon (non-graphitizable carbon), soft carbon (graphitizable carbon), etc. are preferable. Can be used.
  • the particle diameter of graphite is not particularly limited, whether natural or artificial.
  • the negative electrode active material in the nonaqueous electrolyte secondary battery (4) contains a metal oxide that can occlude and release lithium ions.
  • a metal oxide that can occlude and release lithium ions.
  • titanium oxide such as TiO 2
  • lithium titanium oxide lithium titanium oxide
  • tungsten oxide such as WO 3
  • amorphous tin oxide tin silicon oxide, and the like.
  • lithium titanium oxide includes spinel lithium titanate (for example, Li 4 + x Ti 5 + y O 12 (x is ⁇ 1 ⁇ x ⁇ 4, y is ⁇ 1 ⁇ y ⁇ 1)), ramsdellite structure.
  • examples thereof include lithium titanate (for example, Li 2 Ti 3 O 7 ).
  • An example of the amorphous tin oxide is SnB 0.4 P 0.6 O 3.1 .
  • the Suzukei containing oxide SnSiO 3 is illustrated. Among these, it is particularly preferable to use spinel lithium titanate. More specifically, Li 4 Ti 5 O 12 is used.
  • a lithium ion secondary battery using lithium titanate as a negative electrode it is considered that the lithium occlusion and release reactions are performed stably, and as a result, the deterioration of the active material is also suppressed. . That is, it is known that a lithium ion secondary battery using such a metal compound as a negative electrode active material is excellent in cycle characteristics.
  • the metal oxide in combination with the non-aqueous electrolyte secondary battery of the present invention using the electrolytic solution of the present invention the excellent battery characteristics derived from the electrolytic solution of the present invention and the excellent cycle characteristics are compatible. A water electrolyte secondary battery can be obtained.
  • the negative electrode active material in the nonaqueous electrolyte secondary battery (5) includes graphite having a major axis / minor axis ratio (major axis / minor axis) of 1 to 5.
  • Typical graphite having a major axis / minor axis ratio (major axis / minor axis) of 1 to 5 includes spherical graphite, MCMB (mesocarbon microbeads), and the like.
  • Spherical graphite is a carbon material such as artificial graphite, natural graphite, graphitizable carbon, and non-graphitizable carbon, and has a spherical shape or a substantially spherical shape.
  • the spherical graphite particles are obtained by collecting the flakes and compressing them into a spherical shape while pulverizing the raw graphite with an impact pulverizer having a relatively small crushing force.
  • an impact pulverizer having a relatively small crushing force.
  • a hammer mill or a pin mill can be used as the impact pulverizer.
  • the outer peripheral linear velocity of the rotating hammer or pin is preferably about 50 to 200 m / sec.
  • the degree of spheroidization of graphite particles can be expressed by the ratio of the major axis to the minor axis of the particle (major axis / minor axis: hereinafter referred to as aspect ratio). That is, in an arbitrary cross section of the graphite particles, when the axis having the maximum aspect ratio is selected from the axes orthogonal to the center of gravity, the closer the aspect ratio is to 1, the closer to the true sphere. By the spheroidization treatment, the aspect ratio can be easily reduced to 5 or less (1 to 5). Further, if the spheroidization treatment is sufficiently performed, the aspect ratio can be made 3 or less (1 to 3).
  • the graphite used in the present invention has a particle aspect ratio of 1 to 5.
  • the aspect ratio is 1 or less, so that the diffusion path of the electrolytic solution in the negative electrode active material layer is shortened, so that the resistance component due to the electrolytic solution can be reduced, so that the input / output can be improved.
  • the aspect ratio is 1, the graphite has a shape closest to a true sphere, and the electrolyte solution diffusion path can be shortened to the shortest.
  • the ratio [I (110) / I (004)] of diffraction intensity derived from a crystal plane different from the basal plane such as I (110) is included, and how much flat graphite is included.
  • the graphite used in the present invention is preferably in a range where I (110) / I (004) is 0.03 to 1.
  • the graphite particles preferably have a BET specific surface area in the range of 0.5 to 15 m 3 / g. If the BET specific surface area exceeds 15 m 3 / g, the side reaction with the electrolytic solution tends to accelerate, and if it is less than 0.5 m 3 / g, the reaction resistance increases and the input / output may decrease.
  • the negative electrode active material is mainly graphite having an aspect ratio of 1 to 5, it can also contain graphite or amorphous carbon having an aspect ratio outside this range.
  • the nonaqueous electrolyte secondary battery (1) to the nonaqueous electrolyte secondary battery (5) of the present invention occlude charge carriers in addition to the characteristic negative electrode active material that can be used for each nonaqueous electrolyte secondary battery described above. And other negative electrode active materials that can be released.
  • the other negative electrode active material is referred to as a sub negative electrode active material as necessary.
  • the characteristic negative electrode active material in each of the nonaqueous electrolyte secondary batteries of the present invention is referred to as a main negative electrode active material.
  • the secondary negative electrode active material may be capable of occluding and releasing charge carriers, that is, lithium ions.
  • elemental elements that can be used as the secondary negative electrode active material include group 14 elements such as Li, carbon, silicon, germanium, and tin, group 13 elements such as aluminum and indium, group 12 elements such as zinc and cadmium, antimony, A group 15 element such as bismuth, an alkaline earth metal such as magnesium or calcium, and a group 11 element such as silver or gold may be employed alone.
  • the sub-negative electrode active material when silicon or the like is employed as the sub-negative electrode active material, one silicon atom reacts with a plurality of lithiums, so that a high-capacity active material is obtained. However, volume expansion and contraction due to insertion and extraction of lithium become significant. Such a problem may occur.
  • 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 to 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.
  • any one of the above-described sub-negative electrode active materials is used in combination with the metal oxide as the main negative electrode active material, so that non-metal oxide is used in comparison with the case where the metal oxide is used alone.
  • the capacity of the water electrolyte secondary battery can be further increased.
  • the main negative electrode active material and the sub negative electrode active material are used in combination, the main component of the negative electrode active material may be the main negative electrode active material.
  • the main negative electrode active material preferably occupies 50% by mass or more of the entire negative electrode active material, and more preferably 80% by mass or more.
  • the metal oxide negative electrode active material described above is selected from titanium oxide, lithium titanium oxide, tungsten oxide, amorphous tin oxide, and tin silicon oxide. At least one kind is a main component.
  • a main component here means that the applicable component is contained 50 mass% or more of the reference population.
  • the main components that is, titanium oxide, lithium titanium oxide, tungsten oxide, amorphous tin oxide, tin silicon oxide 50% by mass or more
  • the negative electrode can contain other inevitable ingredients.
  • Inevitable inclusions include, for example, Li, Fe, Cr, Cu, Zn, Ca, Mg, S, Si, Na, K, Al, Zr, Ti, P, Ga, Ge, V, Mo, Nb, W, La
  • the at least 1 element chosen from can be illustrated.
  • the binder plays a role of connecting the active material and the conductive additive 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, alkoxysilyl group-containing resins, polyacrylic acid ( Examples thereof include polymers having hydrophilic groups such as PAA) and carboxymethylcellulose (CMC).
  • a conductive additive contained in the negative electrode active material layer as necessary 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), vapor grown carbon fiber (Vapor Growth), which are carbonaceous fine particles. Carbon Fiber (VGCF) is exemplified. These conductive assistants can be added to the active material layer alone or in combination of two or more.
  • a negative electrode active material powder In order to produce a negative electrode of a non-aqueous electrolyte secondary battery, a negative electrode active material powder, a conductive auxiliary agent such as carbon powder, a binder, and an appropriate amount of solvent mixed to form a slurry, a roll coating method, It can be produced by applying on a current collector by a method such as a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method, and drying or curing the binder.
  • the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water.
  • the dried product In order to increase the electrode density, the dried product may be compressed.
  • a positive electrode used for a non-aqueous electrolyte secondary battery has a positive electrode active material that can occlude and release charge carriers.
  • 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.
  • non-aqueous electrolyte secondary battery of the present invention is a lithium ion secondary battery and the potential of the positive electrode is set to 4 V or more with respect to lithium, it is preferable to employ an aluminum current collector.
  • the electrolyte of the present invention hardly corrodes the aluminum current collector. That is, it is considered that the non-aqueous electrolyte secondary battery using the electrolytic solution of the present invention and using the aluminum current collector for the positive electrode hardly causes elution of Al even at a high potential. Although it is not clear why the elution of Al is unlikely to occur, the electrolytic solution of the present invention differs from the conventional electrolytic solution in the types of metal salt and organic solvent, the existing environment, and the metal salt concentration. For this reason, it is estimated that the solubility of Al in the electrolytic solution of the present invention may be lower than that of the conventional electrolytic solution.
  • 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 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 binder for the positive electrode and the conductive additive 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).
  • 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)
  • LiMPO 4 F such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (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 included in the basic composition may be substituted with another metal element.
  • a positive electrode active material that does not include a charge carrier that contributes to charge / discharge can also be used.
  • a positive electrode active material that does not include a charge carrier that contributes to charge / discharge can also be used.
  • S sulfur alone
  • metal sulfides such as TiS 2 , oxides such as V 2 O 5 and MnO 2 , polyaniline and anthraquinone, and these
  • a compound containing an aromatic in the chemical structure a conjugated material such as a conjugated diacetate-based organic substance, or other known materials can be used as the positive electrode active material.
  • a compound having a stable radical such as nitroxide, nitronyl nitroxide, galvinoxyl, phenoxyl, etc. may be adopted as the positive electrode active material.
  • the charge carrier may be added in an ionic state, or may be added in a nonionic state such as a metal or a compound.
  • a lithium foil or the like may be integrated by sticking to a positive electrode and / or a negative electrode.
  • the positive electrode may contain a conductive additive, a binder, and the like, similarly to the negative electrode.
  • the conductive auxiliary agent and the binder are not particularly limited as long as they can be used for the non-aqueous electrolyte secondary battery like the negative electrode described above.
  • a current collecting 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 can be used.
  • An active material may be applied to the surface of the body.
  • a composition for forming an active material layer 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 collected. After applying to the surface of the electric body, it is dried.
  • the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water.
  • the dried product may be compressed.
  • a separator is used for non-aqueous electrolyte secondary batteries as necessary.
  • the separator separates the positive electrode and the negative electrode and allows lithium ions to pass while preventing a short circuit of current due to contact between the two electrodes.
  • natural resins such as polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polymer), polyester, polyacrylonitrile, etc., polysaccharides such as cellulose, amylose, fibroin, keratin, lignin, suberin, etc. Examples thereof include porous bodies, nonwoven fabrics, and woven fabrics using one or more electrically insulating materials such as polymers and ceramics.
  • the separator may have a multilayer structure.
  • the electrolytic solution of the present invention has a slightly high viscosity and a high polarity
  • a membrane in which a polar solvent such as water can easily penetrate is preferable.
  • a film in which a polar solvent such as water soaks into 90% or more of the existing voids is more preferable.
  • a separator is sandwiched between the positive electrode and the negative electrode as necessary 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 to make a non-aqueous solution. It is preferable to use an electrolyte secondary battery.
  • the non-aqueous electrolyte 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.
  • a special structure SEI film derived from the electrolytic solution of the present invention is formed on the negative electrode surface and / or the positive electrode surface.
  • the SEI film includes S and O, and has an S ⁇ O structure. Therefore, the electrolytic solution of the present invention for producing the SEI film particularly contains sulfur element and oxygen element in the chemical structure of the anion of the salt.
  • the SEI film having the special structure is referred to as an S, O-containing film as necessary.
  • the S, O-containing coating contributes to improvement of battery characteristics (improvement of battery life, improvement of input / output characteristics, etc.) of the non-aqueous electrolyte secondary battery through cooperation with the electrolytic solution of the present invention.
