JP2008300313A - Nonaqueous electrolyte and nonaqueous electrolyte battery using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte capable of improving heavy load characteristics after long period storage, and a nonaqueous electrolyte battery using it. <P>SOLUTION: This nonaqueous electrolyte battery is structured such that a sheet-shaped positive electrode 1 having a positive electrode active material and a sheet-shaped negative electrode 2 having a negative electrode active material are laminated through a separator 3 having ion permeability. This nonaqueous electrolyte is impregnated into the separator 3 between the positive electrode 1 and the negative electrode 2. The nonaqueous electrolyte contains cyclic ether, chain ether, Lewis acid salt, and a compound having a sulfonic group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a non-aqueous electrolyte and a non-aqueous electrolyte battery using the same. More specifically, a non-aqueous electrolyte using an organic solvent, a positive electrode using, for example, a 3d transition metal oxide or sulfide as a positive electrode active material, and a negative electrode using, for example, lithium (Li) as a negative electrode active material. And a non-aqueous electrolyte battery using an organic solvent as the electrolyte.

  Non-aqueous electrolyte batteries include lithium batteries having a negative electrode using lithium (Li) or the like as a negative electrode active material and a positive electrode using a 3d transition metal oxide, sulfide or the like as an active material. Improvements have been actively made.

  For example, in the lithium battery described in Patent Document 1, in the lithium battery including a negative electrode having a lithium (Li), a lithium alloy, or a compound of lithium (Li) and carbon (C), the negative electrode is electrochemically formed. It is comprised from what was immersed in the organic solvent which melt | dissolved at least 1 type of noble metal salt from lithium (Li).

Japanese Patent Laid-Open No. 6-52848

As an electrolytic solution used for a lithium battery, generally, a mixed solvent of a cyclic carbonate and a chain carbonate and an electrolyte salt such as lithium hexafluorophosphate (LiPF ₆ ) or lithium perchlorate (LiClO ₄ ) are used. A combination of Lewis acidic salt is used, but when 3d transition metal oxide or sulfide is used as the positive electrode active material, the mixture of cyclic ether and chain ether is combined from the viewpoint of oxidation potential. A solvent can be used, and stable battery characteristics can be obtained by using an ether solvent from the viewpoint of the chemical stability of the active material.

However, when an ether solvent is selected, it is difficult to use it together with a salt having a high Lewis acidity such as lithium hexafluorophosphate (LiPF ₆ ), which is highly versatile and gives high ion conductivity. . In is ether a low dielectric constant solvent, since lithium hexafluorophosphate was not ion dissociation (LiPF ₆₎ is generated and PF ₅ is decomposed, strong Lewis acids such as PF ₅ is on Li metal This is because, for example, the reaction with the film component or the polymerization of a cyclic ether such as dioxolane is promoted, which greatly adversely affects the battery characteristics after long-term storage.

  Accordingly, an object of the present invention is to provide a nonaqueous electrolytic solution capable of improving heavy load characteristics after long-term storage and a nonaqueous electrolytic solution using the same when an ether solvent and a salt having high Lewis acidity are used in combination. To provide a battery.

In order to solve the above-described problem, the first invention
A nonaqueous electrolytic solution comprising a cyclic ether and a chain ether, a Lewis acid salt, and a compound having a sulfone group.

The second invention is
Having a positive electrode and a negative electrode, and a non-aqueous electrolyte,
The non-aqueous electrolyte is a non-aqueous electrolyte battery comprising a cyclic ether and a chain ether, a Lewis acid salt, and a compound having a sulfone group.

In the present invention, as an electrolytic solution, an ether solvent that imparts chemical stability of the active material and lithium hexafluorophosphate (LiPF ₆ ), which is a salt having a high Lewis acidity, can be used in combination. Stability of lithium hexafluorophosphate (LiPF ₆ ) or the like in an ether solvent is increased.

That is, in this invention, a compound having a sulfone group is further contained in an electrolytic solution containing an ether solvent and a Lewis acidic salt such as lithium hexafluorophosphate (LiPF ₆ ).

Since the compound having a sulfone group rapidly decomposes on lithium metal or on the positive electrode active material to form a stable film, PF ₅ and LiF generated in the reaction formula [A] and the film on lithium or the positive electrode active material Contains phosphorus (P), oxygen (O), fluorine (F), and lithium (Li), which suppresses the decomposition of LiPF ₆ while maintaining the equilibrium of the reaction formula [A] by suppressing the reaction with the components. It is thought that it acts such as suppressing the formation of an inorganic film.
LiPF ₆ → LiF + PF ₅ ... Reaction formula [A]

  Since the film component produced by the decomposition of the compound having a sulfone group is stably present on lithium and the positive electrode even during storage, a nonaqueous electrolyte battery such as a lithium battery having excellent long-term storage characteristics can be provided.

Although the action is unknown, in addition to lithium hexafluorophosphate (LiPF ₆ ), lithium perchlorate (LiClO ₄ ), lithium tetrafluoroborate (LiBF ₄ ), lithium trifluoromethanesulfonate (LiCF ₃₎ A similar effect tends to be obtained when a Lewis acidic salt such as SO ₃ ) or lithium hexafluoroarsenate (LiAsF ₆ ) is used.

  According to the present invention, in a nonaqueous electrolyte battery, it is possible to improve heavy load characteristics after long-term storage.

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view showing a configuration of an example of a nonaqueous electrolyte battery according to an embodiment of the present invention. This non-aqueous electrolyte battery is a so-called coin-type battery, and is, for example, a lithium iron disulfide battery using iron disulfide (FeS ₂ ) for the positive electrode and lithium (Li) for the negative electrode.

