Non-aqueous electrolyte, and non-aqueous electrolyte battery using the same

Abstract

The present invention provides a nonaqueous electrolyte battery which has a low internal resistance after the initial charge and discharge, while having excellent low-temperature output characteristics after storage at high temperatures.　The present invention contains a compound represented by general formula (1) as a component of a nonaqueous electrolyte solution. In the formula, X1 represents a carbon atom or a sulfur atom; each of Y1 and Y2 represents an oxygen atom or a methylene group that may be substituted by a halogen atom; r represents 1 or 2; and R1 represents a group that is represented by general formula (2) or a general formula (3), provided that (i) in cases where X1 is a sulfur atom, and Y1 and Y2 are methylene groups, and (ii) in cases where X1 is a carbon atom, and Y1 and Y2 are oxygen atoms, R1 is a group represented by general formula (2).

Description

Technical Field

[0001] The present invention relates to a non-aqueous electrolyte and a non-aqueous electrolyte battery using the same.

Background Art

[0002] In recent years, in addition to power storage systems for small-sized, high-energy density applications such as information-related devices and communication devices, namely personal computers, video cameras, digital cameras, mobile phones, smartphones, etc., there is an urgent and expanding demand for batteries that are high-capacity, high-output, and have a high energy density and can be mounted as auxiliary power sources for electric vehicles, hybrid vehicles, and fuel cell vehicles. Also, the demand for batteries that can be used for a long time is increasing in large-scale, power applications such as power storage. 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] A lithium secondary battery mainly consists of a positive electrode, a non-aqueous electrolyte, and a negative electrode. As the negative electrode constituting the lithium secondary battery, for example, metallic lithium, metal compounds capable of occluding and releasing lithium (for example, simple metals, oxides, alloys with lithium, etc.), carbon materials, etc. are known. In particular, lithium secondary batteries using carbon materials such as coke, artificial graphite, and natural graphite, which can occlude and release lithium, have been widely put into practical use. For example, in a lithium secondary battery using a highly crystallized carbon material such as natural graphite or artificial graphite as the negative electrode material, since the non-aqueous organic solvent in the non-aqueous electrolyte is reductively decomposed on the negative electrode surface during charging, the decomposition products and gases generated thereby inhibit the original electrochemical reaction of the battery, and it has been reported that the cycle characteristics deteriorate. Also, lithium secondary batteries using metallic lithium or its alloys, simple metals such as silicon and tin, oxides, etc. as the negative electrode material have a high initial capacity, but during cycling, the negative electrode material is pulverized. Therefore, compared with the negative electrode of carbon material, the reductive decomposition of the non-aqueous organic solvent is likely to occur. As a result, it is known that the charge-discharge efficiency in the first cycle decreases with the increase in the initial irreversible capacity of the battery, and the battery performance such as battery capacity and cycle characteristics significantly deteriorates.

[0004] When lithium cations are inserted into the negative electrode during the first-cycle charging, the negative electrode reacts with the lithium cations or the negative electrode reacts with the electrolyte solvent, forming a film mainly composed of lithium oxide, lithium carbonate, or lithium alkyl carbonate on the surface of the negative electrode. This film on the electrode surface is called a Solid Electrolyte Interface (SEI), and its properties, such as suppressing the reduction decomposition of the solvent and suppressing the deterioration of battery performance, have a great influence on battery performance. In this way, due to the accumulation of decomposition products of the non-aqueous organic solvent, the generation of gas, and the adverse effects caused by the pulverization of the negative electrode material, the occlusion and release of lithium to the negative electrode cannot be carried out smoothly, and as a result, there is a problem that the battery characteristics such as cycle characteristics are significantly deteriorated. As the positive electrode, for example, LiCoO2, LiMn2O4, LiNiO2, LiFePO4, etc. are known. When a lithium secondary battery using these is at a high temperature in a charged state, the non-aqueous organic solvent in the non-aqueous electrolyte is locally partially oxidized and decomposed at the interface between the positive electrode material and the non-aqueous electrolyte. Therefore, the decomposition products and gas generated thereby inhibit the original electrochemical reaction of the battery, and as a result, it has been reported that the battery performance such as cycle characteristics is deteriorated. Similar to the negative electrode, a film of oxidation decomposition products is also formed on the surface of the positive electrode, and it is also known to play an important role in suppressing the oxidation decomposition of the solvent and suppressing the amount of gas generation.

[0005] As described above, a normal lithium secondary battery has a cause for deteriorating battery performance by inhibiting the movement of lithium ions or causing the battery to swell due to decomposition products and gas generated when the non-aqueous electrolyte decomposes on the positive electrode or the negative electrode.

[0006] In addition to overcoming these problems, in order to improve battery performance including long-term durability and output characteristics, it is important to have high ionic conductivity, low electronic conductivity, and form a stable SEI over a long period of time. An attempt has been widely made to actively form a good SEI by adding a small amount (usually 0.01% by mass or more and 10% by mass or less) of a compound called an additive to the non-aqueous electrolyte. Patent Document 1 describes that by containing 0.1% by weight or more and 4% by weight or less of 1,3 - propane sultone or 1,4 - butane sultone in a non - aqueous organic solvent, the surface of an active and highly crystallized carbon material is coated with a passivation film, thereby improving the cycle characteristics and storage characteristics of the battery. In Patent Document 2 and Patent Document 3, by using a non - aqueous electrolyte containing an unsaturated sultone or a non - aqueous electrolyte containing an unsaturated sultone and ethylene carbonate substituted with fluorine, the decomposition reaction of the solvent on the negative electrode is suppressed, the capacity reduction of the battery during high - temperature storage is suppressed, gas generation is suppressed, and the deterioration of the load characteristics of the battery is suppressed.

[0007] Patent Document 4 describes an attempt to improve the high - temperature storage characteristics by using a non - aqueous electrolyte containing at least one selected from the group consisting of 1,3,2 - dioxathiolane - 2,2 - dioxide derivatives or 1,3 - propanediol cyclic sulfate derivatives. Patent Document 5 describes that by using a non - aqueous electrolyte containing a cyclic sulfone compound bonded with a sulfonyloxy group, a strong SEI having excellent ionic conductivity is formed, enabling the improvement of the cycle characteristics of the battery.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

[0009] Although many non-aqueous electrolytes mainly composed of lithium-ion batteries have already been put into practical use, in applications such as in-vehicle use where they may be used under more severe conditions, it cannot be said that non-aqueous electrolytes with sufficient characteristics have been obtained. Regarding the non-aqueous electrolytes described in Patent Documents 1 to 5 above, it cannot be said that the resistance characteristics after the first charge and discharge and the low-temperature output characteristics after high-temperature storage are sufficient, and further improvement is desired. [Means for Solving the Problems]

[0010] In view of the above circumstances, the present inventors conducted intensive research and found that by including a compound represented by the following general formula (1) in a non-aqueous electrolyte, a non-aqueous electrolyte battery having a low internal resistance after the first charge and discharge and excellent low-temperature output characteristics after high-temperature storage can be obtained, and thus completed the present invention.

[0011] That is, the present inventors found that the above problems can be solved by the following configuration. <1>[ A non-aqueous electrolyte containing a compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent. [Chemical Formula]

[0012] [In general formula (1), X 1 is a carbon atom or a sulfur atom, Y 1 and Y 2 are a methylene group which may be substituted with an oxygen atom or a halogen atom, r is 1 when X 1 is a carbon atom, and when X 1 is a sulfur atom, r is 1 when Y 1 and Y 2 are oxygen atoms, and is 2 otherwise, R 1is a group represented by the following general formula (2) or a group represented by the following general formula (3), provided that (i) X 1 is a sulfur atom and Y 1 and Y 2 are methylene groups, and (ii) X 1 is a carbon atom and Y 1 and Y 2 are oxygen atoms, R 1 is a group represented by the general formula (2), R 2 and R 3 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 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 alkoxy 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 aryl group having 6 to 40 carbon atoms which may be substituted by a halogen atom, or a heteroaryl group having 2 to 40 carbon atoms which may be substituted by a halogen atom.]

[0013]

Chemical formula

[0014] [Chemical formula] [In General Formula (3), Q is a phosphorus atom or a sulfur atom, p is 1 when Q is a phosphorus atom and 2 when Q is a sulfur atom, R 5 is a halogen atom, when p = 1, a plurality of R 5 may be the same as or different from each other, and X in General Formula (1) 1 is a sulfur atom, Y 1 is an oxygen atom, and when Y 2 is a methylene group, Q is a phosphorus atom.]

