Non-aqueous electrolyte, non-aqueous electrolyte battery, and compound

Abstract

Provided are: a non-aqueous electrolyte solution capable of exhibiting excellent initial input / output characteristics when formed into a non-aqueous electrolyte solution battery; a non-aqueous electrolyte solution battery capable of exhibiting excellent initial input / output characteristics; and a compound suitable for use in the non-aqueous electrolyte solution. Provided are: a non-aqueous electrolyte solution; a non-aqueous electrolyte solution battery comprising the non-aqueous electrolyte solution; and a compound represented by any of general formulae (1)-(4) described in the description. The nonaqueous electrolyte solution contains: (I) at least (1) compounds selected from the group consisting of compounds represented by general formula (1), compounds represented by general formula (2), compounds represented by general formula (3), and compounds represented by general formula (4), which are described in the description; (II) a solute; and, (III) a non-aqueous organic solvent.

Description

Technical Field

[0001] The present disclosure relates to non-aqueous electrolytes, non-aqueous electrolyte batteries, and compounds. Background Art

[0002] In recent years, the demand for high-capacity, high-power, and high-energy-density batteries for use as auxiliary power sources in electric vehicles, hybrid vehicles, and fuel cell vehicles has rapidly increased, in addition to power storage systems for small, high-energy-density applications such as information-related devices and communications equipment, namely personal computers, video cameras, digital cameras, mobile phones, and smartphones. Furthermore, the demand for batteries capable of long-term use in power storage systems for large, high-power applications such as electricity storage has also increased. As candidates for these various power storage systems, non-aqueous electrolyte batteries such as lithium-ion batteries, lithium batteries, and lithium-ion capacitors are being actively developed.

[0003] Lithium secondary batteries are mainly composed of a positive electrode, a non-aqueous electrolyte, and a negative electrode. Examples of the negative electrode of a lithium secondary battery include metallic lithium, metal compounds capable of absorbing and releasing lithium (e.g., metal elements, oxides, alloys with lithium, etc.), and carbon materials. In particular, lithium secondary batteries using carbon materials such as coke, artificial graphite, and natural graphite that can absorb and release lithium are widely used. For example, it has been reported that lithium secondary batteries using highly crystalline carbon materials such as natural graphite and artificial graphite as negative electrode materials have a negative effect on the negative electrode surface due to the non-aqueous organic solvent in the non-aqueous electrolyte being reduced and decomposed during charging. Consequently, the decomposition products and gases produced by the non-aqueous solvent interfere with the original electrochemical reaction of the battery, thereby reducing the cycle characteristics.

[0004] In addition, although lithium secondary batteries using lithium metal, its alloys, metal elements such as silicon and tin, oxides, etc. as negative electrode materials have a high initial capacity, the negative electrode material undergoes micronization during the cycle. Therefore, compared with the negative electrode of carbon material, it is easy to cause reductive decomposition of non-aqueous organic solvents. Therefore, as a result, it is known that the battery's initial irreversible capacity increases, and the battery performance such as the battery capacity and cycle characteristics decreases significantly.

[0005] During the first cycle charge, when lithium cations are embedded in the negative electrode, the negative electrode and the lithium cations, or the negative electrode and the electrolyte solvent, react to form a film composed mainly of lithium oxide, lithium carbonate, or alkyl lithium carbonate on the negative electrode surface. This film on the electrode surface is called the Solid Electrolyte Interface (SEI), which inhibits the reductive decomposition of the solvent and the deterioration of battery performance, and its properties have a significant impact on battery performance.

[0006] As described above, due to the accumulation of decomposition products of the non-aqueous organic solvent, gas generation, adverse effects caused by the pulverization of the negative electrode material, etc., lithium absorption and release into the negative electrode cannot proceed smoothly, resulting in a significant deterioration in battery characteristics such as cycle characteristics.

[0007] In addition, as positive electrodes, for example, LiCoO2, LiMn2O4, LiNiO2, and LiFePO4 are known. When a lithium secondary battery using these materials reaches a high temperature in a charged state, a portion of the non-aqueous organic solvent in the non-aqueous electrolyte undergoes oxidative decomposition locally at the interface between the positive electrode material and the non-aqueous electrolyte. The resulting decomposition products and gases interfere with the battery's original electrochemical reaction, resulting in reported reductions in battery performance such as cycle characteristics. It is known that a film based on oxidative decomposition products is formed on the surface of the positive electrode, similar to the negative electrode, and this film also plays an important role in suppressing the oxidative decomposition of the solvent and suppressing the amount of gas generated.

[0008] As described above, conventional lithium secondary batteries have the following reasons for degrading battery performance: decomposition products and gases generated when the non-aqueous electrolyte decomposes on the positive and negative electrodes hinder the movement of lithium ions, or the battery swells, thereby degrading battery performance.

[0009] In order to overcome these problems and improve battery performance represented by long-term durability and output characteristics, it is important to form a SEI with high ion conductivity, low electron conductivity, and long-term stability. The following attempts have been widely made: by adding a small amount (usually more than 0.01 mass% and less than 10 mass%) of a compound called an additive to the non-aqueous electrolyte, a good SEI is actively formed.

[0010] Patent Document 1 describes that the storage characteristics of a battery can be improved by using a non-aqueous electrolyte solution containing a tricarbimide compound such as triallyl cyanurate or triallyl isocyanurate.

[0011] Patent Document 2 describes that the initial charge and discharge capacity, input / output characteristics, and impedance characteristics are improved by using a non-aqueous electrolyte solution containing a fluorosulfonate.

[0012] Patent Document 3 describes that battery characteristics such as cycle characteristics and high-temperature storage characteristics are improved by using a non-aqueous electrolyte solution containing a compound having a cyanuric acid skeleton and at least one compound selected from the group consisting of a halogenated cyclic carbonate compound, a difluorophosphate, and a monofluorosulfonate.

[0013] Patent Document 4 discloses a heterocyclic sulfonyl fluoride additive of a specified structure for use in lithium battery electrolyte compositions. It states that electrolyte compositions containing this additive exhibit excellent electrochemical properties, such as long cycle life, high capacity retention, low resistance accumulation during cycling, and good storage stability. In particular, the examples of Patent Document 4 describe the use of 3,3',3"-(2,4,6-trioxo-[1,3,5]triazine-1,3,5-triyl)-tri-ethanesulfonyl fluoride as the additive.

[0014] Prior art literature

[0015] Patent Literature

[0016] Patent Document 1: Japanese Patent Application Laid-Open No. 7-192757

[0017] Patent Document 2: Japanese Patent Application Laid-Open No. 2013-152956

[0018] Patent Document 3: Japanese Patent Application Laid-Open No. 2014-063733

[0019] Patent Document 4: Japanese Patent Application No. 2020-527284 Summary of the Invention

[0020] Problems to be solved by the invention

[0021] However, the present inventors' research has shown that the initial input / output characteristics are significantly reduced when a non-aqueous electrolyte containing a tricarboximide compound such as triallyl cyanurate or triallyl isocyanurate is used as a non-aqueous electrolyte, as disclosed in Patent Document 1. Furthermore, it has been shown that even when using a non-aqueous electrolyte containing a fluorinated lithium sulfonate as disclosed in Patent Document 2, a non-aqueous electrolyte containing a compound having a cyanuric acid skeleton and a monofluorosulfonate as disclosed in Patent Document 3, or a non-aqueous electrolyte containing an additive as disclosed in Patent Document 4, there is room for improvement in the initial input / output characteristics.

[0022] The present disclosure aims to provide a non-aqueous electrolyte that exhibits excellent initial input / output characteristics when forming a non-aqueous electrolyte battery, a non-aqueous electrolyte battery that exhibits excellent initial input / output characteristics, and a compound suitable for use in the non-aqueous electrolyte.

[0023] Solutions for solving problems

[0024] The present inventors have conducted extensive research in view of the above problems and have found that:

[0025] The above-mentioned problem is solved by providing a non-aqueous electrolyte solution containing (I) at least one compound 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) (hereinafter sometimes referred to as "component (I)"), (II) a solute (hereinafter sometimes referred to as "component (II)") and (III) a non-aqueous organic solvent (hereinafter sometimes referred to as "component (III)"), thereby obtaining a non-aqueous electrolyte battery that can exhibit excellent initial input / output characteristics.

[0026] That is, the present inventors have found that the above-mentioned problems can be solved by the following configuration. [1]

[0028] A non-aqueous electrolyte comprising:

[0029] (I) at least one compound 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);

[0030] (II) solute; and

[0031] (III) Non-aqueous organic solvent.

[0032]

[0033] [In the general formula (1), R 1 ~R 3 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. 1 ~R 3 At least one of them has a group represented by general formula (5).]

[0034]

[0035] [In general formula (2), R 4 ~R 6 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. 4 ~R 6 At least one of them has a group represented by general formula (5).]

[0036]

[0037] [In general formula (3), R 7 ~R 9 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. 7 ~R9 At least one of them has a group represented by general formula (5).]

[0038]

[0039] [In general formula (4), R 10 ~R 12 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. 10 ~R 12 At least one of them has a group represented by general formula (5).]

[0040]

[0041] [In the general formula (5), W represents a phosphorus atom or a sulfur atom. When W is a phosphorus atom, y is 1; when W is a sulfur atom, y is 2.] Each X independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted by a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted by a halogen atom, a heteroaryl group having 2 to 40 carbon atoms which may be substituted by a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted by a halogen atom, an alkenyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an alkynyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an aryloxy group having 6 to 40 carbon atoms which may be substituted by a halogen atom, or a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted by a halogen atom. d represents 0 to 5. M p+ represents a proton, metal cation, or onium cation, and p represents the valence of the cation. q represents a number such that p×q=1.] [2]

[0043] The non-aqueous electrolyte according to [1], wherein X in the general formula (5) is independently a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a trifluoromethyl group, a trifluoroethyl group, a vinyl group, a 2-propenyl group, a 2-propynyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-pentyl group, an n-hexyl group, a trifluoromethoxy group, a trifluoroethoxy group, a hexafluoroisopropoxy group, an vinyloxy group, a 2-propenyloxy group, a 2-propynyloxy group, a phenoxy group, a naphthyl group, a pentafluorophenoxy group, a pyrrolyl group or a pyridyl group. [3]

[0045] The non-aqueous electrolyte according to [1], wherein X in the general formula (5) is independently a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a trifluoromethyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group or a pyridyl group. [4]

[0047] The non-aqueous electrolyte according to any one of [1] to [3], wherein M in the general formula (5) p+ is a proton, a lithium cation, a sodium cation, a potassium cation, a tetraalkylammonium cation or a tetraalkylphosphonium cation. [5]

[0049] The non-aqueous electrolyte solution according to any one of [1] to [4], wherein the concentration of (I) is 0.01 to 5.00% by mass relative to the total amount of the non-aqueous electrolyte solution. [6]

[0051] The non-aqueous electrolyte according to any one of [1] to [5], wherein the aforementioned (II) is at least one selected from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, LiC4F9SO3, LiN(SO2F)2, LiAlO2, LiAlCl4, LiCl and LiI, or at least one selected from the group consisting of NaPF6, NaBF4, NaSbF6, NaAsF6, NaClO4, NaCF3SO3, NaC4F9SO3, NaN(SO2F)2, NaAlO2, NaAlCl4, NaCl and NaI. [7]

[0053] The non-aqueous electrolyte solution according to any one of [1] to [6], 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]

[0055] The non-aqueous electrolyte solution according to [7], wherein the cyclic ester includes a cyclic carbonate. [9]

[0057] The non-aqueous electrolyte solution according to [8], wherein the cyclic carbonate includes at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.

[10]

[0059] The non-aqueous electrolyte solution according to [7], wherein the chain ester includes a chain carbonate.

[11]

[0061] The non-aqueous electrolyte according to

[10] , wherein the chain carbonate comprises at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methylpropyl carbonate.

[12]

[0063] The non-aqueous electrolyte according to any one of [1] to

[11] , further comprising at least one selected from the group consisting of vinylene carbonate, bis(oxalato)borate, difluorooxalatoborate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, (difluorophosphoryl)(fluorosulfonyl)imide salt, difluorophosphate, fluorosulfonate, nitrate, 1,3-propylene sultone, 1,3-propane sultone, 1,6-diisocyanatohexane, dimethyl dicarbonate, ethynyl ethylene carbonate, trans-difluoroethylene carbonate, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, Pentane-2,2-dioxide, methylene methanedisulfonate, 1,2-ethanedisulfonic anhydride, methanesulfonic anhydride, methanesulfonyl fluoride, 1,4-dioxane-2,6-dione, tripropargyl phosphate, tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, tetrafluoro(malonic acid)phosphate, tetrafluoro(picolinic acid)phosphate, 1,3-dimethyl-1,3-divinyl-1,3-bis(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, N,N'-carbonylbis(N-methylaminosulfonyl fluoride), tetravinylsilane, trivinylmethylsilane, tert-butylbenzene, tert-amylbenzene, fluorobenzene, and cyclohexylbenzene.

[13]

[0065] The non-aqueous electrolyte according to any one of [1] to

[12] , further comprising (IV) at least one member selected from the group consisting of a compound represented by the following general formula [1b] and a compound represented by the following general formula [1b'], wherein the content of the aforementioned (IV) in the non-aqueous electrolyte is 10 to 25,000 ppm by mass.

[0066]

[0067] (In the general formula [1b], Y represents a boron atom, R' represents a fluorine atom, n is 0 to 4, and m' is 0 to 2. Q + represents an alkali metal ion, a tetraalkylammonium cation, or a tetraalkylphosphonium cation.)

[0068] Q + [Z] - [1b']

[0069] (In the general formula [1b'], [Z] - The anion portion shown is the structure of the following [1b-1] or a chloride anion. +represents an alkali metal ion, a tetraalkylammonium cation, or a tetraalkylphosphonium cation.)

[0070]

[14]

[0072] The non-aqueous electrolyte according to

[13] , wherein the aforementioned (IV) is a salt compound comprising a counter anion selected from bis(oxalato)borate anion, tetrafluoroborate anion, chloride anion or perchlorate anion and a counter cation selected from lithium cation, sodium cation, potassium cation, tetraalkylammonium cation or tetraalkylphosphonium cation.

[15]

[0074] The non-aqueous electrolyte solution according to

[13] or

[14] , wherein the content of the (IV) in the non-aqueous electrolyte solution is 10 to 8000 ppm by mass.

[16]

[0076] The non-aqueous electrolyte solution according to

[13] or

[14] , wherein the content of the compound (IV) in the non-aqueous electrolyte solution is 50 to 5000 ppm by mass.

[17]

[0078] A non-aqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and the non-aqueous electrolyte described in any one of [1] to

[16] .

[18]

[0080] A compound represented by the following general formula (1), (2), (3) or (4).

[0081]

[0082] [In the general formula (1), R 1 ~R 3 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. 1 ~R 3 At least two of them have a group represented by general formula (5).]

[0083]

[0084] [In general formula (2), R 4 ~R 6 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. 4 ~R 6 At least one of them has a group represented by general formula (5).]

[0085]

[0086] [In general formula (3), R 7 ~R 9 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. 7 ~R 9 At least one of them has a group represented by general formula (5).]

[0087]

[0088] [In general formula (4), R 10 ~R 12 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. 10 ~R 12 At least one of them has a group represented by general formula (5).]