  As shown in FIG. 1, in this non-aqueous electrolyte battery, a sheet-like positive electrode 1 having a positive electrode active material and a sheet-like negative electrode 2 having a negative electrode active material are stacked via a separator 3 having ion permeability. It is set as the structure. The positive electrode 1 is pressure-bonded to the positive electrode current collector 4. The negative electrode 2 is pressure-bonded to the negative electrode current collector 5. The outermost positive electrode battery can 6 and negative electrode battery can 7 are made of, for example, iron plated with nickel, and are sealed by caulking through a sealing gasket 8.

  A separator 3 between the positive electrode 1 and the negative electrode 2 is impregnated with a non-aqueous electrolyte. The separator 3 is disposed between the positive electrode 1 and the negative electrode 2 to prevent these physical contacts and hold the non-aqueous electrolyte in the holes, that is, the separator 3 absorbs the non-aqueous electrolyte. By doing so, lithium ions are allowed to pass during discharge.

As the positive electrode active material, iron disulfide (FeS ₂ ) is obtained by pulverizing pyrite that exists mainly in nature. Chemical synthesis, for example, ferrous chloride (FeCl ₂ ) is converted to hydrogen sulfide (FeCl ₂ ). Iron disulfide obtained by firing in H ₂ S) can also be used.

  As the positive electrode current collector 4, for example, a metal foil such as a copper foil, a nickel foil, a stainless steel foil, or an aluminum foil can be used.

  The negative electrode active material is not particularly limited, and a carbon-based material, lithium metal, or a lithium alloy in which an alloy element such as aluminum (Al) is added to lithium (Li) can be used.

  As the negative electrode current collector 5, for example, a metal foil such as a copper foil, a nickel foil, or a stainless steel foil can be used. If lithium metal or the like is used for the negative electrode 2, the negative electrode current collector 5 may be omitted.

  As the electrolytic solution, an electrolytic solution in which a lithium salt is used as an electrolyte and dissolved in an organic solvent is used. This electrolytic solution contains a Lewis acid salt as an electrolyte, a cyclic ether and a chain ether, and a compound having a sulfone group. By using this electrolytic solution, it is possible to improve heavy load characteristics after long-term storage in a nonaqueous electrolytic battery.

  As the organic solvent, two or more mixed solvents obtained by mixing a cyclic ether and a chain ether are used. Examples of the cyclic ether include 1,3-dioxolane, 2-methyl-1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, diglyme, and derivatives thereof. At least one selected can be used. As the chain ether, for example, at least one selected from 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyl ether, triglyme and derivatives thereof can be used.

The electrolyte includes Lewis acid salts with high Lewis acidity, such as lithium perchlorate (LiClO ₄ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium trifluoromethanesulfonate ( Lithium salts such as LiCF ₃ SO ₃ ) and lithium hexafluoroarsenate (LiAsF ₆ ) can be used.

When lithium hexafluorophosphate (LiPF ₆ ) is used as the lithium salt, the content of lithium hexafluorophosphate (LiPF ₆ ) is from 0.25 mol / kg to which basic battery performance can be maintained. It is preferably 1.5 mol / kg.

  Examples of the compound having a sulfone group include vinyl sulfone represented by the formula (1), unsaturated chain sulfone such as divinyl sulfone represented by the formula (2), and 3-sulfolene represented by the formula (3). Further, cyclic sulfone such as 2-sulfolene represented by formula (4), propene sultone represented by formula (5), and propane sultone represented by formula (6) can be used. In the cyclic sulfone, unsaturated cyclic sulfones represented by the formulas (3) to (5) are preferable. This is because more excellent effects can be obtained.

  The content of the compound having a sulfone group is preferably 0.01 wt% to 5 wt% from the viewpoint of obtaining more excellent heavy load characteristics after storage, and further excellent heavy load characteristics after storage and excellent discharge performance. From the obtained point, 0.5 wt% to 2.5 wt% is more preferable.

  For the separator 3, for example, a polyolefin-based microporous film such as polypropylene or polyethylene can be used.

  This non-aqueous electrolyte battery can be manufactured as described below, for example. First, for example, a positive electrode active material and, if necessary, a conductive agent and a binder are mixed to prepare a positive electrode mixture, which is dispersed in a solvent such as N-methyl-2-pyrrolidone (NMP) and pasted. After that, it is applied to the positive electrode current collector 4, the solvent is dried, and compression molding is performed by a roll press machine or the like to obtain the positive electrode 1.

  For example, a negative electrode active material and, if necessary, a binder are mixed to prepare a negative electrode mixture, which is dispersed in a solvent such as N-methyl-2-pyrrolidone (NMP) and pasted into a negative electrode current collector It apply | coats to the body 5, a solvent is dried, and it is compression-molded with a roll press etc. to make the negative electrode 2. Further, for example, a lithium metal plate may be used as the negative electrode 2, and in that case, the negative electrode current collector 5 may be omitted.

  Next, the negative electrode 2 and the separator 3 are placed in this order on the central portion of the negative electrode battery can 7, the above-described electrolyte is poured from above the separator 3, and the positive electrode battery can 6 containing the positive electrode 1 is covered and the gasket 8 is caulked. . As described above, the nonaqueous electrolyte battery according to the embodiment of the present invention can be manufactured.

In one embodiment, a lithium iron disulfide battery using iron disulfide (FeS ₂ ) for the positive electrode 1 and lithium (Li) for the negative electrode 2 has been described. However, the present invention is not limited to this, It can be applied to a non-aqueous electrolyte battery using an organic solvent as the electrolyte.

Examples of the non-aqueous electrolyte battery include a lithium battery using lithium (Li) or a lithium alloy as the negative electrode. As the lithium battery, in addition to the lithium iron disulfide battery of one embodiment, Examples of the positive electrode include a lithium-manganese dioxide battery and a lithium-copper oxide battery using 3d transition metal oxides such as manganese dioxide (MnO ₂ ) and copper oxide (CuO).