  • the shape of the nonaqueous electrolyte 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.
  • the non-aqueous electrolyte secondary battery of the present invention may be mounted on a vehicle.
  • the vehicle may be a vehicle that uses electric energy from the non-aqueous electrolyte secondary battery for all or a part of its power source.
  • the vehicle may be an electric vehicle or a hybrid vehicle.
  • a non-aqueous electrolyte secondary battery is mounted on a vehicle, a plurality of non-aqueous electrolyte secondary batteries may be connected in series to form an assembled battery.
  • devices equipped with non-aqueous electrolyte secondary batteries include personal computers, portable communication devices, and various household electrical appliances driven by batteries, office equipment, industrial equipment, and the like.
  • non-aqueous electrolyte secondary battery 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 machinery, aircraft Power supplies for spacecrafts and / or auxiliary equipment, auxiliary power sources for vehicles that do not use electricity as power sources, mobile home robot power sources, system backup power sources, uninterruptible power supply power sources
  • it may be used for a power storage device that temporarily stores electric power required for charging in an electric vehicle charging station or the like.
  • the electrolytic solution of the present invention was produced as follows. About 5 mL of 1,2-dimethoxyethane, an organic solvent, was placed in a flask equipped with a stir bar and a thermometer. Under stirring conditions, (CF 3 SO 2 ) 2 NLi, which is a lithium salt, was gradually added to 1,2-dimethoxyethane in the flask so as to keep the solution temperature at 40 ° C. or lower and dissolved. When about 13 g of (CF 3 SO 2 ) 2 NLi was added, the dissolution of (CF 3 SO 2 ) 2 NLi temporarily stagnated. Therefore, the flask was put into a thermostat, and the solution temperature in the flask was 50 ° C.
  • (CF 3 SO 2 ) 2 NLi was dissolved.
  • the dissolution of (CF 3 SO 2 ) 2 NLi stagnated again, so 1 drop of 1,2-dimethoxyethane was added with a pipette (CF 3 SO 2 ) 2 NLi dissolved.
  • (CF 3 SO 2 ) 2 NLi was gradually added, and the entire amount of predetermined (CF 3 SO 2 ) 2 NLi was added.
  • the resulting electrolyte was transferred to a 20 mL volumetric flask and 1,2-dimethoxyethane was added until the volume was 20 mL. This was designated as an electrolytic solution E1.
  • 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.
  • the production was performed 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.
  • the concentration of (CF 3 SO 2 ) 2 NLi in the electrolytic solution E3 was 3.4 mol / L.
  • 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 By using 18.71 g of (FSO 2 ) 2 NLii, an electrolytic solution E9 having a concentration of (FSO 2 ) 2 NLi of 5.0 mol / L was produced in the same manner as the electrolytic solution E7. In the electrolytic solution E9, 2.1 molecules of acetonitrile are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E10 (Electrolytic solution E10) Using 20.21 g of (FSO 2 ) 2 NLi, an electrolytic solution E10 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 electrolyte solution E10, 2 molecules of acetonitrile are contained with respect to 1 molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E11 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 E11. The production was performed in a glove box under an inert gas atmosphere.
  • the concentration of (FSO 2 ) 2 NLi in the electrolytic solution E11 was 3.9 mol / L.
  • two molecules of dimethyl carbonate are contained with respect to one molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E12 Dimethyl carbonate was added to the electrolytic solution E11 for dilution to obtain an electrolytic solution E12 having a (FSO 2 ) 2 NLi concentration of 3.4 mol / L. In the electrolytic solution E12, 2.5 molecules of dimethyl carbonate are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E13 Dimethyl carbonate was added to the electrolytic solution E11 for dilution to obtain an electrolytic solution E13 having a (FSO 2 ) 2 NLi concentration of 2.9 mol / L. In the electrolytic solution E13, three molecules of dimethyl carbonate are contained with respect to one molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E14 Dimethyl carbonate was added to the electrolytic solution E11 for dilution to obtain an electrolytic solution E14 having a concentration of (FSO 2 ) 2 NLi of 2.6 mol / L. In the electrolytic solution E14, 3.5 molecules of dimethyl carbonate are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E15 Dimethyl carbonate was added to the electrolytic solution E11 for dilution to obtain an electrolytic solution E15 having a (FSO 2 ) 2 NLi concentration of 2.0 mol / L. In the electrolytic solution E15, five molecules of dimethyl carbonate are contained with respect to one molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E16 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 E16. The production was performed in a glove box under an inert gas atmosphere.
  • the concentration of (FSO 2 ) 2 NLi in the electrolytic solution E16 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 E17 The electrolyte solution E16 was diluted by adding ethyl methyl carbonate to obtain an electrolyte solution E17 having a (FSO 2 ) 2 NLi concentration of 2.9 mol / L. In the electrolytic solution E17, 2.5 molecules of ethyl methyl carbonate are contained per 1 molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E18 The electrolyte solution E16 was diluted by adding ethyl methyl carbonate to obtain an electrolyte solution E18 having a concentration of (FSO 2 ) 2 NLi of 2.2 mol / L. In the electrolytic solution E18, 3.5 molecules of ethyl methyl carbonate are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E19 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 E19. The production was performed in a glove box under an inert gas atmosphere.
  • the concentration of (FSO 2 ) 2 NLi in the electrolytic solution E19 was 3.0 mol / L.
  • two molecules of diethyl carbonate are contained with respect to one molecule of (FSO 2 ) 2 NLi.
  • Electrolytic solution E20 Diethyl carbonate was added to the electrolytic solution E19 for dilution to obtain an electrolytic solution E20 having a (FSO 2 ) 2 NLi concentration of 2.6 mol / L. In the electrolytic solution E20, 2.5 molecules of diethyl carbonate are contained with respect to (FSO 2 ) 2 NLi1 molecules.
  • Electrolytic solution E21 Diethyl carbonate was added to the electrolytic solution E19 for dilution to obtain an electrolytic solution E21 having a (FSO 2 ) 2 NLi concentration of 2.0 mol / L. In the electrolytic solution E21, 3.5 molecules of diethyl carbonate 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”) was used as the organic solvent, and 3.04 g of LiPF 6 was used as the lithium salt.
  • Electrolytic solution C6 Dimethyl carbonate was added to the electrolytic solution E11 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 E16 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 E19 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 E10, 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 to 2400 cm ⁇ 1 are shown in FIGS. 1 to 10, respectively. Further, IR measurement was performed on the electrolytic solutions E11 to E21, 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 E10 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 solutions E1 and E2 electrolytic solutions E4 to E6, E8, E11, E16, and E19 all exhibited ion conductivity. Therefore, it can be understood that the electrolytic solution of the present invention can function as an electrolytic solution for various batteries.
  • 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.
  • the maximum volatilization rates of the electrolytic solutions E2, E4, E8, E11, and E13 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. It was confirmed that the electrolytic solution of the present invention is difficult to burn.
  • Electrolytes E11, E13, E16, and E19 were placed in containers, 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.
  • Evaluation Example 7 Raman spectrum measurement
  • FIGS. 29 to 35 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 ), and the vertical axis represents the scattering intensity.
  • the electrolyte was sealed in a quartz cell under an inert gas atmosphere and used for measurement.
  • a characteristic peak derived from (FSO 2 ) 2 N of LiFSA dissolved in acetonitrile was observed in 700 to 800 cm ⁇ 1 of the Raman spectra of the electrolytic solutions E8, E9, and C4 shown in FIGS. .
  • FIGS. 29 to 31 it can be seen from FIGS. 29 to 31 that the peak shifts to the higher wavenumber side as the LiFSA concentration increases.
  • a characteristic peak derived from (FSO 2 ) 2 N of LiFSA dissolved in dimethyl carbonate is observed in 700 to 800 cm ⁇ 1 of the Raman spectra of the electrolytic solutions E11, E13, E15, and C6 shown in FIGS. Observed.
  • the peak shifts to the higher wavenumber side as the concentration of LiFSA increases. This phenomenon is similar to that discussed in the previous paragraph.
  • the concentration of the electrolyte is increased, the state in which (FSO 2 ) 2 N corresponding to the anion of the salt interacts with a plurality of Li is shown in the spectrum. It is inferred that the result is reflected.
  • Li transport numbers of the electrolytic solutions E2, E8, C4 and C5 were measured under the following conditions.
  • the NMR tube containing each electrolyte solution was supplied to a PFG-NMR apparatus (ECA-500, JEOL), and the spin echo method was used for 7Li and 19F under conditions of 500 MHz and a magnetic field gradient of 1.26 T / m.
  • the diffusion coefficient of Li ions and anions in each electrolyte was measured while changing the magnetic field pulse width.
  • the Li transport number of the electrolytic solutions E2 and E8 was significantly higher than the Li transport number of the electrolytic solutions C4 and 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.
  • electrolyte solution E8 the Li transport number at the time of changing temperature was measured according to the said Li transport number measurement conditions. The results are shown in Table 8. From the results in Table 8, it can be seen that the electrolytic solution of the present invention maintains a suitable Li transport number regardless of the temperature. It can be said that the electrolytic solution of the present invention maintains a liquid state even at a low temperature.
  • electrolytic solution of the present invention includes 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 production was performed 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 9 shows a list of the electrolyte solutions.
  • Non-aqueous electrolyte secondary battery The nonaqueous electrolyte secondary battery (1) to the nonaqueous electrolyte secondary battery (5) will be specifically described below. In the following embodiments, items are described separately for convenience, and therefore may be duplicated. The following examples and EB and CB described later may correspond to a plurality of examples of the nonaqueous electrolyte secondary battery (1) to the nonaqueous electrolyte secondary battery (5). ⁇ Nonaqueous electrolyte secondary battery (1)> Example 1-1
  • a nonaqueous electrolyte secondary battery of Example 1-1 was produced using the electrolytic solution E8.
  • the graphite (A) powder used was subjected to Raman spectrum analysis.
  • the G / D ratio which is the intensity ratio of the G-band and D-band peaks, was 12.2.
  • This slurry was applied to the surface of an electrolytic copper foil (current collector) having a thickness of 20 ⁇ m using a doctor blade, and a negative electrode active material layer was formed on the copper foil.
  • the current collector and the negative electrode active material layer were firmly and closely joined with a roll press. This was vacuum-dried at 120 ° C. for 6 hours to form a negative electrode having a negative electrode active material layer thickness of about 30 ⁇ m.
  • the basis weight of the negative electrode active material layer was 2.3 mg / cm 2 and the density was 0.86 g / cm 3 .
  • Nonaqueous electrolyte secondary battery A non-aqueous electrolyte secondary battery was produced using the produced negative electrode as an evaluation electrode.
  • the counter electrode was a metal lithium foil (thickness 500 ⁇ m).
  • This nonaqueous electrolyte secondary battery is a nonaqueous electrolyte secondary battery for evaluation, a so-called half cell.
  • the counter electrode was cut to ⁇ 13 mm, the evaluation electrode was cut to ⁇ 11 mm, and a separator (Whatman glass fiber filter paper) having a thickness of 400 ⁇ m was sandwiched between them to form an electrode body battery.
  • This electrode body battery was accommodated in a battery case (CR2032 coin cell manufactured by Hosen Co., Ltd.). Then, electrolyte solution E8 was injected, and the battery case was sealed to obtain a nonaqueous electrolyte secondary battery of Example 1-1. Details of the lithium battery of Example 1-1 and the nonaqueous electrolyte secondary batteries of the following examples and comparative examples are shown in Table 41 at the end of the column of Examples.