[0089]

[0090] [In the general formula (5), W represents a phosphorus atom or a sulfur atom. When W is a phosphorus atom, y is 1; when W is a sulfur atom, y is 2.] Each X independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted by a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted by a halogen atom, a heteroaryl group having 2 to 40 carbon atoms which may be substituted by a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted by a halogen atom, an alkenyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an alkynyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an aryloxy group having 6 to 40 carbon atoms which may be substituted by a halogen atom, or a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted by a halogen atom. d represents 0 to 5. M p+ represents a proton, metal cation, or onium cation, and p represents the valence of the cation. q represents a number such that p×q=1.]

[0091] Effects of the Invention

[0092] The present disclosure provides a nonaqueous electrolyte that exhibits excellent initial input / output characteristics when formed into a nonaqueous electrolyte battery, a nonaqueous electrolyte battery that exhibits excellent initial input / output characteristics, and a compound suitable for use in the nonaqueous electrolyte. DETAILED DESCRIPTION

[0093] Each configuration and combination thereof in the following embodiments are examples, and additions, substitutions, and other changes to the configurations can be made without departing from the spirit of the present disclosure. The present disclosure is not limited to the embodiments but only to the claims.

[0094] In this specification, “to” is used to mean that the numerical values ​​described before and after it are included as the lower limit and the upper limit.

[0095] It should be noted that, in this specification, the initial input / output characteristics refer to the resistance value of a non-aqueous electrolyte battery immediately after the initial charge and discharge operation for battery stabilization. Specifically, it refers to the initial resistance value measured by DC internal resistance after four cycles of charge and discharge for battery stabilization.

[0096] 〔1. Non-aqueous electrolyte〕

[0097] The non-aqueous electrolyte disclosed herein is a non-aqueous electrolyte containing (I) at least one compound 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 non-aqueous organic solvent.

[0098] <About Component (I)>

[0099] The non-aqueous electrolyte solution disclosed herein contains, as component (I), at least one compound 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).

[0100] If the non-aqueous electrolyte containing the above-mentioned component (I) is used for a non-aqueous electrolyte battery (such as a lithium ion secondary battery, a sodium ion secondary battery), the component (I) decomposes at least on the positive electrode and on the negative electrode, and forms a film with good cation conductivity on the surface of at least the positive electrode and the negative electrode. It is believed that the film inhibits direct contact between the non-aqueous organic solvent, the solute and the electrode active material, and reduces the cation dissociation energy of the solute. As a result, the present inventors presume that the effect of reducing the initial resistance of the non-aqueous electrolyte battery is exerted.

[0101] R in the general formula (1) 1 ~R 3 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent. 1 ~R 3 At least one of them has a group represented by general formula (5).

[0102] R 1 ~R 3It may be an organic group having 1 to 15 carbon atoms, or an organic group having 1 to 10 carbon atoms.

[0103] The organic group may be linear, branched, or cyclic.

[0104] The organic group is not particularly limited, and examples thereof include alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, cycloalkoxy, alkenyloxy, alkynyloxy, aryloxy, and heteroaryloxy groups. The organic group may be a group represented by general formula (5).

[0105] The substituent that the organic group may have is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, a cyano group, an isocyanate group, an acryloyloxy group, and a methacryloyloxy group.

[0106] R 1 ~R 3 At least one of them has a group represented by general formula (5). 1 ~R 3 At least one of them is a group represented by the general formula (5), or has a group represented by the general formula (5) as a substituent.

[0107] Can R 1 ~R 3 At least two of them have a structure having a group represented by the general formula (5), and R 1 ~R 3 All of them have structures having groups represented by general formula (5).

[0108] R 1 ~R 3 When two or more of them have a group represented by the general formula (5), the two or more groups represented by the general formula (5) may be the same or different.

[0109] R in general formula (2) 4 ~R 6 , R in general formula (3) 7 ~R 9 and R in general formula (4) 10 ~R 12 The description and specific examples are the same as those of the above R 1 ~R 3 same.

[0110] W in the general formula (5) represents a phosphorus atom or a sulfur atom. W may be a sulfur atom.

[0111] Each of X in the general formula (5) independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted by a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted by a halogen atom, a heteroaryl group having 2 to 40 carbon atoms which may be substituted by a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted by a halogen atom, an alkenyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an alkynyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an aryloxy group having 6 to 40 carbon atoms which may be substituted by a halogen atom, or a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted by a halogen atom.

[0112] The above-mentioned halogen atom may be a fluorine atom.

[0113] The alkyl group may be linear or branched, and may have 1 to 10 carbon atoms. The alkyl group may contain an oxygen atom between carbon-carbon bonds. Specific examples of alkyl groups containing an oxygen atom between carbon-carbon bonds include 2-methoxyethyl and 2-ethoxyethyl.

[0114] The cycloalkyl group may be monocyclic or polycyclic, and may be a cycloalkyl group having 5 to 15 carbon atoms.

[0115] The alkenyl group may be linear or branched, and may have 2 to 10 carbon atoms.

[0116] The alkynyl group may be linear or branched, and may have 2 to 10 carbon atoms.

[0117] The aryl group may be monocyclic or polycyclic, and may have 6 to 20 carbon atoms or 6 to 15 carbon atoms.

[0118] The heteroaryl group may contain at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, may be monocyclic or polycyclic, and may have 2 to 20 carbon atoms or 2 to 15 carbon atoms.

[0119] The alkoxy group may be linear or branched, and may have 1 to 10 carbon atoms.

[0120] The cycloalkoxy group may be monocyclic or polycyclic, and may have 5 to 15 carbon atoms.

[0121] The alkenyloxy group may be linear or branched, and may have 2 to 10 carbon atoms.

[0122] The alkynyloxy group may be linear or branched, and may have 2 to 10 carbon atoms.

[0123] The aryloxy group may be monocyclic or polycyclic, and may have 6 to 20 carbon atoms or 6 to 15 carbon atoms.

[0124] The heteroaryloxy group may contain at least one atom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, may be monocyclic or polycyclic, and may have 2 to 20 carbon atoms or 2 to 15 carbon atoms.

[0125] X in the general formula (5) can each independently be a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a trifluoromethyl group, a trifluoroethyl group, a vinyl group, a 2-propenyl group, a 2-propynyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-pentyl group, an n-hexyl group, a trifluoromethoxy group, a trifluoroethoxy group, a hexafluoroisopropoxy group, an vinyloxy group, a 2-propenyloxy group, a 2-propynyloxy group, a phenoxy group, a naphthyl group, a pentafluorophenoxy group, a pyrrolyl group or a pyridyl group.

[0126] X in the general formula (5) may each independently be a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a trifluoromethyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group or a pyridyl group.

[0127] M in general formula (5) p+ represents a proton, a metal cation or an onium cation, and may be a proton, a lithium cation, a sodium cation, a potassium cation, a tetraalkylammonium cation or a tetraalkylphosphonium cation.

[0128] In the general formula (5), p represents the valence of the cation. q represents a number such that p×q=1. Both p and q may be 1.

[0129] Specific examples of the compound represented by any of the general formulae (1) to (4) are shown below, but the compounds are not limited thereto.

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160] Among the above compounds, from the viewpoint of exhibiting excellent initial input / output characteristics (low initial DC internal resistance), the compounds selected from (1-1-1), (1-1-8), (1-1-11), (1-1-12), (1-1-15), (1-1-16), (1-1-21), (1-1-22), (1-2-8), (1-2-15), (1-2-16), (1-2-23), (1-2-24), (1-3-7), (1-3-8), (1-3-15), (1-3-16), (2-1-1), (2-1-8), (2-1-11), (2-1-12), (2-1-15), (2-1-16), (2-1 -21), (2-1-22), (2-1-23), (2-1-24), (2-1-25), (2-1-26), (2-2-19), (2-2-20), (2-2-21), (2-2-22), (2-2-23), (2-2-24), (2-2-43), (2-2-44), (2-2-45), (2-2-46), (2-2-47), (2-2-48), (2-2-67), (2-2-68), (2-2-69), (2-2-70), (2-2-71), (2-2-72), (2-2-91), (2-2-92), (2-2-93), (2-2-94), (2 -2-95), (2-2-96), (2-3-19), (2-3-20), (2-3-21), (2-3-22), (2-3-23), (2-3-24), (2-3-43), (2-3-44), (2-3-45), (2-3-46), (2-3-47), (2-3-48), (3-1-1), (3-1-8), (3-1-11), (3-1-12), (3-1-15), (3-1-16), (3-1-21), (3-1-22), (3-1-23), (3-1-24), (3-1-25), (3-1-26), (3-2-19), (3-2-20), (3 -2-21)、(3-2-22)、(3-2-23)、(3-2-24)、(3-2-43)、(3-2-44)、(3-2-45)、(3-2-46)、(3-2-47)、(3-2-48)、(3-2-67)、(3-2-68)、(3-2-69)、(3-2-70)、(3-2-71)、(2-2-72)、(3-2-91)、(2-2-92)、(3-2-93)、(3-2-94)、(3-2-95)、(3-2-96)、(3-3-19)、(3-3-20)、(3-3-21)、(3-3-22)、(3-3-23)、(3-3-24)、At least one selected from the group consisting of (3-3-43), (3-3-44), (3-3-45), (3-3-46), (3-3-47), (3-3-48), (4-1-1), (4-1-8), (4-1-11), (4-1-12), (4-1-15), (4-1-16), (4-1-21), (4-1-22), (4-2-8), (4-2-15), (4-2-16), (4-2-23), (4-2-24), (4-3-7), (4-3-8), (4-3-15) and (4-3-16) may be used, and at least one selected from the group consisting of (1-1-1), (1-1-8), (1-1-11), (1-1-12), (4-1-15), (4-1-16), (4-1-21), (4-1-22), (4-2-8), (4-2-15), (4-2-16), (4-2-23), (4-2-24), (4-3-7), (4-3-8), (4-3-15) and (4-3-16) may be used. 15), (1-1-16), (1-1-21), (1-1-22), (1-2-8), (1-2-16), (1-2-24), (1-3-8), (1-3-16), (2-1-1), (2-1-8), (2-1-11), (2-1-15), (2-1-16), (2-1-21), (2-1-22), (2-1-23), (2-1-24), (2-1-25), (2-1-26), (2-2-22), (2-2-23), (2-2-24), (2-2-46), (2-2-47), (2-2-48), (2-2-70), (2-2-71), (2-2-7 2), (2-2-94), (2-2-95), (2-2-96), (2-3-22), (2-3-23), (2-3-24), (2-3-46), (2-3-47), (2-3-48), (3-1-1), (3-1-8), (3-1-11), (3-1-15), (3-1-16), (3-1-21), (3-1-22), (3-1-23), (3-1-24), (3-1-25), (3-1-26), (3-2-22), (3-2-23), (3-2-24), (3-2-46), (3-2-47), (3-2-48), (3-2-70), (3-2- 71), (2-2-72), (3-2-94), (3-2-95), (3-2-96), (3-3-22), (3-3-23), (3-3-24), (3-3-46), (3-3-47), (3-3-48), (4-1-1), (4-1-8), (4-1-11), (4-1-15), (4-1-16), (4-1-21), (4-1-22), (4-2-8), (4-2-16), (4-2-24), (4-3-8) and (4-3-16), and at least one selected from the group consisting of (1-1-1), (1-1-8), (1-1-11), (1-1-15),(1-1-16), (1-1-21), (1-1-22), (1-2-8), (1-2-16), (1-2-24), (2-1-1), (2-1-8), (2-1-11), (2-1-15), (2-1-16), (2-1-21), (2-1-22), (2-1-23), (2-1-24), (2-1-25) 、(2-1-26)、(2-2-22)、(2-2-23)、(2-2-24)、(2-2-46)、(2-2-47)、(2-2-48)、(2-2-70)、(2-2-71)、(2-2-72)、(2-2-94)、(2-2-95)、(2-2-96)、(3-1-1)、(3-1-8)、(3-1-1 1), (3-1-15), (3-1-16), (3-1-21), (3-1-22), (3-1-23), (3-1-24), (3-1-25), (3-1-26), (3-2-22), (3-2-23), (3-2-24), (3-2-46), (3-2-47), (3-2-48), (3-2-70), (3 -2-71), (3-2-72), (3-2-94), (3-2-95), (3-2-96), (4-1-1), (4-1-8), (4-1-11), (4-1-15), (4-1-16), (4-1-21), (4-1-22), (4-2-8), (4-2-16), and (4-2-24).