When lithium (Li) and iron disulfide (FeS ₂ ) are used as active materials, the electrolytic solution according to the present invention is more effective. That is, when lithium (Li) and iron disulfide (FeS ₂ ) are used as the active material, it is preferable to use an ether solvent from the viewpoint of the chemical stability of the active material, such as an ether solvent and LiPF ₆ . By using the Lewis acid salt in combination, excellent battery characteristics can be obtained. However, deterioration of characteristics after storage becomes a problem when used together. Both lithium (Li) and iron disulfide (FeS ₂ ) have a large degree of deterioration due to the effect of decomposition of PF ₆ , and the degree of characteristic deterioration after storage is also large. This characteristic deterioration after storage is suppressed by further adding a compound having a sulfone group.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples. In Examples 1 to 91 and Comparative Examples 1 to 18 described below, the solvent species and composition, and the concentration of the compound having a sulfone group were determined by GC-MASS (Gas Chromatography-MASS; gas chromatography mass). Analysis), NMR (Nuclear Magnetic Resonance) and the like.

<Example 1>
First, the weight ratio of iron disulfide (FeS ₂ ), carbon powder as a conductive agent, and polyvinylidene fluoride (PVdF) as a binder is 95: 1: 4, and N-methyl-2-pyrrolidone (NMP) To make a positive electrode mixture slurry. Next, the positive electrode mixture slurry is applied to the positive electrode current collector, dried at a temperature of 120 ° C. for 2 hours to volatilize N-methyl-2-pyrrolidone (NMP), and then compression-molded at a constant pressure to form a belt shape. A positive electrode was prepared. As the positive electrode current collector, a band-shaped aluminum foil having a thickness of 20 μm was used.

Next, the strip-shaped positive electrode produced as described above is punched into a disk shape, and a disk-shaped metal lithium negative electrode having a thickness of 150 μm and a disk-shaped cell guard separator are laminated in this order: positive electrode, separator, negative electrode Then, it was housed in a nickel-plated iron battery can. Next, in this battery can, lithium hexafluorophosphate (LiPF) was added to a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) were mixed at a volume ratio of 50:50. ₆ ) An electrolyte solution containing 1.0 mol / kg and 1 wt% of 3-sulfolene represented by the formula (3) was injected. Next, the non-aqueous electrolyte battery of Example 1 of R2016 type was produced by caulking the battery can through an insulating sealing gasket.

<Example 2>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) were mixed at a volume ratio of 50:50, tetrahydrofuran (THF) and 1,2-dimethoxyethane (DME) were used. A nonaqueous electrolyte battery of Example 2 was produced in the same manner as Example 1 except that a mixed solvent mixed at a volume ratio of 50:50 was used.

<Example 3>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, tetrahydropyran (THP), 1,2-dimethoxyethane (DME) and A non-aqueous electrolyte battery of Example 3 was produced in the same manner as in Example 1 except that a mixed solvent in which the volume ratio of 50:50 was mixed was used.

<Comparative Example 1>
A nonaqueous electrolyte battery of Comparative Example 1 was produced in the same manner as Example 1 except that 3-sulfolene represented by Formula (3) was not added.

<Comparative example 2>
A nonaqueous electrolyte battery of Comparative Example 2 was produced in the same manner as Example 2 except that 3-sulfolene represented by Formula (3) was not added.

<Comparative Example 3>
A nonaqueous electrolyte battery of Comparative Example 3 was produced in the same manner as Example 3 except that 3-sulfolene represented by Formula (3) was not added.

<Comparative Example 4>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) were mixed at a volume ratio of 50:50, propylene carbonate (PC) and 1,2-dimethoxyethane (DME) A non-aqueous electrolyte battery of Comparative Example 4 in the same manner as in Example 1 except that 3-sulfolene represented by the formula (3) was not added using a mixed solvent in which a volume ratio of 50:50 was mixed. Was made.

<Comparative Example 5>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, propylene carbonate (PC) and 1,2-dimethoxyethane (DME) A non-aqueous electrolyte battery of Comparative Example 5 was produced in the same manner as in Example 1 except that a mixed solvent in which a volume ratio of 50:50 was mixed was used.

<Example 4>
A nonaqueous electrolyte battery of Example 4 was produced in the same manner as Example 1 except that manganese dioxide (MnO ₂ ) was used instead of iron disulfide (FeS ₂ ).

<Example 5>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) were mixed at a volume ratio of 50:50, tetrahydrofuran (THF) and 1,2-dimethoxyethane (DME) were used. A nonaqueous electrolyte battery of Example 5 was produced in the same manner as Example 4 except that a mixed solvent mixed at a volume ratio of 50:50 was used.

<Example 6>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, tetrahydropyran (THP), 1,2-dimethoxyethane (DME) and A non-aqueous electrolyte battery of Example 6 was produced in the same manner as in Example 4 except that a mixed solvent in which the volume ratio was 50:50 was used.

<Comparative Example 6>
A nonaqueous electrolyte battery of Comparative Example 6 was produced in the same manner as Example 4 except that 3-sulfolene represented by Formula (3) was not added.

<Comparative Example 7>
A nonaqueous electrolyte battery of Comparative Example 7 was produced in the same manner as in Example 5 except that 3-sulfolene represented by Formula (3) was not added.

<Comparative Example 8>
A nonaqueous electrolyte battery of Comparative Example 8 was produced in the same manner as in Example 6 except that 3-sulfolene represented by Formula (3) was not added.

<Comparative Example 9>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) were mixed at a volume ratio of 50:50, propylene carbonate (PC) and 1,2-dimethoxyethane (DME) The nonaqueous electrolyte battery of Comparative Example 9 was performed in the same manner as in Example 4 except that 3-sulfolene represented by the formula (3) was not added using a mixed solvent in which the volume ratio of 50:50 was mixed. Was made.

<Comparative Example 10>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, propylene carbonate (PC) and 1,2-dimethoxyethane (DME) A non-aqueous electrolyte battery of Comparative Example 10 was produced in the same manner as in Example 4 except that a mixed solvent in which the volume ratio of 50:50 was mixed was used.

