Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same

Abstract

Provided is a nonaqueous electrolyte solution whereby the cycle characteristics and initial resistance of a nonaqueous electrolyte battery can be improved in a well-balanced fashion, the nonaqueous electrolyte battery being provided with a negative electrode that contains, as negative electrode active materials, graphite and Si and / or a Si metal oxide.　The nonaqueous electrolyte solution contains: (I) at least one selected from the group consisting of a compound represented by general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), and a compound represented by general formula (4); (II) a solute; and (III) a nonaqueous organic solvent.

Description

Nonaqueous electrolyte and nonaqueous electrolyte battery using the same

[0001] The present disclosure relates to a non-aqueous electrolyte containing a specific oxazolidine compound, and a non-aqueous electrolyte battery containing the same.

[0002] In recent years, energy storage systems for applications requiring high energy density in information-related devices or communication devices, i.e., small devices such as personal computers, video cameras, digital still cameras, and mobile phones, as well as large devices requiring high power, such as electric vehicles, hybrid vehicles, fuel cell vehicle auxiliary power sources, and power storage devices, have attracted attention. Non-aqueous electrolyte batteries, such as lithium-ion batteries, lithium batteries, lithium-ion capacitors, and sodium-ion batteries, have been actively developed as candidates. Non-aqueous electrolyte batteries are required to achieve high levels of battery characteristics, such as cycle characteristics, input / output characteristics, storage characteristics, continuous charging characteristics, and safety. Furthermore, in recent years, there has been an increasing demand for higher capacity automotive batteries to extend driving range.

[0003] Although many of these nonaqueous electrolyte batteries have already been put to practical use, further improvements in terms of increasing capacity are desired. In particular, when alloy-based active materials, particularly active materials containing Si atoms, are used as negative electrode active materials, high battery capacity is expected, but it is known that battery performance deteriorates significantly with long-term use. Therefore, efforts have been made to increase capacity and improve durability in order to extend the driving range of, for example, automobiles. To date, optimization of various battery components, including the active materials of the positive and negative electrodes, has been investigated as a means of improving the high-temperature characteristics of nonaqueous electrolyte batteries and their battery characteristics (cycling characteristics) during repeated charge and discharge. Nonaqueous electrolyte-related technologies are no exception, and various additives have been proposed to suppress deterioration due to electrolyte decomposition on the surfaces of active positive and negative electrodes.

[0004] Patent Document 1 reports a nonaqueous electrolyte solution for a nonaqueous electrolyte secondary battery containing a nitrogen-containing heterocyclic compound such as a pyrrolidine compound, an imidazolidine compound, or an oxazolidine compound, as a nonaqueous electrolyte solution having good battery characteristics, such as high charge / discharge efficiency and capacity retention. Patent Document 2 also reports a nonaqueous electrolyte solution containing an oxazolidine compound in a solvent containing a 5- to 7-membered lactone compound. Patent Document 3 further reports that adding a nitrogen-containing cyclic compound containing an ester bond to a nonaqueous electrolyte solution improves the capacity retention at 20°C and 60°C while also imparting flame retardancy to the battery. In recent years, nonaqueous electrolyte batteries using a negative electrode containing Si or a Si metal oxide as the negative electrode active material have attracted attention in an effort to achieve higher capacity. However, the use of a negative electrode containing Si or a Si metal oxide presents various new challenges that are different from those encountered with conventional negative electrodes using only graphite. For example, it is known that the volume expansion and contraction associated with the charge / discharge reaction is so large that particles are crushed with each charge / discharge cycle of the battery, and the exposed Si on the surface reacts with the non-aqueous electrolyte solvent, resulting in problems such as an irreversible increase in capacity and an increase in resistance, and there is a need to improve these problems. Patent Document 4 attempts to improve the cycle characteristics of a battery by using a material containing Si and O as constituent elements and a graphite material as negative electrode active materials in the negative electrode and using a halogenated cyclic carbonate or vinylene carbonate as the electrolyte. Furthermore, Non-Patent Document 1 prepares a battery by using a material containing Si and O as constituent elements and a graphite material as negative electrode active materials in the negative electrode and using an oxazolidine compound as the electrolyte, and investigates the cycle characteristics and film formation characteristics of the battery.

[0005] Patent Document 1: Japanese Patent No. 5109213 Patent Document 2: Japanese Patent No. 4302366 Patent Document 3: Japanese Patent No. 5439345 Patent Document 4: Japanese Patent Laid-Open No. 2011-233245

[0006] Non-patent document 1: Cell Reports Physical Science 2, 100327 (2021)

[0007] However, in a battery using a material containing Si and O as constituent elements and a graphite material as the negative electrode active material as disclosed in Patent Document 4 or Non-Patent Document 1, the battery characteristics may not be fully improved even if a non-aqueous electrolyte containing a compound as disclosed in Patent Documents 1 to 3 is applied, and the inventors have found through their studies that there is room for improvement, particularly in terms of simultaneously improving the cycle characteristics and the initial resistance and improving the balance between them. Therefore, the present disclosure has been made in consideration of the above circumstances, and aims to provide a non-aqueous electrolyte that can improve the cycle characteristics and the initial resistance in a well-balanced manner in a non-aqueous electrolyte battery that contains Si and / or a Si metal oxide and graphite as the negative electrode active material, and a non-aqueous electrolyte battery containing the same.

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result, have found that a nonaqueous electrolyte solution containing the following components can be used in a nonaqueous electrolyte battery having a negative electrode containing Si and / or Si metal oxide and graphite as negative electrode active materials: (I) at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and a compound represented by the following general formula (4), (II) a solute, and (III) a nonaqueous organic solvent, thereby improving the cycle characteristics and initial resistance of the battery in a well-balanced manner, and have completed the present invention. (Hereinafter, the above components (I), (II), and (III) may be referred to as "component (I)," "component (II)," and "component (III)," respectively.)

[0009] [In general formula (1), R 1is a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may be independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have an ether group between any carbon atoms), or (M A a+ ) b (The M A a+ represents a cation selected from a proton, a metal cation, and an onium cation, a represents the valence of the cation, and b represents a number such that a×b=1. 1 But M A a+ ) b In the case of 1 The other moieties are counter anions. 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may each independently be substituted with a halogen atom, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon atoms), and R 2 and R 3 may combine to form a carbonyl group.

[0010] [In general formula (2), R 4 represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may be independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon atoms). 5 and R 6 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may each independently be substituted with a halogen atom, a cyano group, or an isocyano group, or the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between carbon atoms); R 5 and R 6 may combine to form a carbonyl group.

[0011] [In general formula (3), R 7is a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may be independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have an ether group between any carbon atoms), or (M C e+ ) f (The M C e+ represents a cation selected from a proton, a metal cation, and an onium cation, e represents the valence of the cation, and f represents a number such that e×f=1. 7 But (M C e+ ) f In the case of 7 The other moieties are counter anions. 8 and R 9 each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may each independently be substituted with a halogen atom, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon atoms), and R 8 and R 9 may combine to form a carbonyl group.

[0012] [In general formula (4), R 10 represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may be independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon atoms). 11 and R 12 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may each independently be substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon atoms); R 11 and R 12 may combine to form a carbonyl group.

[0013] Preferred aspects of the present disclosure are, for example, as follows: 1. A nonaqueous electrolyte solution for use in a nonaqueous electrolyte battery including a positive electrode and a negative electrode containing Si and / or Si metal oxide and graphite as negative electrode active materials, the nonaqueous electrolyte solution comprising the following components: (I) at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and a compound represented by the following general formula (4), (II) a solute, and (III) a nonaqueous organic solvent.

[0014] [In general formula (1), R 1 is a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may be independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have an ether group between any carbon atoms), or (M A a+ ) b (The M A a+ represents a cation selected from a proton, a metal cation, and an onium cation, a represents the valence of the cation, and b represents a number such that a×b=1. 1 However, (M A a+ ) b In the case of 1 The other moieties are counter anions. 2 and R 3each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may each independently be substituted with a halogen atom, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon atoms), and R 2 and R 3 may combine to form a carbonyl group.

[0015] [In general formula (2), R 4 represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may be independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon atoms). 5 and R 6each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may each independently be substituted with a halogen atom, a cyano group, or an isocyano group, or the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between carbon atoms); R 5 and R 6 may combine to form a carbonyl group.

[0016] [In general formula (3), R 7 is a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may be independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have an ether group between any carbon atoms), or (M C e+ ) f (The M C e+ represents a cation selected from a proton, a metal cation, and an onium cation, e represents the valence of the cation, and f represents a number such that e×f=1. 7 But (M Ce+ ) f In the case of 7 The other moieties are counter anions. 8 and R 9 each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may each independently be substituted with a halogen atom, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon atoms), and R 8 and R 9 may combine to form a carbonyl group.

[0017] [In general formula (4), R 10 represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may be independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon atoms). 11 and R 12each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (some or all of the hydrogen atoms in the hydrocarbon group may each independently be substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon atoms); R 11 and R 12 may combine to form a carbonyl group.