[0161] In addition, from the viewpoint of reducing the rate of increase in DC internal resistance after the cycle test, it is possible to adopt a material selected from (1-1-5), (1-1-6), (1-1-7), (1-1-9), (1-1-13), (1-1-14), (1-1-18), (1-1-19), (1-2-1), (1-2-2), (1-2-3), (1-2-4), (1-2-9), (1-2-10), (1-2-11), (1-2-12), (1-2-17), (1-2-18), (1-2-19), (1-2-20), (1-3-1), (1-3-2), (1-3-3), (1-3-4), (1-3-9), (1-3-10) 、(1-3-11)、(1-3-12)、(2-1-5)、(2-1-6)、(2-1-7)、(2-1-9)、(2-1-13)、(2-1-14)、(2-1-18)、(2-1-19)、(2-2-1)、(2-2-2)、(2-2-3)、(2-2-4)、(2-2-5)、(2-2-6)、(2-2-7)、(2-2-8)、(2-2-9)、(2-2-10)、(2-2-11)、(2-2-12)、(2-2-25)、(2-2-26)、(2-2-27)、(2-2-28)、(2-2-29)、(2-2-30)、(2-2-31)、( 2-2-32), (2-2-33), (2-2-34), (2-2-35), (2-2-36), (2-2-49), (2-2-50), (2-2-51), (2-2-52), (2-2-53), (2-2-54), (2-2-55), (2-2-56), (2-2-57), (2-2-58), (2-2-59), (2-2-60), (2-2-73), (2-2-74), (2-2-75), (2-2-76), (2-2-77), (2-2-78), (2-2-79), (2-2-80), (2-2-81), (2-2-82), (2-2-83) 、(2-2-84)、(2-3-1)、(2-3-2)、(2-3-3)、(2-3-4)、(2-3-5)、(2-3-6)、(2-3-7)、(2-3-8)、(2-3-9)、(2-3-10)、(2-3-11)、(2-3-12)、(2-3-13)、(2-3-25)、(2-3-26)、(2-3-27)、(2-3-28)、(2-3-29)、(2-3-30)、(2-3-31)、(2-3-32)、(2-3-33)、(2-3-34)、(2-3-35)、(2-3-36)、(3-1-5)、(3-1-6)、(3-1-7)、(3-1-9), (3-1-13), (3-1-14), (3-1-18), (3-1-19), (3-2-1), (3-2-2), (3-2-3), (3-2-4), (3-2-5), (3-2-6), (3-2-7), (3-2-8), (3-2-9), (3-2-10), (3-2-11), (3-2-12), (3-2-25), (3-2-26), (3-2-27), (3-2-28), (3-2-29), (3-2-30), (3-2-31), (3-2-32), (3-2-33), (3-2-34), (3-2-35), (3-2-36 ), (3-2-49), (3-2-50), (3-2-51), (3-2-52), (3-2-53), (3-2-54), (3-2-55), (3-2-56), (3-2-57), (3-2-58), (3-2-59), (3-2-60), (3-2-73), (3-2-74), (3-2-75), (3-2-76), (3-2-77), (3-2-78), (3-2-79), (3-2-80), (3-2-81), (3-2-82), (3-2-83), (3-2-84), (3-3-1), (3-3-2), (3-3-3), (3-3-4) 、(3-3-5),(3-3-6),(3-3-7),(3-3-8),(3-3-9),(3-3-10),(3-3-11),(3-3-12),(3-3-13),(3-3-25),(3-3-26),(3-3-27),(3-3-28),(3-3-29),(3-3-30),(3-3-31),(3-3-32),(3-3-33),(3-3-34),(3-3-35),(3-3-36),(4-1-5),(4-1-6),(4-1-7),(4-1-9),(4-1-13),(4-1-14),(4-1-18),(4-1- 19), (4-2-1), (4-2-2), (4-2-3), (4-2-4), (4-2-9), (4-2-10), (4-2-11), (4-2-12), (4-2-17), (4-2-18), (4-2-19), (4-2-20), (4-3-1), (4-3-2), (4-3-3), (4-3-4), (4-3-9), (4-3-10), (4-3-11), and (4-3-12), and at least one selected from the group consisting of (1-1-5), (1-1-6), (1-1-7), (1-1-9), (1-1-13), (1-1-18), (1-1-19),(1-2-1)、(1-2-2)、(1-2-4)、(1-2-9)、(1-2-10)、(1-2-12)、(1-2-17)、(1-2-18)、(1-2-20)、(1-3-1)、(1-3-2)、(1-3-4)、(1-3-9)、(1-3-10)、(1-3-12)、(2-1-5)、(2-1-6)、(2-1-7)、(2-1-9)、(2-1-13)、(2-1-18)、(2-1-19)、(2-2-1)、(2-2-2)、(2-2-3)、(2-2-4)、(2-2-5)、(2-2-6)、(2-2-10)、(2-2-11)、(2-2-12)、(2-2-25)、(2-2-26)、(2-2-27)、(2-2-28)、(2-2-29)、(2-2-30)、(2-2-34)、(2-2-35)、(2-2-36)、(2-2-49)、(2-2-50)、(2-2-51)、(2-2-52)、(2-2-53)、(2-2-54)、(2-2-58)、(2-2-59)、(2-2-60)、(2-2-73)、(2-2-74)、(2-2-75)、(2-2-76)、(2-2-77)、(2-2-78)、(2-2-82)、(2-2-83)、(2-2-84)、(2-3-1)、(2-3-2)、(2-3-3)、(2-3-4)、(2-3-5)、(2-3-6)、(2-3-7)、(2-3-8)、(2-3-9)、(2-3-10)、(2-3-11)、(2-3-12)、(2-3-13)、(2-3-25)、(2-3-26)、(2-3-27)、(2-3-28)、(2-3-29)、(2-3-30)、(2-3-34)、(2-3-35)、(2-3-36)、(3-1-5)、(3-1-6)、(3-1-7)、(3-1-9)、(3-1-13)、(3-1-18)、(3-1-19)、(3-2-1)、(3-2-2)、(3-2-3)、(3-2-4)、(3-2-5)、(3-2-6)、(3-2-10)、(3-2-11)、(3-2-12)、(3-2-25)、(3-2-26)、(3-2-27)、(3-2-28)、(3-2-29)、(3-2-30)、(3-2-34)、(3-2-35)、(3-2-36)、(3-2-49)、(3-2-50)、(3-2-51)、(3-2-52)、(3-2-53)、(3-2-54)、(3-2-58)、(3-2-59)、(3-2-60)、(3-2-73)、(3-2-74), (3-2-75), (3-2-76), (3-2-77), (3-2-78), (3-2-82), (3-2-83), (3-2-84), (3-3-1), (3-3-2), (3-3-3), (3-3-4), (3-3-5), (3-3-6), (3-3-7), (3-3-8), (3-3-9), (3-3-10), (3-3-11), (3-3-12), (3-3-13), (3-3-25), (3-3-26), (3-3-27), (3-3-28), (3-3-29), (3-3-30), (3-3-34), (3-3- 35), (3-3-36), (4-1-5), (4-1-6), (4-1-7), (4-1-9), (4-1-13), (4-1-18), (4-1-19), (4-2-1), (4-2-2), (4-2-4), (4-2-9), (4-2-10), (4-2-12), (4-2-17), (4-2-18), (4-2-20), (4-3-1), (4-3-2), (4-3-4), (4-3-9), (4-3-10) and (4-3-12), and at least one selected from the group consisting of (1-1-5), (1-1-6), (1-1-9), (1-1-13), (1-1-18), (1-1-19), (1-2-1), (1-2-2), (1-2-9), (1-2-10), (1-2-17), (1-2-18), (1-3-1), (1-3-2), (1-3-9), (1-3-10), (2-1-5), (2-1-6), (2-1-9), (2-1-13), (2-1-18), (2-1-19), (2-2-1), (2-2-2), (2-2-3), (2-2-4), (2-2-5), (2-2-6), (2-2-25), (2-2-26), (2-2-27), (2-2-28), (2-2-29), (2- 2-30), (2-2-49), (2-2-50), (2-2-51), (2-2-52), (2-2-53), (2-2-54), (2-2-73), (2-2-74), (2-2-75), (2-2-76), (2-2-77), (2-2-78), (2-3-1), (2-3-2), (2-3-3), (2-3-4), (2-3-5), (2-3-6), (2-3-7), (2-3-8), (2-3-9), (2-3-13), (2-3-25), (2-3-26), (2-3-27), (2-3-28), (2-3-29), (2-3-30),(3-1-5), (3-1-6), (3-1-9), (3-1-13), (3-1-18), (3-1-19), (3-2-1), (3-2-2), (3-2-3), (3-2-4), (3-2-5), (3-2-6), (3-2-25), (3-2-26), (3-2-27), (3-2-28), (3-2-29 ), (3-2-30), (3-2-34), (3-2-35), (3-2-36), (3-2-49), (3-2-50), (3-2-51), (3-2-52), (3-2-53), (3-2-54), (3-2-73), (3-2-74), (3-2-75), (3-2-76), (3-2-77), (3-2- 78), (3-3-1), (3-3-2), (3-3-3), (3-3-4), (3-3-5), (3-3-6), (3-3-7), (3-3-8), (3-3-9), (3-3-13), (3-3-25), (3-3-26), (3-3-27), (3-3-28), (3-3-29), (3-3-30), (4- At least one member selected from the group consisting of (4-1-5), (4-1-6), (4-1-9), (4-1-13), (4-1-18), (4-1-19), (4-2-1), (4-2-2), (4-2-9), (4-2-10), (4-2-17), (4-2-18), (4-3-1), (4-3-2), (4-3-9), and (4-3-10).

[0162] Furthermore, combining the above two viewpoints, we can adopt the following methods: (1-1-2), (1-1-3), (1-1-4), (1-1-11), (1-1-15), (1-1-17), (1-1-20), (1-1-21), (1-1-22), (1-2-5), (1-2-6), (1-2-13), (1-2-14), (1-2-21), (1-2-22), (1-3-5), (1-3-6), (1-3-13), (1-3-14), (1-3-17), (1-3-18), (2-1-2), (2-1-3), (2-1-4), (2-11), (2-1-15), (2-1-17), (2-1-20), (2-1-21), (2-1-22), (2-1-23), (2-1-24), (2-1-25), (2-1-26), (2-2-13), (2-2-14), (2-2-15), (2-2-16), (2-2-17), (2-2-18), (2-2-37), (2-2-38), (2-2-39), (2-2-40), (2-2-41), (2-2-42), (2-2-61), (2-2-62), (2-2-63), (2-2-64), (2-2-65), ( 2-2-66), (2-2-85), (2-2-86), (2-2-87), (2-2-88), (2-2-89), (2-2-90), (2-3-13), (2-3-14), (2-3-15), (2-3-16), (2-3-17), (2-3-18), (2-3-37), (2-3-38), (2-3-39), (2-3-40), (2-3-41), (2-3-42), (2-3-49), (2-3-50), (2-3-51), (2-3-52), (2-3-53), (2-3-54), (2-3-55), (2 At least one member selected from the group consisting of: (4-1-2), (4-1-3), (4-1-4), (4-1-11), (4-1-15), (4-1-17), (4-1-20), (4-1-21), (4-1-22), (4-2-5), (4-2-6), (4-2-13), (4-2-14), (4-2-21), (4-2-22), (4-3-5), (4-3-6), (4-3-13), (4-3-14), (4-3-17), and (4-3-18),It can be selected from (1-1-2), (1-1-3), (1-1-11), (1-1-15), (1-1-17), (1-1-21), (1-1-22), (1-2-6), (1-2-14), (1-2-22), (1-3-6), (1-3-14), (1-3-17), (1-3-18), (2-1-2), (2-1-3), (2-1-11), (2-1-15), (2-1-17), (2-1-21), (2-1-22), (2-1-23), (2-1-24), (2-1-25), (2-1-26), (2-2-16), (2-2-17), (2-2 -18), (2-2-40), (2-2-41), (2-2-42), (2-2-64), (2-2-65), (2-2-66), (2-2-88), (2-2-89), (2-2-90), (2-3-16), (2-3-17), (2-3-18), (2-3-40), (2-3-41), (2-3-42), (2-3-49), (2-3-50), (2-3-51), (2-3-52), (2-3-53), (2-3-54), (2-3-55), (2-3-56), (2-3-57), (2-3-58), (2-3-59), (2-3-60), ( 3-1-2), (3-1-3), (3-1-11), (3-1-15), (3-1-17), (3-1-21), (3-1-22), (3-1-23), (3-1-24), (3-1-25), (3-1-26), (3-2-16), (3-2-17), (3-2-18), (3-2-40), (3-2-41), (3-2-42), (3-2-64), (3-2-65), (3-2-66), (3-2-88), (3-2-89), (3-2-90), (3-3-16), (3-3-17), (3-3-18), (3-3-40), (3-3-41), At least one member selected from the group consisting of (3-3-42), (3-3-49), (3-3-50), (3-3-51), (3-3-52), (3-3-53), (3-3-54), (3-3-55), (3-3-56), (3-3-57), (3-3-58), (3-3-59), (3-3-60), (4-1-2), (4-1-3), (4-1-11), (4-1-15), (4-1-17), (4-1-21), (4-1-22), (4-2-6), (4-2-14), (4-2-22), (4-3-6), (4-3-14), (4-3-17), and (4-3-18),It can be selected from (1-1-3), (1-1-11), (1-1-15), (1-1-21), (1-1-22), (1-2-6), (1-2-14), (1-2-22), (1-3-6), (1-3-14), (1-3-17), (1-3-18), (2-1-3), (2-1-11), (2-1-15), (2-1-21), (2-1-22), (2-1-23), (2-1-24), (2-1-25) 、(2-1-26)、(2-2-16)、(2-2-17)、(2-2-18)、(2-2-40)、(2-2-41)、(2-2-42)、(2-2-64)、(2-2-65)、(2-2-66)、(2-2-88)、(2-2-89)、(2-2-90)、(2-3-16)、(2-3-17)、(2-3-18)、(2-3-40)、(2-3-41)、(2-3-42)、(2-3-54)、( 3-1-3), (3-1-11), (3-1-15), (3-1-21), (3-1-22), (3-1-23), (3-1-24), (3-1-25), (3-1-26), (3-2-16), (3-2-17), (3-2-18), (3-2-40), (3-2-41), (3-2-42), (3-2-64), (3-2-65), (3-2-66), (3-2-88), (3-2-89), (3-2 -90), (3-3-16), (3-3-17), (3-3-18), (3-3-40), (3-3-41), (3-3-42), (3-3-54), (4-1-3), (4-1-11), (4-1-15), (4-1-21), (4-1-22), (4-2-6), (4-2-14), (4-2-22), (4-3-6), (4-3-14), (4-3-17) and (4-3-18). ,

[0163] In the non-aqueous electrolyte of the present disclosure, the lower limit of the total amount of the above-mentioned component (I) (also referred to as "the concentration of (I)") relative to the total amount of the non-aqueous electrolyte (100% by mass) may be 0.01% by mass or more, 0.08% by mass or more, 0.3% by mass or more, or 0.8% by mass or more. The upper limit of the concentration of (I) may be 10.00% by mass or less, 5.0% by mass or less, or 2.5% by mass or less.

[0164] By setting the concentration of (I) to 0.01% by mass or more, it is easy to obtain the effect of suppressing the initial resistance increase of the non-aqueous electrolyte battery using the non-aqueous electrolyte. On the other hand, by setting the concentration of (I) to 10.0% by mass or less, it is possible to suppress the viscosity increase of the non-aqueous electrolyte, thereby easily obtaining the effect of suppressing the resistance increase of the non-aqueous electrolyte battery using the non-aqueous electrolyte.

[0165] In the non-aqueous electrolyte solution of the present disclosure, as component (I), one compound may be used alone, or two or more compounds may be mixed in any combination and ratio depending on the intended use.

[0166] The compound represented by the general formula (1) can be produced by various methods, and the production method is not particularly limited.

[0167] For example, in the case of compound (1-1-11), it can be obtained by reacting cyanate with fluorosulfonyl isocyanate and then reacting with lithium chloride.

[0168] The compound represented by the general formula (2) can be produced by various methods, and the production method is not particularly limited.

[0169] For example, in the case of compound (2-2-2), it can be obtained by mixing 6-(allyloxy)-1,3,5-triazine-2,4(1H,3H)-dione and lithium hydride, and then reacting the mixture with fluorosulfonyl isocyanate.

[0170] The compound represented by the general formula (3) can be produced by various methods, and the production method is not particularly limited.

[0171] For example, in the case of compound (3-3-3), it can be obtained by mixing 4,6-(allyloxy)-1,3,5-triazine-2(1H)-one and lithium hydride, and then reacting the mixture with fluorosulfonyl isocyanate.

[0172] The compound represented by the general formula (4) can be produced by various methods, and the production method is not particularly limited.

[0173] For example, in the case of compound (4-1-11), it can be obtained by mixing cyanuric acid and lithium hydride, and then reacting the mixture with fluorosulfonyl isocyanate.

[0174] It should be noted that the present disclosure also relates to compounds represented by the above general formula (1), (2), (3) or (4).

[0175] The above compounds are suitable for use as additives in non-aqueous electrolytes.

[0176] <About (II) Solute>

[0177] The non-aqueous electrolyte solution of the present disclosure contains a solute.

[0178] The solute is not particularly limited and may be an ionic salt or an ionic salt containing fluorine.

[0179] The solute may be, for example, at least one cation selected from the group consisting of alkali metal ions represented by lithium ions and sodium ions, alkaline earth metal ions, and quaternary ammonium ions and an anion selected from hexafluorophosphate anion, tetrafluoroborate anion, perchlorate anion, hexafluoroarsenate anion, hexafluoroantimonate anion, trifluoromethanesulfonate anion, bis(trifluoromethanesulfonyl)imide anion, bis(pentafluoroethanesulfonyl)imide anion, (trifluoromethanesulfonyl)(pentafluoroethanesulfonyl)imide anion, bis(fluorosulfonyl)imide anion, (trifluoromethanesulfonyl)(fluorosulfonyl)imide anion,

[0180] An ionic salt formed by a pair of at least one anion selected from the group consisting of a (pentafluoroethanesulfonyl)(fluorosulfonyl)imide anion and a tris(trifluoromethanesulfonyl)methide anion.

[0181] The solute may be at least one selected from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, LiC4F9SO3, LiN(SO2F)2, LiAlO2, LiAlCl4, LiCl and LiI, or at least one selected from the group consisting of NaPF6, NaBF4, NaSbF6, NaAsF6, NaClO4, NaCF3SO3, NaC4F9SO3, NaN(SO2F)2, NaAlO2, NaAlCl4, NaCl and NaI.