<Example 7>
A nonaqueous electrolyte battery of Example 7 was produced in the same manner as Example 1 except that copper oxide (CuO) was used instead of iron disulfide (FeS ₂ ).

<Example 8>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) were mixed at a volume ratio of 50:50, tetrahydrofuran (THF) and 1,2-dimethoxyethane (DME) were used. A nonaqueous electrolyte battery of Example 8 was produced in the same manner as Example 7 except that a mixed solvent mixed at a volume ratio of 50:50 was used.

<Example 9>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, tetrahydropyran (THP), 1,2-dimethoxyethane (DME) and A nonaqueous electrolyte battery of Example 9 was produced in the same manner as in Example 7 except that a mixed solvent in which a volume ratio of 50:50 was mixed was used.

<Comparative Example 11>
A nonaqueous electrolyte battery of Comparative Example 11 was produced in the same manner as Example 7 except that 3-sulfolene represented by Formula (3) was not added.

<Comparative Example 12>
A nonaqueous electrolyte battery of Comparative Example 12 was produced in the same manner as in Example 8, except that 3-sulfolene represented by Formula (3) was not added.

<Comparative Example 13>
A nonaqueous electrolyte battery of Comparative Example 13 was produced in the same manner as Example 9 except that 3-sulfolene represented by Formula (3) was not added.

<Comparative example 14>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) were mixed at a volume ratio of 50:50, propylene carbonate (PC) and 1,2-dimethoxyethane (DME) The nonaqueous electrolyte battery of Comparative Example 14 was performed in the same manner as in Example 7 except that 3-sulfolene represented by the formula (3) was not added using a mixed solvent in which a volume ratio of 50:50 was mixed. Was made.

<Comparative Example 15>
Instead of a mixed solvent in which 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, propylene carbonate (PC) and 1,2-dimethoxyethane (DME) A non-aqueous electrolyte battery of Comparative Example 15 was produced in the same manner as in Example 7 except that a mixed solvent in which the volume ratio was 50:50 was used.

<Example 10>
Except for using vinylsulfone represented by formula (1) instead of 3-sulfolene represented by formula (3) and setting the concentration of vinylsulfone represented by formula (1) to 0.005 wt%, A nonaqueous electrolyte battery of Example 10 was produced in the same manner as Example 1.

<Example 11>
A nonaqueous electrolyte battery of Example 11 was produced in the same manner as Example 10 except that the concentration of vinylsulfone represented by Formula (1) was 0.01 wt%.

<Example 12>
A nonaqueous electrolyte battery of Example 12 was produced in the same manner as Example 10 except that the concentration of vinylsulfone represented by Formula (1) was 0.5 wt%.

<Example 13>
A nonaqueous electrolyte battery of Example 13 was produced in the same manner as Example 10 except that the concentration of vinylsulfone represented by Formula (1) was 1 wt%.

<Example 14>
A nonaqueous electrolyte battery of Example 14 was produced in the same manner as Example 10 except that the concentration of vinylsulfone represented by Formula (1) was 2.5 wt%.

<Example 15>
A nonaqueous electrolyte battery of Example 15 was produced in the same manner as Example 10 except that the concentration of vinylsulfone represented by Formula (1) was 5 wt%.

<Example 16>
A nonaqueous electrolyte battery of Example 16 was produced in the same manner as Example 1 except that the concentration of vinylsulfone represented by Formula (1) was 5.5 wt%.

<Example 17>
Instead of 3-sulfolene represented by formula (3), divinylsulfone represented by formula (2) was used, except that the concentration of divinylsulfone represented by formula (2) was 0.005 wt%. A non-aqueous electrolyte battery of Example 17 was produced in the same manner as Example 1.

<Example 18>
A nonaqueous electrolyte battery of Example 18 was produced in the same manner as Example 17 except that the concentration of divinyl sulfone represented by Formula (2) was 0.01 wt%.

<Example 19>
A nonaqueous electrolyte battery of Example 19 was produced in the same manner as in Example 17, except that the concentration of divinyl sulfone represented by Formula (2) was 0.5 wt%.

<Example 20>
A nonaqueous electrolyte battery of Example 20 was produced in the same manner as Example 17 except that the concentration of divinyl sulfone represented by Formula (2) was 1 wt%.

<Example 21>
A nonaqueous electrolyte battery of Example 21 was produced in the same manner as in Example 17, except that the concentration of divinyl sulfone represented by Formula (2) was 2.5 wt%.

<Example 22>
A nonaqueous electrolyte battery of Example 22 was produced in the same manner as Example 17 except that the concentration of divinyl sulfone represented by Formula (2) was 5 wt%.

<Example 23>
A nonaqueous electrolyte battery of Example 23 was produced in the same manner as Example 17 except that the concentration of divinyl sulfone represented by Formula (2) was 5.5 wt%.

<Example 24>
A nonaqueous electrolyte battery of Example 24 was produced in the same manner as Example 1 except that the concentration of 3-sulfolene represented by Formula (3) was 0.005 wt%.

<Example 25>
A nonaqueous electrolyte battery of Example 25 was produced in the same manner as Example 24 except that the concentration of 3-sulfolene represented by Formula (3) was 0.01 wt%.

<Example 26>
A nonaqueous electrolyte battery of Example 26 was produced in the same manner as Example 24 except that the concentration of 3-sulfolene represented by Formula (3) was 0.5 wt%.

<Example 27>
A nonaqueous electrolyte battery of Example 27 was produced in the same manner as Example 24 except that the concentration of 3-sulfolene represented by Formula (3) was 1 wt%.

<Example 28>
A nonaqueous electrolyte battery of Example 28 was produced in the same manner as Example 24 except that the concentration of 3-sulfolene represented by Formula (3) was 2.5 wt%.