[0018] 2. The non-aqueous electrolyte solution according to item 1 above, wherein the concentration of (I) is 0.01 to 11 mass % relative to the total amount of the non-aqueous electrolyte solution. 3. The non-aqueous electrolyte solution according to item 2 above, wherein the concentration of (I) is 0.08 to 10.5 mass % relative to the total amount of the non-aqueous electrolyte solution. 4. The non-aqueous electrolyte solution according to item 3 above, wherein the concentration of (I) is 0.20 to 9 mass % relative to the total amount of the non-aqueous electrolyte solution. 5. The non-aqueous electrolyte solution according to any one of items 1 to 4, wherein (I) is at least one selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2). 6. 6. The nonaqueous electrolyte according to any one of items 1 to 5 above, wherein (II) is at least one selected from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiN(SO2F)2 (hereinafter sometimes referred to as "FSI"), LiAlO2, LiAlCl4, LiCl, and LiI. 7. The nonaqueous electrolyte according to any one of items 1 to 6 above, wherein (III) contains at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids. 8. The nonaqueous electrolyte according to item 7 above, wherein the cyclic ester contains a cyclic carbonate. 9. The nonaqueous electrolyte according to item 8 above, wherein the cyclic carbonate contains at least one selected from the group consisting of ethylene carbonate and propylene carbonate. 10. 11. The non-aqueous electrolyte solution according to item 7 above, wherein the chain ester comprises a chain carbonate. 11. The non-aqueous electrolyte solution according to item 10 above, wherein the chain carbonate comprises at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

[0019] 12. The non-aqueous electrolyte solution further contains cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, t-butylbenzene, t-amylbenzene, 2-fluorotoluene, fluorobenzene, vinylene carbonate (hereinafter sometimes referred to as "VC"), vinylene carbonate oligomer (having a number average molecular weight of 170 to 5000 in terms of polystyrene), vinylethylene carbonate, difluoroanisole, fluoroethylene carbonate (hereinafter sometimes referred to as "FEC"), 1,6-diisocyanatohexane, ethylene carbonate, Nylethylene carbonate, trans-difluoroethylene carbonate, methyl propargyl carbonate, ethyl propargyl carbonate, dipropargyl carbonate, maleic anhydride, succinic anhydride, 1,3-propane sultone, 1,3-propene sultone, 1,4-butane sultone, dimethylvinylene carbonate, 1,3,2-dioxathiolane-2,2-dioxide (hereinafter sometimes referred to as "DTD"), 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, dimethylmeth disulfonate, trimethylenemethane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethenesulfonyl fluoride, phenyl difluorophosphate, 1,2-ethanedisulfonic anhydride, tris(trimethylsilyl)borate, succinonitrile, (ethoxy)pentafluorocyclotriphosphazene, tetrafluoro(picolinato)phosphate, difluoro(picolinato)borate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, difluoro Lithium difluorophosphate (hereinafter sometimes referred to as "DFP"), sodium difluorophosphate, lithium fluorosulfate (hereinafter sometimes referred to as "FS"), sodium fluorosulfate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, lithium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, lithium difluorobis(oxalato)phosphate (hereinafter sometimes referred to as "DFBOP"), sodium difluorobis(oxalato)phosphate, lithium difluorooxalatoborate (hereinafter sometimes referred to as "DFBOP").(hereinafter sometimes referred to as "DFOB"), sodium difluorooxalatoborate, lithium bis(oxalato)borate (hereinafter sometimes referred to as "BOB"), sodium bis(oxalato)borate, lithium tetrafluorooxalatophosphate (hereinafter sometimes referred to as "TFOP"), sodium tetrafluorooxalatophosphate, lithium tris(oxalato)phosphate, sodium tris(oxalato)phosphate, lithium difluoro(malonato)borate, sodium difluoro(malonato)borate, tetrafluoro(malonato)phosphate Lithium phosphate, sodium tetrafluoro(malonato)phosphate, lithium monofluorophosphate, sodium monofluorophosphate, lithium bis(difluorophosphoryl)imide, sodium bis(difluorophosphoryl)imide, lithium (difluorophosphoryl)(fluorosulfonyl)imide (hereinafter sometimes referred to as "DFPFSI"), sodium (difluorophosphoryl)(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, sodium bis(trifluoromethanesulfonyl)imide, bis(pentafluorophosphate), the composition contains at least one selected from the group consisting of lithium bis(pentafluoroethanesulfonyl)imide, sodium bis(pentafluoroethanesulfonyl)imide, lithium bis(pentafluoroethanesulfonyl)imide, sodium bis(pentafluoroethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, sodium bis(pentafluoroethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, sodium bis(pentafluoroethanesulfonyl)imide, lithium bis(pentafluoro ...The non-aqueous electrolyte solution according to any one of items 1 to 11 above. 13. The non-aqueous electrolyte solution according to any one of items 1 to 12 above, further comprising a compound represented by the following general formula (5):

[0020] [In general formula (5), R 13 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, and an oxygen atom may be contained between any carbon atom-carbon atom bond in the alkyl group. Any hydrogen atom in the alkyl group may be substituted with a fluorine atom.] 14. The compound represented by general formula (5) is the following compound 1-1 (hereinafter, sometimes referred to as "TDUTO") and 1-2,

[0021] 15. The nonaqueous electrolyte solution according to any one of items 1 to 14 above, further comprising a compound represented by the following general formula (6): [In general formula (6), R 14 ~R 17 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group. X represents an oxygen atom, a sulfur atom, or an SO group. 16. The nonaqueous electrolyte solution according to item 15 above, wherein the compound of formula (6) is a compound represented by the following formula: 17. The nonaqueous electrolyte solution according to any one of items 1 to 17, wherein the total content of the Si and / or Si metal oxide relative to the total amount of the Si and / or Si metal oxide and graphite is 0.1 to 50 mass %. 18. A nonaqueous electrolyte battery comprising: a positive electrode; a negative electrode containing Si and / or Si metal oxide and graphite as negative electrode active materials; and the nonaqueous electrolyte solution according to any one of items 1 to 17.

[0022] According to the present disclosure, it is possible to provide a nonaqueous electrolyte that can improve cycle characteristics and initial resistance in a well-balanced manner in a nonaqueous electrolyte battery that contains Si and / or Si metal oxide and graphite as a negative electrode active material, and a nonaqueous electrolyte battery that includes the same.

[0023] The configuration of the nonaqueous electrolyte according to the present disclosure will be described in detail below. Regarding Component (I): The additives used in the nonaqueous electrolyte according to the present disclosure are the four types of compounds described above. Here, the meanings of the functional groups described in each formula are as follows. The halogen atom is selected from halogen atoms such as fluorine, chlorine, and bromine. Preferably, the halogen atom is a fluorine atom. The alkyl group having 1 to 10 carbon atoms may be linear or branched, and preferably has 1 to 10 carbon atoms, and preferably 1 to 5 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, and n-decyl. Examples of the alkoxy group having 1 to 10 carbon atoms include alkoxy groups corresponding to the above alkyl groups. Examples of alkenyl groups having 2 to 10 carbon atoms include linear or branched alkenyl groups, and are preferably alkenyl groups having 2 to 5 carbon atoms. The alkenyl group may have two or more unsaturated bonds. Suitable examples of such alkenyl groups include vinyl groups, 1-propenyl groups, 2-propenyl groups, 1-methylvinyl groups, 1-butenyl groups, 2-butenyl groups, 3-butenyl groups, 1-methylpropenyl groups, 1-pentenyl groups, and 1,3-butadienyl groups. Examples of alkenyloxy groups having 2 to 10 carbon atoms include alkenyloxy groups corresponding to the above alkenyl groups.

[0024] Examples of alkynyl groups having 2 to 10 carbon atoms include linear and branched alkynyl groups, and preferred are alkynyl groups having 2 to 5 carbon atoms. The alkynyl group may have two or more unsaturated bonds. Suitable examples of such alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-methylethynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpropynyl, 1,1-dimethyl-2-propynyl, and 1-pentynyl. Examples of alkynyloxy groups having 2 to 10 carbon atoms include alkynyloxy groups corresponding to the above alkynyl groups. Suitable examples of cycloalkyl groups having 3 to 8 carbon atoms include cycloalkyl groups having 3 to 5 carbon atoms, and preferred examples of such cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The cycloalkyl group also includes one having a linking group such as a methylene group, and a suitable example thereof is a cyclohexylmethyl group. The cycloalkoxy group having 3 to 8 carbon atoms is preferably a cycloalkoxy group corresponding to the cycloalkyl group. The aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthalene group. The aryl group also includes one having a linking group such as a methylene group, and a suitable example thereof is a benzyl group. The aryloxy group having 6 to 10 carbon atoms is preferably a phenoxy group or a naphthoxy group. The heteroaryl group having 6 to 10 carbon atoms is an aryl group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, and suitable examples of such heteroaryl groups include a furyl group, a thiophenyl group, a pyrrole group, an imidazole group, a pyrazole group, an oxazole group, a thioxazole group, a pyridyl group, a pyridazine group, a pyrimidine group, a pyrazine group, a triazine group, an indole group, a purine group, and a quinolyl group. Suitable examples of the heteroaryloxy group having 6 to 10 carbon atoms include heteroaryloxy groups corresponding to the above heteroaryl groups.

[0025] The hydrogen atoms of the hydrocarbon group may be optionally substituted with halogen atoms, cyano groups, or isocyano groups. The hydrocarbon group may also have an ether group, hetero atom, carbonyl group, ester group, or ether group between any carbon atoms. (M A a+ ) b M in A a+ is a cation selected from a proton (hydrogen cation), a metal cation, and an onium cation. Suitable metal cations include cations of alkali metals and alkaline earth metals. Suitable alkali metal cations include, for example, lithium cation and sodium cation. Suitable alkaline earth metal cations include, for example, magnesium ion and calcium ion. Suitable onium cations include, for example, trialkylammonium ions and tetraalkylammonium ions, ammonium ions having a spiro skeleton, tetraalkylphosphonium ions, imidazolium ions, and nitronium cations, with trialkylammonium ions, tetraalkylammonium ions, and tetraalkylphosphonium ions being particularly suitable. Note that R 1 However, (M A a+ ) b In the case of 1The moiety other than is a counter anion. All of the compounds of general formulas (1) to (4) can be easily manufactured or prepared by those skilled in the art using known preparation methods. Specifically, for example, compounds of general formula (1) can be prepared with reference to literature such as https: / / doi.org / 10.1016 / S0040-4020(98)01025-4, compounds of general formula (2) can be prepared with reference to literature such as Journal of Pharmacy Research Vol. 4, Issue 10, October 2011, compounds of general formula (3) can be prepared with reference to literature such as https: / / doi.org / 10.1039 / JR9500003213, and compounds of general formula (4) can be prepared with reference to literature such as https: / / doi.org / 10.1039 / D2OB00167E. Representative compounds of general formula (1) include the following compounds: In the compound represented by general formula (1), R 1 When R is an alkyl group, an alkenyl group, or an aryl group, 2 and R 3 Furthermore, among the compounds represented by general formula (1), the following compounds 29, 45, and 48 are preferred in terms of initial resistance and cycle characteristics, with compounds 45 and 48 being particularly preferred.

[0026]

[0027]

[0028] Representative examples of the compound represented by general formula (2) include the following compounds: Among the compounds represented by general formula (2), the following compound 71 is particularly preferable in terms of initial resistance and cycle characteristics.

[0029]

[0030]

[0031] Representative compounds of the compound represented by general formula (3) include the following compounds: 7 is an alkyl group, an alkenyl group, or an aryl group, R 8 and R 9 At the same time, it is preferable that R is not a hydrogen atom in terms of initial resistance. 7 However, in terms of initial resistance and cycle characteristics, it is preferable that the alkyl group have 3 or less carbon atoms.