[0015] <2> X in the general formula (1) 1 is a sulfur atom, and Y 1 and Y 2 is an oxygen atom or a methylene group, the non-aqueous electrolyte according to <1>. <3> R in the general formula (1) 1 is a group represented by the general formula (2), and W in the general formula (2) is a sulfur atom, the non-aqueous electrolyte according to <1> or <2>. <4> Y in the general formula (1) 1 is an oxygen atom, Y 2 is a methylene group, R 1 is a group represented by the general formula (3), and Q in the general formula (3) is a phosphorus atom, the non-aqueous electrolyte according to <1> or <2>.

[0016] <5> R in the general formula (1) 1 is a group represented by the general formula (2), and R in the general formula (2) 4 is a fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, trifluoromethyl group, trifluoroethyl group, ethenyl group, 2-propenyl group, 2-propynyl group, phenyl group, naphthyl group, pentafluorophenyl group, pyrrolyl group, pyridinyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, trifluoromethoxy group, trifluoroethoxy group, ethenyloxy group, 2-propenyloxy group, 2-propynyloxy group, phenoxy group, naphthyloxy group, or pentafluorophenoxy group, the non-aqueous electrolyte according to any one of <1> to <3>. <6> R in the general formula (1) 1is a group represented by the general formula (2), and M in the general formula (2) is a hydrogen atom, a lithium cation, a sodium cation, a potassium cation, a tetraalkylammonium cation, or a tetraalkylphosphonium cation. The non-aqueous electrolyte according to any one of <1> to <3> or <5>.

[0017] <7> R in the general formula (1) 1 is a group represented by the general formula (3), and R in the general formula (3) 5 is a fluorine atom. The non-aqueous electrolyte according to <1> or <4>. <8> R in the general formula (1) 2 and R 3 are each independently a hydrogen atom, 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 tetrafluoroethyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group, or a pyridinyl group. The non-aqueous electrolyte according to any one of <1> to <7>. <9> The non-aqueous organic solvent contains at least one selected from the group consisting of a cyclic carbonate and a chain carbonate. The non-aqueous electrolyte according to any one of <1> to <8>. <10> The cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate, and the chain carbonate is at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate. The non-aqueous electrolyte according to <9>.

[0018] <11> The solute is an ionic salt composed of a pair of at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions and at least one anion selected from the group consisting of hexafluorophosphate anions, tetrafluoroborate anions, trifluoromethanesulfonate anions, fluorosulfonate anions, bis(trifluoromethanesulfonyl)imide anions, bis(fluorosulfonyl)imide anions, and (trifluoromethanesulfonyl)(fluorosulfonyl)imide anion or The non-aqueous electrolyte according to any one of <1> to <10>, which is an ionic salt composed of a pair of at least one anion selected from the group consisting of <12> In the non-aqueous electrolyte according to <11>, the cation of the solute is lithium, sodium, potassium, or magnesium, and the anion is at least one selected from the group consisting of hexafluorophosphate anions, tetrafluoroborate anions, trifluoromethanesulfonate anions, bis(trifluoromethanesulfonyl)imide anions, and bis(fluorosulfonyl)imide anions or and is at least one selected from the group consisting of

[0019] <13> In the non-aqueous electrolyte according to any one of <1> to <12>, the content of the compound represented by the general formula (1) with respect to the total amount of the compound represented by the general formula (1), the solute, and the non-aqueous organic solvent is 0.01% by mass or more and 10.0% by mass or less. <14> A non-aqueous electrolyte battery including at least the non-aqueous electrolyte according to any one of <1> to <13>, a positive electrode, and a negative electrode including at least one selected from the group consisting of a negative electrode material containing lithium metal and a negative electrode material capable of occluding and releasing lithium, sodium, potassium, or magnesium.

Advantages of the Invention

[0020] According to the present invention, it is possible to provide a non-aqueous electrolyte having a low internal resistance after the first charge and discharge and excellent low-temperature output characteristics after high-temperature storage, and a non-aqueous electrolyte battery using the same.

Best Mode for Carrying Out the Invention

[0021] The present invention will be described in detail below. However, the description of the constituent elements described below is an example of an embodiment of the present invention and is not limited to these specific details. Various modifications can be made and implemented within the scope of the gist of the present invention. In this specification, "~" is used to mean including the numerical values described before and after it as the lower limit value and the upper limit value. 〔1. Electrolyte for Non-aqueous Battery〕 The electrolyte for a non-aqueous battery of the present invention is a non-aqueous electrolyte containing a compound represented by the above general formula (1), a solute, and a non-aqueous organic solvent.

[0022] <(I) Regarding the compound represented by the general formula (1)> The compound represented by the general formula (1) will be described. The compound represented by the general formula (1) undergoes reductive decomposition on the negative electrode during the initial charging, and forms a stable film derived from the compound on the negative electrode surface, so that the low-temperature output characteristics after the high-temperature storage of the battery can be improved. On the other hand, a film is also formed on the positive electrode surface. Since this film has excellent ionic conductivity containing a large number of polar groups derived from the compound, it is presumed that the internal resistance of the battery can be reduced and the low-temperature output characteristics after high-temperature storage can be improved.

[0023]

Chemical formula

[0024] In the general formula (1), X 1 is a carbon atom or a sulfur atom. X 1 is preferably a sulfur atom. In the general formula (1), Y 1 and Y 2 are an oxygen atom or a methylene group which may be substituted with a halogen atom. Y 1 and Y 2 When they are a methylene group which may be substituted with a halogen atom, examples of such a group include a methylene group (-CH2-), a fluoromethylene group, a difluoromethylene group, a chloromethylene group, a dichloromethylene group, and the like. Y 1 is preferably an oxygen atom or a methylene group, more preferably an oxygen atom.

[0025] In the general formula (1), R 1is a group represented by the following general formula (2) or a group represented by the following general formula (3). However, (i) when X 1 is a sulfur atom and Y 1 and Y 2 are methylene groups, and (ii) when X 1 is a carbon atom and Y 1 and Y 2 are oxygen atoms, R 1 is a group represented by the general formula (2).

[0026] [Chemical formula] In the general formula (2), each notation has the following meanings. M is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, or a monovalent or divalent onium ion. When M is an alkali metal ion, an alkaline earth metal ion, or a monovalent or divalent onium ion, the bond between the nitrogen atom and M in the general formula (2) is an ionic bond. x is 1 when M is a hydrogen atom, an alkali metal ion, or a monovalent onium ion, and 0.5 when M is an alkaline earth metal ion or a divalent onium ion. W is a phosphorus atom or a sulfur atom, and q is 1 when W is a phosphorus atom and 2 when W is a sulfur atom. R 4is a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, a heteroaryl group having 2 to 40 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an alkenyloxy group having 2 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an alkynyloxy group having 2 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an aryloxy group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, or a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group. When q = 1, a plurality of R 4 may be the same or different from each other.

[0027] When M in the general formula (2) is an alkali metal ion, an alkaline earth metal ion or an onium ion, the bond between the nitrogen atom and M in the general formula (2) is an ionic bond. When M is an alkali metal ion or a monovalent onium ion, the group represented by the general formula (2) is equal to the group represented by the following general formula (2-1).

[0028] [Chemical formula] In the general formula (2-1), each notation has the following meaning. M + is an alkali metal ion or a monovalent onium ion. W is a phosphorus atom or a sulfur atom, q is 1 when W is a phosphorus atom and 2 when W is a sulfur atom. R 4 is a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a heteroaryl group having 2 to 40 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted with a halogen atom, an alkenyloxy group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an alkynyloxy group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an aryloxy group having 6 to 40 carbon atoms which may be substituted with a halogen atom, or a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted with a halogen atom. When q = 1, a plurality of R 4 may be the same as or different from each other.

[0029] In general formula (2), x is 0.5 when M is an alkaline earth metal ion or a divalent onium ion. In this case, the compound represented by general formula (1) is equal to the compound represented by the following general formula (1-1).

[0030]

Chemical formula

[0031] M 2+ is an alkaline earth metal ion or a divalent onium ion. W is a phosphorus atom or a sulfur atom, q is 1 when W is a phosphorus atom, and 2 when W is a sulfur atom. R 4is a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, a heteroaryl group having 2 to 40 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an alkenyloxy group having 2 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an alkynyloxy group having 2 to 20 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, an aryloxy group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group, or a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted with a halogen atom, a halogen atom or an FSO2 group. When q = 1, a plurality of R 4 may be the same or different from each other.

[0032] In the general formula (2), M is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, or a monovalent or divalent onium ion.

[0033] Specific examples of the case where M is an alkali metal ion include a lithium cation, a sodium cation, a potassium cation, etc.

[0034] Specific examples of the case where M is an alkaline earth metal ion include a magnesium cation, a calcium cation, etc.