<Example 29>
A nonaqueous electrolyte battery of Example 29 was produced in the same manner as Example 24 except that the concentration of 3-sulfolene represented by Formula (3) was 5 wt%.

<Example 30>
A nonaqueous electrolyte battery of Example 30 was produced in the same manner as in Example 24 except that the concentration of 3-sulfolene represented by Formula (3) was 5.5 wt%.

<Example 31>
Instead of 3-sulfolene represented by formula (3), 2-sulfolene represented by formula (4) was used, and the concentration of 2-sulfolene represented by formula (4) was 0.005 wt%. A nonaqueous electrolyte battery of Example 31 was made in the same manner as Example 1 except for the above.

<Example 32>
A nonaqueous electrolyte battery of Example 32 was produced in the same manner as Example 31 except that the concentration of 2-sulfolene represented by Formula (4) was 0.01 wt%.

<Example 33>
A nonaqueous electrolyte battery of Example 33 was produced in the same manner as Example 31 except that the concentration of 2-sulfolene represented by Formula (4) was 0.5 wt%.

<Example 34>
A nonaqueous electrolyte battery of Example 34 was produced in the same manner as Example 31 except that the concentration of 2-sulfolene represented by Formula (4) was 1 wt%.

<Example 35>
A nonaqueous electrolyte battery of Example 35 was produced in the same manner as Example 31 except that the concentration of 2-sulfolene represented by Formula (4) was 2.5 wt%.

<Example 36>
A nonaqueous electrolyte battery of Example 36 was made in the same manner as Example 31 except that the concentration of 2-sulfolene represented by formula (4) was 5 wt%.

<Example 37>
A nonaqueous electrolyte battery of Example 37 was made in the same manner as Example 31 except that the concentration of 2-sulfolene represented by Formula (4) was 5.5 wt%.

<Example 38>
Instead of 3-sulfolene represented by formula (3), propene sultone represented by formula (5) was used, except that the concentration of propene sultone represented by formula (5) was 0.005 wt%. In the same manner as in Example 31, a nonaqueous electrolyte battery of Example 38 was produced.

<Example 39>
A nonaqueous electrolyte battery of Example 39 was made in the same manner as Example 38 except that the concentration of propene sultone represented by formula (5) was 0.01 wt%.

<Example 40>
A nonaqueous electrolyte battery of Example 40 was produced in the same manner as Example 38, except that the concentration of propene sultone represented by Formula (5) was 0.5 wt%.

<Example 41>
A nonaqueous electrolyte battery of Example 41 was produced in the same manner as Example 38 except that the concentration of propene sultone represented by Formula (5) was 1 wt%.

<Example 42>
A nonaqueous electrolyte battery of Example 42 was produced in the same manner as Example 38 except that the concentration of propene sultone represented by Formula (5) was 2.5 wt%.

<Example 43>
A nonaqueous electrolyte battery of Example 43 was produced in the same manner as Example 38 except that the concentration of propene sultone represented by Formula (5) was 5 wt%.

<Example 44>
A nonaqueous electrolyte battery of Example 44 was produced in the same manner as Example 38, except that the concentration of propene sultone represented by Formula (5) was 5.5 wt%.

<Example 45>
Instead of 3-sulfolene represented by formula (3), propane sultone represented by formula (6) was used, except that the concentration of propane sultone represented by formula (6) was 0.005 wt%. A nonaqueous electrolyte battery of Example 45 was produced in the same manner as Example 1.

<Example 46>
A nonaqueous electrolyte battery of Example 46 was made in the same manner as Example 45 except that the concentration of propane sultone represented by Formula (6) was 0.01 wt%.

<Example 47>
A nonaqueous electrolyte battery of Example 47 was made in the same manner as Example 45 except that the concentration of propane sultone represented by Formula (6) was 0.5 wt%.

<Example 48>
A nonaqueous electrolyte battery of Example 48 was produced in the same manner as Example 45 except that the concentration of propane sultone represented by Formula (6) was 1 wt%.

<Example 49>
A nonaqueous electrolyte battery of Example 49 was produced in the same manner as Example 45 except that the concentration of propane sultone represented by Formula (6) was 2.5 wt%.

<Example 50>
A nonaqueous electrolyte battery of Example 50 was produced in the same manner as Example 45 except that the concentration of propane sultone represented by Formula (6) was 5 wt%.

<Example 51>
A nonaqueous electrolyte battery of Example 51 was produced in the same manner as Example 45 except that the concentration of propane sultone represented by Formula (6) was 5.5 wt%.

<Comparative Example 16>
A nonaqueous electrolyte battery of Comparative Example 16 was produced in the same manner as in Example 1 except that 3-sulfolene represented by the formula (3) was not added.

<Example 52>
Using manganese dioxide (MnO ₂ ) instead of iron disulfide (FeS ₂ ), using vinyl sulfone represented by formula (1) instead of 3-sulfolene represented by formula (3), formula (1) A nonaqueous electrolyte battery of Example 52 was produced in the same manner as in Example 1 except that the concentration of vinylsulfone represented by the formula (1) was 0.005 wt%.

<Example 53>
A nonaqueous electrolyte battery of Example 53 was made in the same manner as Example 52 except that the concentration of vinylsulfone represented by Formula (1) was 0.01 wt%.

<Example 54>
A nonaqueous electrolyte battery of Example 54 was produced in the same manner as Example 52 except that the concentration of vinylsulfone represented by Formula (1) was 1 wt%.

<Example 55>
A nonaqueous electrolyte battery of Example 55 was made in the same manner as Example 52 except that the concentration of vinylsulfone represented by Formula (1) was 5 wt%.

<Example 56>
A nonaqueous electrolyte battery of Example 56 was made in the same manner as Example 52 except that the concentration of vinylsulfone represented by Formula (1) was 5.5 wt%.