[0032]

[0033]

[0034] Representative compounds represented by general formula (4) include the following compounds:

[0035]

[0036]

[0037] The compounds of component (I) may be used alone or in any combination and ratio of two or more. Among these compounds of component (I), compounds represented by general formula (1), (2), or (3) are particularly preferred from the viewpoint of initial resistance and cycle characteristics. Compounds represented by general formula (1) or (2) are particularly preferred from the viewpoint of initial resistance and cycle characteristics. The concentration of component (I) may be, for example, 0.01 to 11% by mass, preferably 0.08 to 10.5% by mass, and more preferably 0.20 to 9% by mass, based on the total amount of the nonaqueous electrolyte. Within this range, when the nonaqueous electrolyte of the present disclosure is used in a nonaqueous electrolyte battery having a negative electrode containing Si and / or Si metal oxide and graphite as the negative electrode active material, the resulting battery can exhibit a well-balanced improvement in cycle characteristics and initial resistance.

[0038] Regarding component (II) (solute), the solute used in the non-aqueous electrolyte of the present disclosure can be any of various solutes conventionally used in the field of non-aqueous electrolytes, without any particular limitations. Suitable solutes are ionic salts consisting of any cation-anion pair. As long as they exist in an ionic state as cations and anions in a non-aqueous organic solvent, various solutes can be used without any particular limitations. Suitable examples of such solutes include at least one selected from the group consisting of LiPF, LiBF, LiSbF, LiAsF, LiClO, LiN(SOF), LiAlO, LiAlCl, LiCl, and LiI, or at least one selected from the group consisting of NaPF, NaBF, NaSbF, NaAsF, NaClO, NaN(SOF), NaAlO, NaAlCl, NaCl, and NaI.

[0039] In particular, in consideration of the energy density, output characteristics, life, etc. of the nonaqueous electrolyte battery, it is preferable that the cation is at least one selected from the group consisting of lithium, sodium, potassium, magnesium, and quaternary ammonium, and the anion is at least one selected from the group consisting of hexafluorophosphate anion, tetrafluoroborate anion, and bis(fluorosulfonyl)imide anion. In the present disclosure, one type of solute may be used alone, or two or more types may be used in any combination and ratio depending on the application.

[0040] The concentration of the solute relative to the total amount of the nonaqueous electrolyte solution in the present disclosure is not particularly limited as long as it is a concentration that can fully exhibit the function of the solute. For example, the lower limit may be 0.5 mol / L or more, preferably 0.7 mol / L or more, and more preferably 0.9 mol / L or more. The upper limit may be 5 mol / L or less, preferably 4 mol / L or less, and more preferably 2 mol / L or less. A concentration of 0.5 mol / L or more is preferable because the ionic conductivity is less likely to decrease, and the cycle characteristics and output characteristics of the nonaqueous electrolyte battery are less likely to decrease. On the other hand, a concentration of 5 mol / L or less is preferable because the viscosity of the electrolyte solution for a nonaqueous electrolyte battery is less likely to increase, and the ionic conductivity is less likely to decrease. When two or more solutes are used, it is preferable that the total concentration of the solutes is within the above-mentioned range. The liquid temperature when dissolving the solute in the nonaqueous organic solvent described below is not particularly limited, but is preferably -20 to 80°C, more preferably 0 to 60°C, for example.

[0041] Regarding component (III) (non-aqueous organic solvent), the non-aqueous organic solvent used in the non-aqueous electrolyte solution of the present disclosure is not particularly limited as long as it can dissolve the above components (I) and (II), and any non-aqueous organic solvent can be used. Such non-aqueous organic solvents preferably contain at least one selected from the group consisting of cyclic esters, linear esters, cyclic ethers, linear ethers, sulfone compounds, sulfoxide compounds, amide compounds, nitrile compounds, and ionic liquids, and more preferably contain at least one selected from the group consisting of cyclic esters, linear esters, cyclic ethers, linear ethers, sulfone compounds, sulfoxide compounds, and ionic liquids. Note that cyclic carbonates are a sub-concept of cyclic esters, and linear carbonates are a sub-concept of linear esters.

[0042] Specific examples of the non-aqueous organic solvent used in the present disclosure include ethyl methyl carbonate (hereinafter also referred to as "EMC"), dimethyl carbonate (hereinafter also referred to as "DMC"), diethyl carbonate (hereinafter also referred to as "DEC"), methyl propyl carbonate (hereinafter also referred to as "MPC"), ethyl propyl carbonate, methyl butyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, 2,2,2-trifluoroethyl ethyl carbonate, 2,2,2-trifluoroethyl propyl carbonate, bis(2,2,2-trifluoroethyl)carbonate, 1,1,1,3,3,3-hexafluoro-1-propyl methyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propyl ethyl carbonate, and 1,1,1,3,3,3-hexafluoro-1-propyl propyl carbonate. ester, bis(1,1,1,3,3,3-hexafluoro-1-propyl)carbonate, ethylene carbonate (hereinafter also referred to as "EC"), propylene carbonate (hereinafter also referred to as "PC"), butylene carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate, diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, N,N-dimethylformamide, acetonitrile, propionitrile, dimethyl sulfoxide, sulfolane, γ-butyrolactone, and γ-valerolactone, and the like may include at least one of the above specific examples.

[0043] The nonaqueous organic solvent preferably contains at least one selected from the group consisting of cyclic esters and chain esters, which provides excellent input / output characteristics at low temperatures, and the nonaqueous organic solvent preferably contains at least one selected from the group consisting of cyclic carbonates and chain carbonates, which provides excellent cycle characteristics at high temperatures.

[0044] The nonaqueous organic solvent preferably contains a cyclic ester, and the cyclic ester preferably contains a cyclic carbonate. Specific examples of the cyclic carbonate include EC, PC, and butylene carbonate, and among these, it is preferable to contain at least one selected from the group consisting of EC and PC.

[0045] It is also preferable that the nonaqueous organic solvent contains a chain ester, and that the chain ester contains a chain carbonate. Specific examples of the chain carbonate include EMC, DMC, DEC, MPC, ethyl propyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, 2,2,2-trifluoroethyl ethyl carbonate, 1,1,1,3,3,3-hexafluoro-1-propyl methyl carbonate, and 1,1,1,3,3,3-hexafluoro-1-propyl ethyl carbonate, and among these, it is preferable that the solvent contains at least one selected from the group consisting of EMC, DMC, DEC, and MPC. Specific examples of the chain ester include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate, and methyl 3,3,3-trifluoropropionate. The nonaqueous organic solvent of the present disclosure may be used alone, or two or more types may be used in any combination and ratio depending on the application. Among these, at least one selected from the group consisting of PC, EC, DEC, DMC, and EMC is particularly preferred from the viewpoints of electrochemical stability against oxidation-reduction and chemical stability related to heat and reactions with the solute. The concentration of the nonaqueous organic solvent of the present disclosure is not particularly limited as long as it functions as a nonaqueous organic solvent, but may be, for example, 40 to 99% by mass, preferably 50 to 95% by mass, and particularly preferably 70 to 93% by mass, based on the total amount (100% by mass) of the nonaqueous electrolyte.

[0046] Regarding Other Additives The nonaqueous electrolyte solution of the present disclosure is constituted of the above-described components (I), (II), and (III) as basic constituents. However, other additives commonly used in this technical field (hereinafter also referred to as "other additives") may be added to the nonaqueous electrolyte solution of the present disclosure in any proportion, as long as the gist of the present disclosure is not impaired. Examples of such other additives include cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, t-butylbenzene, t-amylbenzene, 2-fluorotoluene, fluorobenzene, vinylene carbonate, vinylene carbonate oligomers (having a number average molecular weight of 170 to 5,000 in terms of polystyrene), vinylethylene carbonate, difluoroanisole, fluoroethylene carbonate, 1,6-diisocyanatohexane, ethynylethylene carbonate, trans-difluoroethylene carbonate, methyl propargyl carbonate, ethyl propargyl carbonate, dipropargyl carbonate, maleic anhydride, succinic anhydride, 1,3-propane sultone, 1,3-propene sultone, and 1,4-butane. Examples of suitable fluoropolymers include methyl methyl ether, methyl vinylene carbonate, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, dimethylmethane disulfonate, trimethylenemethane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethenesulfonyl fluoride, phenyl difluorophosphate, 1,2-ethanedisulfonic anhydride, tris(trimethylsilyl)borate, succinonitrile, (ethoxy)pentafluorocyclotriphosphazene, tetrafluoro(picolinato)phosphate, difluoro(picolinato)borate, and 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane.

[0047] Other additives include, for example, lithium difluorophosphate, sodium difluorophosphate, lithium fluorosulfate, sodium fluorosulfate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, lithium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, lithium difluorobis(oxalato)phosphate, sodium difluorobis(oxalato)phosphate, lithium difluorooxalatoborate, sodium difluorooxalatoborate, lithium bis(oxalato)borate, sodium bis(oxalato)borate, lithium tetrafluorooxalatophosphate, sodium tetrafluorooxalatophosphate, lithium tris(oxalato)phosphate, sodium tris(oxalato)phosphate, lithium difluoro(malonato)borate, sodium difluoro(malonato)borate, lithium tetrafluoro(malonato)phosphate, sodium tetrafluoro(malonato)phosphate, lithium monofluorophosphate, sodium monofluorophosphate, lithium bis(difluorophosphoryl)imide, sodium bis(difluorophosphoryl)imide Thorium, (difluorophosphoryl)(fluorosulfonyl)imide lithium, (difluorophosphoryl)(fluorosulfonyl)imide sodium, bis(trifluoromethanesulfonyl)imide lithium, bis(trifluoromethanesulfonyl)imide sodium, bis(pentafluoroethanesulfonyl)imide lithium, bis(pentafluoroethanesulfonyl)imide sodium, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide lithium, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide sodium, (trifluoromethanesulfonyl)(fluorosulfonyl)imide lithium, (trifluoromethanesulfonyl)(fluorosulfonyl)imide sodium, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide lithium, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide sodium, tris(trifluoromethanesulfonyl)methide lithium, tris(trifluoromethanesulfonyl)methide sodium, lithium acrylate, sodium acrylate, lithium methacrylate,Examples of such additives include carboxylates such as sodium methacrylate, sulfates such as lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, and sodium ethyl sulfate, lithium nitrate, lithium nitrite, sodium nitrite, and sodium nitrite. In the present disclosure, the concentration of the other additives may be, for example, 0.01% by mass to 10% by mass relative to the total amount of the nonaqueous electrolyte. Furthermore, the nonaqueous electrolyte of the present disclosure may further contain a compound represented by the following general formula (5) in order to improve cycle capacity retention and gas generation during cycle testing:

[0048] In general formula (5), R 13 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, and an oxygen atom may be present between any carbon atom-carbon atom bond in the alkyl group. Any hydrogen atom in the alkyl group may be substituted with a fluorine atom. The range of alkyl groups includes the range of alkyl groups having 1 to 10 carbon atoms described above, as well as alkyl groups having up to 12 carbon atoms. All compounds represented by general formula (5) can be easily manufactured or prepared by those skilled in the art using known preparation methods. Specifically, compounds represented by general formula (5) can be prepared by methods disclosed in literature such as Can. J. Chem., 79, 1040-1048 (2001). Suitable examples of such compounds include Compounds 1-1 and 1-2 shown below.