[0035] Specific examples of the case where M is a monovalent or divalent onium ion include tetraalkylammonium cations, tetraalkylphosphonium cations, tetraalkylalkylenediamines, etc. Examples of the alkyl group in the tetraalkylammonium cation, tetraalkylphosphonium cation, and tetraalkylalkylenediamine include alkyl groups having 1 to 6 carbon atoms, specifically, an ethyl group, an n-propyl group, an n-butyl group, etc. Examples of the alkylene group in the tetraalkylalkylenediamine include alkylene groups having 1 to 6 carbon atoms, specifically, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, etc. Specific examples of the tetraalkylalkylenediamine include tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylbutylenediamine, etc.

[0036] M is preferably a hydrogen atom, a lithium cation, a sodium cation, a potassium cation, a tetraalkylammonium cation or a tetraalkylphosphonium cation, more preferably a hydrogen atom, a lithium cation, a sodium cation or a potassium cation, and still more preferably a lithium cation. In the general formula (2), W is a phosphorus atom or a sulfur atom. It is preferable that W is a sulfur atom.

[0037] In the general formula (2), R 4is a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted by a halogen atom, a halogen atom or an FSO2 group, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted by a halogen atom or an FSO2 group, an alkenyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom or an FSO2 group, an alkynyl group having 2 to 20 carbon atoms which may be substituted by a halogen atom or an FSO2 group, an aryl group having 6 to 40 carbon atoms which may be substituted by a halogen atom or an FSO2 group, a heteroaryl group having 2 to 40 carbon atoms which may be substituted by a halogen atom or an FSO2 group, an alkoxy group having 1 to 20 carbon atoms which may be substituted by a halogen atom or an FSO2 group, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted by a halogen atom or an FSO2 group, an alkenyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom or an FSO2 group, an alkynyloxy group having 2 to 20 carbon atoms which may be substituted by a halogen atom or an FSO2 group, an aryloxy group having 6 to 40 carbon atoms which may be substituted by a halogen atom or an FSO2 group, or a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted by a halogen atom or an FSO2 group; when q = 1, a plurality of R 4 may be the same or different from each other.

[0038] R 4 Specific examples of the case where R is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. R 4 Examples of the halogen atom when the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, cycloalkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, and heteroaryloxy group represented by R have a halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. R 4When the alkyl group is an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an FSO2 group, examples of the alkyl group include linear or branched alkyl groups, and fluorine-substituted or unsubstituted alkyl groups are preferred. Specifically, examples include 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 2,2,2-trifluoroethyl group, a 3-fluoropropyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a hexafluoroisopropyl group, and the like.

[0039] R 4 When the cycloalkyl group is a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom or an FSO2 group, examples of the cycloalkyl group include fluorine-substituted or unsubstituted cycloalkyl groups. Specifically, examples include a cyclopentyl group, a cyclohexyl group, and the like. R 4 When the alkenyl group is an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom or an FSO2 group, examples of the alkenyl group include linear or branched alkenyl groups, and fluorine-substituted or unsubstituted alkenyl groups are preferred. Specifically, examples include an ethenyl group, a 2-propenyl group, and the like. R 4 When the alkynyl group is an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom or an FSO2 group, examples of the alkynyl group include linear or branched alkynyl groups, and fluorine-substituted or unsubstituted alkynyl groups are preferred. Specifically, examples include a 2-propynyl group, and the like.

[0040] R 4When the aryl group is an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom or an FSO2 group, a fluorine-substituted or unsubstituted aryl group is preferable. Specifically, a phenyl group, a naphthyl group, a pentafluorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2-fluorosulfonylphenyl group (the “(o-FSO2)-C6H4-” group, the same applies hereinafter), a 3-fluorosulfonylphenyl group (the “(m-FSO2)-C6H4-” group, the same applies hereinafter), a 4-fluorosulfonylphenyl group (the “(p-FSO2)-C6H4-” group, the same applies hereinafter), etc. may be mentioned. R 4 When the heteroaryl group is a heteroaryl group having 2 to 40 carbon atoms which may be substituted with a halogen atom or an FSO2 group, a fluorine-substituted or unsubstituted heteroaryl group is preferable. Specifically, a pyrrolyl group, a pyridinyl group, etc. may be mentioned. R 4 When the alkoxy group is an alkoxy group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an FSO2 group, a linear or branched alkoxy group may be mentioned. A fluorine-substituted or unsubstituted alkoxy group is preferable. Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-pentyloxy group, an n-hexyloxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 3-fluoropropoxy group, a 3,3,3-trifluoropropoxy group, a 2,2,3,3,3-pentafluoropropoxy group, a 2,2,3,3-tetrafluoropropoxy group, a hexafluoroisopropoxy group, etc. may be mentioned.

[0041] R 4 When the cycloalkoxy group is a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted with a halogen atom or an FSO2 group, a fluorine-substituted or unsubstituted cycloalkoxy group is preferable. Specifically, a cyclopentyloxy group, a cyclohexyloxy group, etc. may be mentioned. R 4When it is an alkenyloxy group having 2 to 20 carbon atoms which may be substituted with a halogen atom or an FSO2 group, examples of the alkenyloxy group include linear or branched alkenyloxy groups, and fluorine-substituted or unsubstituted alkenyloxy groups are preferred. Specifically, ethenyloxy group, 2-propenyloxy group and the like can be mentioned. R 4 When it is an alkynyloxy group having 2 to 20 carbon atoms which may be substituted with a halogen atom or an FSO2 group, examples of the alkynyloxy group include linear or branched alkynyloxy groups, and fluorine-substituted or unsubstituted alkynyloxy groups are preferred. Specifically, 2-propynyloxy group and the like can be mentioned.

[0042] R 4 When it is an aryloxy group having 6 to 40 carbon atoms which may be substituted with a halogen atom or an FSO2 group, examples of the aryloxy group include fluorine-substituted or unsubstituted aryloxy groups. Specifically, phenoxy group, naphthyloxy group, pentafluorophenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-fluorophenoxy group, 2-fluorosulfonylphenoxy group, 3-fluorosulfonylphenoxy group, 4-fluorosulfonylphenoxy group and the like can be mentioned. R 4 When it is a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted with a halogen atom or an FSO2 group, examples of the heteroaryloxy group include fluorine-substituted or unsubstituted heteroaryloxy groups. Specifically, pyrrolyloxy group, pyridinyloxy group and the like can be mentioned.

[0043] R 4Examples include a fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, trifluoromethyl group, trifluoroethyl group, ethenyl group, 2-propenyl group, 2-propynyl group, phenyl group, naphthyl group, pentafluorophenyl group, pyrrolyl group, pyridinyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group, trifluoromethoxy group, trifluoroethoxy group, ethenyloxy group, 2-propenyloxy group, 2-propynyloxy group, phenoxy group, naphthyloxy group, or pentafluorophenoxy group. Among them, a fluorine atom, methyl group, ethyl group, n-propyl group, trifluoromethyl group, ethenyl group, 2-propenyl group, 2-propynyl group, phenyl group, methoxy group, 2-propenyloxy group, 2-propynyloxy group, phenoxy group, or pentafluorophenoxy group is more preferred. Particularly, from the perspective of reducing the initial internal resistance, R 4 Examples include a fluorine atom, methyl group, or methoxy group. From the perspective of improving the low-temperature output characteristics after high-temperature storage, R 4 Examples include a fluorine atom, methyl group, or ethenyl group.

[0044]

Chemical formula

[0045] In general formula (1), from the viewpoint of reducing the internal resistance after the first charge and discharge, R 1 is more preferably the above formula (3), and from the viewpoint of improving the low-temperature output characteristics after high-temperature storage, R 1 is more preferably the above formula (2). In general formula (1), R 2 and R 3 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, or a heteroaryl group having 2 to 40 carbon atoms which may be substituted with a halogen atom. R 2 or R 3 Specific examples when it is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

[0046] R 2 or R 3 Examples of the halogen atom when the alkyl group, alkenyl group, alkynyl group, alkoxy group, cycloalkyl group, aryl group, or heteroaryl group represented by has a halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. R 2 or R 3When the alkyl group is an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, examples of the alkyl group include linear or branched alkyl groups, and fluorine-substituted or unsubstituted alkyl groups are preferred. Specifically, 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 tetrafluoroethyl group, etc. may be mentioned.

[0047] R 2 Or R 3 When the alkenyl group is an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, examples of the alkenyl group include linear or branched alkenyl groups, and fluorine-substituted or unsubstituted alkenyl groups are preferred. Specifically, an ethenyl group, a 2-propenyl group, etc. may be mentioned. R 2 Or R 3 When the alkynyl group is an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, examples of the alkynyl group include linear or branched alkynyl groups, and fluorine-substituted or unsubstituted alkynyl groups are preferred. Specifically, a 2-propynyl group, etc. may be mentioned. R 2 Or R 3 When the alkoxy group is an alkoxy group having 1 to 20 carbon atoms which may be substituted with a halogen atom, examples of the alkoxy group include linear or branched alkoxy groups, and fluorine-substituted or unsubstituted alkoxy groups are preferred. Specifically, a methoxy group, an ethoxy group, an n-propoxy group, etc. may be mentioned.