<Example 57>
Implementation was performed except that divinyl sulfone represented by formula (2) was used instead of vinyl sulfone represented by formula (1) and the concentration of divinyl sulfone represented by formula (2) was 0.005 wt. In the same manner as in Example 52, a nonaqueous electrolyte battery of Example 57 was produced.

<Example 58>
A nonaqueous electrolyte battery of Example 58 was produced in the same manner as Example 57 except that the concentration of divinyl sulfone represented by formula (2) was 0.01 wt%.

<Example 59>
A nonaqueous electrolyte battery of Example 59 was made in the same manner as Example 57 except that the concentration of divinyl sulfone represented by Formula (2) was 1 wt%.

<Example 60>
A nonaqueous electrolyte battery of Example 60 was made in the same manner as Example 57 except that the concentration of divinyl sulfone represented by Formula (2) was 5 wt%.

<Example 61>
A nonaqueous electrolyte battery of Example 61 was made in the same manner as Example 57 except that the concentration of divinyl sulfone represented by Formula (2) was 5.5 wt%.

<Example 62>
Except for using 3-sulfolene represented by formula (3) instead of vinylsulfone represented by formula (1), the concentration of 3-sulfolene represented by formula (3) was 0.005 wt%. A nonaqueous electrolyte battery of Example 62 was produced in the same manner as Example 52.

<Example 63>
A nonaqueous electrolyte battery of Example 63 was made in the same manner as Example 62 except that the concentration of 3-sulfolene represented by Formula (3) was 0.01 wt%.

<Example 64>
A nonaqueous electrolyte battery of Example 64 was made in the same manner as Example 62 except that the concentration of 3-sulfolene represented by Formula (3) was 1 wt%.

<Example 65>
A nonaqueous electrolyte battery of Example 65 was made in the same manner as Example 62 except that the concentration of 3-sulfolene represented by Formula (3) was 5 wt%.

<Example 66>
A nonaqueous electrolyte battery of Example 66 was made in the same manner as Example 62 except that the concentration of 3-sulfolene represented by Formula (3) was 5.5 wt%.

<Example 67>
Other than the point that 2-sulfolene represented by formula (4) was used in place of vinylsulfone represented by formula (1), the concentration of 2-sulfolene represented by formula (4) was 0.005 wt%. Produced the nonaqueous electrolyte battery of Example 67 in the same manner as in Example 52.

<Example 68>
A nonaqueous electrolyte battery of Example 68 was made in the same manner as Example 67 except that the concentration of 2-sulfolene represented by Formula (4) was 0.01 wt%.

<Example 69>
A nonaqueous electrolyte battery of Example 69 was made in the same manner as Example 67 except that the concentration of 2-sulfolene represented by Formula (4) was 1 wt%.

<Example 70>
A nonaqueous electrolyte battery of Example 70 was produced in the same manner as Example 67 except that the concentration of 2-sulfolene represented by Formula (4) was 5 wt%.

<Example 71>
A nonaqueous electrolyte battery of Example 71 was made in the same manner as Example 67 except that the concentration of 2-sulfolene represented by Formula (4) was 5.5 wt%.

<Comparative Example 17>
A nonaqueous electrolyte battery of Comparative Example 17 was produced in the same manner as in Example 52 except that the vinyl sulfone represented by the formula (1) was not added.

<Example 72>
Using copper oxide (CuO) instead of iron disulfide (FeS ₂ ), using vinyl sulfone represented by formula (1) instead of 3-sulfolene represented by formula (3), A nonaqueous electrolyte battery of Example 72 was produced in the same manner as in Example 1 except that the vinylsulfone concentration represented was 0.005 wt%.

<Example 73>
A nonaqueous electrolyte battery of Example 73 was made in the same manner as Example 72 except that the concentration of vinylsulfone represented by Formula (1) was 0.01 wt%.

<Example 74>
A nonaqueous electrolyte battery of Example 74 was made in the same manner as Example 72 except that the concentration of vinylsulfone represented by Formula (1) was 1 wt%.

<Example 75>
A nonaqueous electrolyte battery of Example 75 was produced in the same manner as Example 72 except that the concentration of vinyl sulfone represented by Formula (1) was 5 wt%.

<Example 76>
A nonaqueous electrolyte battery of Example 76 was made in the same manner as Example 72 except that the concentration of vinylsulfone represented by Formula (1) was 5.5 wt%.

<Example 77>
Implementation was performed except that divinyl sulfone represented by formula (2) was used instead of vinyl sulfone represented by formula (1) and the concentration of divinyl sulfone represented by formula (2) was 0.005 wt. In the same manner as in Example 72, a nonaqueous electrolyte battery of Example 77 was produced.

<Example 78>
A nonaqueous electrolyte battery of Example 78 was produced in the same manner as Example 77, except that the concentration of divinyl sulfone represented by Formula (2) was 0.01 wt%.

<Example 79>
A nonaqueous electrolyte battery of Example 79 was produced in the same manner as Example 77 except that the concentration of divinyl sulfone represented by Formula (2) was 1 wt%.

<Example 80>
A nonaqueous electrolyte battery of Example 80 was produced in the same manner as Example 77 except that the concentration of divinyl sulfone represented by formula (2) was 5 wt%.

<Example 81>
A nonaqueous electrolyte battery of Example 81 was produced in the same manner as Example 77 except that the concentration of divinyl sulfone represented by formula (2) was 5.5 wt%.

<Example 82>
Except for using 3-sulfolene represented by formula (3) instead of vinylsulfone represented by formula (1), the concentration of 3-sulfolene represented by formula (3) was 0.005 wt%. A nonaqueous electrolyte battery of Example 82 was produced in the same manner as Example 72.

<Example 83>
A nonaqueous electrolyte battery of Example 83 was made in the same manner as Example 82 except that the concentration of 3-sulfolene represented by Formula (3) was 0.01 wt%.

<Example 84>
A nonaqueous electrolyte battery of Example 84 was made in the same manner as Example 82 except that the concentration of 3-sulfolene represented by Formula (3) was 1 wt%.