[0049] The concentration of such a compound may be, for example, 0.01 to 10 mass %, and preferably 0.1 to 5 mass %, relative to the total amount of the nonaqueous electrolyte solution of the present disclosure. In addition, the nonaqueous electrolyte solution of the present disclosure may further contain a compound represented by the following general formula (6) in order to improve the cycle capacity retention rate and gas generation during cycle testing. In general formula (6), R 14 ~R 17each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group. X represents an oxygen atom, a sulfur atom, or an SO group. From the viewpoint of initial resistance, the compound of formula (6) is preferably a compound represented by the following formula: Any compound of general formula (6) can be easily manufactured or prepared by a person skilled in the art using known preparation methods. For example, the compound represented by the above formula is a known compound and is commercially available, for example, from Tokyo Chemical Industry Co., Ltd. The concentration of such a compound may be, for example, 0.01 to 10 mass% relative to the total amount of the nonaqueous electrolyte solution of the present disclosure, and may preferably be 0.1 to 5 mass%. Furthermore, the nonaqueous electrolyte solution of the present disclosure may contain a polymer, and the nonaqueous electrolyte may be quasi-solidified with a gelling agent or crosslinked polymer, as in the case of use in a nonaqueous electrolyte battery known as a polymer battery. Polymer solid electrolytes also include those containing a nonaqueous organic solvent as a plasticizer.

[0050] Regarding nonaqueous electrolyte batteries, the configuration of a nonaqueous electrolyte battery using the nonaqueous electrolyte of the present disclosure will be described. The nonaqueous electrolyte battery of the present disclosure basically employs the configuration used in conventional nonaqueous electrolyte batteries. That is, it comprises a positive electrode and a negative electrode capable of absorbing and releasing lithium, a current collector, a separator, a container, and the like. In particular, when applied to nonaqueous electrolyte batteries including a negative electrode having Si and / or Si metal oxide and graphite as the negative electrode active material, which is desired from the viewpoint of high capacity, the nonaqueous electrolyte of the present disclosure can achieve a balanced improvement in both cycle performance and initial resistance, which have not been achieved until now. That is, when used in a nonaqueous electrolyte battery including a negative electrode containing Si and / or Si metal oxide and graphite as the negative electrode active material, the nonaqueous electrolyte of the present disclosure can provide a nonaqueous electrolyte battery that can achieve a balanced improvement in both capacity retention after cycling and initial resistance. Note that the nonaqueous electrolyte battery of the present disclosure is preferably a nonaqueous electrolyte secondary battery.

[0051] [Positive Electrode] The positive electrode may contain, as a positive electrode active material, at least one selected from the group consisting of an oxide containing at least nickel and a phosphate containing nickel.

[0052] [Positive Electrode Active Material] In the case of a lithium ion battery in which the cations in the non-aqueous electrolyte are mainly lithium, the positive electrode active material constituting the positive electrode is not particularly limited as long as it contains at least one selected from the group consisting of nickel-containing oxides and nickel-containing phosphates and is a variety of chargeable and dischargeable materials. Examples of the positive electrode active material include (A) a lithium transition metal composite oxide containing nickel or, in addition to nickel, one or more metals selected from the group consisting of manganese, cobalt, and aluminum, and having a layered structure; (B) a lithium manganese composite oxide having a spinel structure and containing nickel; (C) a lithium-containing olivine-type phosphate containing nickel; and (D) a lithium-excess layered transition metal oxide having a layered rock salt structure and containing nickel.

[0053] (A) Lithium Transition Metal Composite Oxide) Positive Electrode Active Material (A) Examples of lithium transition metal composite oxides containing nickel or nickel plus one or more metals selected from the group consisting of manganese, cobalt, and aluminum and having a layered structure include lithium-nickel composite oxide, lithium-nickel-cobalt composite oxide, lithium-nickel-cobalt-aluminum composite oxide, lithium-nickel-manganese composite oxide, and lithium-nickel-manganese-cobalt composite oxide. These lithium transition metal composite oxides may also be used in which some of the transition metal atoms constituting the main component are replaced with other elements such as Al, Ti, V, Cr, Fe, Cu, Zn, Mg, Ga, Zr, Si, B, Ba, Y, and Sn. Specific examples of lithium-nickel composite oxides include LiNiO 2 , LiNiO 2 to which different elements such as Mg, Zr, Al, and Ti have been added, and LiNiO 2 particle powders in which aluminum oxide is coated on a portion of the particle surface.

[0054] Lithium nickel cobalt composite oxide and lithium nickel cobalt aluminum composite oxide are represented by the following general formula [1-1]: Li a Ni 1-b-c Co b M 1c O2 [1-1] In formula [1-1], M 1 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, and B, and a satisfies the conditions of 0.9≦a≦1.2, and b and c satisfy the conditions of 0.1≦b≦0.3 and 0≦c≦0.1. These can be prepared, for example, in accordance with the manufacturing method described in JP-A-2009-137834. Specifically, LiNi 0.8 Co 0.2 O2 and LiNi 0.85 Co 0.10 Al 0.05 O2, LiNi 0.87 Co 0.10 Al 0.03 O2, LiNi 0.6 Co 0.3 Al 0.1 O2 and the like are preferred.

[0055] Specific examples of lithium-nickel-manganese composite oxides include LiNi 0.5 Mn 0.5 O2, LiCo 0.5 Mn 0.5 Examples of the lithium-nickel-manganese-cobalt composite oxide include lithium-containing composite oxides represented by the following general formula [1-2]: Li d Ni e Mn f Co g M 2 h [1-2] In formula [1-2], M 2 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, B, and Sn, d is 0.9≦d≦1.2, and e, f, g, and h satisfy the conditions of e+f+g+h=1, 0<e≦0.9, 0<f≦0.5, 0<g≦0.5, and h≧0.

[0056] The lithium-nickel-manganese-cobalt composite oxide preferably contains manganese in the range shown in the general formula [1-2] in order to enhance the structural stability and improve the safety of lithium batteries at high temperatures, and more preferably contains cobalt in the range shown in the general formula [1-2] in order to enhance the high-rate characteristics of lithium ion batteries. Specifically, for example, a lithium-nickel-manganese-cobalt composite oxide having a charge / discharge range of 4.3 V or more, such as Li[Ni 1 / 3 Mn 1 / 3 Co 1 / 3 ]O2 (hereinafter, sometimes referred to as "NCM111"), Li[Ni 0.45 Mn 0.35 Co 0.2 ]O2, Li[Ni 0.5 Mn 0.3 Co 0.2 ]O2, Li[Ni 0.6 Mn 0.2 Co 0.2 ]O2 (hereinafter, sometimes referred to as "NCM622"), Li[Ni 0.8 Mn 0.1 Co 0.1 ]O2 (hereinafter, sometimes referred to as "NCM811"), Li[Ni 0.49 Mn 0.3 Co 0.2 Zr 0.01 ]O2, Li[Ni 0.49 Mn 0.3 Co 0.2 Mg 0.01 ]O2 and the like are preferred.

[0057] ((B) Lithium manganese composite oxide having a spinel structure) Positive electrode active material (B) Examples of lithium manganese composite oxides having a spinel structure include spinel-type lithium manganese composite oxides represented by the general formula [1-3]: Li j (Mn 2-k M 3 k )O4 [1-3] Formula [1-3], M 3contains Ni and may contain at least one metal element selected from the group consisting of Co, Fe, Mg, Cr, Cu, Al, and Ti. j is 1.05≦j≦1.15, and k is 0<k≦0.20. Specifically, for example, LiMn 1.9 Ni 0.1 O4, LiMn 1.5 Ni 0.5 O4, etc.

[0058] ((C) Lithium-containing olivine-type phosphate) Positive electrode active material (C) Examples of the lithium-containing olivine-type phosphate include those represented by the following general formula [1-4]: LiFe 1-n M 4 n PO4 [1-4] Formula [1-4] In, M 4 contains Ni and may also contain at least one selected from Co, Mn, Cu, Zn, Nb, Mg, Al, Ti, W, Zr, and Cd, where n is 0<n≦1. Specifically, LiNiPO4 and the like are suitable examples.

[0059] ((D) Lithium-Rich Layered Transition Metal Oxide) Positive Electrode Active Material (D) Examples of lithium-rich layered transition metal oxides having a layered rock salt structure include those represented by the following general formula [1-5]: xLiM 5 O2・(1-x)Li2M 6 O3 [1-5] In formula [1-5], x is a number satisfying 0<x<1, and M 5 has an average oxidation number of 3 + At least one metal element is M 6 has an average oxidation number of 4 + In formula [1-5], M is at least one metal element. 5 is preferably one or more trivalent metal elements selected from Mn, Ni, Co, Fe, V, and Cr, but may be divalent and tetravalent metals in equal amounts to make the average oxidation number trivalent.

[0060] In addition, in the formula [1-5], M 6 is preferably one or more metal elements selected from Mn, Zr and Ti. 5 and M6 Nickel is always included in either of the following. 0.5 Mn 0.5 O2] 0.5[Li2MnO3] or 0.5[LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2]・0.5[Li2MnO3], 0.5[LiNi 0.375 Co 0.25 Mn 0.375 O2]・0.5[Li2MnO3], 0.5[LiNi 0.375 Co 0.125 Fe 0.125 Mn 0.375 O2]・0.5[Li2MnO3], 0.45[LiNi 0.375 Co 0.25 Mn 0.375 Suitable examples of the positive electrode active material (D) represented by the general formula [1-5] include 0.10[LiTiO]·0.45[LiMnO]. The positive electrode active material (D) represented by the general formula [1-5] is known to exhibit high capacity upon high-voltage charging of 4.4 V (based on Li) or higher (see, for example, U.S. Patent No. 7,135,252). These positive electrode active materials can be prepared according to the manufacturing methods described in, for example, JP 2008-270201 A, WO 2013 / 118661 A, and JP 2013-030284 A.