[0048] R 2 Or R 3 When the cycloalkyl group is a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom, fluorine-substituted or unsubstituted cycloalkyl groups are preferred. Specifically, a cyclopentyl group, a cyclohexyl group, etc. may be mentioned. R 2 Or R 3When the aryl group has 6 to 40 carbon atoms which may be substituted by a halogen atom, the aryl group is preferably a fluorine-substituted or unsubstituted aryl group. Specifically, examples thereof include a phenyl group, a naphthyl group, a pentafluorophenyl group and the like. R 2 or R 3 When the heteroaryl group has 2 to 40 carbon atoms which may be substituted by a halogen atom, the heteroaryl group is preferably a fluorine-substituted or unsubstituted heteroaryl group. Specifically, examples thereof include a pyrrolyl group, a pyridinyl group and the like.

[0049] R 2 and R 3 are each independently preferably selected from a hydrogen atom, 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 tetrafluoroethyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group, and a pyridinyl group. R 2 is a hydrogen atom, and R 3 is more preferably selected from a hydrogen atom, 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 tetrafluoroethyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group, and a pyridinyl group. R 2 is a hydrogen atom or a fluorine atom, and R 3 is still more preferably selected from a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, and a phenyl group. R 2 is a hydrogen atom, and R 3 is particularly preferably a hydrogen atom or a fluorine atom. Specific examples of the compound represented by the general formula (1) are shown below, but are not limited thereto. M in the following formula has the same meaning as M in the general formula (2).

[0050]

Chemical formula

[0051]

Chem.

[0052]

Chem.

[0053]

Chem.

[0054]

Chem.

[0055]

Chem.

[0056]

Chem.

[0057]

Chem.

[0058]

Chem.

[0059]

Chem.

[0060]

Chem.

[0061] [Chemistry]

[0062] [Chemistry]

[0063] [Chemistry] In addition, the above compound is a reference example.

[0064] [Chemistry]

[0065] [Chemistry]

[0066] Among the specific examples of the compound represented by the general formula (1), at least one selected from the group consisting of the compounds represented by the above formulas (1-1) to (1-18), ( (3-1) to (3-7), (4-1) to (4-7), and (6-1) to (6-7) by is preferably at least one selected from the group consisting of the compounds represented. Furthermore, from the viewpoint of reducing the internal resistance after the first charge and discharge, the compounds represented by the formulas (1-1), (1-2), (1-6), (1-9), (1-11), (1-12), (1-15), (1-16), (1-18), ( (3-1), (4-1), and (6-1) by is more preferably at least one selected from the group consisting of the compounds represented. From the viewpoint of reducing the internal resistance after the first charge and discharge, the compounds represented by the formulas (1-1), (1-2), (1-11), (1-15), (1-16), ( (3-1), and (4-1) by are more preferable. From the viewpoint of improving the low-temperature output characteristics after high-temperature storage, the compounds represented by the formulas (1-1), (1-2), (1-6), (1-9), (1-16), (1-18), andThe compound represented by formula (4-1) is more preferable, and from the viewpoint of exhibiting the above two effects in a well-balanced manner, formulas (1-1), (1-16), ( It is particularly preferable that the compound is represented by (3-1) and (4-1).

[0067] In the non-aqueous electrolyte of the present invention, the compound represented by the general formula (1) is preferably used as an additive. In the above non-aqueous electrolyte, the content of the compound represented by the general formula (1) with respect to the total amount (100% by mass) of the compound represented by the general formula (1), the solute, and the non-aqueous organic solvent is preferably 0.01% by mass or more and 10.0% by mass or less. If it is 0.01% by mass or more, the effect of improving the characteristics of the non-aqueous electrolyte battery can be easily obtained. On the other hand, if it is 10.0% by mass or less, it is easy to exhibit a good cycle characteristic improvement effect. More preferably, it is 0.2% by mass or more and 5.0% by mass or less, and still more preferably, it is in the range of 0.5% by mass or more and 2.0% by mass or less.

[0068] Only one kind of the compound represented by the general formula (1) may be used, or a plurality of kinds may be used in combination. Among the general formula (1), R 1 Although the synthesis method of the compound represented by the general formula (2) is not particularly limited, for example, it can be obtained by subjecting the corresponding hydroxy cyclic sulfonic acid ester or hydroxy cyclic carboxylic acid ester and the corresponding isocyanate to an ion exchange reaction with the corresponding cation species. Among the general formula (1), R 1 Although the synthesis method of the compound represented by the general formula (3) is not particularly limited, for example, it can be obtained by reacting the corresponding hydroxy cyclic sulfonic acid ester or hydroxy cyclic carboxylic acid ester with the corresponding s sulfonyl chloride in the presence of an organic base or an inorganic base.

[0069] <Regarding the solute (II)> The non-aqueous electrolyte of the present invention contains a solute. The solute is not particularly limited, but is preferably an ionic salt, more preferably an ionic salt containing fluorine. For example, at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions, and hexafluorophosphate anions, tetrafluoroborate anions, trifluoromethanesulfonate anions, fluorosulfonate anions, bis(trifluoromethanesulfonyl)imide anions, bis(fluorosulfonyl)imide anions, and (Trifluoromethanesulfonyl)(fluorosulfonyl)imide anions or It is preferably an ionic salt composed of a pair of at least one anion selected from the group consisting of.

[0070] It is more preferable that the solute is an ionic salt composed of a pair of at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions, and at least one anion selected from the group consisting of hexafluorophosphate anions, tetrafluoroborate anions, bis(fluorosulfonyl)imide anions, trifluoromethanesulfonate anions, and bis(trifluoromethanesulfonyl)imide anions. In addition, the cation of the ionic salt as the solute is lithium, sodium, potassium or magnesium, and the anion is hexafluorophosphate anions, tetrafluoroborate anions, trifluoromethanesulfonate anions, bis(trifluoromethanesulfonyl)imide anions, and Bis(fluorosulfonyl)imide anions or It is preferable that it is at least one selected from the group consisting of in terms of high solubility in the above non-aqueous organic solvent and its electrochemical stability.

[0071] It is more preferable that the cation of the solute is lithium, sodium, potassium, or magnesium, and the anion is at least one selected from the group consisting of hexafluorophosphate anion, tetrafluoroborate anion, bis(fluorosulfonyl)imide anion, trifluoromethanesulfonate anion, and bis(trifluoromethanesulfonyl)imide anion. There is no particular limitation on the concentration of these solutes. However, as the solute concentration in the non-aqueous electrolyte, the lower limit is 0.5 mol / L or more, preferably 0.7 mol / L or more, more preferably 0.9 mol / L or more, and the upper limit is 2.5 mol / L or less, preferably 2.2 mol / L or less, more preferably 2.0 mol / L or less. By setting it to 0.5 mol / L or more, it is possible to suppress the deterioration of the cycle characteristics and output characteristics of the non-aqueous electrolyte battery due to the decrease in ionic conductivity. By setting it to 2.5 mol / L or less, it is possible to suppress the decrease in ionic conduction due to the increase in the viscosity of the non-aqueous electrolyte for the non-aqueous battery, and the deterioration of the cycle characteristics and output characteristics of the non-aqueous electrolyte battery. Further, these solutes may be used alone or in combination of two or more.

[0072] <(III) Regarding non-aqueous organic solvents> The type of the non-aqueous organic solvent used in the non-aqueous electrolyte of the present invention is not particularly limited, and any non-aqueous organic solvent can be used. Specifically, it is preferably at least one selected from the group consisting of ethyl methyl carbonate (hereinafter referred to as "EMC"), dimethyl carbonate (hereinafter referred to as "DMC"), diethyl carbonate (hereinafter 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-hexafluoro-1-propyl) carbonate, ethylene carbonate (hereinafter referred to as "EC"), propylene carbonate (hereinafter referred to as "PC"), butylene carbonate, fluoroethylene carbonate (hereinafter referred to as "FEC"), difluoroethylene carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, ethyl 2-fluoropropionate, diethyl ether, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, furan, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, N,N-dimethylformamide, acetonitrile, propionitrile, dimethyl sulfoxide, sulfolane, γ-butyrolactone, and γ-valerolactone. In the present invention, an ionic liquid having a salt structure may also be used as the non-aqueous organic solvent.

[0073] Further, it is preferable that the non-aqueous organic solvent is at least one selected from the group consisting of cyclic carbonates and chain carbonates in terms of excellent cycle characteristics at high temperatures. Also, it is preferable that the non-aqueous organic solvent is at least one selected from the group consisting of esters in terms of excellent input / output characteristics at low temperatures. Specific examples of the cyclic carbonate include EC, PC, butylene carbonate, and FEC, etc. Among them, at least one selected from the group consisting of EC, PC, and FEC is preferable. Specific examples of the chain carbonate 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, etc. Among them, at least one selected from the group consisting of EMC, DMC, DEC, and methyl propyl carbonate is preferable.