<Example 85>
A nonaqueous electrolyte battery of Example 85 was produced in the same manner as Example 82 except that the concentration of 3-sulfolene represented by Formula (3) was 5 wt%.

<Example 86>
A nonaqueous electrolyte battery of Example 86 was produced in the same manner as Example 82 except that the concentration of 3-sulfolene represented by Formula (3) was 5.5 wt%.

<Example 87>
Other than the point that 2-sulfolene represented by formula (4) was used in place of vinylsulfone represented by formula (1), the concentration of 2-sulfolene represented by formula (4) was 0.005 wt%. Produced a nonaqueous electrolyte battery of Example 87 in the same manner as in Example 72.

<Example 88>
A nonaqueous electrolyte battery of Example 88 was made in the same manner as Example 87 except that the concentration of 2-sulfolene represented by Formula (4) was 0.01 wt%.

<Example 89>
A nonaqueous electrolyte battery of Example 89 was produced in the same manner as Example 87 except that the concentration of 2-sulfolene represented by Formula (4) was 1 wt%.

<Example 90>
A nonaqueous electrolyte battery of Example 90 was produced in the same manner as Example 87 except that the concentration of 2-sulfolene represented by Formula (4) was 5 wt%.

<Example 91>
A nonaqueous electrolyte battery of Example 91 was produced in the same manner as Example 87, except that the concentration of 2-sulfolene represented by formula (4) was 5.5 wt%.

<Comparative Example 18>
A nonaqueous electrolyte battery of Comparative Example 18 was produced in the same manner as Example 72 except that the vinyl sulfone represented by Formula (1) was not added.

(test)
For the non-aqueous electrolyte batteries of Examples 1 to 91 and Comparative Examples 1 to 18, the 10 mA capacity (discharge current 10 mA final voltage 0.9 V) of the battery immediately after fabrication and the temperature environment of 60 ° C. after fabrication The battery was measured for 10 mA capacity (discharge current: 10 mA, final voltage: 0.9 V) after storage for 50 days. As the retention rate after storage, the capacity ratio of the battery after storage for 50 days in a temperature environment at 60 ° C. with respect to the capacity of the battery immediately after preparation (10 mA capacity of the battery after storage / 10 mA capacity of the battery immediately after preparation) was calculated.

  Moreover, about the non-aqueous electrolyte battery of Example 1- Example 91 and Comparative Example 1- Comparative Example 18, about 10% of battery capacity was discharged by preliminary discharge, and discharge of 10 mA-0.9V termination was performed. The discharge capacity ratio calculated with the discharge capacity when no compound having a sulfone group was added as 1 was determined as the discharge performance ratio. That is, as the discharge performance ratio, (discharge performance ratio) = (discharge capacity in each specification obtained under the above conditions / discharge capacity when no compound having a sulfone group in each specification was obtained in the above conditions). Asked.

  Table 1 shows the 10 mA discharge performance ratio and the retention rate after storage of Examples 1 to 3 and Comparative Examples 1 to 5. Table 2 shows the 10 mA discharge performance ratio and the retention rate after storage of Examples 4 to 6 and Comparative Examples 6 to 10. Table 3 shows the 10 mA discharge performance ratio and the retention rate after storage of Examples 7 to 9 and Comparative Examples 11 to 15. Table 10 shows the 10 mA discharge performance ratio and the retention rate after storage of Examples 10 to 51 and Comparative Example 16. Table 5 shows the 10 mA discharge performance ratio and the retention rate after storage of Examples 52 to 71 and Comparative Example 17. Table 6 shows the 10 mA discharge performance ratio and the retention rate after storage of Examples 72 to 91 and Comparative Example 18.

(Evaluation)
As shown in Table 1, Example 1 uses iron disulfide (FeS ₂ ) for the positive electrode, and the volume ratio of 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) is 50:50. Using the mixed solvent mixed in (3), 3-sulfolene represented by the formula (3) is contained as a compound having a sulfone group. In Example 1, the retention rate after storage was remarkably improved as compared with Comparative Example 1 except that 3-sulfolene represented by the formula (3) was not added as a compound having a sulfone group.

Example 2 uses a mixed solvent in which iron disulfide (FeS ₂ ) is used as a positive electrode, tetrahydrofuran (THF) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, and sulfone groups are formed. The compound having 3-sulfolene represented by the formula (3) is contained. In Example 2, the retention rate after storage was remarkably improved as compared with Comparative Example 2 except that 3-sulfolene represented by the formula (3) was not added as a compound having a sulfone group.

Example 3 uses a mixed solvent in which iron disulfide (FeS ₂ ) is used for the positive electrode and tetrahydropyran (THP) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50. 3-sulfolene represented by the formula (3) is contained as a compound having In Example 3, the retention rate after storage was remarkably improved as compared with Comparative Example 3 except that 3-sulfolene represented by the formula (3) was not added as a compound having a sulfone group.

Comparative Example 5 uses iron disulfide (FeS ₂ ) for the positive electrode, a mixed solvent in which propylene carbonate (PC) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, and a sulfone group. 3-sulfolene represented by the formula (3) is contained as a compound having When this Comparative Example 5 was compared with the same Comparative Example 4 except that 3-sulfolene represented by the formula (3) was not added as a compound having a sulfone group, the effect of improving the retention rate after storage was as follows. It was smaller than Examples 1 to 3 using an ether solvent.

As shown in Table 2, Example 4 uses manganese dioxide (MnO ₂ ) for the positive electrode, and 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) in a volume ratio of 50:50. Using a mixed solvent mixture, 3-sulfolene represented by the formula (3) is contained as a compound having a sulfone group. In Example 4, the retention rate after storage was remarkably improved as compared with Comparative Example 6 except that 3-sulfolene represented by the formula (3) was not added as a compound having a sulfone group.