[0061] The positive electrode active material may contain at least one selected from the above (A) to (D) as a main component, but other components that may be contained include, for example, transition element chalcogenides such as FeS, TiS, TiO, VO, MoO, and MoS, conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, radical-generating polymers, and carbon materials.

[0062] [Positive Electrode Current Collector] The positive electrode has a positive electrode current collector. As the positive electrode current collector, for example, aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used.

[0063] [Positive Electrode Active Material Layer] The positive electrode comprises, for example, a positive electrode active material layer formed on at least one surface of a positive electrode current collector. The positive electrode active material layer is composed of, for example, the above-described positive electrode active material, a binder, and, if necessary, a conductive agent. Examples of binders include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene butadiene rubber (hereinafter also referred to as "SBR"), carboxymethyl cellulose, methyl cellulose, cellulose acetate phthalate, hydroxypropyl methyl cellulose, polyvinyl alcohol, and the like. Examples of conductive agents that can be used include carbon materials such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (granular graphite or flake graphite), and fluorinated graphite. For the positive electrode, it is preferable to use acetylene black or ketjen black, which have low crystallinity.

[0064] [Negative Electrode] As described above, Si and / or Si metal oxide and graphite are used as the negative electrode active material. Specifically, the negative electrode active material in the present disclosure includes Si and / or Si metal oxide and graphite. The Si metal oxide is a compound represented by SiOx, where x has a value of 0.5 to 1.5. The negative electrode active material may include silicon metal or may include Si metal oxide (SiOx). The total content of Si and / or Si metal oxide contained in the negative electrode active material may be 0.1 to 50% by mass, preferably 0.1 to 30% by mass, where the total amount of the Si and / or Si metal oxide and graphite contained in the negative electrode active material is 100% by mass.

[0065] As the graphite contained in the negative electrode active material, various types of artificial graphite and natural graphite are used. Graphite exhibits very little change in its crystalline structure due to the absorption and desorption of lithium, resulting in high energy density and excellent cycle characteristics. The shape of the graphite may be fibrous, spherical, granular, or flaky. Furthermore, amorphous carbon or graphite coated with amorphous carbon is more preferred because it reduces the reactivity between the material surface and the electrolyte. When graphite is used in particulate form, its particle size may be, for example, 5 to 30 μm, preferably 8 to 15 μm, in terms of average particle size d50. In the case of a lithium-ion battery in which the cations in the nonaqueous electrolyte are mainly lithium, the graphite is capable of doping and dedoping lithium ions. Examples include graphite with an X-ray diffraction lattice plane (002 plane) d value of 0.340 nm or less, and graphite with an X-ray diffraction lattice plane (002 plane) d value of more than 0.340 nm. These negative electrode active materials can be used alone or in combination of two or more.

[0066] [Negative Electrode Current Collector] The negative electrode has a negative electrode current collector. As the negative electrode current collector, for example, copper, stainless steel, nickel, titanium, or an alloy thereof can be used.

[0067] [Negative Electrode Active Material Layer] The negative electrode has, for example, a negative electrode active material layer formed on at least one surface of a negative electrode current collector. The negative electrode active material layer is composed of, for example, the above-mentioned negative electrode active material, a binder, and, if necessary, a conductive agent. Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, SBR, carboxymethyl cellulose, methyl cellulose, cellulose acetate phthalate, hydroxypropyl methyl cellulose, and polyvinyl alcohol. Examples of the conductive agent that can be used include carbon materials such as acetylene black, ketjen black, furnace black, and carbon fiber.

[0068] [Method for producing electrodes (positive and negative electrodes)] The electrodes can be obtained, for example, by dispersing and kneading predetermined amounts of an active material, a binder, and, if necessary, a conductive agent in a solvent such as N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP") or water, applying the resulting paste to a current collector, and drying to form an active material layer. The resulting electrode is preferably compressed by a method such as a roll press to adjust it to an electrode with an appropriate density.

[0069] [Separator] The nonaqueous electrolyte battery of the present disclosure may include a separator. Examples of separators used to prevent contact between the positive electrode and the negative electrode include nonwoven fabrics or porous sheets made of polyolefins such as polypropylene and polyethylene, cellulose, paper, or glass fiber. These films are preferably microporous so that the electrolyte can penetrate and ions can easily pass through. Examples of polyolefin separators include microporous polymer films such as porous polyolefin films, which electrically insulate the positive electrode and negative electrode and are permeable to lithium ions. Specific examples of porous polyolefin films include porous polyethylene films alone, or multilayer films formed by stacking porous polyethylene films and porous polypropylene films. Other examples include composite films of porous polyethylene and polypropylene films. The nonaqueous electrolyte of the present disclosure may be impregnated into the separator and retained therein. There are no particular limitations on the impregnation method, and any known method may be used. Specifically, the electrolyte can be finally injected into a battery equipped with a positive electrode, a separator, and a negative electrode to impregnate the battery.

[0070] [Exterior Body] As the exterior body of the nonaqueous electrolyte battery of the present disclosure, for example, a coin-shaped, cylindrical, or rectangular metal can, or a laminated exterior body, etc. Suitable examples of metal can materials include nickel-plated steel plate, stainless steel plate, nickel-plated stainless steel plate, aluminum or its alloy, nickel, titanium, etc. As the laminated exterior body, for example, an aluminum laminate film, a SUS laminate film, or a laminate film of silica-coated polypropylene, polyethylene, etc., can be used.

[0071] The configuration of the nonaqueous electrolyte battery according to this embodiment is not particularly limited, and may be, for example, a configuration in which an electrode element in which a positive electrode and a negative electrode are arranged opposite each other and a nonaqueous electrolyte are enclosed in an exterior body. The shape of the nonaqueous electrolyte battery is not particularly limited, and an electrochemical device having a shape such as a coin, a cylinder, a square, or an aluminum laminate sheet can be assembled from the above-mentioned components. A nonaqueous electrolyte battery containing the nonaqueous electrolyte of the present disclosure can be produced, for example, by impregnating a separator with the nonaqueous electrolyte, and assembling the separator between a positive electrode having at least one selected from the group consisting of nickel-containing oxides and phosphates as a positive electrode active material and a negative electrode containing Si and / or Si metal oxide and graphite as a negative electrode active material.

[0072] Hereinafter, the present disclosure will be described in more detail with reference to Examples, Comparative Examples, and Reference Examples, but the scope of the present disclosure is not limited in any way by these Examples, Comparative Examples, and Reference Examples.

[0073] [Preparation of non-aqueous electrolyte solutions in Examples, Comparative Examples, and Reference Examples] Comparative Example 0: EC, DMC, and EMC were used as non-aqueous organic solvents, and FEC was used as an additive, and they were mixed so that the volume ratio of EC:FEC:DMC:EMC was 3:0.2:3:3.8. Next, lithium hexafluorophosphate (LiPF) was added and dissolved as a solute so that the content in the non-aqueous electrolyte solution was 1.00 mol / L, thereby preparing a base non-aqueous electrolyte solution.

[0074] Examples 1-1 to 1-7: Non-aqueous electrolyte solution 1-1 of the example was prepared by dissolving the following compound (1a) as a compound represented by general formula (1) in Comparative Example 0 (base non-aqueous electrolyte solution) to the concentration shown in the following Table 1. Similarly, non-aqueous electrolyte solutions 1-2 to 1-7 of Examples 1-2 to 1-7 were prepared by varying the concentration of compound (1a), respectively.

[0075]

[0076] Comparative Examples 1 to 5: Comparative nonaqueous electrolyte solutions 1 to 5 of Comparative Examples 1-1 to 1-5 were prepared in the same manner as in Example 1-3, except that the following compounds (comparative compounds) different from the compound represented by general formula (1) in Example 1-1 were used.

[0077]

[0078] Reference Examples 1-1 to 1-6: Reference Examples 1-1 to 1-6 (and Comparative Example 0a) relate to the same nonaqueous electrolyte as Examples 1-1 to 1-7 (and Comparative Example 0), but while Examples 1-1 to 1-7 (and Comparative Example 0) are used for nonaqueous electrolyte batteries including a negative electrode in which Si and / or Si metal oxide and graphite are used as negative electrode active materials (specifically, the "silicon-containing graphite negative electrode" described below), Reference Examples 1-1 to 1-6 (and Comparative Example 0a) were prepared for use in nonaqueous electrolyte batteries including a negative electrode in which graphite is used as the negative electrode active material (specifically, the "graphite negative electrode" described below). In other words, the effects of different negative electrode configurations are evaluated for nonaqueous electrolytes of the same composition.

[0079] Preparation of NCM811 positive electrode: Li[Ni 0.8 Mn 0.1 Co 0.1 ]O2 powder 92.0 mass %, polyvinylidene fluoride (hereinafter also referred to as "PVDF") 3.5 mass % as a binder, acetylene black 4.5 mass % as a conductive material were mixed, and NMP was further mixed with Li[Ni 0.8 Mn 0.1 Co 0.1The paste was applied to both sides of an aluminum foil (A1085), dried, pressed, and punched into a 4 cm × 5 cm piece to obtain a test NCM811 positive electrode.

[0080] Preparation of silicon-containing graphite negative electrode: 85% by mass of artificial graphite powder, 7% by mass of nanosilicon, 3% by mass of conductive material (HS-100 manufactured by Denka), 2% by mass of carbon nanofiber (VGCF manufactured by Showa Denko), 2% by mass of styrene butadiene rubber, and 1% by mass of sodium carboxymethyl cellulose (hereinafter also referred to as "CMC") were mixed, and water was further added to prepare a negative electrode composite paste. This paste was applied to copper foil, dried, pressed, and then punched out to 4.5 cm x 5.5 cm to obtain a silicon-containing graphite negative electrode for testing. In the following tables, the active material of the negative electrode is referred to as "Si-graphite."

[0081] Preparation of graphite negative electrode: A graphite negative electrode was prepared in the same manner as in the preparation of the silicon-containing graphite negative electrode, except that "85% by mass of artificial graphite powder and 7% by mass of nanosilicon" was changed to "92% by mass of artificial graphite powder."