[0182] These solutes may be used alone or in combination of two or more in any ratio depending on the intended use.

[0183] Among them, when considering the energy density, output characteristics, life, etc. of the non-aqueous electrolyte battery, the cation can be at least one selected from the group consisting of lithium, sodium, potassium, magnesium and quaternary ammonium, and the anion can be at least one selected from the group consisting of hexafluorophosphate anion, tetrafluoroborate anion, bis(trifluoromethanesulfonyl)imide anion, and bis(fluorosulfonyl)imide anion.

[0184] The total amount of solute in the non-aqueous electrolyte disclosed herein (hereinafter also referred to as "solute concentration") is not particularly limited, and the lower limit may be 0.5 mol / L or more, 0.7 mol / L or more, or 0.9 mol / L or more. In addition, the upper limit of the solute concentration may be 5.0 mol / L or less, 4.0 mol / L or less, or 2.0 mol / L or less. By making the solute concentration 0.5 mol / L or more, it is easy to suppress the reduction in the cycle characteristics and output characteristics of the non-aqueous electrolyte battery caused by the reduction in ionic conductivity, and by setting it to 5.0 mol / L or less, it is easy to suppress the reduction in ionic conductivity, the reduction in the cycle characteristics and output characteristics of the non-aqueous electrolyte battery caused by the increase in the viscosity of the non-aqueous electrolyte.

[0185] <Regarding (III) Non-aqueous Organic Solvents>

[0186] The type of the nonaqueous organic solvent used in the nonaqueous electrolyte solution of the present disclosure is not particularly limited, and any nonaqueous organic solvent can be used.

[0187] The nonaqueous organic solvent may contain at least one selected from the group consisting of cyclic esters, chain esters, cyclic ethers, chain ethers, sulfone compounds, sulfoxide compounds, and ionic liquids.

[0188] Specifically, it can 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, 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, 1,1,1,3,3,3-hexafluoro-1-propyl propyl carbonate, bis(1,1,1,3,3,3- At least one member selected from the group consisting of hexafluoro-1-propyl) carbonate, ethylene carbonate (hereinafter also referred to as "EC"), propylene carbonate (hereinafter also referred to as "PC"), butylene carbonate, fluoroethylene carbonate (hereinafter also referred to as "FEC"), difluoroethylene carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate, ethyl 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.

[0189] In the present disclosure, an ionic liquid having a salt structure may be used as the non-aqueous organic solvent.

[0190] In order to achieve excellent input / output characteristics at low temperatures, the non-aqueous electrolyte solution may contain at least one selected from the group consisting of cyclic esters and chain esters as a non-aqueous organic solvent.

[0191] In order to achieve excellent cycle characteristics at high temperatures, the non-aqueous electrolyte may contain at least one selected from the group consisting of cyclic carbonates and chain carbonates as a non-aqueous organic solvent.

[0192] The non-aqueous organic solvent contains a cyclic ester, and the cyclic ester may be a cyclic carbonate.

[0193] Specific examples of the cyclic carbonate include EC, PC, butylene carbonate, and FEC. Among them, the cyclic carbonate may be at least one selected from the group consisting of EC, PC, and FEC.

[0194] The non-aqueous organic solvent contains a chain ester, and the chain ester may be a chain carbonate.

[0195] Specific examples of the above-mentioned linear carbonates include EMC, DMC, DEC, methyl propyl carbonate, 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. Among them, the carbonate may be at least one selected from the group consisting of EMC, DMC, DEC, and methyl propyl carbonate.

[0196] Specific examples of the chain esters include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, and ethyl 2-fluoropropionate.

[0197] <About other additives>

[0198] Unless the gist of the present disclosure is impaired, commonly used additive components may be further added to the non-aqueous electrolyte solution of the present disclosure at any ratio.

[0199] Specific examples of other additives include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene, biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, dimethyl vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, trans-difluoroethylene carbonate, propargyl methyl carbonate, propargyl ethyl carbonate, dipropargyl carbonate, maleic anhydride, succinic anhydride, propane sultone, 1, 3-Propane sultone, 1,3-propylene sultone, butane sultone, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, methylene methanedisulfonate, dimethylene methanedisulfonate, trimethylene methanedisulfonate, methyl methanesulfonate, 1,6-diisocyanatohexane, tris(trimethylsilyl)borate, succinonitrile, (ethoxy) Pentafluorocyclotriphosphazene, lithium difluorobis(oxalato)phosphate, sodium difluorobis(oxalato)phosphate, potassium difluorobis(oxalato)phosphate, lithium difluorooxalatoborate, sodium difluorooxalatoborate, potassium difluorooxalatoborate, lithium bis(oxalato)borate, sodium bis(oxalato)borate, potassium bis(oxalato)borate, lithium tetrafluorooxalatophosphate, sodium tetrafluorooxalatophosphate, potassium tetrafluorooxalatophosphate, lithium tri(oxalato)phosphate, sodium tri(oxalato)phosphate, potassium tri(oxalato)phosphate, difluorophosphoric acid Compounds having an overcharge prevention effect, a negative electrode coating formation effect, and a positive electrode protection effect, such as lithium, sodium difluorophosphate, potassium difluorophosphate, lithium monofluorophosphate, sodium monofluorophosphate, potassium monofluorophosphate, lithium fluorosulfonate, sodium fluorosulfonate, potassium fluorosulfonate, lithium bis(difluorophosphoryl)imide, sodium bis(difluorophosphoryl)imide, potassium bis(difluorophosphoryl)imide, lithium nitrate, sodium nitrate, potassium nitrate, methanesulfonyl fluoride, ethylenesulfonyl fluoride, and phenyl difluorophosphate.

[0200] The non-aqueous electrolyte solution of the present disclosure may further contain at least one selected from the group consisting of vinylene carbonate, bis(oxalato)borate, difluorooxalatoborate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, (difluorophosphoryl)(fluorosulfonyl)imide salt, difluorophosphate, fluorosulfonate, nitrate, 1,3-propylene sultone, 1,3-propane sultone, 1,6-diisocyanatohexane, dimethyl dicarbonate, ethynyl ethylene carbonate, trans-difluoroethylene carbonate, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, -dioxide, methylene methanedisulfonate, 1,2-ethanedisulfonic anhydride, methanesulfonic anhydride, methanesulfonyl fluoride, 1,4-dioxane-2,6-dione, tripropargyl phosphate, tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, tetrafluoro(malonic acid)phosphate, tetrafluoro(picolinic acid)phosphate, 1,3-dimethyl-1,3-divinyl-1,3-bis(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, N,N'-carbonylbis(N-methylaminosulfonyl fluoride), tetravinylsilane, trivinylmethylsilane, tert-butylbenzene, tert-amylbenzene, fluorobenzene and cyclohexylbenzene.

[0201] The content of the additive in the non-aqueous electrolyte solution may be 0.01% by mass or more and 5.0% by mass or less relative to the total amount of the non-aqueous electrolyte solution.

[0202] The non-aqueous electrolyte solution of the present disclosure may contain a compound represented by the following general formula (6) as another additive.

[0203]

[0204] [In general formula (6), R 6 ~R 8 Each independently represents a fluorine atom, an organic group selected from a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched 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 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may contain a fluorine atom, an oxygen atom, or an unsaturated bond. 6 ~R 8 At least one of them is a fluorine atom.

[0205] M m+is an alkali metal cation, an alkaline earth metal cation or an onium cation, and m represents an integer having the same valence as the corresponding cation.]

[0206] If the compound represented by the general formula (6) (salt having an imide anion) has at least one PF bond or SF bond, excellent low-temperature characteristics are obtained. The more the number of PF bonds and SF bonds in the salt having an imide anion is, the more improved the low-temperature characteristics can be. Therefore, in the salt having an imide anion represented by the general formula (6), R 6 ~R 8 A compound composed entirely of fluorine atoms.

[0207] In addition, in the salt having an imide anion represented by the general formula (6), R 6 ~R 8 At least one of them is a fluorine atom, and R 6 ~R 8 At least one of them is selected from compounds of hydrocarbon groups having 6 or less carbon atoms which may contain a fluorine atom.

[0208] In addition, in the salt having an imide anion represented by the general formula (6), R 6 ~R 8 At least one of them is a fluorine atom, and R 6 ~R 8 At least one of the compounds is selected from methyl, methoxy, ethyl, ethoxy, propyl, propoxy, vinyl, allyl, allyloxy, ethynyl, 2-propynyl, 2-propynyloxy, phenyl, phenoxy, 2,2-difluoroethyl, 2,2-difluoroethoxy, 2,2,2-trifluoroethyl, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropyl, 2,2,3,3-tetrafluoropropoxy, 1,1,1,3,3,3-hexafluoroisopropyl and 1,1,1,3,3,3-hexafluoroisopropoxy.

[0209] The counter cation M of the salt having an imide anion represented by the above general formula (6) is m+ The ion may be selected from the group consisting of lithium ion, sodium ion, potassium ion and tetraalkylammonium ion.

[0210] In the above general formula (6), R 6 ~R 8 Examples of the alkyl and alkoxy groups include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropyl and 1,1,1,3,3,3-hexafluoroisopropyl, and fluorinated alkyl groups, and alkoxy groups derived from these groups.

[0211] Examples of the alkenyl group and alkenyloxy group include alkenyl groups having 2 to 10 carbon atoms such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl and 1,3-butadienyl, fluorine-containing alkenyl groups, and alkenyloxy groups derived from these groups.

[0212] Examples of the alkynyl group and alkynyloxy group include alkynyl groups having 2 to 10 carbon atoms, such as ethynyl, 2-propynyl and 1,1-dimethyl-2-propynyl, fluorine-containing alkynyl groups, and alkynyloxy groups derived from these groups.

[0213] Examples of the cycloalkyl group and the cycloalkoxy group include cycloalkyl groups having 3 to 10 carbon atoms such as cyclopentyl and cyclohexyl, fluorine-containing cycloalkyl groups, and cycloalkoxy groups derived from these groups.

[0214] Examples of the cycloalkenyl group and the cycloalkenyloxy group include cycloalkenyl groups having 3 to 10 carbon atoms such as cyclopentenyl and cyclohexenyl, fluorine-containing cycloalkenyl groups, and cycloalkenyloxy groups derived from these groups.

[0215] Examples of the aryl group and the aryloxy group include aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl and xylyl, fluorine-containing aryl groups, and aryloxy groups derived from these groups.

[0216] Specific examples and synthesis methods of the salt having an imide anion represented by the general formula (6) include those described in International Publication No. 2017 / 111143.

[0217] The content of the other additives in the non-aqueous electrolyte solution may be 0.01% by mass or more and 8.0% by mass or less relative to the total amount of the non-aqueous electrolyte solution.

[0218] In addition, when the ionic salt mentioned as a solute is less than 0.5 mol / L, which is the lower limit of the suitable concentration of the solute, in the non-aqueous electrolyte, it can be used as an "other additive" to exert a negative electrode coating formation effect and a positive electrode protection effect. In this case, the content in the non-aqueous electrolyte is preferably 0.01% by mass to 5.0% by mass.

[0219] Examples of the ionic salt in this case include, for example, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium (trifluoromethanesulfonyl)(fluorosulfonyl)imide when the non-aqueous electrolyte battery is a lithium ion battery. Examples of the ionic salt include sodium hexafluorophosphate, sodium tetrafluoroborate, sodium trifluoromethanesulfonate, sodium bis(trifluoromethanesulfonyl)imide, sodium bis(fluorosulfonyl)imide, and sodium (trifluoromethanesulfonyl)(fluorosulfonyl)imide when the non-aqueous electrolyte battery is a sodium ion battery.

[0220] In addition, among the ionic salts cited as solutes, a salt compound in which the counter anion is at least one selected from the group consisting of tetrafluoroborate anion, chloride anion and perchlorate anion, and the counter cation is at least one selected from the group consisting of lithium cation, sodium cation, potassium cation, tetraalkylammonium cation and tetraalkylphosphonium cation can be included in the non-aqueous electrolyte as the above-mentioned "other additives".

[0221] In addition, from the perspective of improving the durability (lifespan) of the battery, a salt compound in which the counter anion is a bis(oxalato)borate anion and the counter cation is at least one selected from the group consisting of lithium cations, sodium cations, potassium cations, tetraalkylammonium cations and tetraalkylphosphonium cations can be included in the non-aqueous electrolyte.

[0222] The total concentration of the salt compounds may be 50 to 5000 mass ppm, 50 to 3000 mass ppm, or 50 to 1000 mass ppm relative to the total amount of the non-aqueous electrolyte.

[0223] In addition, alkali metal salts other than the above-mentioned solutes may be used as additives.

[0224] Specific examples include carboxylates such as lithium acrylate, sodium acrylate, lithium methacrylate, and sodium methacrylate; and sulfate esters such as lithium methyl sulfate, sodium methyl sulfate, lithium ethyl sulfate, and sodium ethyl sulfate.

[0225] The non-aqueous electrolyte of the present invention may contain, from the viewpoint of improving the durability (lifespan) of the battery, 0.01 to 5.0% by mass of at least one selected from the group consisting of vinylene carbonate, fluoroethylene carbonate, lithium bis(oxalato)borate, lithium difluorooxalatoborate, lithium difluorobis(oxalato)phosphate, lithium tetrafluorooxalatophosphate, lithium bis(fluorosulfonyl)imide, lithium (difluorophosphoryl)(fluorosulfonyl)imide, lithium difluorophosphate, lithium fluorosulfonate, 1,3-propylene sultone, 1,3-propane sultone, 1,3,2-dioxathiolane-2,2-dioxide, and 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, relative to the total amount of the non-aqueous electrolyte.

[0226] In addition, from the same viewpoint, when the non-aqueous electrolyte battery is a sodium ion battery, it can contain 0.01 to 5.0% by mass of at least one selected from vinylene carbonate, fluoroethylene carbonate, sodium bis(oxalato)borate, sodium difluorooxalatoborate, sodium difluorobis(oxalato)phosphate, sodium tetrafluorooxalatophosphate, sodium bis(fluorosulfonyl)imide, sodium (difluorophosphoryl)(fluorosulfonyl)imide, sodium difluorophosphate, sodium fluorosulfonate, 1,3-propylene sultone, 1,3-propane sultone, 1,3,2-dioxathiolane-2,2-dioxide and 4-propyl-1,3,2-dioxathiolane-2,2-dioxide.

[0227] In addition, the non-aqueous electrolyte solution of the present invention further contains (IV) in addition to the above-mentioned (I) to (III) at least one member selected from the group consisting of a compound represented by the following general formula [1b] and a compound represented by the following general formula [1b'], and when the content of the above-mentioned (IV) in the non-aqueous electrolyte solution is 10 to 25000 mass ppm, it is easy to improve the initial DC internal resistance and the DC internal resistance increase rate after the cycle test with good balance, which is preferred.

[0228] It should be noted that, for non-aqueous electrolytes, “it is easy to improve the initial DC internal resistance and the rate of increase in DC internal resistance after the cycle test in a well-balanced manner” means that, for the case where the content of (IV) in the non-aqueous electrolyte is less than 10 mass ppm, “the initial DC internal resistance and the rate of increase in DC internal resistance after the cycle test are equal to or higher than those of the initial DC internal resistance and the rate of increase in DC internal resistance after the cycle test, and at least one of the initial DC internal resistance and the rate of increase in DC internal resistance after the cycle test is better”.