[0074] Specific examples of the ester include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl 2-fluoropropionate, and ethyl 2-fluoropropionate, etc.

[0075] <Regarding Other Additives> As long as the gist of the present invention is not impaired, additive components generally used in the non-aqueous electrolyte of the present invention may be further added at an arbitrary ratio. Specific examples include cyclohexylbenzene, cyclohexylfluorobenzene, fluorobenzene, biphenyl, difluoroanisole, tert-butylbenzene, tert-amylbenzene, 2-fluorotoluene, 2-fluorobiphenyl, vinylene carbonate, dimethylvinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, trans-difluoroethylene carbonate, methyl propargyl carbonate, ethyl propargyl carbonate, dipropargyl carbonate, maleic anhydride, succinic anhydride, 1,3-propanesultone (PS), 1-propene-1,3-sultone (PRS), butanesultone, 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 tris(oxalato)phosphate, lithium difluorophosphate, lithium ethylfluorophosphate, lithium fluorophosphate, ethenesulfonyl fluoride, lithium fluorosulfonate, trifluoromethanesulfonyl fluoride, methanesulfonyl fluoride, phenyl difluorophosphate, and other compounds having an overcharge prevention effect, a negative electrode film formation effect, or a positive electrode protection effect.

[0076] The content of the other additive in the non-aqueous electrolyte is preferably 0.01% by mass or more and 8.0% by mass or less based on the total amount of the non-aqueous electrolyte.

[0077] In addition, when the content of the ionic salt listed as the solute in the non-aqueous electrolyte is less than 0.5 mol / L, which is the lower limit of the preferred concentration of the solute, it can exhibit a negative electrode film formation effect and a positive electrode protection effect as "other additives". In this case, the content in the non-aqueous electrolyte is preferably 0.01% by mass or more and 5.0% by mass or less. Examples of the ionic salt in this case include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, lithium fluorosulfonate (hereinafter sometimes referred to as LiSO3F), sodium fluorosulfonate, potassium fluorosulfonate, magnesium fluorosulfonate, lithium bis(trifluoromethanesulfonyl)imide, sodium bis(trifluoromethanesulfonyl)imide, potassium bis(trifluoromethanesulfonyl)imide, magnesium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, sodium bis(fluorosulfonyl)imide, potassium bis(fluorosulfonyl)imide, magnesium bis(fluorosulfonyl)imide, lithium (trifluoromethanesulfonyl)(fluorosulfonyl)imide, sodium (trifluoromethanesulfonyl)(fluorosulfonyl)imide, potassium (trifluoromethanesulfonyl)(fluorosulfonyl)imide, magnesium (trifluoromethanesulfonyl)(fluorosulfonyl)imide etc. may be mentioned.

[0078] In addition, an alkali metal salt other than the above solutes (lithium salt, sodium salt, potassium salt, and magnesium salt) may be used as an additive. Specifically, 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 methyl sulfate may be mentioned.

[0079] In addition, the non-aqueous electrolyte of the present invention may contain a polymer, and as in the case of being used in a non-aqueous electrolyte battery called a polymer battery, it is also possible to use the non-aqueous electrolyte after pseudo-solidifying it with a gelling agent or a cross-linked polymer. The polymer solid electrolyte also includes those containing a non-aqueous organic solvent as a plasticizer.

[0080] The above polymer is not particularly limited as long as it is an aprotic polymer capable of dissolving the compound represented by the above general formula (1), the above solute, and the above other additives. For example, polymers having polyethylene oxide in the main chain or side chain, homopolymers or copolymers of polyvinylidene fluoride, methacrylic acid ester polymers, polyacrylonitrile, and the like can be mentioned. When a plasticizer is added to these polymers, an aprotic non-aqueous organic solvent among the above non-aqueous organic solvents is preferable.

[0081] [2. Non-aqueous electrolyte battery] The non-aqueous electrolyte battery of the present invention includes at least (a) the non-aqueous electrolyte of the present invention, (i) a positive electrode, and (u) a negative electrode having at least one selected from the group consisting of a negative electrode material containing a lithium metal, a negative electrode material capable of occluding and releasing lithium, sodium, potassium, or magnesium. Further, it preferably includes (e) a separator, an exterior body, and the like.

[0082] [(i) Positive electrode] (i) The positive electrode preferably contains at least one kind of oxide and / or polyanion compound as a positive electrode active material.

[0083] [Positive electrode active material] In the case of a lithium-ion secondary battery in which cations in a non-aqueous electrolyte are mainly lithium, (a) the positive electrode active material constituting the positive electrode is not particularly limited as long as it is various materials capable of charge and discharge. For example, (A) a lithium transition metal composite oxide containing at least one or more metals of nickel, manganese, and cobalt and having a layered structure, (B) a lithium manganese composite oxide having a spinel structure, (C) a lithium-containing olivine-type phosphate, and (D) a lithium-rich layered transition metal oxide having a layered rock salt-type structure. And those containing at least one kind.

[0084] ((A) Lithium transition metal composite oxide) Positive electrode active material (A) Examples of the lithium transition metal composite oxide containing at least one or more metals of nickel, manganese, and cobalt and having a layered structure include, for example, lithium-cobalt composite oxide, lithium-nickel composite oxide, lithium-nickel-cobalt composite oxide, lithium-nickel-cobalt-aluminum composite oxide, lithium-cobalt-manganese composite oxide, lithium-nickel-manganese composite oxide, lithium-nickel-manganese-cobalt composite oxide, and the like. Further, those in which a part of the transition metal atoms that are the main components of these lithium transition metal composite oxides are substituted with other elements such as Al, Ti, V, Cr, Fe, Cu, Zn, Mg, Ga, Zr, Si, B, Ba, Y, Sn may be used.

[0085] Specific examples of the lithium-cobalt composite oxide and the lithium-nickel composite oxide include LiCoO2, LiNiO2, and lithium cobaltate (LiCo 0.98 Mg 0.01 Zr 0.01 O2, LiCo 0.98 Mg 0.01 Al 0.01 O2, LiCo 0.975 Mg 0.01 Zr 0.005 Al 0.01For example, lithium cobaltate with a rare earth compound fixed on its surface as described in WO2014 / 034043 may also be used. Further, as described in JP-A-2002-151077 and the like, those in which a part of the particle surface of LiCoO2 particle powder is coated with aluminum oxide may also be used.

[0086] The lithium nickel cobalt composite oxide or lithium nickel cobalt aluminum composite oxide is represented by the general formula

[11] . Li a Ni 1-b-c Co b M 1 c O2

[11] In formula

[11] , M 1 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, and B, a satisfies 0.9 ≦ a ≦ 1.2, and b and c satisfy the conditions of 0.1 ≦ b ≦ 0.3 and 0 ≦ c ≦ 0.1. These can be prepared, for example, according to the production methods described in JP-A-2009-137834 and the like. Specifically, LiNi 0.8 Co 0.2 O2, LiNi 0.85 Co 0.10 Al 0.05 O2, LiNi 0.87 Co 0.10 Al 0.03 O2, LiNi 0.6 Co 0.3 Al 0.1 O2 and the like can be mentioned.

[0087] Specific examples of the lithium cobalt manganese composite oxide and lithium nickel manganese composite oxide include LiNi 0.5 Mn 0.5 O2, LiCo 0.5 Mn 0.5 O2 and the like can be mentioned. Examples of the lithium nickel manganese cobalt composite oxide include lithium-containing composite oxides represented by the general formula

[12] . Li d Ni e Mn f Co g M 2 h O2

[12] In formula

[12] , M 2 is at least one element selected from the group consisting of Al, Fe, Mg, Zr, Ti, B, and Sn; d satisfies 0.9 ≤ d ≤ 1.2; and e, f, g, and h satisfy the conditions e + f + g + h = 1, 0 ≤ e ≤ 0.9, 0 ≤ f ≤ 0.5, 0 ≤ g ≤ 0.5, and h ≥ 0. The lithium nickel manganese cobalt composite oxide preferably contains manganese within the range shown in the general formula

[12] to enhance the structural stability and improve the safety at high temperatures in a lithium secondary battery. More preferably, it further contains cobalt within the range shown in the general formula

[12] to enhance the high-rate characteristics of a lithium ion secondary battery. Specifically, for example, 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, 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, Li[Ni 0.8 Mn 0.1 Co 0.1 O2, etc. can be mentioned.