[0082] Fabrication of nonaqueous electrolyte secondary battery (hereinafter simply referred to as "nonaqueous electrolyte battery" or "cell"): In an argon atmosphere with a dew point of -50°C or less, a terminal was welded to the above-mentioned NCM811 positive electrode, and then a polyethylene separator (5 cm x 6 cm) was placed on each side. A silicon-containing graphite negative electrode, to which a terminal had been previously welded, was placed on each side so that the separator was sandwiched between the positive electrode and the negative electrode, with the negative electrode active material surface facing the positive electrode active material surface. The resulting assembly was placed in an aluminum laminate bag with an opening on one side. The nonaqueous electrolyte prepared in the Examples and Comparative Examples was vacuum-injected, and the opening was then heat-sealed to prepare an aluminum laminate nonaqueous electrolyte battery. For the Reference Example, a nonaqueous electrolyte battery was fabricated in the same manner as described above, except that a graphite negative electrode was used as the negative electrode.

[0083] [Evaluation Conditions] (Initial Charge / Discharge) Each of the nonaqueous electrolyte batteries (cells) prepared as described above was left to stand for 12 hours (impregnation time: 12 hours) at an ambient temperature of 25° C., and then conditioned under the following conditions at an ambient temperature of 25° C. That is, as the initial charge / discharge, the battery was charged at a constant current / constant voltage of 0.1 C rate (9 mA) to an upper charge voltage of 4.3 V, and discharged at a constant current of 0.2 C rate to a discharge cut-off voltage of 2.7 V. Thereafter, the battery was charged at a constant current / constant voltage of 0.2 C rate to an upper charge voltage of 4.3 V, and discharged at a constant current of 0.2 C rate to a discharge cut-off voltage of 2.7 V. This charge / discharge cycle was repeated three times.

[0084] (Initial Resistance) The cell that had been subjected to the above conditioning was charged to 4.3 V at 25° C. and a rate of 0.2 C, and then impedance measurement was carried out in an environment of −20° C. to measure the resistance, which was taken as the initial resistance.

[0085] (Cycle Characteristics) A charge / discharge test was conducted at an ambient temperature of 25°C on the cells whose initial resistances had been measured, and the cycle characteristics were evaluated. Charge / discharge cycles were repeated at a current of 90 mA using a constant current / constant voltage method, with a charge upper limit voltage of 4.3 V and a discharge lower limit voltage of 2.7 V. The degree of cell deterioration was evaluated based on the discharge capacity retention rate at the 400th cycle in the charge / discharge test at an ambient temperature of 25°C. The "post-cycle discharge capacity retention rate," expressed as the discharge capacity retention rate at the 400th cycle, was calculated using the following formula: The discharge capacity at the first cycle in the charge / discharge test at an ambient temperature of 25°C was defined as the initial discharge capacity. Post-cycle discharge capacity retention rate (%) = (discharge capacity at the 400th cycle / initial discharge capacity) × 100. The results of the initial resistance and cycle characteristics were expressed as relative values, with the results for the base nonaqueous electrolyte (Comparative Example 0 or 0a) being set at 100. The same applies hereinafter.

[0086]

[0087] Evaluation: As can be seen from the results in Table 1, in nonaqueous electrolyte batteries including a negative electrode having Si and / or Si metal oxide and graphite as the negative electrode active material, when compared at the same concentration, the Examples using (I) of the present disclosure are found to be significantly improved in both characteristics, post-cycle discharge capacity retention rate (hereinafter also simply referred to as "cycle characteristics") and initial resistance, compared to the Comparative Examples using the Comparative Compound. Furthermore, when the Examples of the present disclosure are compared with the Reference Examples, it is found that the nonaqueous electrolyte according to the present disclosure is found to be significantly improved in both characteristics, post-cycle characteristics and initial resistance, when used in a nonaqueous electrolyte battery having Si and / or Si metal oxide and graphite as the negative electrode active material, compared to when used in a nonaqueous electrolyte battery having graphite as the negative electrode active material.

[0088] Examples 1-8 to 1-14: Non-aqueous electrolyte solution 1-8 of the example was prepared by dissolving the following compound (1b) as a compound represented by general formula (1) in Comparative Example 0 (base non-aqueous electrolyte solution) to the concentration shown in Table 2 below. Similarly, non-aqueous electrolyte solutions 1-9 to 1-14 of the example were prepared by varying the concentration of compound (1b). Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as the examples in Table 1.

[0089]

[0090] Reference Examples 1-7 to 1-12: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the reference examples in Table 1, except that the same non-aqueous electrolytes as in Examples 1-8 to 1-13 were used.

[0091]

[0092] Evaluation: Also in Table 2, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0093] Examples 1-15 to 1-21: In Comparative Example 0 (base nonaqueous electrolyte), the following compound (1c) was dissolved as a compound represented by general formula (1) to the concentration shown in Table 3 below, to prepare nonaqueous electrolyte 1-15 of the example. Similarly, nonaqueous electrolytes 1-16 to 1-21 of the example were prepared by varying the concentration of compound (1c). Furthermore, nonaqueous electrolyte batteries were fabricated and evaluated in the same manner as the examples in Table 1.

[0094]

[0095] Reference Examples 1-13 to 1-18: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 1-15 to 1-20 were used.

[0096]

[0097] Evaluation: Also in Table 3, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0098] Examples 1-22 to 1-28: In Comparative Example 0 (base nonaqueous electrolyte), the following compound (1d) was dissolved as a compound represented by general formula (1) to the concentration shown in Table 4 below, to prepare nonaqueous electrolyte 1-22 of the example. Similarly, nonaqueous electrolytes 1-23 to 1-28 of the example were prepared by varying the concentration of compound (1d). Furthermore, nonaqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples in Table 1.

[0099]

[0100] Reference Examples 1-19 to 1-24: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 1-22 to 1-27 were used.

[0101]

[0102] Evaluation: Also in Table 4, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0103] Examples 1-29 to 1-35: In Comparative Example 0 (base nonaqueous electrolyte), the following compound (1e) was dissolved as a compound represented by general formula (1) to the concentration shown in Table 5 below, to prepare nonaqueous electrolyte 1-29 of the example. Similarly, nonaqueous electrolytes 1-30 to 1-35 of the example were prepared by varying the concentration of compound (1e). Furthermore, nonaqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples in Table 1.

[0104]

[0105] Reference Examples 1-25 to 1-30: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 1-29 to 1-34 were used.

[0106]

[0107] Evaluation: Also in Table 5, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0108] Examples 1-36 to 1-42: In Comparative Example 0 (base nonaqueous electrolyte), the following compound (1f) was dissolved as a compound represented by general formula (1) to the concentration shown in Table 6 below, to prepare nonaqueous electrolyte 1-36 of the example. Similarly, nonaqueous electrolytes 1-37 to 1-42 of the example were prepared by varying the concentration of compound (1f). Furthermore, nonaqueous electrolyte batteries were fabricated and evaluated in the same manner as the examples in Table 1.

[0109]

[0110] Reference Examples 1-31 to 1-36: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 1-36 to 1-41 were used.

[0111]

[0112] Evaluation: Also in Table 6, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0113] Examples 2-1 to 2-7: In Comparative Example 0 (base nonaqueous electrolyte), the following compound (2a) was dissolved as a compound represented by general formula (2) to the concentration shown in Table 7 below, to prepare nonaqueous electrolyte 2-1 of the example. Similarly, nonaqueous electrolytes 2-2 to 2-7 of the example were prepared by varying the concentration of compound (2a). Furthermore, nonaqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples in Table 1.

[0114]

[0115] Reference Examples 2-1 to 2-7: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 2-1 to 2-7 were used.

[0116]

[0117] Evaluation: Also in Table 7, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0118] Examples 2-8 to 2-14: Non-aqueous electrolyte solution 2-8 of the example was prepared by dissolving the following compound (2b), which is a compound represented by general formula (2), in Comparative Example 0 (base non-aqueous electrolyte solution) to the concentration shown in Table 8 below. Similarly, non-aqueous electrolyte solutions 2-9 to 2-14 of the example were prepared by varying the concentration of compound (2b). Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as the examples in Table 1.

[0119]

[0120] Reference Examples 2-8 to 2-14: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 2-8 to 2-14 were used.

[0121]

[0122] Evaluation: Also in Table 8, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0123] Examples 2-15 to 2-21: In Comparative Example 0 (base nonaqueous electrolyte), the following compound (2c) was dissolved as a compound represented by general formula (2) to the concentration shown in Table 9 below, to prepare nonaqueous electrolyte 2-15 of the example. Similarly, nonaqueous electrolytes 2-16 to 2-21 of the example were prepared by varying the concentration of compound (2c). Furthermore, nonaqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples in Table 1.

[0124]

[0125] Reference Examples 2-15 to 2-20: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 2-15 to 2-20 were used.

[0126]

[0127] Evaluation: Also in Table 9, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0128] Examples 2-22 to 2-28: Non-aqueous electrolyte solution 2-22 of the example was prepared by dissolving the following compound (2d), which is a compound represented by general formula (2), in Comparative Example 0 (base non-aqueous electrolyte solution) to the concentration shown in Table 10 below. Similarly, non-aqueous electrolyte solutions 2-23 to 2-28 of the example were prepared by varying the concentration of compound (2d). Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as the examples in Table 1.

[0129]

[0130] Reference Examples 2-21 to 2-26: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 2-22 to 2-27 were used.

[0131]

[0132] Evaluation: Also in Table 10, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0133] Examples 2-29 to 2-35: In Comparative Example 0 (base nonaqueous electrolyte), the following compound (2e) was dissolved as a compound represented by general formula (2) to the concentration shown in Table 11 below, to prepare nonaqueous electrolyte 2-29 of the example. Similarly, nonaqueous electrolytes 2-30 to 2-35 of the example were prepared by varying the concentration of compound (2e). Furthermore, nonaqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples in Table 1.

[0134]

[0135] Reference Examples 2-27 to 2-32: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 2-29 to 2-34 were used.

[0136]

[0137] Evaluation: Also in Table 11, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0138] Examples 2-36 to 2-42: Non-aqueous electrolyte solution 2-36 of the example was prepared by dissolving the following compound (2f), which is a compound represented by general formula (2), in Comparative Example 0 (base non-aqueous electrolyte solution) to the concentration shown in Table 12 below. Similarly, non-aqueous electrolyte solutions 2-37 to 2-42 of the example were prepared by varying the concentration of compound (2f). Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as the examples in Table 1.