[0229]

[0230] (In the general formula [1b], Y represents a boron atom, R' represents a fluorine atom, n is 0 to 4, and m' is 0 to 2. Q + represents an alkali metal ion, a tetraalkylammonium cation, or a tetraalkylphosphonium cation.)

[0231] Q + [Z] - [1b']

[0232] (In the general formula [1b'], [Z] - The anion portion shown is the structure of the following [1b-1] or a chloride anion. + represents an alkali metal ion, a tetraalkylammonium cation, or a tetraalkylphosphonium cation.)

[0233]

[0234] Regarding (IV) the compound represented by the general formula [1b] and the compound represented by the general formula [1b']

[0235] (IV) may be a salt compound comprising a counter anion selected from bis(oxalato)borate anion, tetrafluoroborate anion, chloride anion or perchlorate anion and a counter cation selected from lithium cation, sodium cation, potassium cation, tetraalkylammonium cation or tetraalkylphosphonium cation.

[0236] Specific examples of the compound represented by the general formula [1b] and the compound represented by the general formula [1b′] include the following compounds, but are not limited to these compounds.

[0237] Lithium bis(oxalato)borate

[0238] Lithium difluorooxalatoborate

[0239] Lithium tetrafluoroborate

[0240] Lithium perchlorate

[0241] Lithium chloride

[0242] Sodium bis(oxalato)borate

[0243] Sodium difluorooxalatoborate

[0244] Sodium tetrafluoroborate

[0245] Sodium perchlorate

[0246] Sodium chloride

[0247] Among them, from the viewpoint of easily improving the initial DC internal resistance and the rate of increase in DC internal resistance after the cycle test in a well-balanced manner, a group selected from lithium bis(oxalato)borate, lithium difluorooxalatoborate, lithium tetrafluoroborate, lithium perchlorate, sodium bis(oxalato)borate, sodium difluorooxalatoborate, sodium tetrafluoroborate, sodium perchlorate, potassium bis(oxalato)borate, potassium difluorooxalatoborate, potassium tetrafluoroborate and potassium perchlorate can be used.

[0248] Lithium and sodium are often used as cations in secondary batteries. Therefore, a cation selected from the group consisting of lithium bis(oxalato)borate, lithium difluorooxalatoborate, lithium tetrafluoroborate, lithium perchlorate, sodium bis(oxalato)borate, sodium difluorooxalatoborate, sodium tetrafluoroborate, and sodium perchlorate can be used.

[0249] For the content of (IV) in the nonaqueous electrolyte, relative to the total amount of electrolyte, the lower limit can be 10 mass ppm (parts per million), can be 30 mass ppm, can be 50 mass ppm, can be 70 mass ppm. In addition, relative to the total amount of electrolyte, the upper limit can be 25000 mass ppm, can be 15000 mass ppm, can be 8000 mass ppm, can be 7000 mass ppm, can be 5000 mass ppm. By making the content of (IV) be more than 10 mass ppm, thus easily and well-balancedly improve the initial DC internal resistance and the DC internal resistance increase rate after the cycle test. In addition, by being set to below 8000 mass ppm, thus easily and well-balancedly improve the initial DC internal resistance and the DC internal resistance increase rate after the cycle test.

[0250] The compound represented by the general formula [1b] and the compound represented by the general formula [1b'] can be produced by various methods. There are no particular limitations on the production method. For example, lithium bis(oxalato)borate, lithium tetrafluoroborate, lithium perchlorate, and lithium chloride can use commercial products such as Kishida Chemical Co., Ltd. Lithium difluorooxalatoborate can use commercial products such as Merck Ltd. Sodium salts can also be commercially available products or those obtained by cation exchange of the above lithium salts.

[0251] In addition, when the non-aqueous electrolyte battery is a lithium ion battery, the content of cations other than lithium in the non-aqueous electrolyte of the present disclosure is preferably 1000 mass ppm or less from the perspective of initial input / output characteristics and the rate of increase in DC internal resistance after a cycle test. It is more preferably 500 mass ppm or less, and particularly preferably 300 mass ppm or less.

[0252] It should be noted that even if the content of cations other than lithium in the non-aqueous electrolyte is about 2000 mass ppm, the non-aqueous electrolyte containing the aforementioned (I) and a specified amount (10 to 25000 mass ppm in the non-aqueous electrolyte) of the aforementioned (IV) can easily improve the initial DC internal resistance and the DC internal resistance increase rate after the cycle test in a well-balanced manner. This is advantageous in terms of managing the content of cations other than lithium contained in the raw materials during the preparation of the non-aqueous electrolyte. From the above viewpoint, when the non-aqueous electrolyte battery is a lithium ion battery, the content of cations other than lithium in the non-aqueous electrolyte containing the aforementioned (I) and a specified amount of the aforementioned (IV) can be 2000 mass ppm or less. It should be noted that, from the viewpoint of easily improving the initial DC internal resistance and the DC internal resistance increase rate after the cycle test in a well-balanced manner, the less the content of cations other than lithium in the non-aqueous electrolyte, the better, for example, preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and particularly preferably 300 mass ppm or less.

[0253] It should be noted that the non-aqueous electrolyte battery is a lithium ion battery, and the non-aqueous electrolyte when the non-aqueous electrolyte contains cations other than lithium, for example, can be cited as follows: the cation species of the solute is lithium, the cation species of (I) is lithium, and the cation species of "salt compounds other than this (such as the aforementioned (IV))" is a non-aqueous electrolyte composition of a substance other than lithium.

[0254] The content of cations other than lithium in the non-aqueous electrolyte of a lithium ion battery can be determined by ICP emission spectroscopy.

[0255] In the case of a sodium ion battery, the content of cations other than sodium in the non-aqueous electrolyte of the present disclosure is preferably 500 ppm by mass or less, taking into account both initial input / output characteristics and the rate of increase in DC internal resistance after cycle testing. A content of 400 ppm by mass or less, and particularly preferably 200 ppm by mass or less, is more preferred.

[0256] It should be noted that even if the content of cations other than sodium in the non-aqueous electrolyte is about 700 mass ppm, it is easy to improve the initial DC internal resistance and the DC internal resistance increase rate after the cycle test in a non-aqueous electrolyte containing the aforementioned (I) and a specified amount (10 to 25,000 mass ppm in the non-aqueous electrolyte). This is advantageous in terms of managing the content of cations other than sodium contained in the raw materials during the preparation of the non-aqueous electrolyte. From the above viewpoint, when the non-aqueous electrolyte battery is a sodium ion battery, the content of cations other than sodium in the non-aqueous electrolyte containing the aforementioned (I) and a specified amount of the aforementioned (IV) can be 700 mass ppm or less. It should be noted that, from the viewpoint of easily improving the initial DC internal resistance and the DC internal resistance increase rate after the cycle test in a well-balanced manner, the lower the content of cations other than sodium in the non-aqueous electrolyte, the better, for example, preferably 500 mass ppm or less, more preferably 400 mass ppm or less, and particularly preferably 200 mass ppm or less.

[0257] It should be noted that the non-aqueous electrolyte battery is a sodium ion battery, and the non-aqueous electrolyte when the non-aqueous electrolyte contains cations other than sodium, for example, can be cited as follows: the cation species of the solute is sodium, the cation species of (I) is sodium, and the cation species of "salt compounds other than this (such as the aforementioned (IV)" is a non-aqueous electrolyte composition of a substance other than sodium.

[0258] The content of cations other than sodium in the non-aqueous electrolyte of a sodium ion battery can be determined by ICP emission spectroscopy.

[0259] The non-aqueous electrolyte disclosed herein may also contain a polymer. For example, in non-aqueous electrolyte batteries known as polymer batteries, the non-aqueous electrolyte may be pseudo-solidified using a gelling agent or a cross-linked polymer. Polymer solid electrolytes also include those containing a non-aqueous organic solvent as a plasticizer.

[0260] The polymer is not particularly limited as long as it is an aprotic polymer that can dissolve the component (I), the solute, and the other additives. For example, polymers having polyethylene oxide in the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylate polymers, polyacrylonitrile, etc. can be mentioned. When a plasticizer is added to these polymers, an aprotic non-aqueous organic solvent can also be used in the non-aqueous organic solvent.

[0261] 〔2. Non-aqueous electrolyte battery〕

[0262] The non-aqueous electrolyte battery of the present disclosure comprises at least the non-aqueous electrolyte of the present disclosure, a negative electrode, and a positive electrode, and may further comprise a separator, an outer shell, and the like.

[0263] The nonaqueous electrolyte battery of the present disclosure preferably includes at least a positive electrode, a negative electrode, a separator, and the nonaqueous electrolyte of the present disclosure.

[0264] The non-aqueous electrolyte battery disclosed herein is preferably a non-aqueous electrolyte secondary battery.

[0265] The negative electrode is not particularly limited, and a material that can reversibly intercalate and deintercalate alkali metal ions represented by lithium ions and sodium ions, or alkaline earth metal ions can be used.

[0266] For example, in the case of a lithium-ion secondary battery in which the cation is mainly lithium, the negative electrode active material constituting the negative electrode is a material capable of being doped / dedoped with lithium ions. For example, a material containing at least one selected from the following substances can be mentioned: a carbon material having a d value of 0.340 nm or less in the (002) plane of the lattice in X-ray diffraction, a carbon material having a d value of more than 0.340 nm in the (002) plane of the lattice in X-ray diffraction, an oxide of one or more metals selected from Si, Sn, and Al, an alloy containing one or more metals selected from Si, Sn, and Al, or an alloy of these metals or alloys with lithium, and lithium titanium oxide. These negative electrode active materials can be used alone or in combination of two or more. In addition, lithium metal, metal nitrides, tin compounds, conductive polymers, etc. can also be used.

[0267] In addition, as the negative electrode active material, a material containing Si and / or Si metal oxide and a carbon material can be suitably mentioned. The above-mentioned Si is silicon metal. In addition, the Si metal oxide can be a compound shown as SiOx (x is a value of 0.5 to 1.5). With respect to the total content of Si and / or Si metal oxide contained in the negative electrode active material at this time, when the total amount of the above-mentioned Si and / or Si metal oxide and carbon material contained in the negative electrode active material is set to 100 mass%, it can be set to 0.1 to 50 mass%, preferably 0.1 to 30 mass%. As the above-mentioned carbon material, graphite is preferred, and various artificial graphites, natural graphites, and hard carbon (non-graphitizable carbon) can be used. Since graphite has very little change in crystal structure accompanying the storage and release of lithium, high energy density and excellent cycle characteristics can be obtained. The shape of graphite can be any of fibrous, spherical, granular or scaly. In addition, amorphous carbon and graphite covered with amorphous carbon on the surface are more preferred because the reactivity of the material surface with the electrolyte is reduced.

[0268] These negative electrode active materials may be used alone or in combination of two or more.

[0269] For example, in the case of a sodium ion secondary battery in which the cation is mainly sodium, as the negative electrode active material constituting the negative electrode, sodium metal, alloys of sodium metal and other metals such as tin, intermetallic compounds, various carbon materials represented by hard carbon, metal oxides such as titanium oxide, metal nitrides, tin (elemental substance), tin compounds, activated carbon, conductive polymers, etc. can also be used. In addition to these, phosphorus (elemental substance) such as red phosphorus and black phosphorus, phosphorus compounds such as Co-P, Cu-P, Sn-P, Ge-P, Mo-P, antimony (elemental substance), antimony compounds such as Sb / C and Bi-Sb, etc. can also be used. These negative electrode active materials can be used alone or in combination of two or more.

[0270] The positive electrode is not particularly limited, and a material capable of reversibly intercalating and deintercalating alkali metal ions or alkaline earth metal ions, typified by lithium ions and sodium ions, can be used.

[0271] For example, when the cation is lithium, as the positive electrode material, lithium-containing transition metal composite oxides such as LiCoO2, LiNiO2, LiMnO2, and LiMn2O4 can be used; these lithium-containing transition metal composite oxides are formed by mixing multiple transition metals such as Co, Mn, and Ni; and these lithium-containing transition metal composite oxides are formed by replacing part of the transition metal with a metal other than a transition metal. Specifically, the following can be mentioned: Li[Ni 1 / 3 Mn 1 / 3 Co 1 / 3 ]O2、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、LiNi 0.8 Co 0.2 O2、LiNi 0.85 Co 0.10 Al 0.05 O2、LiNi0.87 Co 0.10 Al 0.03 O2、LiNi 0.90 Co 0.07 Al 0.03 O2、LiNi 0.6 Co 0.3 Al 0.1 O2、LiNi 0.5 Mn 1.5 O4、LiNi 0.5 Mn 0.5 O2、LiNi 0.1 Mn 1.9 O4、LiCo 0.5 Mn 0.5 O2, 0.5[LiNi 0.5 Mn 0.5 O2]·0.5[Li2MnO3]、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 O2]·0.10[Li2TiO3]·0.45[Li2MnO3], etc.

[0272] In addition, phosphate compounds of transition metals such as LiFePO4, LiCoPO4, LiMnPO4, etc., which are called olivine, oxides such as TiO2, V2O5, MoO3, sulfides such as TiS2, FeS, or conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, free radical-generating polymers, carbon materials, etc. can also be used.

[0273] For example, when the cation is sodium, NaCrO2, NaFe 0.5 Co 0.5 O2、NaFe 0.4 Mn 0.3 Ni 0.3 O2、NaNi 0.5 Ti 0.3 Mn 0.2 O2、NaNi1 / 3 Ti 1 / 3 Mn 1 / 3 O2、NaNi 0.33 Ti 0.33 Mn 0.16 Mg 0.17 O2、Na 2 / 3 Ni 1 / 3 Ti 1 / 6 Mn 1 / 2 O2、Na 2 / 3 Ni 1 / 3 Mn 2 / 3 O2 and other sodium-containing transition metal composite oxides; these sodium-containing transition metal composite oxides are mixed with a variety of transition metals such as Co, Mn, Ni; these sodium-containing transition metal composite oxides are partially replaced by metals other than other transition metals; NaFePO4, NaVPO4F, Na3V2(PO4)3, Na2Fe2(SO4)3 and other polyanionic compounds; composition formula Na a M b [Fe(CN)6] c Sodium salts of the Prussian blue analogues shown (M represents Cr, Mn, Fe, Co, Ni, Cu or Zn, 0≤a≤2, 0.5≤b≤1.5, 0.5≤c≤1.5); oxides such as TiO2, V2O5, MoO3; sulfides such as TiS2, FeS; or conductive polymers such as polyacetylene, polyparaphenylene, polyaniline, and polypyrrole, activated carbon, free radical-generating polymers, carbon materials, etc.

[0274] Acetylene black, Ketjen black, carbon fiber, or graphite can be added to the positive and negative electrode materials as conductive materials, and polytetrafluoroethylene, polyvinylidene fluoride, or SBR resin can be added as a binder. In addition, electrode sheets formed into sheets can also be used.

[0275] As a separator for preventing contact between the positive electrode and the negative electrode, a nonwoven fabric or a porous sheet made of polypropylene, polyethylene, paper, glass fiber, or the like can be used.

[0276] The above elements are assembled into electrochemical devices in the shape of coins, cylinders, squares, or aluminum laminates.

[0277] Example

[0278] Hereinafter, the present disclosure will be described in further detail based on Examples, but the present disclosure is not limited to these descriptions at all.