  • Example 1-2 Example 1-1 was used except that SNO grade graphite (average particle size 10 ⁇ m) graphite (hereinafter sometimes referred to as graphite (B)) from SEC Carbon Co. was used instead of graphite (A). A negative electrode was produced, and the nonaqueous electrolyte secondary battery of Example 1-2 was obtained in the same manner as in Example 1-1. The graphite (B) used was subjected to Raman spectrum analysis in the same manner as in Example 1-1. As a result, the G / D ratio, which is the intensity ratio of the G-band and D-band peaks, was 4.4.
  • Example 1-3 A negative electrode was prepared in the same manner as in Example 1-1 except that graphite (C) having an average particle diameter of 10 ⁇ m was used in place of graphite (A), and the other examples were the same as in Example 1-1. -3 non-aqueous electrolyte secondary battery was obtained.
  • the graphite (C) used was subjected to Raman spectrum analysis in the same manner as in Example 1-1. As a result, the G / D ratio, which is the intensity ratio of the G-band and D-band peaks, was 16.0.
  • Example 1-4 A nonaqueous electrolyte secondary battery of Example 1-4 was obtained in the same manner as Example 1-3 except that the electrolytic solution E11 was used.
  • Example 1-1 (Comparative Example 1-1) Example 1-1 was used except that graphite of the product name SG-BH (average particle size 20 ⁇ m) (hereinafter sometimes referred to as graphite (D)) of Ito Graphite Industries Co., Ltd. was used instead of graphite (A). A negative electrode was produced in the same manner, and the nonaqueous electrolyte secondary battery of Comparative Example 1-1 was obtained in the same manner as in Example 1-1. The graphite (D) used was subjected to Raman spectrum analysis in the same manner as in Example 1-1. As a result, the G / D ratio, which is the intensity ratio of the G-band and D-band peaks, was 3.4.
  • Example 1-1 was used except that instead of graphite (A), graphite with the product name SG-BH8 (average particle size: 8 ⁇ m) of Ito Graphite Industries Co., Ltd. (hereinafter sometimes referred to as graphite (E)) was used.
  • a negative electrode was produced in the same manner, and the nonaqueous electrolyte secondary battery of Comparative Example 1-2 was obtained in the same manner as in Example 1-1.
  • the graphite (E) used was subjected to Raman spectrum analysis in the same manner as in Example 1-1. As a result, the G / D ratio, which is the intensity ratio of the G-band and D-band peaks, was 3.2.
  • Comparative Example 1-3 A nonaqueous electrolyte secondary battery of Comparative Example 1-3 was obtained in the same manner as Example 1-1 except that the electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • Comparative Example 1-4 A nonaqueous electrolyte secondary battery of Comparative Example 1-4 was obtained in the same manner as Example 1-2 except that the electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • Comparative Example 1-5 A nonaqueous electrolyte secondary battery of Comparative Example 1-5 was obtained in the same manner as Example 1-3 except that the electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • Comparative Example 1-6 A nonaqueous electrolyte secondary battery of Comparative Example 1-6 was obtained in the same manner as Comparative Example 1-1 except that the electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • Comparative Example 1-7 A nonaqueous electrolyte secondary battery of Comparative Example 1-7 was obtained in the same manner as Comparative Example 1-2 except that the electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • Table 6 shows the configurations of the nonaqueous electrolyte secondary batteries of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-7.
  • Example 1-5 In the non-aqueous electrolyte secondary battery of Example 1-5, the same negative electrode as in Example 1-1 was used.
  • This slurry was applied to the surface of an aluminum foil (current collector) using a doctor blade and dried to produce a positive electrode having a positive electrode active material layer having a thickness of about 25 ⁇ m.
  • NCM 523 Li [Ni 0.5 Co 0.2 Mn 0.3 ] O 2 is referred to as NCM 523 as necessary.
  • ⁇ Nonaqueous electrolyte secondary battery> Using the positive electrode, the negative electrode, and the electrolytic solution E8, a laminated lithium ion secondary battery, which is a kind of non-aqueous electrolyte secondary battery, was manufactured. Specifically, an experimental filter paper having a thickness of 260 ⁇ m 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. Then, the electrolyte solution of the present invention was injected into the bag-like laminated film. Thereafter, the remaining one side was sealed to obtain a laminate type lithium ion secondary battery in which the four sides were hermetically sealed and the electrode plate group and the electrolyte were sealed. Note that the positive electrode and the negative electrode have a tab that can be electrically connected to the outside, and a part of the tab extends to the outside of the laminated lithium ion secondary battery.
  • Example 1-6 A nonaqueous electrolyte secondary battery of Example 1-6 was produced in the same manner as Example 1-5 except that the electrolytic solution E4 was used.
  • Comparative Example 1-8 A nonaqueous electrolyte secondary battery of Comparative Example 1-8 was obtained in the same manner as Example 1-5 except that the electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • FIG. 46 shows a DSC chart of the nonaqueous electrolyte secondary batteries of Example 1-5 and Comparative Example 1-8
  • FIG. 47 shows a DSC chart of the nonaqueous electrolyte secondary batteries of Example 1-6 and Comparative Example 1-8. Respectively.
  • nonaqueous electrolyte secondary battery of Example 1-1 has a current capacity approximately twice that of Comparative Example 1-1 in the range of 0.5 C to 2 C, and can be charged at high speed.
  • Comparative Examples 1-1 and 1-2 it is difficult to improve the cycle capacity retention rate only by combining a negative electrode using graphite having a G / D ratio of less than 4 as a negative electrode active material and the electrolytic solution of the present invention. Further, as in Comparative Examples 1-3 and 1-7, when a conventional electrolyte is used, it is difficult to improve the rate capacity characteristics regardless of the G / D ratio of graphite. However, as in Examples 1-1 to 1-3, by combining the electrolytic solution of the present invention with a negative electrode using graphite having a G / D ratio of 3.5 or more as a negative electrode active material, Both the cycle capacity maintenance rate can be improved.
  • the higher the G / D ratio the more the rate capacity characteristics and the cycle capacity retention rate tend to be improved, and it is considered that the G / D ratio is more preferably 10 or more.
  • the electrolytic solution is the electrolytic solution of the present invention, and the G / D ratio is 3.5 or more. It can be understood that the rate capacity characteristics and the cycle capacity retention ratio are improved by using the graphite together.
  • Example 1--7 ⁇ Negative electrode>
  • SNO grade graphite (average particle size: 15 ⁇ m) graphite (hereinafter sometimes referred to as graphite (A)) manufactured by SEC Carbon Co., Ltd. was used. 98 parts by mass of graphite (A) as a negative electrode active material, 1 part by mass of styrene butadiene rubber as a binder, and 1 part by mass of carboxymethyl cellulose were mixed. This mixture was dispersed in an appropriate amount of ion-exchanged water to prepare a slurry-like negative electrode mixture.
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • the graphite (A) powder used was subjected to Raman spectrum analysis.
  • the G / D ratio which is the intensity ratio of the G-band and D-band peaks, was 12.2.
  • This slurry was applied to the surface of an electrolytic copper foil (current collector) having a thickness of 20 ⁇ m using a doctor blade, and a negative electrode active material layer was formed on the copper foil.
  • the positive electrode includes a positive electrode active material layer and a current collector covered with the positive electrode active material layer.
  • the positive electrode active material layer has a positive electrode active material, a binder, and a conductive additive.
  • the positive electrode active material is made of LiNi 0.5 Co 0.2 Mn 0.3 O 2 .
  • the binder is made of PVDF, and the conductive additive is made of AB.
  • the current collector is made of an aluminum foil having a thickness of 20 ⁇ m.
  • NCM523, PVDF and AB are mixed so as to have the above mass ratio, and NMP as a solvent is added to obtain a paste-like positive electrode material.
  • the paste-like positive electrode material was applied to the surface of the current collector using a doctor blade to form a positive electrode active material layer.
  • the positive electrode active material layer was dried at 80 ° C. for 20 minutes to remove NMP by volatilization.
  • the aluminum foil having the positive electrode active material layer formed on the surface thereof was compressed using a roll press, and the aluminum foil and the positive electrode active material layer were firmly bonded.
  • the joined product was heated in a vacuum dryer at 120 ° C. for 6 hours, cut into a predetermined shape, and a positive electrode was obtained.
  • Nonaqueous electrolyte secondary battery of Example 1-7 was obtained in the same manner as Example 1-5, except that the above positive electrode, negative electrode, and electrolytic solution E8 were used, and a cellulose nonwoven fabric (thickness 20 ⁇ m) was used as the separator. It was.
  • Comparative Example 1-9 A nonaqueous electrolyte secondary battery of Comparative Example 1-9 was obtained in the same manner as Example 1-7, except that electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • Evaluation conditions are 80% charged state (SOC), 0 ° C., 25 ° C., operating voltage range 3V-4.2V, and capacity 13.5 mAh.
  • SOC 80%, 0 ° C. is a region in which input characteristics are difficult to be obtained, for example, when used in a refrigerator room.
  • the input characteristics of Example 1-7 and Comparative Example 1-9 were evaluated three times for 2-second input and 5-second input, respectively.
  • Tables 12 and 13 show the evaluation results of the input characteristics. “2-second input” in the table means an input after 2 seconds from the start of charging, and “5-second input” means an input after 5 seconds from the start of charging.
  • Example 1-7 At both 0 ° C. and 25 ° C., the input (charging) characteristics of Example 1-7 are improved compared to Comparative Example 1-9. This is an effect obtained by using graphite having a GD ratio of 3.5 or more and the electrolytic solution of the present invention. In particular, since it exhibits a high input (charge) characteristic even at 0 ° C., lithium in the electrolytic solution even at a low temperature. It is shown that the movement of ions proceeds smoothly.
  • Example 1-8 A nonaqueous electrolyte secondary battery of Example 1-8 using the electrolytic solution E11 was produced as follows.
  • the copper foil coated with the slurry was dried to remove NMP, and then the copper foil was pressed to obtain a bonded product.
  • the obtained joined product was heat-dried at 120 ° C. for 6 hours with a vacuum dryer to obtain a copper foil on which an active material layer was formed. This was the working electrode.
  • the mass of the active material on copper foil was 2.214 mg, and the mass of the active material per 1 cm ⁇ 2> of copper foil was 1.48 mg.
  • the density of natural graphite and PVdF before pressing was 0.68 g / cm 3
  • the density of the active material layer after pressing was 1.025 g / cm 3 .
  • the counter electrode was metal Li.
  • the working electrode, the counter electrode, and the electrolytic solution E11 were accommodated in a battery case (CR2032 type coin cell case manufactured by Hosen Co., Ltd.) having a diameter of 13.82 mm to obtain a nonaqueous electrolyte secondary battery of Example 1-8.
  • a battery case CR2032 type coin cell case manufactured by Hosen Co., Ltd.
  • Example 1-9 A nonaqueous electrolyte secondary battery of Example 1-9 was obtained in the same manner as in Example 1-8, except that electrolytic solution E8 was used instead of electrolytic solution E11.
  • Example 1-10 A nonaqueous electrolyte secondary battery of Example 1-10 was obtained in the same manner as in Example 1-8, except that electrolytic solution E16 was used instead of electrolytic solution E11.
  • Example 1-11 A nonaqueous electrolyte secondary battery of Example 1-11 was obtained in the same manner as in Example 1-8, except that electrolytic solution E19 was used instead of electrolytic solution E11.
  • Comparative Example 1-10 A nonaqueous electrolyte secondary battery of Comparative Example 1-10 was obtained in the same manner as Example 1-8 except that the electrolytic solution C5 was used instead of the electrolytic solution E11.
  • nonaqueous electrolyte secondary batteries of Examples 1-8 to 1-11 are reversibly charged and discharged in the same manner as the general nonaqueous electrolyte secondary battery of Comparative Example 1-10.