[0088] ((B) Lithium Manganese Composite Oxide with Spinel Structure) Positive Electrode Active Material (B) Examples of the lithium manganese composite oxide having a spinel structure include, for example, a spinel-type lithium manganese composite oxide represented by the general formula

[13] . Li j (Mn 2-k M 3 k )O4

[13] In formula

[13] , M 3 is at least one metal element selected from the group consisting of Ni, Co, Fe, Mg, Cr, Cu, Al, and Ti, j is 1.05 ≦ j ≦ 1.15, and k is 0 ≦ k ≦ 0.20. Specifically, for example, LiMnO2, LiMn2O4, LiMn 1.95 Al 0.05 O4, LiMn 1.9 Al 0.1 O4, LiMn 1.9 Ni 0.1 O4, LiMn 1.5 Ni 0.5 O4, etc. may be mentioned.

[0089] ((C) Lithium-containing olivine-type phosphate) Positive electrode active material (C) Examples of the lithium-containing olivine-type phosphate include those represented by the general formula

[14] . LiFe 1-n M 4 n PO4

[14] In formula

[14] , M 4 is at least one selected from Co, Ni, Mn, Cu, Zn, Nb, Mg, Al, Ti, W, Zr, and Cd, and n is 0 ≦ n ≦ 1. Specifically, for example, LiFePO4, LiCoPO4, LiNiPO4, LiMnPO4, etc. may be mentioned, and among them, LiFePO4 and / or LiMnPO4 are preferable.

[0090] ((D) Lithium-excess layered transition metal oxide) Positive electrode active material (D) Examples of the lithium-excess layered transition metal oxide having a layered rock salt structure include those represented by the general formula

[15] . xLiM 5 O2·(1-x)Li2M 6 O3

[15] In formula

[15] , x is a number satisfying 0 < x < 1, and M 5 is at least one metal element having an average oxidation number of 3 + and M 6 is at least one metal element having an average oxidation number of 4 + . In formula

[15] , M 5 is preferably one metal element selected from trivalent Mn, Ni, Co, Fe, V, and Cr, but the average oxidation number may be made trivalent with an equal amount of divalent and tetravalent metals.

[0091] Also, in formula

[15] , M 6 is preferably one or more metal elements selected from Mn, Zr, and Ti. Specifically, 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. are exemplified. The positive electrode active material (D) represented by this general formula

[15] is known to exhibit a high capacity during high-voltage charging of 4.4 V (Li standard) or more (for example, US Patent 7,135,252). These cathode active materials can be prepared, for example, according to the production methods described in JP-A-2008-270201, WO2013 / 118661, JP-A-2013-030284, etc.

[0092] As the cathode active material, at least one selected from the above (A) to (D) may be contained as a main component. In addition, examples of those contained therein include transition element chalcogenides such as FeS2, TiS2, TiO2, V2O5, MoO3, and MoS2, or conductive polymers such as polyacetylene, polyphenylene, polyaniline, and polypyrrole, activated carbon, polymers that generate radicals, carbon materials, and the like.

[0093] [Cathode current collector] (i) The cathode has a cathode current collector. As the cathode current collector, for example, aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used.

[0094] [Cathode active material layer] (i) In the cathode, for example, a cathode active material layer is formed on at least one surface of the cathode current collector. The cathode active material layer is composed of, for example, the aforementioned cathode active material, a binder, and, if necessary, a conductive agent. Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene-butadiene rubber (SBR), carboxymethyl cellulose or its salt, methyl cellulose or its salt, cellulose acetate phthalate or its salt, hydroxypropyl methyl cellulose or its salt, polyvinyl alcohol or its salt, and the like. As the conductive agent, for example, carbon materials such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (granular graphite and flaky graphite), and fluorinated graphite can be used. In the cathode, it is preferable to use acetylene black or ketjen black with low crystallinity.

[0095] <(iii) Anode> The negative electrode material is not particularly limited. However, in the case of lithium batteries and lithium-ion batteries, lithium metal, an alloy of lithium metal and other metals, an intermetallic compound, various carbon materials (artificial graphite, natural graphite, etc.), metal oxides, metal nitrides, tin (elemental), tin compounds, silicon (elemental), silicon compounds, activated carbon, conductive polymers, etc. are used. The carbon material is, for example, easily graphitizable carbon, hardly graphitizable carbon (hard carbon) with an interplanar spacing of the (002) plane of 0.37 nm or more, graphite with an interplanar spacing of the (002) plane of 0.34 nm or less, etc. More specifically, there are pyrolytic carbon, cokes, glassy carbon fibers, fired bodies of organic polymer compounds, activated carbon or carbon blacks, etc. Among these, cokes include pitch coke, needle coke or petroleum coke, etc. The fired body of an organic polymer compound refers to a material obtained by firing a phenol resin, a furan resin, etc. at an appropriate temperature to carbonize it. The carbon material is preferable because the change in crystal structure accompanying the absorption and release of lithium is very small, so that a high energy density can be obtained and excellent cycle characteristics can be obtained. Note that the shape of the carbon material may be any of fibrous, spherical, granular or flaky. Also, amorphous carbon or a graphite material coated with amorphous carbon on the surface is more preferable because the reactivity between the material surface and the non-aqueous electrolyte is reduced. (c) The negative electrode preferably contains at least one kind of negative electrode active material.

[0096] [Negative electrode active material] In the case of a lithium-ion secondary battery in which cations in the non-aqueous electrolyte are mainly lithium, (c) as the negative electrode active material constituting the negative electrode, those capable of doping and de-doping lithium ions are used. For example, (e) a carbon material having a d value of the lattice plane (002 plane) in X-ray diffraction of 0.340 nm or less, (f) a carbon material having a d value of the lattice plane (002 plane) in X-ray diffraction exceeding 0.340 nm, (g) an oxide of one or more metals selected from Si, Sn, and Al, (h) one or more metals selected from Si, Sn, and Al or an alloy containing these metals or an alloy of these metals or alloys and lithium, and (i) at least one selected from lithium titanate. These negative electrode active materials can be used alone or in combination of two or more.

[0097] ((e) a carbon material having a d value of the lattice plane (002 plane) in X-ray diffraction of 0.340 nm or less) Negative electrode active material (e) Examples of the carbon material having a d value of the lattice plane (002 plane) in X-ray diffraction of 0.340 nm or less include pyrolytic carbons, cokes (e.g., pitch coke, needle coke, petroleum coke, etc.), graphites, fired products of organic polymer compounds (e.g., those obtained by firing and carbonizing phenol resin, furan resin, etc. at an appropriate temperature), carbon fibers, activated carbon, etc. These may be graphitized. The carbon material has an interplanar spacing (d002) of the (002) plane measured by X-ray diffraction method of 0.340 nm or less. Among them, graphite having a true density of 1.70 g / cm 3 or a highly crystalline carbon material having properties close to it is preferred.

[0098] ((f) a carbon material having a d value of the lattice plane (002 plane) in X-ray diffraction exceeding 0.340 nm) Negative electrode active material (f) As carbon materials with a d-value of the lattice plane (002 plane) in X-ray diffraction exceeding 0.340 nm, amorphous carbon can be mentioned. This is a carbon material whose stacking order hardly changes even when heat-treated at a high temperature of 2000 °C or higher. For example, non-graphitizable carbon (hard carbon), mesocarbon microbeads (MCMB) fired at 1500 °C or lower, mesophase pitch carbon fiber (MCF), etc. are exemplified. Carbotron (registered trademark) P manufactured by Kuraray Co., Ltd. is a typical example thereof.

[0099] ((G) Oxides of one or more metals selected from Si, Sn, and Al) Negative electrode active material (G) Examples of oxides of one or more metals selected from Si, Sn, and Al include silicon oxide, tin oxide, etc. that can be doped and de-doped with lithium ions. In addition, there is SiO having a structure in which ultrafine particles of Si are dispersed in SiO2. x When this material is used as a negative electrode active material, since Si that reacts with Li is ultrafine particles, charge and discharge are smoothly performed. On the other hand, since the SiO x particles themselves have a small surface area, the paintability when used as a composition (paste) for forming the negative electrode active material layer and the adhesiveness of the negative electrode binder layer to the current collector are also good.

[0100] Note that since SiO x has a large volume change accompanying charge and discharge, by using SiO x and graphite of the above-mentioned negative electrode active material (E) in a specific ratio in combination as the negative electrode active material, high capacity and good charge and discharge cycle characteristics can be achieved simultaneously.