[0279] <Synthesis example 1-1>

[0280] Synthesis of compound (1-1-11)

[0281]

[0282] In a 50 ml eggplant-shaped flask, 30 g of acetonitrile (hereinafter also referred to as "MeCN"), 0.26 g (2 mmol) of isocyanuric acid, and 0.048 g (6 mmol) of lithium hydride were added. After stirring at 20-30°C for 1 hour, 0.81 g (6.5 mmol) of fluorosulfonyl isocyanate was slowly added. After stirring at or below 30°C for 1 hour, the mixture was concentrated to obtain 0.97 g of compound (1-1-11) (93% recovery).

[0283] <Synthesis example 1-2>

[0284] Synthesis of compound (1-3-1)

[0285]

[0286] In a 50 ml eggplant-shaped flask, 30 g of MeCN, 0.21 g (1 mmol) of diallyl isocyanurate, and 0.008 g (1 mmol) of lithium hydride were added. After stirring at 20-30°C for 1 hour, 0.14 g (1.1 mmol) of fluorosulfonyl isocyanate was slowly added. After stirring at or below 40°C for 15 hours, the mixture was concentrated to obtain 0.33 g of compound (1-3-1) (96% recovery).

[0287] 1 H NMR (CD3CN)σ H 5.91-5.79, 5.23-5.13, 4.42ppm,

[0288] 19 F NMR (CD3CN)σ F 48.0ppm.

[0289] <Synthesis example 2-1>

[0290] Synthesis of compound (2-2-2)

[0291]

[0292] In a 50 ml eggplant-shaped flask, 30 g of MeCN, 0.17 g (1 mmol) of 6-(allyloxy)-1,3,5-triazine-2,4(1H,3H)-dione, and 0.016 g (2 mmol) of lithium hydride were added. After stirring at 20-30°C for 1 hour, 0.25 g (2 mmol) of fluorosulfonyl isocyanate was slowly added. After stirring at or below 40°C for 15 hours, the mixture was concentrated to obtain 0.41 g of compound (2-2-2) (95% recovery). 1 H NMR (CD3CN)σ H6.10-5.92, 5.41-5.21, 4.83ppm,

[0293] 19 F NMR (CD3CN)σ F 48.0ppm, 48.2ppm

[0294] <Synthesis example 3-1>

[0295] Synthesis of compound (3-3-3)

[0296]

[0297] To a 50 ml eggplant-shaped flask, 30 g of ethyl methyl carbonate (hereinafter also referred to as "EMC"), 0.21 g (1 mmol) of 4,6-(allyloxy)-1,3,5-triazin-2(1H)-one, and 0.008 g (1 mmol) of lithium hydride were added. After stirring at 20-30°C for 10 minutes, 0.12 g (1 mmol) of fluorosulfonyl isocyanate was slowly added. After stirring for 2 hours at or below 40°C, the mixture was concentrated to obtain 0.33 g of compound (3-3-3) (97% recovery).

[0298] 1 H NMR (CD3CN)σ H 6.08-5.95, 5.48-5.25, 4.93ppm, 4.79ppm

[0299] 19 F NMR (CD3CN)σ F 48.0ppm

[0300] <Synthesis example 3-2>

[0301] Synthesis of compound (3-3-54)

[0302]

[0303] In a 50 ml eggplant-shaped flask, 30 g of EMC, 0.18 g (1 mmol) of 4-methoxy,6-propargyloxy-1,3,5-triazin-2(1H)-one, and 0.008 g (1 mmol) of lithium hydride were added. After stirring at 20-30°C for 10 minutes, 0.12 g (1 mmol) of fluorosulfonyl isocyanate was slowly added. After stirring for 3 hours below 40°C, the mixture was concentrated to obtain 0.29 g of compound (3-3-54) (95% recovery).

[0304] 1 H NMR (CD3CN)σ H 4.92ppm, 4.03ppm, 2.83ppm,

[0305] 19 F NMR (CD3CN)σ F 47.5ppm

[0306] <Synthesis example 4-1>

[0307] Synthesis of compound (4-3-1)

[0308]

[0309] In a 50 ml eggplant-shaped flask, 30 g of EMC and 0.21 g (1 mmol) of diallyl cyanurate lithium salt were added. After stirring at 20-30°C for 10 minutes, 0.19 g (1.5 mmol) of fluorosulfonyl isocyanate was slowly added. After stirring at or below 40°C for 2 hours, the formation of compound (4-3-1) was confirmed by NMR.

[0310] 1 H NMR (CD3CN)σ H 6.07-5.96, 5.41-5.27, 4.86ppm

[0311] 19 F NMR (CD3CN)σ F 48.0ppm

[0312] <Synthesis example 4-2>

[0313] Synthesis of compound (4-1-11)

[0314]

[0315] Compound (4-1-11) was synthesized in the same manner as in the synthesis of compound (4-3-1), except that the starting materials were changed according to the structure of the target product.

[0316] Furthermore, the above compounds were subjected to cation exchange reactions to obtain the following compounds (1-1-11-Na), (1-3-1-Na), (2-2-2-Na), (3-3-3-Na), (4-1-11-Na), and (4-3-1-Na).

[0317]

[0318] <Example 1-1>

[0319] (Preparation of Non-aqueous Electrolyte 1-1)

[0320] As a non-aqueous organic solvent, a mixed solvent of ethylene carbonate (hereinafter also referred to as "EC"), dimethyl carbonate (hereinafter also referred to as "DMC"), and EMC in a volume ratio of 3:3:4 was used. Lithium hexafluorophosphate (hereinafter also referred to as "LiPF6") as a solute was dissolved in this solvent at a concentration of 1.0 mol / L, and the compound represented by the above formula (1-1-11), which is a compound represented by general formula (1), was dissolved in this solvent at a concentration of 0.05% by mass relative to the total amount of the non-aqueous electrolyte to prepare a non-aqueous electrolyte solution 1-1. It should be noted that the above preparation was performed while maintaining the liquid temperature at 25°C.

[0321] <Examples 1-2 to 1-12>

[0322] (Preparation of non-aqueous electrolyte solutions 1-2 to 1-12)

[0323] Non-aqueous electrolyte solutions 1-2 to 1-12 were prepared by dissolving the compound represented by general formula (1) in the same manner as in the preparation of non-aqueous electrolyte solution 1-1, except that the type and concentration of the compound were changed as shown in Table 1.

[0324] <Examples 2-1 to 2-6>

[0325] (Preparation of non-aqueous electrolyte solutions 2-1 to 2-6)

[0326] Non-aqueous electrolyte solutions 2-1 to 2-6 were prepared by using the compound represented by general formula (2) instead of the compound represented by general formula (1) and dissolving them in the same manner as in the preparation of the non-aqueous electrolyte solution 1-1 except that the concentrations thereof were changed as shown in Table 1.

[0327] <Examples 3-1 to 3-6>

[0328] (Preparation of non-aqueous electrolyte solutions 3-1 to 3-6)

[0329] Non-aqueous electrolyte solutions 3-1 to 3-6 were prepared by using the compound represented by general formula (3) instead of the compound represented by general formula (1) and dissolving them in the same manner as in the preparation of the non-aqueous electrolyte solution 1-1 except that the concentrations thereof were changed as shown in Table 1.

[0330] <Examples 4-1 to 4-12>

[0331] (Preparation of non-aqueous electrolyte solutions 4-1 to 4-12)

[0332] Non-aqueous electrolyte solutions 4-1 to 4-12 were prepared by using the compound represented by general formula (4) instead of the compound represented by general formula (1) and dissolving them in the same manner as in the preparation of the non-aqueous electrolyte solution 1-1 except that the concentrations thereof were changed as shown in Table 1.

[0333] <Examples 5-1 to 5-9>

[0334] (Preparation of non-aqueous electrolyte solutions 5-1 to 5-9)

[0335] Non-aqueous electrolyte solutions 5-1 to 5-9 were prepared by changing the type and concentration of the compound represented by general formula (1), (2), (3) or (4) as shown in Table 2 and dissolving them in the same manner as in the preparation of the above-mentioned non-aqueous electrolyte solution 1-1.

[0336] <Comparative Example 1-1>

[0337] (Preparation of Comparative Non-aqueous Electrolyte 1-1)

[0338] Comparative non-aqueous electrolyte solution 1-1 was prepared by dissolving the solution in the same manner as in the preparation of non-aqueous electrolyte solution 1-1, except that the compound represented by general formula (1) was not added.

[0339] <Comparative Examples 1-2 to 1-4>

[0340] (Comparative Preparation of Non-aqueous Electrolyte Solutions 1-2 to 1-4)

[0341] The compound represented by the following formula (6-1), (6-2) or (6-3) was used instead of the compound represented by the general formula (1). The concentration was changed as shown in Table 1. In addition, the same steps as those for the preparation of the non-aqueous electrolyte 1-1 were used for dissolution to prepare comparative non-aqueous electrolytes 1-2 to 1-4. It should be noted that compounds (6-1) and (6-2) were purchased from Tokyo Chemical Industry Co., Ltd. For (6-3), with reference to Patent Document 4, 0.71 g (5.7 mmol) of ethylenesulfonyl fluoride and 0.25 g (1.89 mmol) of cyanuric acid were dissolved in 30 ml of ethanol, and then 0.16 g (1.9 mmol) of sodium acetate was added at ice bath temperature, and the mixture was stirred at room temperature for 12 hours. The obtained suspension was filtered and washed with water, ethanol and diethyl ether. The product was dried under reduced pressure to obtain a white solid, and the obtained substance was used.

[0342]

[0343] <Examples 6-1 to 6-6, Comparative Examples 2-1 to 2-4>

[0344] (Preparation of Non-aqueous Electrolyte Solutions 6-1 to 6-6 and Comparative Non-aqueous Electrolyte Solutions 2-1 to 2-4)

[0345] Furthermore, vinylene carbonate (hereinafter also referred to as "VC") as another additive (1) and lithium bis(oxalato)borate (hereinafter also referred to as "BOB") as another additive (2) were added and dissolved in a manner to give the concentrations described in Table 3. In addition, non-aqueous electrolytes 6-1 to 6-6 and comparative non-aqueous electrolytes 2-1 to 2-4 were obtained in the same manner as in the preparation of non-aqueous electrolytes 1-4, 1-10, 2-4, 3-4, 4-4 and 4-10 and comparative non-aqueous electrolytes 1-1 to 1-4, respectively.

[0346] <Examples 7-1 to 7-6, Comparative Examples 3-1 to 3-4> ~ <Examples 13-1 to 13-6, Comparative Examples 9-1 to 9-4>

[0347] As shown in Tables 3 and 4, the other additive (2) was changed from BOB to the compound shown in each table. Dissolution was performed in the same manner as in the preparation of non-aqueous electrolyte solutions 6-1 to 6-6 and comparative non-aqueous electrolyte solutions 2-1 to 2-4 to prepare the non-aqueous electrolyte solutions and comparative non-aqueous electrolyte solutions shown in each table. It should be noted that "DFBOP" refers to lithium difluorobis(oxalato)phosphate, "DFOB" refers to lithium difluorooxalatoborate, "TFOP" refers to lithium tetrafluorooxalatophosphate, "DTD" refers to 1,3,2-dioxathiolane-2,2-dioxide, "DFPFSI" refers to lithium (difluorophosphoryl)(fluorosulfonyl)imide, "FS" refers to lithium fluorosulfonate, and "TV-Si" refers to tetravinylsilane.

[0348] <Examples 14-1 to 14-6, Comparative Examples 10-1 to 10-4> ~ <Examples 37-1 to 37-6, Comparative Examples 33-1 to 33-4>

[0349] As described in Tables 5 to 10, the compounds listed in "Additional solutes" in each table were added as solutes in the amounts described, and other additives (2) were replaced with the compounds described in each table. Dissolution was performed in the same manner as in the preparation of non-aqueous electrolyte solutions 6-1 to 6-6 and comparative non-aqueous electrolyte solutions 2-1 to 2-4 to prepare the non-aqueous electrolyte solutions and comparative non-aqueous electrolyte solutions described in each table. It should be noted that "DFP" refers to lithium difluorophosphate, "FSI" refers to lithium bis(fluorosulfonyl)imide, and "BF4" refers to lithium tetrafluoroborate.

[0350] <Examples 38-1 to 38-12, Comparative Examples 34-1 to 34-4> ~ <Examples 66-1 to 66-6, Comparative Examples 58-1 to 58-4>

[0351] As a non-aqueous organic solvent, a mixed solvent of EC, fluoroethylene carbonate (hereinafter also referred to as "FEC"), DMC, and EMC in a volume ratio of 3:0.2:3:3.8 was used, and LiPF6 and FSI as solutes were dissolved in the solvent in a manner to become concentrations of 1.0 mol / L and 0.1 mol / L, respectively. As described in Tables 11 to 18, other additives (2) were changed to the compounds described in each table, and the amount of the compound described in the "additional solute" of each table was added as a further solute. Except for this, the electrolyte solutions described in Tables 1 to 6, Table 9, and Table 10 were dissolved in the same manner as in the preparation, and the non-aqueous electrolyte solutions and comparative non-aqueous electrolyte solutions described in each table were prepared.

[0352] <Example 67-1>

[0353] (Preparation of Non-aqueous Electrolyte 67-1)

[0354] A non-aqueous organic solvent was prepared by dissolving a mixed solvent of EC, propylene carbonate (hereinafter also referred to as "PC"), FEC, and EMC in a volume ratio of 2:1:0.2:6.8. Sodium hexafluorophosphate (hereinafter also referred to as "NaPF6") as a solute at a concentration of 1.0 mol / L and a compound represented by the above formula (1-1-11-Na) as a compound represented by general formula (1) at a concentration of 0.05% by mass relative to the total amount of the non-aqueous electrolyte solution in the solvent to prepare a non-aqueous electrolyte solution 67-1. The preparation was performed while maintaining the solution temperature at 25°C.

[0355] <Examples 67-2 to 67-12>

[0356] (Preparation of non-aqueous electrolyte solutions 67-2 to 67-12)

[0357] Except for changing the type and concentration of the compound represented by general formula (1) as shown in Table 19, the same dissolution procedure as that for the preparation of the non-aqueous electrolyte solution 67-1 was followed to prepare non-aqueous electrolyte solutions 67-2 to 67-12.

[0358] <Examples 68-1 to 68-6>

[0359] (Preparation of non-aqueous electrolyte solutions 68-1 to 68-6)

[0360] Non-aqueous electrolyte solutions 68-1 to 68-6 were prepared by using a compound represented by general formula (2) instead of the compound represented by general formula (1) and changing its concentration as shown in Table 19. In addition, the compound was dissolved in the same manner as in the preparation of the above-mentioned non-aqueous electrolyte solution 67-1.

[0361] <Examples 69-1 to 69-6>

[0362] (Preparation of non-aqueous electrolyte solutions 69-1 to 69-6)

[0363] Non-aqueous electrolyte solutions 69-1 to 69-6 were prepared by using a compound represented by general formula (3) instead of the compound represented by general formula (1) and changing its concentration as shown in Table 19. In addition, the compound was dissolved in the same manner as in the preparation of the above-mentioned non-aqueous electrolyte solution 67-1.

[0364] <Examples 70-1 to 70-12>

[0365] (Preparation of Non-aqueous Electrolyte Solutions 70-1 to 70-12)

[0366] Non-aqueous electrolyte solutions 70-1 to 70-12 were prepared by using a compound represented by general formula (4) instead of the compound represented by general formula (1) and changing its concentration as shown in Table 19. In addition, the compound was dissolved in the same manner as in the preparation of the above-mentioned non-aqueous electrolyte solution 67-1.