  • the nonaqueous electrolyte secondary batteries of Examples 1-8 to 1-11 had a capacity reduction at rates of 0.2 C, 0.5 C, and 1 C compared to the nonaqueous electrolyte secondary battery of Comparative Example 1-10. It is suppressed. From these results, it was confirmed that the nonaqueous electrolyte secondary battery of each example, that is, the nonaqueous electrolyte secondary battery of the present invention showed excellent rate characteristics. Furthermore, the nonaqueous electrolyte secondary batteries of Examples 1-8 and 1-9 are suppressed in capacity reduction even at the rate of 2C compared to the nonaqueous electrolyte secondary battery of Comparative Example 1-10. That is, the nonaqueous electrolyte secondary batteries of Examples 1-8 and 1-9 show particularly excellent rate characteristics.
  • Each non-aqueous electrolyte secondary battery is CC charged (constant current charge) to 25 ° C. and a voltage of 2.0 V, and is subjected to CC discharge (constant current discharge) to a voltage of 0.01 V.
  • a discharge cycle was performed. Specifically, first, charge / discharge is performed for 3 cycles at a charge / discharge rate of 0.1C, and then charge / discharge is performed for each charge / discharge rate in 3 cycles in the order of 0.2C, 0.5C, 1C, 2C, 5C, Finally, 3 cycles of charge and discharge were performed at 0.1 C.
  • any of the nonaqueous electrolyte secondary batteries performed a charge / discharge reaction satisfactorily and exhibited a suitable capacity retention rate.
  • the capacity retention rates of the half cells of Examples 1-9, 1-10, and 1-11 were remarkably excellent.
  • Example 1-12 A nonaqueous electrolyte secondary battery of Example 1-12 was obtained in the same manner as Example 1-2 except that the electrolytic solution E9 was used.
  • the voltage curve of the nonaqueous electrolyte secondary battery of Example 1-12 at each current rate is higher than the voltage curve of the nonaqueous electrolyte secondary battery of Comparative Example 1-4. You can see that. From this result, it was confirmed that the nonaqueous electrolyte secondary battery of the present invention exhibits excellent rate characteristics even in a low temperature environment.
  • the nonaqueous electrolyte secondary battery of Example 1-2 has a capacity higher than that of the nonaqueous electrolyte secondary battery of Comparative Example 1-4 at any rate of 0.2C, 0.5C, 1C, and 2C. The decline of the was suppressed. That is, the non-aqueous electrolyte secondary battery of Example 1-2 exhibited excellent rate characteristics. This result also confirmed that the non-aqueous electrolyte secondary battery of the present invention using the electrolytic solution of the present invention exhibits excellent rate characteristics.
  • the nonaqueous electrolyte secondary battery of Comparative Example 1-4 has a tendency to increase the polarization when a current is passed at a rate of 1 C with repeated charge and discharge, and the capacity obtained from reaching 2 V to 0.01 V Fell rapidly.
  • the nonaqueous electrolyte secondary battery of Example 1-2 there was almost no increase or decrease in polarization even after repeated charge and discharge, and the capacity was suitably maintained. This can also be confirmed from the fact that the three curves overlap in FIG.
  • the reason why the polarization increased in the nonaqueous electrolyte secondary battery of Comparative Example 1-4 is that the amount sufficient for the reaction interface with the electrode due to the uneven Li concentration generated in the electrolyte when rapidly charging and discharging was repeated. It can be considered that the electrolyte solution can no longer supply Li, that is, the Li concentration of the electrolyte solution is unevenly distributed. In the non-aqueous electrolyte secondary battery of Example 1-2, it is considered that the uneven distribution of the Li concentration of the electrolytic solution could be suppressed by using the electrolytic solution of the present invention having a high Li concentration.
  • the measuring device was manufactured by Rigaku [SmartLab], and the optical system was a concentration method.
  • This slurry was applied to the surface of an electrolytic copper foil (current collector) having a thickness of 20 ⁇ m using a doctor blade, and a negative electrode active material layer was formed on the copper foil.
  • Nonaqueous electrolyte secondary battery Using the negative electrode produced above as an evaluation electrode, a non-aqueous electrolyte secondary battery was produced.
  • the counter electrode was a metal lithium foil (thickness 500 ⁇ m).
  • the counter electrode was cut to ⁇ 13 mm, the evaluation electrode was cut to ⁇ 11 mm, and a separator (Whatman glass fiber filter paper) having a thickness of 400 ⁇ m was sandwiched between them to form an electrode body battery.
  • This electrode body battery was accommodated in a battery case (CR2032 coin cell manufactured by Hosen Co., Ltd.). Then, the electrolyte solution E8 was injected, the battery case was sealed, and the nonaqueous electrolyte secondary battery of Example 2-1 was obtained. Details of the nonaqueous electrolyte secondary battery of Example 2-1 and the nonaqueous electrolyte secondary batteries of the following examples and comparative examples are shown in Table 42 at the end of the column of Examples.
  • Comparative Example 2-1 A nonaqueous electrolyte secondary battery of Comparative Example 2-1 was obtained in the same manner as in Example 2-1, except that the electrolytic solution C5 was used instead of the electrolytic solution E8.
  • FIG. 57 clearly shows that the nonaqueous electrolyte secondary battery of Example 2-1 can be charged and discharged. Also, from FIG. 58, the nonaqueous electrolyte secondary battery of Example 2-1 has better rate capacity characteristics than the nonaqueous electrolyte secondary battery of Comparative Example 2-1, and functions as a battery for high-speed charging and high input / output. I understand that
  • Example 2-2 A negative electrode was produced in the same manner as in Example 1-1 except that soft carbon having a crystallite size (L) of 4.2 nm was selected and this soft carbon was used. A nonaqueous electrolyte secondary battery of Example 2-2 was obtained in the same manner as Example 1-1 except that this negative electrode was used.
  • Example 2-3 A nonaqueous electrolyte secondary battery of Example 2-3 was obtained in the same manner as Example 2-1, except that the electrolytic solution E11 was used.
  • Example 2-4 A nonaqueous electrolyte secondary battery of Example 2-4 was obtained in the same manner as Example 2-2, except that the same electrolytic solution E11 as in Example 2-3 was used.
  • Comparative Example 2-2 A negative electrode was produced in the same manner as in Example 2-1, except that graphite having a crystallite size (L) of 28 nm was selected and this graphite was used. A nonaqueous electrolyte secondary battery of Comparative Example 2-2 was obtained in the same manner as in Example 2-1, except that this negative electrode was used.
  • Example 2-3 A negative electrode was produced in the same manner as in Example 2-1, except that graphite having a crystallite size (L) of 42 nm was selected and this graphite was used.
  • a nonaqueous electrolyte secondary battery of Comparative Example 2-3 was obtained in the same manner as Example 2-1, except that this negative electrode was used.
  • Example 2-4 Using the same hard carbon as in Example 2-1, a negative electrode was produced in the same manner as in Example 2-1.
  • a nonaqueous electrolyte secondary battery of Comparative Example 2-4 was obtained in the same manner as in Example 2-1, except that this negative electrode was used and the electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • Example 2-5 Using the same soft carbon as in Example 2-2, a negative electrode was produced in the same manner as in Example 2-1.
  • a nonaqueous electrolyte secondary battery of Comparative Example 2-5 was obtained in the same manner as in Example 2-1, except that this negative electrode was used and the electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • Comparative Example 2-6 A negative electrode was produced in the same manner as in Comparative Example 2-2.
  • a nonaqueous electrolyte secondary battery of Comparative Example 2-6 was obtained in the same manner as in Example 2-1, except that this negative electrode was used and the electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • Comparative Example 2--7 A negative electrode was produced in the same manner as in Comparative Example 2-3.
  • a nonaqueous electrolyte secondary battery of Comparative Example 2-7 was obtained in the same manner as in Example 2-1, except that this negative electrode was used and the electrolytic solution C5 was used instead of the electrolytic solution of the present invention.
  • Example 3-1 A nonaqueous electrolyte secondary battery of Example 3-1 was manufactured using the above-described electrolytic solution E8 and a negative electrode active material made of silicon-carbon composite powder.
  • the silicon-carbon composite powder is obtained by mixing Si powder having a particle diameter of 50 nm and acetylene black at a mass ratio of 6: 4 and using a planetary ball mill to form a composite.
  • lithium foil metallic lithium
  • electrolytic solution E8 electrolytic solution E8
  • a non-aqueous electrolyte secondary battery was manufactured using the above negative electrode, positive electrode and electrolyte. Specifically, a Whatman glass fiber filter paper having a thickness of 400 ⁇ m was sandwiched between the positive electrode and the negative electrode to form an electrode plate group. This electrode group was accommodated in a battery case (CR2032 coin cell manufactured by Hosen Co., Ltd.). An electrolytic solution was further injected into the battery case. After injecting the electrolyte, the battery case was sealed to obtain the nonaqueous electrolyte secondary battery of Example 3-1. Details of the nonaqueous electrolyte secondary battery of Example 4-1 and each of the following batteries are shown in Table 43 at the end of the column of the example.
  • Example 3-2 The nonaqueous electrolyte secondary battery of Example 3-2 is the same as the nonaqueous electrolyte secondary battery of Example 3-1, except for the composition of the negative electrode mixture.
  • the negative electrode mixture in the non-aqueous electrolyte secondary battery of Example 3-2 was 75 parts by mass of silicon-carbon composite powder as the negative electrode active material, 15 parts by mass of graphite as the negative electrode active material, and as the binder. And 10 parts by mass of polyamideimide (PAI).
  • PAI polyamideimide
  • Example 3-3 The nonaqueous electrolyte secondary battery of Example 3-3 is the same as the nonaqueous electrolyte secondary battery of Example 3-2 except that the electrolytic solution E11 is used.
  • Comparative Example 3-1 The non-aqueous electrolyte secondary battery of Comparative Example 3-1 is the same as the non-aqueous electrolyte secondary battery of Example 3-1 except that the electrolytic solution C5 was used.
  • Comparative Example 3-2 The nonaqueous electrolyte secondary battery of Comparative Example 3-2 is the same as the nonaqueous electrolyte secondary battery of Example 3-2 except that the same electrolytic solution C5 as Comparative Example 3-1 was used.
  • the constant current (CC) charge / discharge was performed with respect to each nonaqueous electrolyte secondary battery.
  • the voltage range was 2V to 0.01V, and the C rate was 0.1C.
  • Table 19 shows the discharge capacity of each non-aqueous electrolyte secondary battery.
  • the charge / discharge curves of the nonaqueous electrolyte secondary batteries of Example 3-2 and Comparative Example 3-2 are shown in FIG.
  • a charge / discharge curve of the nonaqueous electrolyte secondary battery of Example 3-3 is shown in FIG.
  • Example 3-1 and Comparative Example 3-1 use the same negative electrode mixture
  • Example 3-2 and Comparative Example 3-2 use the same negative electrode mixture.
  • the non-aqueous electrolyte secondary battery of Example 3-1 using the same negative electrode mixture was compared with the non-aqueous electrolyte secondary battery of Comparative Example 3-1, and Example 3-2 using the same negative electrode mixture
  • the discharge capacity of the non-aqueous electrolyte secondary battery is improved by using the electrolyte solution of the present invention as the electrolyte solution.
  • the nonaqueous electrolyte secondary battery using DMC as the organic solvent for the electrolytic solution is similar to the nonaqueous electrolyte secondary battery of the example. It turns out that it fully charges / discharges. From this result, it can be seen that the electrolytic solution of the present invention using a chain carbonate as an organic solvent is also useful for combining with a composite material of silicon and carbon.
  • Example 4-1 A nonaqueous electrolyte secondary battery of Example 4-1 was manufactured using the above-described electrolytic solution E8.
  • the negative electrode in the nonaqueous electrolyte secondary battery of Example 4-1 includes a negative electrode active material, a binder, and a conductive additive.