[0101] ((H) One or more metals selected from Si, Sn, and Al, or an alloy containing these metals, or an alloy of these metals or alloys with lithium) Negative electrode active material (H) Examples of the one or more metals selected from Si, Sn, and Al, alloys containing these metals, or alloys of these metals or alloys with lithium include metals such as silicon, tin, and aluminum, silicon alloys, tin alloys, aluminum alloys, etc. Materials in which these metals or alloys are alloyed with lithium during charge and discharge can also be used. Preferred specific examples thereof include those described in WO2004 / 100293, JP-A-2008-016424, etc., such as simple metals (e.g., in powder form) such as silicon (Si) and tin (Sn), the metal alloys, compounds containing the metal, alloys containing tin (Sn) and cobalt (Co) in the metal, etc. When the metal is used as an electrode, it can exhibit a high charge capacity and is preferred because the volume expansion and contraction during charge and discharge are relatively small. Further, these metals are known to exhibit a high charge capacity because they alloy with Li during charging when used as the negative electrode of a lithium-ion secondary battery, and are also preferred in this regard. Furthermore, for example, negative electrode active materials formed from silicon pillars with a submicron diameter, negative electrode active materials composed of fibers made of silicon, etc., described in WO2004 / 042851, WO2007 / 083155, etc. may also be used.

[0102] ((I) Lithium titanate oxide) Negative electrode active material (I) Examples of the lithium titanate oxide include lithium titanate having a spinel structure and lithium titanate having a lamellarite structure. Examples of the lithium titanate having a spinel structure include, for example, Li 4+α Ti5O 12 (α varies within the range of 0 ≤ α ≤ 3 by the charge and discharge reaction). Examples of the lithium titanate having a lamellarite structure include, for example, Li 2+β Ti3O7 (β varies within the range of 0 ≤ β ≤ 3 by the charge and discharge reaction). These negative electrode active materials can be prepared, for example, according to the production methods described in JP-A-2007-018883, JP-A-2009-176752, etc.

[0103] On the other hand, in the case of a sodium-ion secondary battery in which cations in the non-aqueous electrolyte are mainly sodium, as the negative electrode active material, hard carbon, oxides such as TiO2, V2O5, MoO3, etc. are used. For example, in the case of a sodium-ion secondary battery in which cations in the non-aqueous electrolyte are mainly sodium, as the positive electrode active material, sodium-containing transition metal composite oxides such as NaFeO2, NaCrO2, NaNiO2, NaMnO2, NaCoO2, etc., those in which a plurality of transition metals such as Fe, Cr, Ni, Mn, Co, etc. of these sodium-containing transition metal composite oxides are mixed, those in which a part of the transition metals of these sodium-containing transition metal composite oxides are replaced with metals other than other transition metals, transition metal phosphate compounds such as Na2FeP2O7, NaCo3(PO4)2P2O7, sulfides such as TiS2, FeS2, or conductive polymers such as polyacetylene, polyphenylene, polyaniline, and polypyrrole, activated carbon, polymers that generate radicals, carbon materials, etc. are used.

[0104] [Negative electrode current collector] (c) The negative electrode has a negative electrode current collector. As the negative electrode current collector, for example, copper, stainless steel, nickel, titanium, or alloys thereof can be used. [Negative electrode active material layer] (c) The negative electrode, for example, has a negative electrode active material layer formed on at least one surface of the negative electrode current collector. The negative electrode active material layer is composed of, for example, the aforementioned negative electrode active material, a binder, and, if necessary, a conductive agent. Examples of the binder include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, styrene butadiene rubber (SBR), carboxymethyl cellulose or its salt, methyl cellulose or its salt, cellulose acetate phthalate or its salt, hydroxypropyl methyl cellulose or its salt, polyvinyl alcohol or its salt, etc. As the conductive agent, for example, carbon materials such as acetylene black, ketjen black, furnace black, carbon fiber, graphite (granular graphite and flaky graphite), fluorinated graphite, etc. can be used.

[0105] 〔Method for manufacturing electrodes ((a) positive electrode and (c) negative electrode)〕 The electrode can be obtained, for example, by dispersing and kneading an active material, a binder, and, if necessary, a conductive agent in a predetermined blending amount in a solvent such as N-methyl-2-pyrrolidone (NMP) or water, and applying and drying the resulting paste onto a current collector to form an active material layer. The obtained electrode is preferably compressed by a method such as roll pressing to adjust it to an electrode with an appropriate density.

[0106] <(e) Separator> The above non-aqueous electrolyte battery can be provided with a (e) separator. As the separator for preventing contact between the (a) positive electrode and the (c) negative electrode, polyolefins such as polypropylene and polyethylene, and further, non-woven fabrics or porous sheets made of cellulose, paper, or glass fiber, etc. are used. These films or sheets are preferably micro-porous so that the non-aqueous electrolyte can penetrate and ions can easily permeate. Examples of the polyolefin separator include a micro-porous polymer film such as a porous polyolefin film, which electrically insulates the positive electrode and the negative electrode and allows lithium ions to permeate. Specific examples of the porous polyolefin film include, for example, a porous polyethylene film alone, or a multi-layer film formed by laminating a porous polyethylene film and a porous polypropylene film. Also, films obtained by compounding a porous polyethylene film and a polypropylene film, etc. can be mentioned.

[0107] 〔Outer package〕 In constructing a non-aqueous electrolyte battery, as the exterior body of the non-aqueous electrolyte battery, for example, metal cans such as coin type, cylindrical type, square type, etc., or laminate exterior bodies can be used. As the metal can material, for example, steel plates plated with nickel, stainless steel plates, stainless steel plates plated with nickel, aluminum or its alloys, nickel, titanium, etc. can be mentioned. As the laminate exterior body, for example, aluminum laminate films, laminate films made of SUS, laminate films such as polypropylene or polyethylene coated with silica, etc. can be used.

[0108] The configuration of the non-aqueous electrolyte battery according to this embodiment is not particularly limited, but for example, it can be configured such that an electrode element in which a positive electrode and a negative electrode are arranged opposite to each other and a non-aqueous electrolyte are enclosed in an exterior body. The shape of the non-aqueous electrolyte battery is not particularly limited, but an electrochemical device having a shape such as coin-shaped, cylindrical, square, or aluminum laminate sheet type can be assembled from the above elements.

Examples

[0109] Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited to these descriptions in any way.

[0110] 〔Preparation of non-aqueous electrolytes according to examples and comparative examples〕 <Example 1-1> (Preparation of non-aqueous electrolyte 1-1) As a non-aqueous organic solvent, a mixed solvent having a volume ratio of ethylene carbonate (hereinafter referred to as "EC"), propylene carbonate (hereinafter referred to as "PC"), dimethyl carbonate (hereinafter referred to as "DMC"), and ethyl methyl carbonate (hereinafter referred to as "EMC") of 2:1:3:4 was used. In this solvent, lithium hexafluorophosphate (hereinafter referred to as "LiPF6") was dissolved as a solute so that the concentration became 1.0 mol / L with respect to the total amount of the non-aqueous electrolyte, and the compound represented by the above formula (1-1) as the compound represented by the general formula (1) was dissolved so that the concentration became 0.05% by mass with respect to the total amount of the non-aqueous electrolyte, thereby obtaining a non-aqueous electrolyte 1-1. The above preparation was carried out while maintaining the liquid temperature at 25°C. The compound represented by the formula (1-1) was obtained by reacting 4-hydroxy-1,2-oxathiolane-2,2-dioxide with sulfuryl fluoride isocyanate and performing an ion exchange reaction with the corresponding cation species.

[0111] <Examples 1-2 to 1-38> (Preparation of non-aqueous electrolytes 1-2 to 1-38) Non-aqueous electrolytes 1-2 to 1-38 were prepared in the same procedure as the preparation of the non-aqueous electrolyte 1-1 except that the type and concentration of the compound represented by the general formula (1) were changed as shown in Table 1. The compound represented by the general formula (1) used in each example was obtained by reacting the corresponding hydroxy cyclic sulfonic acid ester or hydroxy cyclic carboxylic acid ester with the corresponding isocyanate and performing an ion exchange reaction with the corresponding cation species, or by reacting the corresponding hydroxy cyclic sulfonic acid ester or hydroxy cyclic carboxylic acid ester with the corresponding s sulfonyl chloride in the presence of an organic base or an inorganic base.

[0112] <Comparative Example 1-1> (Preparation of comparative non-aqueous electrolyte 1-1) A comparative non-aqueous electrolyte 1-1 was prepared in the same procedure as the preparation of the non-aqueous electrolyte 1-1 except that the compound represented by the general formula (1) was not added. <Comparative Examples 1-2 to 1-3> (Preparation of Comparative Non-aqueous Electrolytes 1-2 to 1-3) Comparative non-aqueous electrolytes 1-2 to 1-3 were prepared in the same procedure as the preparation of the non-aqueous electrolyte 1-4, except that the compound represented by the general formula (1) was changed to the following Compound Nos. 11-1 to 11-2. Compound No. 11-1 is a commercially available product (manufactured by Kishida Chemical), and Compound No. 11-2 was obtained by reacting 3-hydroxytetrahydrothiophene-1,1-dioxide with methanesulfonyl chloride in the presence of triethanolamine.