[0139]

[0140] Reference Examples 2-33 to 2-38: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 2-36 to 2-41 were used.

[0141]

[0142] Evaluation: Also in Table 12, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0143] Examples 3-1 to 3-7: Non-aqueous electrolyte solution 3-1 of the example was prepared by dissolving the following compound (3a) as a compound represented by general formula (3) in Comparative Example 0 (base non-aqueous electrolyte solution) to the concentration shown in Table 13 below. Similarly, non-aqueous electrolyte solutions 3-2 to 3-7 of the example were prepared by varying the concentration of compound (3a). Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as the examples in Table 1.

[0144]

[0145] Reference Examples 3-1 to 3-6: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the reference examples in Table 1, except that the same non-aqueous electrolytes as in Examples 3-1 to 3-6 were used.

[0146]

[0147] Evaluation: Also in Table 13, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, significantly improves both the cycle characteristics and the initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0148] Examples 3-8 to 3-14: Non-aqueous electrolyte solution 3-8 of the example was prepared by dissolving the following compound (3b), which is a compound represented by general formula (3), in Comparative Example 0 (base non-aqueous electrolyte solution) to the concentration shown in Table 14 below. Similarly, non-aqueous electrolyte solutions 3-9 to 3-14 of the example were prepared by varying the concentration of compound (3b). Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as the examples in Table 1.

[0149]

[0150] Reference Examples 3-7 to 3-12: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 3-8 to 3-13 were used.

[0151]

[0152] Evaluation: Also in Table 14, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0153] Examples 4-1 to 4-7: In Comparative Example 0 (base nonaqueous electrolyte), the following compound (4a) was dissolved as a compound represented by general formula (4) to the concentration shown in Table 15 below, to prepare nonaqueous electrolyte 4-1 of the example. Similarly, nonaqueous electrolytes 4-2 to 4-7 of the example were prepared by varying the concentration of compound (4a). Furthermore, nonaqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples in Table 1.

[0154]

[0155] Reference Examples 4-1 to 4-6: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 4-1 to 4-6 were used.

[0156]

[0157] Evaluation: Also in Table 15, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0158] Examples 4-8 to 4-14: Non-aqueous electrolyte solution 4-8 of the example was prepared by dissolving the following compound (4b), which is a compound represented by general formula (4), in Comparative Example 0 (base non-aqueous electrolyte solution) to the concentration shown in Table 16 below. Similarly, non-aqueous electrolyte solutions 4-9 to 4-14 of the example were prepared by varying the concentration of compound (4b). Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as the examples in Table 1.

[0159]

[0160] Reference Examples 4-7 to 4-12: Non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the Reference Examples in Table 1, except that the same non-aqueous electrolytes as in Examples 4-8 to 4-13 were used.

[0161]

[0162] Evaluation: Also in Table 16, when comparing the Examples of the present disclosure with the Comparative Examples, it can be seen that the nonaqueous electrolyte according to the present disclosure, when used in a nonaqueous electrolyte battery using Si and / or Si metal oxide and graphite as the negative electrode active material, exhibits significantly improved characteristics in both cycle characteristics and initial resistance, compared to when used in a nonaqueous electrolyte battery using graphite as the negative electrode active material.

[0163] Comparative Example 17-1 (Preparation of Base Comparative Non-Aqueous Electrolyte Solution 17) EC:FEC:DMC:EMC were mixed in a volume ratio of 3:0.2:3:3.8 to prepare a non-aqueous organic solvent containing other additives, and LiPF was dissolved in the solvent as a solute so that its content in the non-aqueous electrolyte solution was 1.00 mol / L. Furthermore, VC and DFOB represented by the following formula were each dissolved as other additives to the concentrations shown in Table 17 below to prepare base non-aqueous electrolyte solution 17. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0164]

[0165] Examples 17-1 to 17-16: Non-aqueous electrolyte solutions 17-1 to 17-16 of the examples were prepared by dissolving various compounds according to component (I) of the present disclosure in base non-aqueous electrolyte solution 17 to the concentrations shown in Table 17 below. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0166]

[0167] The results shown in Table 17 show that even when the nonaqueous electrolyte solution contains other additives, when the nonaqueous electrolyte solution according to the examples containing various compounds according to component (I) of the present disclosure is used, in a nonaqueous electrolyte battery using Si-graphite as the negative electrode active material, both the cycle characteristics and the initial resistance are significantly improved compared to when base nonaqueous electrolyte solution 17 is used.

[0168] Comparative Example 18-1 (Preparation of Base Comparative Non-Aqueous Electrolyte Solution 18) Base non-aqueous electrolyte solution 18 was prepared in the same manner as base non-aqueous electrolyte solution 17, except that VC and BOB represented by the following formula were dissolved as other additives to the concentrations shown in Table 18. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0169]

[0170] Examples 18-1 to 18-16: Non-aqueous electrolyte solutions 18-1 to 18-16 of the examples were prepared by dissolving various compounds according to component (I) of the present disclosure in base non-aqueous electrolyte solution 18 to the concentrations shown in Table 18 below. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0171]

[0172] The results shown in Table 18 show that even when the nonaqueous electrolyte solution contains other additives, when the nonaqueous electrolyte solution according to the examples containing various compounds according to component (I) of the present disclosure is used, in a nonaqueous electrolyte battery using Si-graphite as the negative electrode active material, both the cycle characteristics and the initial resistance are significantly improved compared to when base nonaqueous electrolyte solution 18 is used.

[0173] Comparative Example 19-1 (Preparation of Base Non-Aqueous Electrolyte Solution 19) Base non-aqueous electrolyte solution 19 was prepared in the same manner as base non-aqueous electrolyte solution 17, except that VC and TFOP represented by the following formula were dissolved as other additives to the concentrations shown in Table 19. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0174]

[0175] Examples 19-1 to 19-16: Non-aqueous electrolyte solutions 19-1 to 19-16 of the examples were prepared by dissolving various compounds according to component (I) of the present disclosure in base non-aqueous electrolyte solution 19 to the concentrations shown in Table 19 below. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0176]

[0177] The results shown in Table 19 show that even when the nonaqueous electrolyte solution contains other additives, when the nonaqueous electrolyte solutions according to the examples containing various compounds according to component (I) of the present disclosure are used, in a nonaqueous electrolyte battery using Si-graphite as the negative electrode active material, both the cycle characteristics and the initial resistance are significantly improved compared to when base nonaqueous electrolyte solution 19 is used.

[0178] Comparative Example 20-1 (Preparation of Base Non-Aqueous Electrolyte Solution 20) Base non-aqueous electrolyte solution 20 was prepared in the same manner as base non-aqueous electrolyte solution 17, except that VC and DFBOP represented by the following formula were dissolved as other additives to the concentrations shown in Table 20. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0179]

[0180] Examples 20-1 to 20-16: Non-aqueous electrolyte solutions 20-1 to 20-16 of the examples were prepared by dissolving various compounds according to component (I) of the present disclosure in base non-aqueous electrolyte solution 20 to the concentrations shown in Table 20 below. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0181]

[0182] The results shown in Table 20 show that even when the nonaqueous electrolyte contains other additives, when the nonaqueous electrolyte according to the examples containing various compounds according to component (I) of the present disclosure is used, in a nonaqueous electrolyte battery using Si-graphite as the negative electrode active material, both the cycle characteristics and the initial resistance are significantly improved compared to when base nonaqueous electrolyte 20 is used.

[0183] Comparative Example 21-1 (Preparation of Base Non-Aqueous Electrolyte Solution 21) Base non-aqueous electrolyte solution 21 was prepared in the same manner as base non-aqueous electrolyte solution 17, except that other additives, VC, DFP represented by the following formula, and FS represented by the following formula, were dissolved to the concentrations shown in Table 21. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0184]

[0185] Examples 21-1 to 21-16: Non-aqueous electrolyte solutions 21-1 to 21-16 of the examples were prepared by dissolving various compounds according to component (I) of the present disclosure in base non-aqueous electrolyte solution 21 to the concentrations shown in Table 21 below. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0186]

[0187] The results shown in Table 21 show that even when the nonaqueous electrolyte solution contains other additives, when the nonaqueous electrolyte solution according to the examples containing various compounds according to component (I) of the present disclosure is used, in a nonaqueous electrolyte battery using Si-graphite as the negative electrode active material, both the cycle characteristics and the initial resistance are significantly improved compared to when base nonaqueous electrolyte solution 21 is used.

[0188] Comparative Example 22-1 (Preparation of Base Non-Aqueous Electrolyte Solution 22) Base non-aqueous electrolyte solution 22 was prepared in the same manner as base non-aqueous electrolyte solution 17, except that other additives, VC, DFP, and DFPFSI represented by the following formula, were dissolved to the concentrations shown in Table 22. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0189]

[0190] Examples 22-1 to 22-16: Non-aqueous electrolyte solutions 22-1 to 22-16 of the examples were prepared by dissolving various compounds according to component (I) of the present disclosure in base non-aqueous electrolyte solution 22 to the concentrations shown in Table 22 below. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0191]

[0192] The results shown in Table 22 show that even when the nonaqueous electrolyte solution contains other additives, when the nonaqueous electrolyte solution according to the examples containing various compounds according to component (I) of the present disclosure is used, in a nonaqueous electrolyte battery using Si-graphite as the negative electrode active material, both the cycle characteristics and the initial resistance are significantly improved compared to when base nonaqueous electrolyte solution 22 is used.

[0193] Comparative Example 23-1 (Preparation of Base Non-Aqueous Electrolyte Solution 23) FSI shown below was dissolved as an additional solute, and VC and DTD represented by the following formula were dissolved as other additives to the concentrations shown in Table 23 below to prepare base non-aqueous electrolyte solution 23. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0194]

[0195] Examples 23-1 to 23-16: Non-aqueous electrolyte solutions 23-1 to 23-16 of the examples were prepared by dissolving various compounds according to component (I) of the present disclosure in base non-aqueous electrolyte solution 23 to the concentrations shown in Table 23 below. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0196]

[0197] The results shown in Table 23 show that even when the nonaqueous electrolyte contains additional solutes or other additives, when the nonaqueous electrolyte according to the examples containing various compounds according to component (I) of the present disclosure is used, in a nonaqueous electrolyte battery using Si-graphite as the negative electrode active material, both the cycle characteristics and the initial resistance are significantly improved compared to when base nonaqueous electrolyte 23 is used.