  • a negative electrode active material 90 parts by mass of lithium titanate (Li 4 Ti 5 O 12 , so-called LTO) as a negative electrode active material, 2 parts by mass of SBR as a binder, 2 parts by mass of CMC as a binder, and ketjen black (as a conductive additive) 6 parts by weight of KB) was taken and mixed.
  • This mixture was dispersed in an appropriate amount of ion-exchanged water to prepare a slurry-like negative electrode mixture.
  • This negative electrode mixture was applied to the negative electrode current collector in a film form using a doctor blade.
  • the negative electrode current collector a copper foil having a thickness of 20 ⁇ m was used.
  • the composite of the negative electrode mixture and the negative electrode current collector was dried and then pressed using a roller press to obtain a bonded product.
  • the bonded product after pressing was heated in a vacuum dryer at 100 ° C. for 6 hours, and cut into a predetermined shape to obtain a negative electrode.
  • the nonaqueous electrolyte secondary battery of Example 4-1 As the positive electrode in the nonaqueous electrolyte secondary battery of Example 4-1, lithium foil (metallic lithium) was used. That is, the nonaqueous electrolyte secondary battery of Example 4-1 is a half cell for evaluation. By charging and discharging the half cell, the effect of the negative electrode and the electrolyte on the battery characteristics of the nonaqueous electrolyte secondary battery can be evaluated.
  • a non-aqueous electrolyte secondary battery was manufactured using the above negative electrode, positive electrode, and electrolytic solution E8. Specifically, a Whatman glass fiber filter paper having a thickness of 400 ⁇ m was sandwiched between the positive electrode and the negative electrode to form an electrode plate group. This electrode group was accommodated in a battery case (CR2032 coin cell manufactured by Hosen Co., Ltd.). An electrolytic solution was further injected into the battery case. After injecting the electrolytic solution, the battery case was sealed to obtain the nonaqueous electrolyte secondary battery of Example 4-1. Details of the nonaqueous electrolyte secondary battery of Example 4-1 and each of the following batteries are shown in Table 44 at the end of the column of the example.
  • Example 4-2 The nonaqueous electrolyte secondary battery of Example 4-2 was manufactured in the same manner as Example 4-1, except that the electrolytic solution E11 was used instead of the electrolytic solution E8.
  • Example 4-3 The nonaqueous electrolyte secondary battery of Example 4-3 was manufactured in the same manner as Example 4-1, except that the electrolytic solution E13 was used instead of the electrolytic solution E8.
  • Example 4-1 The nonaqueous electrolyte secondary battery of Comparative Example 1 is different from Example 4-1 in the components of the electrolytic solution. In the nonaqueous electrolyte secondary battery of Comparative Example 4-1, the electrolytic solution C5 was used. Other configurations are the same as those of the embodiment 4-1.
  • FIG. 61 shows the charge / discharge curve (second cycle) of the nonaqueous electrolyte secondary battery of Example 4-1
  • FIG. 62 shows the charge / discharge curve (second cycle) of the half cell of Comparative Example 4-1. Based on the charge / discharge curves shown in FIG. 61 and FIG.
  • Example 4-1 discharge of the nonaqueous electrolyte secondary batteries of Example 4-1 and Comparative Example 4-1
  • the energy density at the time (mWh / g) and the charge / discharge efficiency (%) were calculated.
  • the energy density is a density per 1 g of the negative electrode active material layer (that is, solid mass of LTO, binder, etc.).
  • the charge / discharge efficiency was calculated based on (energy density during discharge / energy density during charge) ⁇ 100 (%).
  • Table 20 shows the energy density and charge / discharge efficiency of the nonaqueous electrolyte secondary batteries of Example 4-1 and Comparative Example 4-1. Charge / discharge efficiency can also be rephrased as energy efficiency.
  • the non-aqueous electrolyte secondary batteries of Example 4-1 and Comparative Example 4-1 using lithium titanium oxide (LTO) as the negative electrode active material differ only in the electrolyte solution.
  • LTO lithium titanium oxide
  • the energy density and the charge / discharge efficiency vary greatly depending on the electrolyte.
  • the non-aqueous electrolyte secondary battery of Example 4-1 using the electrolytic solution of the present invention has a higher energy than the non-aqueous electrolyte secondary battery of Comparative Example 4-1 using a normal electrolytic solution. High density and excellent charge / discharge efficiency. As shown in FIGS.
  • the magnitude of polarization in the nonaqueous electrolyte secondary battery of Example 4-1 is the same as that of the nonaqueous electrolyte 2 of Comparative Example 4-1. It is smaller than the magnitude of polarization in the secondary battery. Therefore, it is considered that the nonaqueous electrolyte secondary battery of Example 4-1 is superior in energy density and charge / discharge efficiency as compared with the nonaqueous electrolyte secondary battery of Comparative Example 4-1.
  • the electrolyte solution of the present invention used in the nonaqueous electrolyte secondary battery of Example 4-1 contains a large amount of cation of the supporting salt. In the nonaqueous electrolyte secondary battery of Example 4-1, It is presumed that since the cation is sufficiently supplied to the negative electrode, the reaction resistance is lowered and the polarization is suppressed.
  • non-aqueous electrolyte secondary battery of Example 4-1 uses lithium titanium oxide as the negative electrode active material. For this reason, the non-aqueous electrolyte secondary battery of Example 4-1 is provided with excellent cycle characteristics derived from lithium titanium oxide.
  • the working voltage range was 1.3 V to 2.5 V (Li standard), and the C rate was 0.1 C.
  • CC charging / discharging was repeated 3 cycles.
  • the charge / discharge curve of the nonaqueous electrolyte secondary battery of Example 4-2 is shown in FIG. 63
  • the charge / discharge curve of the nonaqueous electrolyte secondary battery of Example 4-3 is shown in FIG. As shown in FIGS.
  • Example 5-1 A nonaqueous electrolyte secondary battery of Example 5-1 was produced using the electrolytic solution E8.
  • ⁇ Negative electrode> 98 parts by mass of Ito Graphite Industries Co., Ltd. product name SG-BH8 (average particle size 8 ⁇ m), and 1 part by mass of SBR and 1 part by mass of CMC as a binder were mixed. This mixture was dispersed in an appropriate amount of ion-exchanged water to prepare a slurry.
  • the graphite particles used had an aspect ratio of 2.1, and I (110) / I (004) measured by X-ray diffraction was 0.035.
  • the aspect ratio was calculated by measuring the major axis and the minor axis of the active material section using a scanning electron microscope (SEM) after preparing an electrode section observation sample using a JEOL cross section polisher.
  • SEM scanning electron microscope
  • X-ray diffraction was measured by Rigaku [SmartLab], using an optical system using a concentration method, and I (110) / I (004) was calculated from the ratio of integrated intensities of I (110) and I (004). .
  • the slurry was applied in the form of a film using a doctor blade on the surface of an electrolytic copper foil (current collector) having a thickness of 20 ⁇ m.
  • the copper foil coated with the slurry was dried to remove water, and then the copper foil was pressed to obtain a bonded product.
  • the obtained joined product was dried by heating at 100 ° C. for 6 hours with a vacuum dryer to obtain a copper foil on which a negative electrode active material layer was formed. This was used as a negative electrode.
  • the basis weight of the negative electrode active material layer in this negative electrode was about 8.5 mg / cm 2 .
  • the positive electrode includes a positive electrode active material layer and a current collector covered with the positive electrode active material layer.
  • the positive electrode active material layer has a positive electrode active material, a binder, and a conductive additive.
  • the positive electrode active material is NCM523.
  • the binder is made of PVdF.
  • the conductive auxiliary agent is made of AB.
  • the current collector is made of an aluminum foil having a thickness of 20 ⁇ m.
  • NCM523, PVdF and AB are mixed so as to have the above mass ratio, and NMP as a solvent is added to obtain a paste-like positive electrode material.
  • the paste-like positive electrode material was applied to the surface of the current collector using a doctor blade to form a positive electrode active material layer.
  • the positive electrode active material layer was dried at 80 ° C. for 20 minutes to remove NMP by volatilization.
  • the aluminum foil having the positive electrode active material layer formed on the surface thereof was compressed using a roll press, and the aluminum foil and the positive electrode active material layer were firmly bonded.
  • the joined product was heated in a vacuum dryer at 120 ° C. for 6 hours, cut into a predetermined shape, and a positive electrode was obtained.
  • ⁇ Nonaqueous electrolyte secondary battery> Using the positive electrode, the negative electrode, and the electrolytic solution E8, a laminated lithium ion secondary battery, which is a kind of non-aqueous electrolyte secondary battery, was manufactured. Specifically, a cellulose nonwoven fabric (thickness 20 ⁇ m) was sandwiched as a separator 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 was poured into the bag-like laminated film.
  • this lithium ion secondary battery is referred to as the nonaqueous electrolyte secondary battery of Example 5-1. Details of the non-aqueous electrolyte secondary battery of Example 5-1 and each of the following batteries are shown in Table 45 at the end of the column of the example.
  • Example 5-1 A negative electrode was produced in the same manner as in Example 5-1, except that graphite having an aspect ratio of 6.5 (SNO grade (average particle size: 10 ⁇ m) from SEC Carbon Co., Ltd.) was used as the active material. A negative electrode having the same basis weight as in Example 5-1 was formed. Other than that, a nonaqueous electrolyte secondary battery of Comparative Example 5-1 was obtained in the same manner as Example 5-1. I (110) / I (004) measured by X-ray diffraction was 0.027.
  • Comparative Example 5-2 A nonaqueous electrolyte secondary battery of Comparative Example 5-2 was obtained in the same manner as in Example 5-1, except that the electrolytic solution C5 was used instead of the electrolytic solution E8.
  • Evaluation conditions are 80% charged state (SOC), 0 ° C., 25 ° C., operating voltage range 3V-4.2V, and capacity 13.5 mAh.
  • SOC 80%, 0 ° C. is a region in which input characteristics are difficult to be obtained, for example, when used in a refrigerator room.
  • the input characteristics of Example 5-1 and Comparative Examples 5-1 and 5-2 were evaluated three times for 2-second input and 5-second input, respectively.
  • Tables 21 and 22 show the evaluation results of the input characteristics. “2-second input” in the table means an input after 2 seconds from the start of charging, and “5-second input” means an input after 5 seconds from the start of charging.
  • Example 5-1 and Comparative Example 5-1 the electrolytic solution of the present invention used in Example 5-1 and Comparative Example 5-1 is abbreviated as “FSA”, and the electrolytic solution used in Comparative Example 5-2 is designated as “ECPF”. Abbreviated.
  • Example 5-1 At both 0 ° C. and 25 ° C., the input / output characteristics of Example 5-1 are improved compared to Comparative Example 5-1 and Comparative Example 5-2.
  • graphite having a predetermined aspect ratio since it exhibits high input / output characteristics even at 0 ° C., the migration of lithium ions in the electrolytic solution can be achieved even at low temperatures. It has been shown to proceed smoothly.
  • the positive electrode includes a positive electrode active material layer and a current collector covered with the positive electrode active material layer.
  • the positive electrode active material layer has a positive electrode active material, a binder, and a conductive additive.
  • the positive electrode active material is NCM523.
  • the binder is made of PVdF.
  • the conductive auxiliary agent is made of AB.
  • the current collector is made of an aluminum foil having a thickness of 20 ⁇ m.
  • NCM523, PVdF and AB were mixed at the above mass ratio, and NMP as a solvent was added to obtain a paste-like positive electrode mixture.
  • the paste-like positive electrode mixture was applied to the surface of the current collector using a doctor blade to form a positive electrode active material layer.
  • the positive electrode active material layer was dried at 80 ° C. for 20 minutes to remove NMP by volatilization.
  • the aluminum foil having the positive electrode active material layer formed on the surface thereof was compressed using a roll press, and the aluminum foil and the positive electrode active material layer were firmly bonded.