[0113]

Chemical formula

[0114] 〔Fabrication of Non-aqueous Electrolyte Batteries〕 (Fabrication of NCM811 Positive Electrode) LiNi 0.8 Mn 0.1 Co 0.1 To 91.0% by mass of LiNiMnCoO₂ powder, 4.5% by mass of polyvinylidene fluoride (hereinafter referred to as PVDF) as a binder and 4.5% by mass of acetylene black as a conductive material were mixed, and further N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added to prepare a positive electrode composite paste. This paste was applied to both sides of an aluminum foil (A1085), dried and pressed, and then punched into a size of 4 × 5 cm to obtain a test NCM811 positive electrode. (Fabrication of Graphite Negative Electrode) To 92.0% by mass of artificial graphite powder, 8.0% by mass of PVDF as a binder was mixed, and further NMP was added to prepare a negative electrode composite paste. This paste was applied to one side of a copper foil, dried and pressed, and then punched into a size of 4 × 5 cm to obtain a test graphite negative electrode. (Fabrication of Non-aqueous Electrolyte Batteries) An aluminum laminate exterior cell (capacity: 30 mAh) equipped with the above test NCM811 positive electrode, the above test graphite negative electrode, and a cellulose separator was impregnated with the non-aqueous electrolytes 1-1 to 1-38 and comparative non-aqueous electrolytes 1-1 to 1-3 described in Table 1, respectively, to obtain non-aqueous electrolyte batteries according to Examples 1-1 to 1-38 and Comparative Examples 1-1 to 1-3.

[0115] 〔Evaluation〕 For each of the non-aqueous electrolyte batteries of Examples 1-1 to 1-38 and Comparative Examples 1-1 to 1-3, the following evaluations were carried out. <Initial DC internal resistance> First, using the fabricated cells, conditioning was carried out at an ambient temperature of 25°C under the following conditions. That is, as the first charge-discharge, constant current-constant voltage charging was performed at a charging upper limit voltage of 4.3 V and a 0.1C rate (3 mA), and discharging was performed at a constant current of 0.2C rate (6 mA) until the discharge cut-off voltage of 3.0 V. Thereafter, constant current-constant voltage charging was performed at a charging upper limit voltage of 4.3 V and a 0.2C rate (6 mA), and a charge-discharge cycle of discharging at a constant current of 0.2C rate (6 mA) until the discharge cut-off voltage of 3.0 V was repeated 3 times. After performing the above conditioning, at an ambient temperature of 25°C, constant current charging was performed at a 0.2C rate for 150 minutes, and discharging was performed at a constant current for 10 seconds at predetermined current values (0.2C, 0.5C, 1.0C, 2.0C, 5.0C). The voltage at the 10th second was measured and plotted against the current value. The least squares method was applied to each plot to obtain an approximate straight line. The value of the slope of the approximate straight line was taken as the initial DC internal resistance.

[0116] <Discharge capacity after high-temperature storage (-20°C)> After performing the above conditioning, charging was performed at a constant current-constant voltage at a 0.2C rate (6 mA) until the charging upper limit voltage of 4.3 V, and discharging was performed at a constant current of 0.2C rate (6 mA) until the discharge cut-off voltage of 3.0 V at an ambient temperature of -20°C to obtain the initial discharge capacity at -20°C. The discharge capacity at this time was taken as discharge capacity α. Next, this cell was charged at a constant current-constant voltage at a 0.2C rate (6 mA) until the charging upper limit voltage of 4.3 V at an ambient temperature of 25°C, and then stored at an ambient temperature of 60°C for 10 days. Thereafter, discharging was performed at a constant current of 0.2C rate (6 mA) until the discharge cut-off voltage of 3.0 V at an ambient temperature of 25°C. Next, constant current and constant voltage charging was performed at a rate of 0.2C (6 mA) up to a charging upper limit voltage of 4.3 V, and constant current discharging was performed at a rate of 0.2C (6 mA) up to a discharge cut-off voltage of 3.0 V at an environmental temperature of -20°C to obtain the discharge capacity at -20°C after high-temperature storage. The discharge capacity at this time is defined as the discharge capacity β. The low-temperature output characteristics after high-temperature storage were determined from the -20°C discharge capacity retention rate (%) after high-temperature storage. The -20°C discharge capacity retention rate (%) after high-temperature storage here is defined as "(discharge capacity β / discharge capacity α) × 100".

[0117] The results are shown in Table 1. Note that each evaluation result is shown as a relative value when the result of Comparative Example 1-1 is taken as 100.

[0118]

Table 1

[0119] Comparing the above results, it was confirmed that by using the compound represented by the general formula (1), the initial internal resistance decreased and the low-temperature output characteristics after high-temperature storage improved with respect to Comparative Examples 1-1 to 1-3.

[0120] From the perspective of the decrease in internal resistance after the first charge and discharge, the compounds represented by formulas (1-1), (1-2), (1-11), (1-15), (1-16), ( 3-1), and (4-1) by are more preferable. From the perspective of improving the low-temperature output characteristics after high-temperature storage, the compounds represented by formulas (1-1), (1-2), (1-6), (1-9), (1-16), (1-18), and and (4-1) are more preferable. From the perspective of achieving a good balance between the above two effects, the compounds represented by formulas (1-1), (1-16), ( 3-1) and (4-1) are particularly preferable.

Claims

1. A non-aqueous electrolyte characterized by containing a compound represented by the following general formula (1), a solute, and a non-aqueous organic solvent. 【Chemical Formula 1】 In the general formula (1), X 1 is a carbon atom or a sulfur atom, Y 1 and Y 2 are methylene groups which may be substituted with an oxygen atom or a halogen atom, r is 1 when 1 X is a carbon atom, and r is 1 when 1 X is a sulfur atom and 1 and Y 2 are oxygen atoms, and r is 2 otherwise, R 1 is a group represented by the following general formula (2), R 2 and R 3 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 20 carbon atoms which may be substituted with a halogen atom, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom, an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, or a heteroaryl group having 2 to 40 carbon atoms which may be substituted with a halogen atom. 【Chemical Formula 2】 In the general formula (2), M is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, or a monovalent or divalent onium ion. When M is an alkali metal ion, an alkaline earth metal ion, or a monovalent or divalent onium ion, the bond between the nitrogen atom and M in the general formula (2) is an ionic bond. x is 1 when M is a hydrogen atom, an alkali metal ion, or a monovalent onium ion, and x is 0.5 when M is an alkaline earth metal ion or a divalent onium ion. W is a phosphorus atom or a sulfur atom. q is 1 when W is a phosphorus atom and 2 when W is a sulfur atom. R 4 is a halogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, a cycloalkyl group having 5 to 20 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, an alkenyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, an alkynyl group having 2 to 20 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, a heteroaryl group having 2 to 40 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, an alkoxy group having 1 to 20 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, a cycloalkoxy group having 5 to 20 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, an alkenyloxy group having 2 to 20 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, an alkynyloxy group having 2 to 20 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, an aryloxy group having 6 to 40 carbon atoms which may be substituted with a halogen atom or an FSO 2 group, or a heteroaryloxy group having 2 to 40 carbon atoms which may be substituted with a halogen atom or an FSO 2 group. When q = 1, the plurality of Rs 4 may be the same or different from each other.

2. X in the general formula (1) 1is a sulfur atom, and Y 1 and Y 2 is an oxygen atom or a methylene group, the non-aqueous electrolyte according to claim 1.

3. In the general formula (2), W is a sulfur atom, the non-aqueous electrolyte according to claim 1 or 2.

4. R in the general formula (2) 4 is 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, an ethenyl group, a 2-propenyl group, a 2-propynyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group, a pyridinyl group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-pentyloxy group, an n-hexyloxy group, a trifluoromethoxy group, a trifluoroethoxy group, an ethenyloxy group, a 2-propenyloxy group, a 2-propynyloxy group, a phenoxy group, a naphthyloxy group, or a pentafluorophenoxy group, the non-aqueous electrolyte according to any one of claims 1 to 3.

5. In the general formula (2), M is a hydrogen atom, a lithium cation, a sodium cation, a potassium cation, a tetraalkylammonium cation, or a tetraalkylphosphonium cation, the non-aqueous electrolyte according to any one of claims 1 to 4.

6. R in the general formula (1) 2 and R 3 are each independently a hydrogen atom, 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 tetrafluoroethyl group, a phenyl group, a naphthyl group, a pentafluorophenyl group, a pyrrolyl group, or a pyridinyl group, the non-aqueous electrolyte according to any one of claims 1 to 5.

7. The non-aqueous electrolytic solution according to any one of claims 1 to 6, wherein the non-aqueous organic solvent contains at least one selected from the group consisting of cyclic carbonates and chain carbonates.

8. The non-aqueous electrolytic solution according to claim 7, wherein the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, and fluoroethylene carbonate, and the chain carbonate is at least one selected from the group consisting of ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, and methyl propyl carbonate.

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