[0198] Comparative Example 24-1 (Preparation of Base Non-Aqueous Electrolyte Solution 24) LiBF4 as an additional solute, and VC and TDUTO represented by the following formula as other additives were dissolved to the concentrations shown in Table 24 below to prepare base non-aqueous electrolyte solution 24. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0199]

[0200] Examples 24-1 to 24-16: Non-aqueous electrolyte solutions 24-1 to 24-16 of the examples were prepared by dissolving various compounds according to component (I) of the present disclosure in base non-aqueous electrolyte solution 24 to the concentrations shown in Table 24 below. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0201]

[0202] The results shown in Table 24 show that even when the nonaqueous electrolyte contains additional solutes or other additives, when the nonaqueous electrolyte according to the examples containing various compounds according to component (I) of the present disclosure is used, in a nonaqueous electrolyte battery using Si-graphite as the negative electrode active material, both the cycle characteristics and the initial resistance are significantly improved compared to when base nonaqueous electrolyte 24 is used.

[0203] Comparative Example 25-1 (Preparation of Base Non-Aqueous Electrolyte Solution 25) As other additives, VC, DFP, and diglycolic acid anhydride (DGA) represented by the following formula were dissolved to the concentrations shown in Table 25 below to prepare base non-aqueous electrolyte solution 25. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0204]

[0205] Examples 25-1 to 25-16: Non-aqueous electrolyte solutions 25-1 to 25-16 of the examples were prepared by dissolving various compounds according to component (I) of the present disclosure in base non-aqueous electrolyte solution 25 to the concentrations shown in Table 25 below. Furthermore, non-aqueous electrolyte batteries were fabricated and evaluated in the same manner as in the examples of Table 1.

[0206]

[0207] The results shown in Table 25 show that even when the nonaqueous electrolyte contains other additives, when the nonaqueous electrolyte according to the examples containing various compounds according to component (I) of the present disclosure is used, in a nonaqueous electrolyte battery using Si-graphite as the negative electrode active material, both the cycle characteristics and the initial resistance are significantly improved compared to when base nonaqueous electrolyte 25 is used.

Claims

1. A nonaqueous electrolyte used in a nonaqueous electrolyte battery having a positive electrode and a negative electrode containing Si and / or Si metal oxide and graphite as negative electrode active materials, the nonaqueous electrolyte comprising the following components: (I) at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), and a compound represented by the following general formula (4), (II) a solute, and (III) a nonaqueous organic solvent. [In general formula (1), R 1 is a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (a part or all of the hydrogen atoms of the hydrocarbon group may be each independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have an ether group between any carbon-carbon atom), or (M A a+ ) b (The above M A a+ represents a cation selected from a proton, a metal cation, and an onium cation, a represents the valence of the cation, and b represents a number such that a×b=1. 1 However, (M A a+ ) b In the case of R 1 The other sites are counter anions. 2 and R 3 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (a part or all of the hydrogen atoms of the hydrocarbon group may each independently be substituted with a halogen atom, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon-carbon atoms), and R 2 and R 3 may combine together to form a carbonyl group. [In general formula (2), R 4 represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (a part or all of the hydrogen atoms of the hydrocarbon group may be independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon-carbon atoms). 5 and R 6 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (a part or all of the hydrogen atoms of the hydrocarbon group may each independently be substituted with a halogen atom, a cyano group, or an isocyano group, or may have a heteroatom, a carbonyl group, an ester group, or an ether group between the carbon atoms); R 5 and R 6 may combine together to form a carbonyl group. [In general formula (3), R 7 is a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (a part or all of the hydrogen atoms of the hydrocarbon group may be each independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have an ether group between any carbon-carbon atom), or (M C e+ ) f (The above M C e+ represents a cation selected from a proton, a metal cation, and an onium cation, e represents the valence of the cation, and f represents a number such that e×f=1. 7 But (M C e+ ) f In the case of R 7 The other sites are counter anions. 8 and R 9 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (a part or all of the hydrogen atoms of the hydrocarbon group may each independently be substituted with a halogen atom, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon-carbon atoms), and R 8 and R 9 may combine together to form a carbonyl group. [In general formula (4), R 10 represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (a part or all of the hydrogen atoms of the hydrocarbon group may be independently substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon-carbon atoms). 11 and R 12 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkoxy group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a heteroaryl group having 6 to 10 carbon atoms, and a heteroaryloxy group having 6 to 10 carbon atoms (a part or all of the hydrogen atoms of the hydrocarbon group may each independently be substituted with a halogen atom, a cyano group, or an isocyano group, and the hydrocarbon group may have a heteroatom, a carbonyl group, an ester group, or an ether group between any carbon-carbon atoms); R 11 and R 12 may combine together to form a carbonyl group.

2. The nonaqueous electrolyte according to claim 1, wherein the concentration of (I) is 0.01 to 11 mass % based on the total amount of the nonaqueous electrolyte.

3. The nonaqueous electrolyte according to claim 2, wherein the concentration of (I) is 0.08 to 10.5 mass % based on the total amount of the nonaqueous electrolyte.

4. The nonaqueous electrolyte according to claim 3, wherein the concentration of (I) is 0.20 to 9 mass % based on the total amount of the nonaqueous electrolyte.

5. The nonaqueous electrolyte according to claim 1, wherein the compound (I) is at least one selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2).

6. The nonaqueous electrolyte according to claim 1, wherein (II) is at least one selected from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiN(SO2F)2, LiAlO2, LiAlCl4, LiCl, and LiI.

7. The nonaqueous electrolyte according to claim 1, wherein the (III) contains at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids.

8. The non-aqueous electrolyte according to claim 7, wherein the cyclic ester comprises a cyclic carbonate.

9. The nonaqueous electrolyte according to claim 8, wherein the cyclic carbonate comprises at least one selected from the group consisting of ethylene carbonate and propylene carbonate.

10. The nonaqueous electrolyte according to claim 7, wherein the chain ester comprises a chain carbonate.

11. The nonaqueous electrolyte according to claim 10, wherein the chain carbonate comprises at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

12. The non-aqueous electrolyte further comprises cyclohexylbenzene, cyclohexylfluorobenzene, biphenyl, 2-fluorobiphenyl, t-butylbenzene, t-amylbenzene, 2-fluorotoluene, fluorobenzene, vinylene carbonate, an oligomer of vinylene carbonate (having a number average molecular weight of 170 to 5000 in terms of polystyrene), vinylethylene carbonate, difluoroanisole, fluoroethylene carbonate, 1,6-diisocyanatohexane, ethynylethylene carbonate, trans-difluoroethylene carbonate, methyl ... Chill propargyl carbonate, ethyl propargyl carbonate, dipropargyl carbonate, maleic anhydride, succinic anhydride, 1,3-propane sultone, 1,3-propene sultone, 1,4-butane sultone, dimethylvinylene carbonate, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylenemethane disulfonate, dimethylmethane disulfonate, trimethylenemethane disulfonate, methyl methanesulfonate, methanesulfonyl fluoride, ethene sulfonyl fluoride, phenyl difluorophosphate, 1,2-ethanedisulfonic anhydride, tris(trimethylsilyl)borate, succinonitrile, (ethoxy)pentafluorocyclotriphosphazene, tetrafluoro(picolinato)phosphate, difluoro(picolinato)borate, 1,3-dimethyl-1,3-divinyl-1,3-di(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, lithium difluorophosphate, sodium difluorophosphate, lithium fluorosulfate, sodium fluorosulfate, trifluoromethyl lithium ethanesulfonate, sodium trifluoromethanesulfonate, lithium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, lithium difluorobis(oxalato)phosphate, sodium difluorobis(oxalato)phosphate, lithium difluorooxalatoborate, sodium difluorooxalatoborate, lithium bis(oxalato)borate, sodium bis(oxalato)borate, lithium tetrafluorooxalatophosphate, sodium tetrafluorooxalatophosphate, lithium tris(oxalato)phosphate,Sodium tris(oxalato)phosphate, lithium difluoro(malonato)borate, sodium difluoro(malonato)borate, lithium tetrafluoro(malonato)phosphate, sodium tetrafluoro(malonato)phosphate, lithium monofluorophosphate, sodium monofluorophosphate, lithium bis(difluorophosphoryl)imide, sodium bis(difluorophosphoryl)imide, lithium (difluorophosphoryl)(fluorosulfonyl)imide, sodium (difluorophosphoryl)(fluorosulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, sodium bis(trifluoromethanesulfonyl)imide, lithium bis(pentafluoroethanesulfonyl)imide, sodium bis(pentafluoroethanesulfonyl)imide, lithium (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide, The non-aqueous electrolyte solution according to claim 1, which contains at least one selected from the group consisting of (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide sodium, (trifluoromethanesulfonyl)(fluorosulfonyl)imide lithium, (trifluoromethanesulfonyl)(fluorosulfonyl)imide sodium, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide lithium, (pentafluoroethanesulfonyl)(fluorosulfonyl)imide sodium, tris(trifluoromethanesulfonyl)methide lithium, tris(trifluoromethanesulfonyl)methide sodium, lithium acrylate, sodium acrylate, lithium methacrylate, sodium methacrylate, lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, sodium ethyl sulfate, lithium nitrate, lithium nitrite, sodium nitrite, and sodium nitrite.

13. The nonaqueous electrolyte according to claim 1, further comprising a compound represented by the following general formula (5): [In general formula (5), R 13 each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms, and an oxygen atom may be contained between any carbon atom-carbon atom bond in the alkyl group. In addition, any hydrogen atom in the alkyl group may be substituted with a fluorine atom.

14. The compound represented by the general formula (5) is the following compound: The nonaqueous electrolyte according to claim 13, which is at least one selected from the group consisting of:

15. The nonaqueous electrolyte according to claim 1, further comprising a compound represented by the following general formula (6): [In general formula (6), R 14 ~R 17 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group; and X represents an oxygen atom, a sulfur atom, or an SO2 group.

16. The nonaqueous electrolyte according to claim 15, wherein the compound of formula (6) is a compound represented by the following formula:

17. The nonaqueous electrolyte according to claim 1, wherein the total content of the Si and / or Si metal oxide with respect to the total amount of the Si and / or Si metal oxide and graphite is 0.1 to 50 mass %.

18. A nonaqueous electrolyte battery comprising: a positive electrode; a negative electrode containing Si and / or Si metal oxide and graphite as negative electrode active materials; and the nonaqueous electrolyte according to any one of claims 1 to 17.

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