  • the joined product was heated in a vacuum dryer at 120 ° C. for 6 hours, cut into a predetermined shape, and a positive electrode was obtained.
  • the negative electrode includes a negative electrode active material layer and a current collector covered with the negative electrode active material layer.
  • the negative electrode active material layer has a negative electrode active material and a binder.
  • 98 parts by mass of graphite as a negative electrode active material and 1 part by mass of SBR and 1 part by mass of CMC were mixed as a binder. This mixture was dispersed in an appropriate amount of ion-exchanged water to prepare a slurry-like negative electrode mixture.
  • the slurry-like negative electrode mixture was applied to a copper foil having a thickness of 20 ⁇ m, which is a negative electrode current collector, so as to form a film using a doctor blade to form a negative electrode active material layer.
  • the composite material of the negative electrode active material layer and the current collector was dried and pressed, and the bonded product after pressing was heated in a vacuum dryer at 100 ° C. for 6 hours, cut into a predetermined shape, and used as a negative electrode.
  • the graphite particles used had an aspect ratio of 2.1.
  • Nonaqueous electrolyte secondary battery of Example 5-2 was obtained in the same manner as in Example 5-1, except that the above positive electrode and negative electrode were used and the above-described electrolytic solution E11 was used as the electrolytic solution.
  • Comparative Example 5-3 A nonaqueous electrolyte secondary battery of Comparative Example 5-3 was obtained in the same manner as in Example 5-2 except that the electrolytic solution C5 was used instead of the electrolytic solution E11.
  • Example 25 Cycle durability
  • the battery was charged to 4.1 V under the conditions of CC charging at a temperature of 25 ° C. and 1 C, and after resting for 1 minute, the CC of 1 C
  • 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 at the 500th cycle was measured, and the results are shown in Table 23.
  • 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).
  • FIG. 65 shows the change in the discharge capacity retention rate during the cycle test.
  • the amount of voltage change when the CC discharge was performed for 10 seconds at 3 C was measured from the difference between the post-voltage and the current value according to Ohm's law.
  • the non-aqueous electrolyte secondary battery of Example 5-2 has a low resistance even after cycling.
  • the nonaqueous electrolyte secondary battery of Example 5-2 has a high capacity retention rate and is hardly deteriorated.
  • the nonaqueous electrolyte secondary battery of the present invention can take will be described in more detail with reference to test examples and reference test examples.
  • the non-aqueous electrolyte secondary battery of the test example is EB
  • the non-aqueous electrolyte secondary battery of the reference test example is CB.
  • the difference between EB and CB lies in the electrolytic solution, and EB uses the electrolytic solution of the present invention.
  • a film S, O-containing film
  • the following nonaqueous electrolyte secondary batteries include those described above.
  • a nonaqueous electrolyte secondary battery EB1 using the electrolytic solution E8 was produced as follows.
  • the positive electrode was produced in the same manner as the positive electrode of the non-aqueous electrolyte secondary battery in Example 5-1, and the negative electrode was produced in the same manner as the negative electrode in the non-aqueous electrolyte secondary battery in Example 5-2.
  • a nonaqueous electrolyte secondary battery EB1 was obtained in the same manner as in Example 5-1, except that experimental filter paper (Toyo Filter Paper Co., Ltd., cellulose, thickness: 260 ⁇ m) was used as the separator.
  • experimental filter paper Toyo Filter Paper Co., Ltd., cellulose, thickness: 260 ⁇ m
  • the nonaqueous electrolyte secondary battery EB2 is the same as EB1 except that the electrolytic solution E4 is used.
  • the nonaqueous electrolyte secondary battery EB3 is the same as EB1 except that the electrolytic solution E11 is used.
  • the nonaqueous electrolyte secondary battery EB4 is the same as EB1 except that the electrolytic solution E11 is used, the mixing ratio of the positive electrode active material, the conductive additive and the binder, and the separator.
  • the basis weight of the active material layer in the positive electrode was 5.5 mg / cm 2 and the density was 2.5 g / cm 3 .
  • the basis weight of the active material layer in the negative electrode was 3.8 mg / cm 2 , and the density was 1.1 g / cm 3 .
  • a cellulose nonwoven fabric with a thickness of 20 ⁇ m was used as the separator.
  • the nonaqueous electrolyte secondary battery EB5 is the same as EB4 except that the electrolytic solution E8 is used.
  • EB6 In the nonaqueous electrolyte secondary battery EB6, the type of the binder for the negative electrode and the mixing ratio of the negative electrode active material and the binder are the same as those of EB4.
  • the nonaqueous electrolyte secondary battery EB7 is the same as EB6 except that the electrolytic solution E8 is used.
  • the nonaqueous electrolyte secondary battery CB1 is the same as EB1 except that the electrolytic solution C5 is used.
  • the nonaqueous electrolyte secondary battery CB2 is the same as EB4 except that the electrolytic solution C5 is used.
  • the nonaqueous electrolyte secondary battery CB3 is the same as EB6 except that the electrolytic solution C5 is used.
  • the film formed on the negative electrode surface of EB1 to EB7 is abbreviated as the negative electrode S, O-containing film of EB1 to EB7, and the film formed on the negative electrode surface of CB1 to CB3 is referred to as CB1 to CB3.
  • CB3 negative electrode film Abbreviated as CB3 negative electrode film.
  • the film formed on the surface of the positive electrode in EB1 to EB7 is abbreviated as the film containing the positive electrode S, O of EB1 to EB7, and the film formed on the surface of the positive electrode in CB1 to CB3 is made of CB1 to CB3.
  • FIG. 70 shows the result of analysis for elemental sulfur.
  • the electrolytic solution in EB1 and the electrolytic solution in EB2 contain sulfur element (S), oxygen element and nitrogen element (N) in the salt.
  • the electrolyte solution in CB1 does not contain these in the salt.
  • the electrolyte solutions in EB1, EB2, and CB1 all contain a fluorine element (F), a carbon element (C), and an oxygen element (O) in the salt.
  • each of the negative electrode S, O-containing film and the negative electrode film contains a component derived from the chemical structure of the anion of the metal salt (that is, the supporting salt).
  • S elemental sulfur
  • FIG. 70 The analysis result of elemental sulfur (S) shown in FIG. 70 was analyzed in more detail. About the analysis result of EB1 and EB2, peak separation was performed using the Gauss / Lorentz mixed function. 71 shows the analysis result of EB1, and FIG. 72 shows the analysis result of EB2.
  • the negative electrode film of CB1 did not contain S exceeding the detection limit, but S was detected from the negative electrode S, O-containing film of EB1 and the negative electrode S, O-containing film of EB2. Further, the negative electrode S, O-containing film of EB1 contained more S than the negative electrode S, O-containing film of EB2. Since S was not detected from the negative electrode S, O-containing film of CB1, S contained in the negative electrode S, O-containing film of each test example was derived from inevitable impurities and other additives contained in the positive electrode active material. It can be said that it originates from the metal salt in the electrolyte solution.
  • the S element ratio in the negative electrode S, O-containing film of EB1 is 10.4 atomic% and the S element ratio in the negative electrode S, O-containing film of EB2 is 3.7 atomic%
  • the S element ratio in the negative electrode S, O-containing film is 2.0 atomic% or more, preferably 2.5 atomic% or more, more preferably 3.0 atomic% or more, More preferably, it is 3.5 atomic% or more.
  • the elemental ratio (atomic%) of S indicates the peak intensity ratio of S when the sum of the peak intensities of S, N, F, C, and O is 100% as described above.
  • the upper limit value of the element ratio of S is not particularly defined, but to be strong, it should be 25 atomic% or less.
  • FIGS. 73 is a BF (Bright-field) -STEM image
  • FIGS. 74 to 76 are element distribution images by STEM-EDX in the same observation region as FIG. 74 shows the analysis result for C
  • FIG. 75 shows the analysis result for O
  • FIG. 76 shows the analysis result for S. 74 to 76 show the analysis results of the negative electrode in the discharged nonaqueous electrolyte secondary battery.
  • FIG. 73 there is a black portion in the upper left part of the STEM image. This black part is derived from Pt deposited in the pretreatment of FIB processing.
  • a portion above the Pt-derived portion (referred to as a Pt portion) can be regarded as a contaminated portion after Pt deposition. Therefore, in FIGS. 74 to 76, only the portion below the Pt portion was examined.
  • C was layered below the Pt portion. This is considered to be a layered structure of graphite as a negative electrode active material.
  • O exists in the part corresponding to the outer periphery and interlayer of graphite.
  • S exists in the part corresponding to the outer periphery and interlayer of graphite. From these results, it is surmised that the negative electrode S, O-containing film containing S and O, such as the S ⁇ O structure, is formed between the surface and the interlayer of graphite.
  • the thickness of the negative electrode S, O-containing film increases after charging. From this result, it is presumed that the negative electrode S, O-containing film has a fixing portion that stably exists with respect to charging and discharging and an adsorption portion that increases and decreases with charging and discharging. And it is estimated that the thickness of the negative electrode S, O-containing film increased or decreased during charging / discharging due to the presence of the adsorbing portion.
  • the positive electrode S, O-containing film of EB1 also contains S and O.
  • the positive electrode S, O-containing film of EB1 also has an S ⁇ O structure derived from the electrolytic solution of the present invention, like the negative electrode S, O-containing film of EB1. I understand that.
  • the height of the peak existing in the vicinity of 529 eV decreases after the cycle.
  • This peak is considered to indicate the presence of O derived from the positive electrode active material.
  • photoelectrons excited by O atoms in the positive electrode active material pass through the S, O-containing coating and are detected. It is thought that it was done. Since this peak decreased after the cycle, it is considered that the thickness of the S, O-containing film formed on the positive electrode surface increased with the cycle.
  • O and S in the positive electrode S and O-containing film increased during discharging and decreased during charging. From this result, it is considered that O and S enter and leave the positive electrode S and O-containing film with charge and discharge. From this fact, the concentration of S and O in the positive electrode S and O-containing coating is increased or decreased during charging or discharging, or the presence of an adsorbing portion in the positive electrode S and O-containing coating as well as the negative electrode S and O-containing coating. It is estimated that the thickness increases or decreases.
  • the positive electrode S, O-containing coating and the negative electrode S, O-containing coating were analyzed by XPS.
  • EB4 was set to 25 ° C. and a working voltage range of 3.0 V to 4.1 V, and CC charge / discharge was repeated 500 cycles at a rate of 1C.
  • the XPS spectrum of the positive electrode S, O-containing film was measured in a discharge state of 3.0 V and a charge state of 4.0 V.
  • the negative electrode S, O-containing coating in the 3.0V discharge state before the cycle test (that is, after the first charge / discharge) and the negative electrode S, O-containing coating in the 3.0V discharge state after 500 cycles are measured by XPS.
  • FIG. 79 and FIG. 80 show the analysis results of the positive electrode S, O-containing film of EB4 measured by XPS. Specifically, FIG. 79 shows the analysis result for sulfur element, and FIG. 80 shows the analysis result for oxygen element.
  • Table 26 shows the S element ratio (atomic%) of the negative electrode S, O-containing coating. The S element ratio was calculated in the same manner as the above-mentioned item “S element ratio of negative electrode S, O-containing film”.
  • the negative electrode S, O-containing film of EB4 contained 2.0 atomic% or more of S even after the first charge / discharge and after 500 cycles. From this result, it can be seen that the negative electrode S, O-containing film in the nonaqueous electrolyte secondary battery of the present invention contains 2.0 atomic% or more of S before or after the cycle.
  • EB4 to EB7 and CB2 and CB3 were subjected to a high temperature storage test that was stored at 60 ° C. for 1 week.
  • the positive electrode S, O-containing film and negative electrode S, O-containing film of EB4 to EB7, and CB2, CB3 The positive electrode film and the negative electrode film were analyzed.