[0367] <Examples 71-1 to 71-9>

[0368] (Preparation of Non-aqueous Electrolyte Solutions 71-1 to 71-9)

[0369] The types and concentrations of the compounds represented by general formula (1), (2), (3) or (4) were changed as shown in Table 20. In addition, the non-aqueous electrolyte solutions 71-1 to 71-9 were prepared by dissolving them in the same manner as in the preparation of the above-mentioned non-aqueous electrolyte solution 67-1.

[0370] <Comparative Example 59-1>

[0371] (Preparation of Comparative Non-aqueous Electrolyte 59-1)

[0372] Comparative non-aqueous electrolyte solution 59-1 was prepared by dissolving the solution in the same manner as in the preparation of non-aqueous electrolyte solution 67-1, except that the compound represented by general formula (1) was not added.

[0373] <Comparative Examples 59-2 to 59-4>

[0374] (Comparative Preparation of Non-aqueous Electrolyte Solutions 59-2 to 59-4)

[0375] Comparative non-aqueous electrolytes 59-2 to 59-4 were prepared by using the compound represented by the above formula (6-1) or (6-2) instead of the compound represented by the general formula (1), changing its concentration as shown in Table 19, and dissolving it in the same steps as the preparation of the non-aqueous electrolyte 67-1.

[0376] <Examples 72-1 to 72-6, Comparative Examples 60-1 to 60-4>

[0377] (Preparation of Non-aqueous Electrolyte Solutions 72-1 to 72-6 and Comparative Non-aqueous Electrolyte Solutions 60-1 to 60-4)

[0378] Furthermore, sodium difluorobis(oxalato)phosphate (hereinafter also referred to as "DFBOP-Na") as another additive (1) was added and dissolved in a manner to obtain the concentrations described in Table 21. In addition, non-aqueous electrolytes 72-1 to 72-6 and comparative non-aqueous electrolytes 60-1 to 60-4 were obtained in the same manner as in the preparation of non-aqueous electrolytes 67-4, 67-10, 68-4, 69-4, 70-4 and 70-10 and comparative non-aqueous electrolytes 59-1 to 59-4.

[0379] <Examples 73-1 to 73-6, Comparative Examples 61-1 to 61-4> ~ <Examples 78-1 to 78-6, Comparative Examples 66-1 to 66-4>

[0380] As shown in Tables 21 and 22, the nonaqueous electrolytes and comparative nonaqueous electrolytes described in each table were prepared by dissolving the electrolytes in the same manner as in the preparation of nonaqueous electrolyte solutions 72-1 to 72-6 and comparative nonaqueous electrolyte solutions 60-1 to 60-4, except that the other additive (1) was changed from DFBOP-Na to the compound described in each table. It should be noted that "DFOB-Na" refers to sodium difluorooxalatoborate, "TFOP-Na" refers to sodium tetrafluorooxalatophosphate, "DFPFSI-Na" refers to sodium (difluorophosphoryl)(fluorosulfonyl)imide, and "FS-Na" refers to sodium fluorosulfonate.

[0381] <Examples 79-1 to 79-6, Comparative Examples 67-1 to 67-4> ~ <Examples 99-1 to 99-6, Comparative Examples 87-1 to 87-4>

[0382] As described in Tables 23 to 28, the nonaqueous electrolytes and comparative nonaqueous electrolytes described in each table were prepared by dissolving the compounds described in "Additional Solutes" in each table in the same manner as described in the preparation of nonaqueous electrolyte solutions 72-1 to 72-6 and comparative nonaqueous electrolyte solutions 60-1 to 60-4, except that the amounts described were added to the compounds described in "Additional Solutes" in each table and that the other additive (1) was replaced with the compounds described in each table. It should be noted that "DFP-Na" refers to sodium difluorophosphate, "FSI-Na" refers to sodium bis(fluorosulfonyl)imide, and "BF4-Na" refers to sodium tetrafluoroborate.

[0383] <Examples 100-1 to 100-5 (Na, K, Li)> ~ <Examples 117-1 to 117-5 (Na, K, Li)>

[0384] As shown in Tables 29 to 34 and 45 to 47, Na-BOB, K-BOB, Li-BOB, Na-BF4, K-BF4, Li-BF4, Na-ClO4, K-ClO4, and Li-ClO4 as other additives were dissolved in non-aqueous electrolyte solutions 1-4, 1-10, 2-4, 3-4, 4-4, and 4-10 at the contents shown in each table to prepare the non-aqueous electrolyte solutions described in each table. It should be noted that "Na-BOB" refers to sodium bis(oxalatoborate), "K-BOB" refers to potassium bis(oxalatoborate), "Li-BOB" refers to lithium bis(oxalatoborate), "Na-BF4" refers to sodium tetrafluoroborate, "K-BF4" refers to potassium tetrafluoroborate, "Li-BF4" refers to lithium tetrafluoroborate, "Na-ClO4" refers to sodium perchlorate, "K-ClO4" refers to potassium perchlorate, and "Li-ClO4" refers to lithium perchlorate. The contents of cations other than Li in the non-aqueous electrolyte solutions described in Tables 29 to 34 and 45 to 47 were determined by ICP emission spectroscopy. Note that the contents of cations other than Li in the non-aqueous electrolyte solutions described in Tables 1 to 10 were all less than 1 mass ppm.

[0385] <Examples 118-1 to 118-5 (Na, K, Li)> ~ <Examples 135-1 to 135-5 (Na, K, Li)>

[0386] As shown in Tables 35 to 40 and 48 to 50, Na-BOB, K-BOB, Li-BOB, Na-BF4, K-BF4, Li-BF4, Na-ClO4, K-ClO4, and Li-ClO4 as other additives were dissolved in non-aqueous electrolyte solutions 38-4, 38-10, 39-4, 40-4, 41-4, and 41-10 to prepare the non-aqueous electrolyte solutions described in each table. The content of cations other than Li in the non-aqueous electrolyte solutions described in Tables 35 to 40 and 48 to 50 was determined by ICP emission spectroscopy. It should be noted that the content of cations other than Li in the non-aqueous electrolyte solutions described in Tables 11 to 18 was less than 1 mass ppm.

[0387] <Examples 136-1 to 136-5 (Na, K, Li)> ~ <Examples 147-1 to 147-5 (Na, K, Li)>

[0388] As shown in Tables 41 to 44 and 51 to 52, Li-BF4, K-BF4, Na-BF4, Li-ClO4, K-ClO4, and Na-ClO4 as other additives were dissolved in non-aqueous electrolytes 67-4, 67-10, 68-4, 69-4, 70-4, and 70-10 in the amounts shown in each table to prepare the non-aqueous electrolytes described in each table. The content of cations other than Na in the non-aqueous electrolytes described in Tables 41 to 44 and 51 to 52 was determined by ICP emission spectroscopy. It should be noted that the content of cations other than Na in the non-aqueous electrolytes described in Tables 19 to 28 was all less than 1 mass ppm.

[0389] [Manufacturing of non-aqueous electrolyte batteries]

[0390] (Production of NCM622 positive electrode)

[0391] At 90 mass% LiNi 0.6 Co 0.2 Mn 0.2 O2 powder was mixed with 5% by mass of polyvinylidene fluoride (PVDF) as a binder and 5% by mass of acetylene black as a conductive material. N-methyl-2-pyrrolidone (NMP) was also added to prepare a positive electrode composite material paste. This paste was applied to both sides of aluminum foil (A1085), dried, pressed, and then punched into 4 cm x 5 cm pieces to produce the NCM622 positive electrode for testing.

[0392] (Production of NCM811 positive electrode)

[0393] At 92.0 mass% LiNi 0.8 Mn 0.1 Co 0.1 O2 powder was mixed with 3.5% by mass of PVDF as a binder and 4.5% by mass of acetylene black as a conductive material, and NMP was further added to prepare a positive electrode composite material paste. This paste was applied to both sides of aluminum foil (A1085), dried, pressed, and then punched into 4 cm x 5 cm pieces to produce the NCM811 positive electrode for testing.

[0394] (Sodium ion battery positive electrode: NaNi 0.5 Ti 0.3 Mn 0.2 Production of O2 positive electrode)

[0395] 90% by mass of NaNi as the positive electrode active material 0.5 Ti 0.3 Mn 0.2O2, 5% by mass of acetylene black as a conductive agent, and 5% by mass of PVDF as a binder were mixed, and NMP as a solvent was further added to prepare a positive electrode composite material paste. The paste was applied to both sides of aluminum foil (A1085), dried, pressed, and then punched into 4 cm × 5 cm pieces to obtain NaNi for testing. 0.5 Ti 0.3 Mn 0.2 O2 positive electrode.

[0396] (Production of LFP positive electrode)

[0397] A positive electrode composite paste was prepared by mixing 90.0% LiFePO4 powder with 5% PVDF as a binder, 5% acetylene black as a conductive material, and NMP. This paste was applied to both sides of aluminum foil (A1085), dried, pressed, and then punched into 4 cm x 5 cm pieces to produce the LFP positive electrode for testing.

[0398] (Production of natural graphite negative electrode)

[0399] A negative electrode composite material paste was prepared by mixing 92% by mass of natural graphite powder, 3% by mass of a conductive material (HS-100 manufactured by Denka Company Limited), 2% by mass of carbon nanofibers (VGCF manufactured by Showa Denko), 2% by mass of styrene-butadiene rubber (hereinafter referred to as "SBR"), and 1% by mass of sodium carboxymethylcellulose (hereinafter referred to as "CMC") with water. This paste was applied to copper foil, dried, pressed, and then punched into 4.5 cm x 5.5 cm pieces to produce a natural graphite negative electrode for testing.

[0400] (Fabrication of Silicon-Containing Graphite Anode)

[0401] A negative electrode composite material paste was prepared by mixing 85% artificial graphite powder with 7% nanosilicon, 3% conductive material (HS-100 manufactured by Denka Company Limited), 2% carbon nanofiber (VGCF manufactured by Showa Denko), 2% SBR, 1% CMC, and water. This paste was applied to copper foil, dried, pressed, and then punched into 4.5 cm x 5.5 cm pieces to produce a silicon-containing graphite negative electrode for testing.

[0402] (Fabrication of Hard Carbon Anode)

[0403] A negative electrode composite paste was prepared by mixing 90% by mass of hard carbon powder (Carbotron P, manufactured by KUREHA CORPORATION) with 10% by mass of PVDF as a binder, and adding NMP as a solvent. This paste was applied to aluminum foil (A1085), dried, pressed, and then punched into 4.5 cm × 5.5 cm sheets to produce a hard carbon negative electrode for testing.

[0404] (Manufacturing of non-aqueous electrolyte batteries)

[0405] In an argon atmosphere with a dew point below -50°C, terminals were welded to the NCM622 positive electrode. The electrodes were then sandwiched on either side with two polyethylene separators (5 cm x 6 cm). Furthermore, two natural graphite negative electrodes, pre-welded with terminals, were sandwiched on the outside, with the negative electrode active material surface facing the positive electrode active material surface. These electrodes were then placed in an aluminum laminate bag with one opening, vacuum-filled with a nonaqueous electrolyte, and the opening was sealed with heat. This produced the aluminum laminate nonaqueous electrolyte batteries (lithium-ion batteries) of the Examples and Comparative Examples listed in Tables 1-10, 29-34, and 45-47.

[0406] In the Examples and Comparative Examples in Tables 11 to 18, 35 to 40, and 48 to 50, nonaqueous electrolyte batteries (lithium ion batteries) were similarly produced using NCM811 as the positive electrode and silicon-containing graphite as the negative electrode.

[0407] In addition, in the Examples and Comparative Examples in Tables 19 to 28, 41 to 44, and 51 to 52, NaNi 0.5 Ti 0.3 Mn 0.2 A non-aqueous electrolyte battery (sodium ion battery) was similarly manufactured using an O2 positive electrode as the positive electrode and a hard carbon negative electrode as the negative electrode.

[0408] In addition, in the embodiments and comparative examples of Tables 53 to 65, non-aqueous electrolyte batteries (lithium ion batteries-LFP positive electrodes-) were similarly prepared using the non-aqueous electrolytes described in the respective tables, using LFP positive electrodes as positive electrodes, and using natural graphite negative electrodes as negative electrodes.

[0409] 〔evaluate〕

[0410] Initial charge and discharge test: lithium-ion battery

[0411] First, the fabricated battery cells were conditioned at an ambient temperature of 25°C under the following conditions. Specifically, as an initial charge and discharge test, constant-current and constant-voltage charging was performed at a charge upper limit voltage of 4.2V and 5mA, followed by constant-current discharge at 10mA until the discharge cutoff voltage reached 2.5V. Subsequently, constant-current and constant-voltage charging was performed at a charge upper limit voltage of 4.2V and 10mA, followed by constant-current discharge at 10mA until the discharge cutoff voltage reached 2.5V. This charge and discharge cycle was repeated three times.

[0412] Initial charge and discharge test: sodium ion battery

[0413] First, the fabricated battery cells were conditioned at an ambient temperature of 25°C under the following conditions. Specifically, as an initial charge and discharge test, constant-current and constant-voltage charging was performed at a charge upper limit voltage of 4.1V and 5mA, followed by constant-current discharge at 10mA until the discharge cutoff voltage reached 1.5V. Subsequently, constant-current and constant-voltage charging was performed at a charge upper limit voltage of 4.1V and 10mA, followed by constant-current discharge at 10mA until the discharge cutoff voltage reached 1.5V. This charge and discharge cycle was repeated three times.

[0414] Initial charge and discharge test: Lithium-ion battery - LFP positive electrode -

[0415] First, the fabricated battery cells were conditioned at an ambient temperature of 25°C under the following conditions. Specifically, as an initial charge and discharge test, constant-current and constant-voltage charging was performed at a charge upper limit voltage of 3.5V and 5mA, followed by constant-current discharge at 10mA until the discharge cutoff voltage reached 2.0V. Subsequently, constant-current and constant-voltage charging was performed at a charge upper limit voltage of 3.5V and 10mA, followed by constant-current discharge at 10mA until the discharge cutoff voltage reached 2.0V. This charge and discharge cycle was repeated three times.

[0416] <Initial DC internal resistance measurement: Lithium-ion battery>

[0417] For the non-aqueous electrolyte battery that has undergone the above-mentioned initial charge and discharge, a constant current charge of 10 mA is performed for 150 minutes at an ambient temperature of 25°C, and a constant current discharge of 10 seconds is performed at a specified current value (5 mA, 10 mA, 25 mA, 50 mA, 100 mA). The voltage at the 10th second is measured and plotted against the current value. The least squares method is applied to each plot to obtain an approximate straight line. The value of the slope of the approximate straight line is used as the initial DC internal resistance. The smaller the value, the better the initial input / output characteristics.

[0418] <Initial DC internal resistance measurement: Sodium ion battery>

[0419] Evaluation was performed in the same manner as for lithium-ion batteries. A smaller value indicates better initial input / output characteristics.

[0420] Initial DC internal resistance measurement: Lithium-ion battery - LFP positive electrode -

[0421] Evaluation was performed in the same manner as for lithium-ion batteries. A smaller value indicates better initial input / output characteristics.