  • CC-CV charging was performed at a rate of 0.33 C from 3.0 V to 4.1 V.
  • the charge capacity at this time was set as a standard (SOC100), 20% of the standard was CC discharged and adjusted to SOC80, and then a high-temperature storage test was started.
  • CC-CV discharge was performed to 3.0V at 1C.
  • membrane was measured.
  • 81 to 84 show the analysis results of the positive electrode S, O-containing films of EB4 to EB7 and the positive electrode films of CB2 and CB3 measured by XPS.
  • 85 to 88 show the analysis results of the EB4 to EB7 negative electrode S, O-containing films and the CB2 and CB3 negative electrode films measured by XPS.
  • FIG. 81 shows the analysis results for the elemental sulfur in the positive electrode S, O-containing coatings of EB4 and EB5 and the positive electrode coating of CB2.
  • FIG. 82 shows the analysis results of the elemental sulfur of the positive electrode S, O-containing film of EB6 and EB7 and the positive electrode film of CB3.
  • FIG. 83 shows the analysis results of oxygen elements in the positive electrode S, O-containing film of EB4 and EB5 and the positive electrode film of CB2.
  • FIG. 84 shows analysis results of oxygen elements in the positive electrode S, O-containing films of EB6 and EB7 and the positive electrode film of CB3.
  • FIG. 81 shows the analysis results for the elemental sulfur in the positive electrode S, O-containing coatings of EB4 and EB5 and the positive electrode coating of CB2.
  • FIG. 82 shows the analysis results of the elemental sulfur of the positive electrode S, O-containing film of EB6 and EB7 and the positive electrode film of CB3.
  • FIG. 83 shows
  • FIG. 85 shows the analysis results of sulfur elements in the negative electrode S, O-containing films of EB4 and EB5 and the negative electrode film of CB2.
  • FIG. 86 shows the analysis results of sulfur elements in the negative electrode S, O-containing films of EB6 and EB7 and the negative electrode film of CB3.
  • FIG. 87 shows the results of analysis of oxygen elements in the negative electrode S, O-containing films of EB4 and EB5 and the negative electrode film of CB2.
  • FIG. 88 shows the analysis results of oxygen elements in the negative electrode S, O-containing films of EB6 and EB7 and the negative electrode film of CB3.
  • CB2 and CB3 using the conventional electrolytic solution do not contain S in the positive electrode film
  • EB4 to EB7 using the electrolytic solution of the present invention contain positive electrodes S and O.
  • the film contained S.
  • EB4 to EB7 all contained O in the positive electrode S, O-containing coating.
  • a peak around 170 eV indicating the presence of SO 2 (S ⁇ O structure) was detected from the positive electrode S, O-containing films in EB4 to EB7.
  • a stable positive electrode S containing S and O is used both when AN is used as the organic solvent for the electrolytic solution and when DMC is used. It can be seen that an O-containing film is formed. Moreover, since this positive electrode S, O containing film is not influenced by the kind of negative electrode binder, it is thought that O in the positive electrode S, O containing film does not originate in CMC. Further, as shown in FIGS. 83 and 84, when DMC was used as the organic solvent for the electrolyte, an O peak derived from the positive electrode active material was detected in the vicinity of 530 eV. For this reason, when DMC is used as the organic solvent for the electrolytic solution, it is considered that the thickness of the positive electrode S, O-containing film is thinner than when AN is used.
  • the XPS spectra of the negative electrode S, O-containing film and the negative electrode film after the above high-temperature storage test and discharge were measured, and the discharge in the negative electrode S, O-containing film of EB4, EB5 and the negative electrode film of CB2
  • the ratio of S element at the time was calculated. Specifically, for each negative electrode S, O-containing film or negative electrode film, the element ratio of S was calculated when the sum of the peak intensities of S, N, F, C, and O was 100%. The results are shown in Table 27.
  • the negative electrode film of CB2 did not contain S exceeding the detection limit, but S was detected from the negative electrode S, O-containing films of EB4 and EB5. Further, the negative electrode S, O-containing film of EB5 contained more S than the negative electrode S, O-containing film of EB4. Further, from this result, it is understood that the S element ratio in the negative electrode S, O-containing film is 2.0 atomic% or more even after high temperature storage.
  • EB8 uses the electrolytic solution E11.
  • E11 is the same as the nonaqueous electrolyte secondary battery of Example 5-1, except for the composition of the negative electrode mixture, the mixing ratio of the negative electrode active material and the conductive additive, the separator, and the electrolytic solution.
  • EB9 uses the electrolytic solution E13.
  • EB9 is the same as EB8 except for the electrolytic solution.
  • EB10 is the same as EB8 except that electrolytic solution E8 is used.
  • CB4 is the same as EB8 except that electrolytic solution C5 is used.
  • CC charging / discharging that is, constant current charging / discharging
  • room temperature in the range of 3.0 V to 4.1 V (vs. Li standard).
  • the AC impedance after the first charge / discharge and the AC impedance after 100 cycles were measured.
  • the reaction resistances of the electrolytic solution, the negative electrode, and the positive electrode were each analyzed.
  • FIG. 89 two circular 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) is called the first arc.
  • 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. 89 continuous with the first arc.
  • Table 28 shows the resistance (so-called solution resistance) of the electrolytic solution after the first charge / discharge, the reaction resistance of the negative electrode, and the reaction resistance of the positive electrode
  • Table 29 shows each resistance after 100 cycles.
  • the negative electrode reaction resistance and the positive electrode reaction resistance after 100 cycles tend to be lower than the respective resistances after the first charge / discharge.
  • each non-aqueous electrolyte secondary battery has a difference in durability even though the same polymer (CMC-SBR) having a hydrophilic group is used as a binder for the negative electrode. That is, after 100 cycles shown in Table 29, the negative electrode reaction resistance and the positive electrode reaction resistance of the nonaqueous electrolyte secondary batteries of EB8, EB9, and EB10 are the negative electrode reaction resistance and the positive electrode reaction resistance of the nonaqueous electrolyte secondary battery of CB4.
  • CMC-SBR polymer having a hydrophilic group
  • the non-aqueous electrolyte secondary battery of CB4 did not use the electrolytic solution of the present invention, whereas the non-aqueous electrolyte secondary batteries of EB8, EB9, and EB10 used the electrolytic solution of the present invention. It is thought to be caused by. That is, it can be said that the nonaqueous electrolyte secondary battery of the present invention using the electrolytic solution of the present invention is excellent in durability because the reaction resistance is reduced after the cycle.
  • EB8, EB9, and EB10 use the electrolytic solution of the present invention, and S and O-containing films derived from the electrolytic solution of the present invention are formed on the surfaces of the negative electrode and the positive electrode.
  • CB4 which does not use the electrolytic solution of the present invention, the S, O-containing film is not formed on the surfaces of the negative electrode and the positive electrode.
  • the negative electrode reaction resistance and the positive electrode reaction resistance of EB8, EB9, and EB10 are lower than CB4. From this, in each test example, it is guessed that the negative electrode reaction resistance and the positive electrode reaction resistance were reduced due to the presence of the S, O-containing film derived from the electrolytic solution of the present invention.
  • the solution resistance of the electrolyte solution in EB10 and CB4 is substantially the same, and the solution resistance of the electrolyte solution in EB8 and EB9 is higher than that of EB10 and CB4.
  • the solution resistance of each electrolyte solution in each non-aqueous electrolyte secondary battery is substantially the same after the first charge / discharge and after 100 cycles. For this reason, it is considered that durability deterioration of each electrolyte solution does not occur, and the difference between the negative electrode reaction resistance and the positive electrode reaction resistance generated in the above reference test examples and test examples is not related to the durability deterioration of the electrolyte solution. It is thought that this occurs in the electrode itself.
  • the internal resistance of the non-aqueous electrolyte 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 28 and Table 29, it can be said that EB8 and EB9 are particularly excellent in durability, and then EB10 is excellent in durability from the viewpoint of suppressing the increase in internal resistance of the nonaqueous electrolyte secondary battery. .
  • EC in the electrolytic solution is considered to be a material for the SEI film.
  • EC is blended in the electrolytic solution.
  • EB8 EB9, and EB10 did not include EC as a material for SEI, they exhibited a capacity retention rate equivalent to that of CB4 including EC. This is thought to be because the S and O-containing coating derived from the electrolytic solution of the present invention is present on the positive electrode and the negative electrode in the nonaqueous electrolyte secondary battery of each test example.
  • EB8 showed a very high capacity retention rate even after 500 cycles, and was particularly excellent in durability. Therefore, when DMC was selected as the organic solvent, it was more durable than when AN was selected. It can be said that the property is improved.
  • the remaining capacity of EB8 and EB10 is larger than the remaining capacity of CB4. From this result, it can be said that the S, O-containing coating derived from the electrolytic solution of the present invention and formed on the positive electrode and the negative electrode contributes to an increase in the remaining capacity.
  • Nonaqueous electrolyte secondary battery EB11 was produced in the same manner as EB1 except for the basis weight of the positive electrode and the negative electrode.
  • the basis weight of the active material layer in the positive electrode was 5.5 mg / cm 2
  • the basis weight of the active material layer in the negative electrode was 4.0 mg / cm 2 .
  • the basis weight of the active material layer here refers to the basis weight after roll press and drying.
  • the basis weight of the active material layer in the positive electrode was 11.0 mg / cm 2
  • the basis weight of the active material layer in the negative electrode was 8.0 mg / cm 2 .
  • Nonaqueous electrolyte secondary battery CB5 was produced in the same manner as CB1 except for the weights of the positive electrode and the negative electrode.
  • the basis weight of the active material layer in the positive electrode was 5.5 mg / cm 2 as in EB11, and the basis weight of the active material layer in the negative electrode was also 4.0 mg / cm 2 as in EB11. Note that the basis weight of the active material layer in the positive electrodes of EB11 and CB5 and the basis weight of the active material layer in the negative electrode were half of EB1 and CB1.
  • the basis weight of the positive electrode and the negative electrode in the nonaqueous electrolyte secondary battery of Comparative Example 5-2 was the same as that of the nonaqueous electrolyte secondary battery of Example 5-1.
  • Rate capacity characteristics The rate capacity characteristics of EB1 and CB1 were evaluated by the following methods. The capacity of each battery was adjusted to 160 mAh / g. The evaluation condition was that each non-aqueous electrolyte secondary battery was charged at a rate of 0.1 C, 0.2 C, 0.5 C, 1 C, 2 C, and then discharged, and the capacity of the working electrode at each rate (discharge) Capacity). Table 33 shows the discharge capacity after 0.1 C discharge and after 1 C discharge. The discharge capacity shown in Table 33 is the capacity calculated per mass (g) of the positive electrode active material.
  • the nonaqueous electrolyte secondary battery of the present invention is excellent in rate capacity characteristics. As described above, this is because the electrolyte in the non-aqueous electrolyte secondary battery of the present invention is different from the conventional one, and S, O formed on the negative electrode and / or the positive electrode of the non-aqueous electrolyte secondary battery of the present invention. It is thought that the contained film is also different from the conventional film.
  • Evaluation Example 32 Output characteristic evaluation at 0 °, SOC 20%
  • the output characteristics of EB1 and CB1 described above were evaluated.
  • the evaluation conditions are a state of charge (SOC) 20%, 0 ° C., a working voltage range 3V-4.2V, and a 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.
  • Evaluation of the output characteristics of EB1 and CB1 was performed three times for each of the 2-second output and the 5-second output. The evaluation results of the output characteristics are shown in Table 34.
  • the ratio of the output at 0 ° C. to the output at 25 ° C. (0 ° C. output / 25 ° C. output) at the output of 2 seconds and 5 seconds is about the same as CB1, and EB1 was found to be able to suppress a decrease in output at a low temperature to the same extent as CB1.
  • EB4 was charged and discharged at 25 ° C. for 3 cycles, then disassembled in a 3V discharge state, and the positive electrode was taken out. Separately, EB4 was charged and discharged at 25 ° C. for 500 cycles, then disassembled in a 3V discharge state, and the positive electrode was taken out. Separately from this, EB4 was charged and discharged at 25 ° C. for 3 cycles, then left at 60 ° C. for one month, disassembled in a 3V discharge state, and the positive electrode was taken out. Each positive electrode was washed with DMC three times to obtain a positive electrode for analysis. In addition, the positive electrode S and O containing film was formed in the said positive electrode, and the structural information of the molecule
  • Each positive electrode for analysis was analyzed by TOF-SIMS.
  • a time-of-flight secondary ion mass spectrometer was used as a mass spectrometer, and positive secondary ions and negative secondary ions were measured.
  • Bi was used as the primary ion source, and the primary acceleration voltage was 25 kV.
  • Ar-GCIB Ar1500 was used as the sputter ion source.
  • Tables 37 to 39 The measurement results are shown in Tables 37 to 39.
  • the positive ion intensity (relative value) of each fragment is a relative value with the total positive ion intensity of all detected fragments as 100%.
  • the negative ionic strength (relative value) of each fragment described in Table 39 is a relative value where the sum of the negative ionic strengths of all the detected fragments is 100%.
  • the fragments presumed to be derived from the solvent of the electrolytic solution were only C 3 H 3 and C 4 H 3 detected as positive secondary ions.
  • a fragment presumed to be derived from a salt of the electrolytic solution is mainly detected as a negative secondary ion, and has a higher ionic strength than the above-described fragment derived from a solvent.
  • fragments containing Li are mainly detected as positive secondary ions, and the ionic strength of the fragments containing Li accounts for a large proportion of positive secondary ions and negative secondary ions.
  • the main component of the S, O-containing film is a component derived from the metal salt contained in the electrolytic solution, and that the S, O-containing film contains a large amount of Li.
  • SNO 2 , SFO 2 , S 2 F 2 NO 4, and the like have also been detected as fragments estimated to be derived from salts.
  • the conventional electrolyte solution introduced in, for example, JP-A-2013-145732 that is, a conventional electrolyte solution containing EC as an organic solvent, LiPF 6 as a metal salt, and LiFSA as an additive
  • S is taken into the decomposition product of the organic solvent.
  • S is considered to exist as ions such as C p H q S (p and q are independent integers) in the negative electrode film and / or the positive electrode film.
  • the fragment containing S detected from the S, O-containing film is mainly a fragment reflecting the anion structure, not the C p H q S fragment. This also reveals that the S, O-containing coating is fundamentally different from the coating formed on the conventional nonaqueous electrolyte secondary battery.
  • a nonaqueous electrolyte secondary battery using the electrolytic solution E8 was produced as follows.
  • An aluminum foil (JIS A1000 series) having a diameter of 13.82 mm, an area of 1.5 cm 2 and a thickness of 20 ⁇ m was used as a working electrode, and the counter electrode was metal Li.
  • As the separator Whatman glass fiber filter paper having a thickness of 400 ⁇ m: No. 1825-055 was used.
  • a working electrode, a counter electrode, a separator, and an electrolyte solution of E8 were housed in a battery case (CR2032-type coin cell case manufactured by Hosen Co., Ltd.) to obtain a nonaqueous electrolyte secondary battery EB12.
  • EB13 A nonaqueous electrolyte secondary battery EB13 was obtained in the same manner as EB12 except that the electrolytic solution E11 was used instead of the electrolytic solution E8.
  • EB14 A nonaqueous electrolyte secondary battery EB14 was obtained in the same manner as EB12 except that the electrolytic solution E16 was used instead of the electrolytic solution E8.
  • EB15 A nonaqueous electrolyte secondary battery EB15 was obtained in the same manner as EB12 except that the electrolytic solution E19 was used instead of the electrolytic solution E8.
  • EB16 A nonaqueous electrolyte secondary battery EB16 was obtained in the same manner as EB12 except that the electrolytic solution E13 was used instead of the electrolytic solution E8.
  • CB6 A nonaqueous electrolyte secondary battery CB6 was obtained in the same manner as EB12 except that the electrolytic solution C5 was used instead of the electrolytic solution E8.
  • CB7 A nonaqueous electrolyte secondary battery CB7 was obtained in the same manner as EB12 except that the electrolytic solution C6 was used instead of the electrolytic solution E8.
  • 91 to 99 are graphs showing the relationship between the potential and response current for EB12 to EB15 and CB6. Further, graphs showing the relationship between the potential and response current with respect to EB13, EB16, and CB7 are shown in FIGS.
  • the electrolytes E8, E11, E16, and E19 can be said to be suitable electrolytes for batteries using aluminum as a current collector or the like.
  • a nonaqueous electrolyte secondary battery EB17 using the electrolytic solution E8 was produced as follows. 94 parts by mass of NCM523 as a positive electrode active material, 3 parts by mass of AB as a conductive additive, and 3 parts by mass of PVdF as a binder were mixed. This mixture was dispersed in an appropriate amount of NMP to obtain a slurry-like positive electrode mixture. An aluminum foil (JIS A1000 series) having a thickness of 20 ⁇ m was prepared as a positive electrode current collector. The surface of the positive electrode current collector was applied using a doctor blade so that the positive electrode mixture was in the form of a film. NMP was removed by volatilization by drying the positive electrode current collector coated with the positive electrode mixture at 80 ° C.
  • the negative electrode mixture was applied to the surface of the negative electrode current collector in the form of a film using a doctor blade.
  • the negative electrode current collector coated with the negative electrode mixture was dried to remove water, and then a composite of the negative electrode mixture and the negative electrode current collector was pressed to obtain a bonded product.
  • the obtained joined product was heat-dried at 100 ° C. for 6 hours with a vacuum dryer to obtain a negative electrode in which a negative electrode active material layer was formed on the negative electrode current collector.
  • 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 nonaqueous electrolyte secondary battery EB17 in which the four sides were hermetically sealed, and the electrode plate group and the electrolyte were sealed.
  • a nonaqueous electrolyte secondary battery EB18 using the electrolytic solution E8 was produced as follows.
  • the positive electrode was manufactured in the same manner as the positive electrode of EB17.
  • 90 parts by mass of natural graphite as a negative electrode active material and 10 parts by mass of PVdF as a binder were mixed. This mixture was dispersed in an appropriate amount of ion-exchanged water to obtain a slurry-like negative electrode mixture.
  • a copper foil having a thickness of 20 ⁇ m was prepared as a negative electrode current collector.
  • the negative electrode mixture was applied to the surface of the copper foil in the form of a film using a doctor blade.
  • the composite of the negative electrode mixture and the negative electrode current collector was dried to remove water, and then pressed to obtain a bonded product.
  • the obtained joined product was heat-dried at 120 ° C. for 6 hours with a vacuum dryer to obtain a negative electrode in which a negative electrode active material layer was formed on the negative electrode current collector.
  • a nonaqueous electrolyte secondary battery EB18 was obtained in the same manner as EB17.
  • CB8 A nonaqueous electrolyte secondary battery CB8 was obtained in the same manner as EB17 except that the electrolytic solution C5 was used.
  • CB9 A nonaqueous electrolyte secondary battery CB9 was obtained in the same manner as EB18 except that the electrolytic solution C5 was used.
  • “2 second input” means an input after 2 seconds from the start of charging
  • “5 seconds input” means an input after 5 seconds from the start of charging.
  • the input of EB17 was significantly higher than the input of CB8 regardless of the difference in temperature.
  • the EB18 input was significantly higher than the CB9 input.
  • the battery input density of EB17 was significantly higher than that of CB8.
  • the battery input density of EB18 was significantly higher than the battery input density of CB9.
  • “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 EB17 was significantly higher than the output of CB8 regardless of the difference in temperature.
  • the output of EB18 was significantly higher than that of CB9.
  • the battery output density of EB17 was significantly higher than that of CB8.
  • the battery output density of EB18 was significantly higher than that of CB9.
  • a nonaqueous electrolyte secondary battery EB19 using the electrolytic solution E8 was produced as follows.
  • the positive electrode was manufactured in the same manner as the positive electrode of EB17.
  • a negative electrode was obtained in the same manner as in EB17.
  • As a separator experimental filter paper (Toyo Filter Paper Co., Ltd., cellulose, thickness 260 ⁇ m) was prepared.
  • a nonaqueous electrolyte secondary battery EB19 was obtained in the same manner as EB17.
  • CB10 A nonaqueous electrolyte secondary battery CB10 was obtained in the same manner as EB19 except that the electrolytic solution C5 was used.
  • FIG. 106 shows a DSC chart when the positive electrode active material layer in the charged state of EB19 and the electrolyte coexist.
  • FIG. 107 shows DSC charts when the positive electrode active material layer in the charged state of CB10 and the electrolyte coexist, respectively.
  • the non-aqueous electrolyte secondary battery using the electrolytic solution of the present invention is more reactive with the positive electrode active material and the electrolytic solution than the non-aqueous electrolyte secondary battery using the conventional electrolytic solution. It can be seen that it is low and has excellent thermal stability.
  • the nonaqueous electrolyte secondary battery of the present invention can be used for secondary batteries, electric double layer capacitors, lithium ion capacitors, and the like. It is also useful as a non-aqueous electrolyte secondary battery for motor drive of electric vehicles and hybrid vehicles, personal computers, portable communication devices, home appliances, office equipment, industrial equipment, etc. Especially, large capacity and high output are required. It can be optimally used for driving a motor of a simple electric vehicle or hybrid vehicle.

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Abstract

La présente invention concerne l'amélioration des caractéristiques de batterie par la combinaison optimale d'un électrolyte et d'un matériau d'électrode négative actif. Dans une batterie secondaire à électrolyte non aqueux, l'électrolyte utilisé contient un sel métallique et un solvant organique ayant un hétéroatome et illustre la relation Is > Io, où, pour des intensités de sommet dérivées du solvant organique dans un spectre de spectroscopie vibratoire, Io est l'intensité d'un sommet inhérent au solvant organique et Is est l'intensité d'un sommet auquel le sommet inhérent au solvant organique se décale. On utilise comme électrode négative n'importe quel élément parmi les éléments (1) à (5) : (1) graphite ayant un rapport G/D de 3,5 ou plus, ledit rapport G/D étant le rapport du sommet de la bande G et du sommet de la bande D dans un spectre Raman ; (2) matériau de carbone ayant une taille de cristallite de 20 nm ou moins, ladite taille de cristallite étant calculée à partir de la moitié de la largeur d'un sommet apparaissant à 2θ = 20° à 30° dans un profil de diffraction de rayon x mesuré par un procédé de diffraction de rayon x ; (3) élément de silicium et/ou élément d'étain ; (4) oxyde métallique pouvant absorber et libérer des ions au lithium ; (5) graphite ayant un rapport d'axe majeur sur axe mineur (axe majeur/ axe mineur) de 1 à 5.
PCT/JP2014/004911 2013-09-25 2014-09-25 Batterie secondaire à électrolyte non aqueux WO2015045387A1 (fr)

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WO2017022731A1 (fr) * 2015-07-31 2017-02-09 日立化成株式会社 Batterie rechargeable au lithium-ion
WO2017179411A1 (fr) * 2016-04-15 2017-10-19 国立大学法人東京大学 Batterie secondaire au lithium-ion
CN108140894A (zh) * 2015-10-05 2018-06-08 国立大学法人东京大学 在电极表面具备覆膜的二次电池的制造方法
US20180204686A1 (en) * 2015-08-04 2018-07-19 Nippon Electric Glass Co., Ltd. Negative electrode active material for power storage device

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