[0422] <Cycle test (45°C): Lithium-ion battery>

[0423] For the non-aqueous electrolyte battery that has completed the above-mentioned initial DC internal resistance measurement, a constant current discharge of 10mA is performed until the discharge end voltage is 2.5V, and it is allowed to stand at an ambient temperature of 45°C for 3 hours. Thereafter, a constant current constant voltage charge is performed at a charging upper limit voltage of 4.2V and 75mA, and a constant current discharge is performed at 75mA until the discharge end voltage is 2.5V. The charge and discharge at 75mA in this 45°C environment is repeated for 1000 cycles. Thereafter, at an ambient temperature of 25°C, it is allowed to stand for 3 hours, a constant current constant voltage charge is performed at a charging upper limit voltage of 4.2V and 10mA, and a constant current discharge is performed at 10mA until the discharge end voltage is 2.5V.

[0424] <Cycle test (45°C): Sodium ion battery>

[0425] Evaluation was performed in the same manner as for the lithium-ion battery except that the upper limit charge voltage was changed to 4.1 V and the discharge end voltage was changed to 1.5 V.

[0426] Cycle test (45°C): Lithium-ion battery - LFP cathode -

[0427] Evaluation was performed in the same manner as for the lithium-ion battery except that the upper limit charge voltage was changed to 3.5 V and the discharge end voltage was changed to 2.0 V.

[0428] <DC internal resistance measurement after cycle test: Lithium-ion battery>

[0429] The non-aqueous electrolyte battery that had completed the aforementioned cycle test (45°C) was charged and discharged in the same manner as for the initial DC internal resistance measurement. At an ambient temperature of 25°C, the battery was charged at a constant current of 10 mA for 150 minutes. The voltage at 10 seconds was measured and plotted against the current value. The least squares method was applied to each plot to determine an approximate straight line. The slope of the approximate straight line was used as the DC internal resistance after the cycle test.

[0430] <DC internal resistance measurement after cycle test: Sodium ion battery>

[0431] Evaluation was performed in the same manner as for the lithium-ion battery.

[0432] <DC internal resistance measurement after cycle test: Lithium-ion battery - LFP positive electrode->

[0433] Evaluation was performed in the same manner as for the lithium-ion battery.

[0434] <DC internal resistance increase rate after cycle test: lithium-ion battery>

[0435] The DC internal resistance increase rate after the cycle test was calculated using the following formula. The smaller the value, the better the input / output characteristics after the life characteristics.

[0436] Increase rate of DC internal resistance after cycle test (%) = (DC internal resistance after cycle test / initial DC internal resistance) × 100

[0437] <DC internal resistance increase rate after cycle test: sodium ion battery>

[0438] The evaluation was performed in the same manner as for lithium-ion batteries. The smaller the value, the better the input / output characteristics after indicating the life characteristics.

[0439] <DC internal resistance increase rate after cycle test: Lithium-ion battery-LFP positive electrode->

[0440] The evaluation was performed in the same manner as for lithium-ion batteries. The smaller the value, the better the input / output characteristics after indicating the life characteristics.

[0441] It should be noted that in each table, the initial DC internal resistance and the rate of increase in DC internal resistance after the cycle test are expressed as relative values ​​when the evaluation results of the comparative non-aqueous electrolyte solution containing no component (I), compound (6-1), compound (6-2) and compound (6-3) are taken as 100.

[0442] In each table, “R1” represents the initial DC internal resistance (relative value), and “R2” represents the rate of increase in DC internal resistance after the cycle test (relative value).

[0443] [Table 1]

[0444]

[0445] [Table 2]

[0446]

[0447] [Table 3]

[0448]

[0449] [Table 4]

[0450]

[0451] [Table 5]

[0452]

[0453] [Table 6]

[0454]

[0455] [Table 7]

[0456]

[0457] [Table 8]

[0458]

[0459] [Table 9]

[0460]

[0461] [Table 10]

[0462]

[0463] [Table 11]

[0464]

[0465] [Table 12]

[0466]

[0467] [Table 13]

[0468]

[0469] [Table 14]

[0470]

[0471] [Table 15]

[0472]

[0473] [Table 16]

[0474]

[0475] [Table 17]

[0476]

[0477] [Table 18]

[0478]

[0479] [Table 19]

[0480]

[0481] [Table 20]

[0482]

[0483] [Table 21]

[0484]

[0485] [Table 22]

[0486]

[0487] [Table 23]

[0488]

[0489] [Table 24]

[0490]

[0491] [Table 25]

[0492]

[0493] [Table 26]

[0494]

[0495] [Table 27]

[0496]

[0497] [Table 28]

[0498]

[0499] [Table 29]

[0500]

[0501] [Table 30]

[0502]

[0503] [Table 31]

[0504]

[0505] [Table 32]

[0506]

[0507] [Table 33]

[0508]

[0509] [Table 34]

[0510]

[0511] [Table 35]

[0512]

[0513] [Table 36]

[0514]

[0515] [Table 37]

[0516]

[0517] [Table 38]

[0518]

[0519] [Table 39]

[0520]

[0521] [Table 40]

[0522]

[0523] [Table 41]

[0524]

[0525] [Table 42]

[0526]

[0527] [Table 43]

[0528]

[0529] [Table 44]

[0530]

[0531] [Table 45]

[0532]

[0533] [Table 46]

[0534]

[0535] [Table 47]

[0536]

[0537] [Table 48]

[0538]

[0539] [Table 49]

[0540]

[0541] [Table 50]

[0542]

[0543] [Table 51]

[0544]

[0545] [Table 52]

[0546]

[0547] [Table 53]

[0548]

[0549] [Table 54]

[0550]

[0551] [Table 55]

[0552]

[0553] [Table 56]

[0554]

[0555] [Table 57]

[0556]

[0557] [Table 58]

[0558]

[0559] [Table 59]

[0560]

[0561] [Table 60]

[0562]

[0563] [Table 61]

[0564]

[0565] [Table 62]

[0566]

[0567] [Table 63]

[0568]

[0569] [Table 64]

[0570]

[0571] [Table 65]

[0572]

[0573] As shown in Tables 1 to 44 and 53 to 62, the non-aqueous electrolyte batteries using the non-aqueous electrolytes comprising components (I) to (III) of the present disclosure have low initial DC internal resistance and exhibit excellent initial input / output characteristics. Furthermore, it can be seen that when component (I) is (1-3-1), (2-2-2), (3-3-3), or (4-3-1), the increase in DC internal resistance after the cycle test is small and excellent.

[0574] Tables 45 to 52 and 63 to 65 show that, when compared under the same conditions of the type and concentration of component (I) and the same type of anion of component (IV), in the case of lithium-ion batteries, the lower the content of cations other than lithium in the non-aqueous electrolyte, the more balanced the improvement in initial DC internal resistance and the rate of increase in DC internal resistance after the cycle test. Similarly, in the case of sodium-ion batteries, the lower the content of cations other than sodium in the non-aqueous electrolyte, the more balanced the improvement in initial DC internal resistance and the rate of increase in DC internal resistance after the cycle test.

[0575] Industrial applicability

[0576] The present disclosure provides a nonaqueous electrolyte that exhibits excellent initial input / output characteristics when formed into a nonaqueous electrolyte battery, a nonaqueous electrolyte battery that exhibits excellent initial input / output characteristics, and a compound suitable for use in the nonaqueous electrolyte.

[0577] While the present disclosure has been described in detail and with reference to specific embodiments, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the present disclosure.

[0578] This application is based on the Japanese patent application (Japanese Patent Application No. 2023-016464) filed on February 6, 2023, the contents of which are incorporated herein by reference.

Claims

1. A non-aqueous electrolyte comprising: (I) at least one compound 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) solute; and (III) a non-aqueous organic solvent, In the general formula (1), R 1 ~R 3 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent, wherein R 1 ~R 3 At least one of them has a group represented by general formula (5), In the general formula (2), R 4 ~R 6 are optionally the same or different from each other, and are a hydrogen atom or an organic group having 1 to 20 carbon atoms and optionally having a substituent, wherein R 4 ~R 6 At least one of them has a group represented by general formula (5), In the general formula (3), R 7 ~R 9 are optionally the same or different from each other, and are a hydrogen atom or an organic group having 1 to 20 carbon atoms and optionally having a substituent, wherein R 7 ~R 9 At least one of them has a group represented by general formula (5), In the general formula (4), R 10 ~R 12 are optionally the same or different from each other, and are a hydrogen atom or an organic group having 1 to 20 carbon atoms and optionally having a substituent, wherein R 10 ~R 12 At least one of them has a group represented by general formula (5), In the general formula (5), W represents a phosphorus atom or a sulfur atom, and when W is a phosphorus atom, y is 1, and when W is a sulfur atom, y is 2, and X each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted by a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted by a halogen atom, a heteroaryl group having 2 to 40 carbon atoms which may be substituted by a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted by a halogen atom, an alkenyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an alkynyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an aryloxy group having 6 to 40 carbon atoms which may be substituted by a halogen atom, or a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted by a halogen atom, d represents 0 to 5, M represents p+ represents a proton, a metal cation, or an onium cation, p represents the valence of the cation, and q represents a number satisfying p×q=1.

2. The non-aqueous electrolyte according to claim 1, wherein In the general formula (5), X is independently a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a trifluoromethyl group, a trifluoroethyl group, a vinyl group, a 2-propenyl group, a 2-propynyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-pentyl group, an n-hexyl group, a trifluoromethoxy group, a trifluoroethoxy group, a hexafluoroisopropoxy group, an vinyloxy group, a 2-propenyloxy group, a 2-propynyloxy group, a phenoxy group, a naphthyl group, a pentafluorophenoxy group, a pyrrolyl group or a pyridyl group.

3. The non-aqueous electrolyte according to claim 1, wherein X in the general formula (5) is independently a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a trifluoromethyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group or a pyridyl group.

4. The non-aqueous electrolyte according to any one of claims 1 to 3, wherein M in the general formula (5) p+ is a proton, a lithium cation, a sodium cation, a potassium cation, a tetraalkylammonium cation or a tetraalkylphosphonium cation.

5. The non-aqueous electrolyte according to any one of claims 1 to 3, wherein The concentration of (I) is 0.01 to 10.00% by mass based on the total amount of the non-aqueous electrolyte.

6. The non-aqueous electrolyte according to any one of claims 1 to 3, wherein The (II) is at least one selected from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, LiC4F9SO3, LiN(SO2F)2, LiAlO2, LiAlCl4, LiCl and LiI, or at least one selected from the group consisting of NaPF6, NaBF4, NaSbF6, NaAsF6, NaClO4, NaCF3SO3, NaC4F9SO3, NaN(SO2F)2, NaAlO2, NaAlCl4, NaCl and NaI.

7. The non-aqueous electrolyte according to any one of claims 1 to 3, wherein The (III) comprises 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 includes a cyclic carbonate.

9. The non-aqueous electrolyte according to claim 8, wherein The cyclic carbonate includes at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate.

10. The non-aqueous electrolyte according to claim 7, wherein The chain ester includes a chain carbonate.

11. The non-aqueous electrolyte according to claim 10, wherein The chain carbonate includes at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methylpropyl carbonate.

12. The non-aqueous electrolyte according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of vinylene carbonate, bis(oxalato)borate, difluorooxalatoborate, difluorobis(oxalato)phosphate, tetrafluorooxalatophosphate, (difluorophosphoryl)(fluorosulfonyl)imide salt, difluorophosphate, fluorosulfonate, nitrate, 1,3-propylene sultone, 1,3-propane sultone, 1,6-diisocyanatohexane, dimethyl dicarbonate, ethynyl ethylene carbonate, trans-difluoroethylene carbonate, 1,3,2-dioxathiolane-2,2-dioxide, 4-propyl-1,3,2-dioxathiolane-2,2-dioxide, Cyclopentane-2,2-dioxide, methylene methanedisulfonate, 1,2-ethanedisulfonic anhydride, methanesulfonic anhydride, methanesulfonyl fluoride, 1,4-dioxane-2,6-dione, tripropargyl phosphate, tris(trimethylsilyl)borate, (ethoxy)pentafluorocyclotriphosphazene, tetrafluoro(malonic acid)phosphate, tetrafluoro(picolinic acid)phosphate, 1,3-dimethyl-1,3-divinyl-1,3-bis(1,1,1,3,3,3-hexafluoroisopropyl)disiloxane, N,N'-carbonylbis(N-methylaminosulfonyl fluoride), tetravinylsilane, trivinylmethylsilane, tert-butylbenzene, tert-amylbenzene, fluorobenzene, and cyclohexylbenzene.

13. The non-aqueous electrolyte according to any one of claims 1 to 3, further comprising (IV) at least one member selected from the group consisting of a compound represented by the following general formula [1b] and a compound represented by the following general formula [1b'], wherein the content of (IV) in the non-aqueous electrolyte is 10 to 25,000 ppm by mass. In the general formula [1b], Y represents a boron atom, R' represents a fluorine atom, n is 0 to 4, m' is 0 to 2, Q + represents an alkali metal ion, a tetraalkylammonium cation or a tetraalkylphosphonium cation, Q + [Z] - [1b’] In the general formula [1b'], [Z] - The anion portion shown is the structure of the following [1b-1] or a chloride anion, Q + represents an alkali metal ion, a tetraalkylammonium cation or a tetraalkylphosphonium cation, 14. The non-aqueous electrolyte according to claim 13, wherein The (IV) is a salt compound comprising a counter anion selected from bis(oxalato)borate anion, tetrafluoroborate anion, chloride anion or perchlorate anion and a counter cation selected from lithium cation, sodium cation, potassium cation, tetraalkylammonium cation or tetraalkylphosphonium cation.

15. The non-aqueous electrolyte according to claim 13, wherein The content of (IV) in the non-aqueous electrolyte is 10 to 8000 ppm by mass.

16. The non-aqueous electrolyte according to claim 13, wherein The content of (IV) in the non-aqueous electrolyte is 50 to 5000 ppm by mass. 17 . A non-aqueous electrolyte battery comprising at least a positive electrode, a negative electrode, a separator, and the non-aqueous electrolyte according to claim 1 .

18. A compound represented by the following general formula (1), (2), (3) or (4), In the general formula (1), R 1 ~R 3 are optionally the same or different from each other and are a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have a substituent, wherein R 1 ~R 3 At least two of them have a group represented by general formula (5), In the general formula (2), R 4 ~R 6 are optionally the same or different from each other, and are a hydrogen atom or an organic group having 1 to 20 carbon atoms and optionally having a substituent, wherein R 4 ~R 6 At least one of them has a group represented by general formula (5), In the general formula (3), R 7 ~R 9 are optionally the same or different from each other, and are a hydrogen atom or an organic group having 1 to 20 carbon atoms and optionally having a substituent, wherein R 7 ~R 9 At least one of them has a group represented by general formula (5), In the general formula (4), R 10 ~R 12 are optionally the same or different from each other, and are a hydrogen atom or an organic group having 1 to 20 carbon atoms and optionally having a substituent, wherein R 10 ~R 12 At least one of them has a group represented by general formula (5), In the general formula (5), W represents a phosphorus atom or a sulfur atom, and when W is a phosphorus atom, y is 1, and when W is a sulfur atom, y is 2, and X each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted by a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted by a halogen atom, a heteroaryl group having 2 to 40 carbon atoms which may be substituted by a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted by a halogen atom, an alkenyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an alkynyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom, an aryloxy group having 6 to 40 carbon atoms which may be substituted by a halogen atom, or a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted by a halogen atom, d represents 0 to 5, M represents p+ represents a proton, a metal cation, or an onium cation, p represents the valence of the cation, and q represents a number satisfying p×q=1.

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