Example 5 uses manganese dioxide (MnO ₂ ) for the positive electrode, uses a mixed solvent in which tetrahydrofuran (THF) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, and has a sulfone group. It contains 3-sulfolene represented by the formula (3) as a compound. In Example 5, the retention rate after storage was remarkably improved as compared with Comparative Example 7 except that 3-sulfolene represented by the formula (3) was not added as a compound having a sulfone group.

Example 6 uses manganese dioxide (MnO ₂ ) for the positive electrode, a mixed solvent in which tetrahydropyran (THP) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, and sulfone groups are formed. The compound having 3-sulfolene represented by the formula (3) is contained. In Example 6, the retention rate after storage was remarkably improved as compared with Comparative Example 8 except that 3-sulfolene represented by the formula (3) was not added as a compound having a sulfone group.

In Comparative Example 10, manganese dioxide (MnO ₂ ) was used for the positive electrode, a mixed solvent in which propylene carbonate (PC) and 1,2-dimethoxyethane (DME) were mixed at a volume ratio of 50:50, and a sulfone group was formed. The compound having 3-sulfolene represented by the formula (3) is contained. When this Comparative Example 10 was compared with the same Comparative Example 9 except that succinic anhydride was not added as a compound having a sulfone group, the effect of improving the retention rate after storage was obtained using an ether solvent. It was small compared with Example 4-6.

  As shown in Table 3, Example 7 uses copper oxide (CuO) for the positive electrode and mixes 1,3-dioxolane (DOL) and 1,2-dimethoxyethane (DME) in a volume ratio of 50:50. Using the mixed solvent, 3-sulfolene represented by the formula (3) is contained as a compound having a sulfone group. In Example 7, the retention rate after storage was remarkably improved as compared with Comparative Example 11 except that 3-sulfolene represented by the formula (3) was not added as a compound having a sulfone group.

  Example 8 is a compound having a sulfone group using a mixed solvent in which copper oxide (CuO) is used for the positive electrode and tetrahydrofuran (THF) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50. Containing 3-sulfolene represented by the formula (3). In Example 8, the retention rate after storage was remarkably improved as compared with Comparative Example 12 except that 3-sulfolene represented by the formula (3) was not added as a compound having a sulfone group.

  Example 9 uses copper oxide (CuO) for the positive electrode, uses a mixed solvent in which tetrahydropyran (THP) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50, and has a sulfone group. It contains 3-sulfolene represented by the formula (3) as a compound. In Example 9, the retention rate after storage was remarkably improved from the same Comparative Example 13 except that 3-sulfolene represented by the formula (3) was not added as a compound having a sulfone group.

  Comparative Example 15 has a sulfone group using a mixed solvent in which copper oxide (CuO) is used for the positive electrode and propylene carbonate (PC) and 1,2-dimethoxyethane (DME) are mixed at a volume ratio of 50:50. It contains 3-sulfolene represented by the formula (3) as a compound. When this Comparative Example 15 was compared with the same Comparative Example 14 except that 3-sulfolene represented by Formula (3) was not added as a compound having a sulfone group, the effect of improving the retention rate after storage was It was small as compared with Examples 7 to 9 using an ether solvent.

As shown in Table 4, Examples 10 to 16 using iron disulfide (FeS ₂ ) for the positive electrode and using an electrolyte containing vinyl sulfone represented by the formula (1) as the compound having a sulfone group. Then, when the content of the vinyl sulfone represented by the formula (1) is smaller than 0.01 wt%, the effect of containing the vinyl sulfone represented by the formula (1) is small, and the retention rate after storage is low. It was low. Moreover, when the content of the vinyl sulfone represented by the formula (1) is 0.5 wt% or more, the effect of containing the vinyl sulfone represented by the formula (1) is large, and the retention rate after storage becomes higher. It was. Furthermore, when the content of the vinyl sulfone represented by the formula (1) exceeds 2.5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is deteriorated and the retention rate after storage is also lowered. Furthermore, when the content of the vinyl sulfone represented by the formula (1) exceeds 5 wt%, the retention rate after storage further decreased.

In Examples 17 to 23, in which iron disulfide (FeS ₂ ) was used for the positive electrode and an electrolytic solution containing divinyl sulfone represented by the formula (2) was used as the compound having a sulfone group, the formula (2 When the content of divinyl sulfone represented by) is less than 0.01 wt%, the effect of containing divinyl sulfone represented by formula (2) was small, and the retention rate after storage was low. Moreover, when the content of divinyl sulfone represented by the formula (2) is 0.5 wt% or more, the effect of containing the divinyl sulfone represented by the formula (2) is large, and the retention rate after storage becomes higher. It was. Furthermore, when the content of divinyl sulfone represented by the formula (2) exceeds 2.5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated and the maintenance rate after storage is also lowered. . Furthermore, when the content of divinyl sulfone represented by the formula (2) exceeds 5 wt%, the retention rate after storage further decreases.

Further, in Examples 24 to 30 in which iron disulfide (FeS ₂ ) was used for the positive electrode and an electrolyte containing 3-sulfolene represented by the formula (3) was used as the compound having a sulfone group, When the content of 3-sulfolene represented by 3) is smaller than 0.01 wt%, the effect of containing 3-sulfolene represented by formula (3) is small, and the retention rate after storage is low. . Moreover, when the content of 3-sulfolene represented by the formula (3) is 0.5 wt% or more, the effect of containing the 3-sulfolene represented by the formula (3) is large, and the retention rate after storage is more It became high. Furthermore, when the content of 3-sulfolene represented by the formula (3) exceeds 2.5 wt%, the positive electrode is considered to deteriorate, so that the discharge performance is remarkably deteriorated and the maintenance rate after storage is also lowered. It was. Furthermore, when the content of 3-sulfolene represented by the formula (3) exceeds 5 wt%, the retention rate after storage further decreases.

Furthermore, in Examples 31 to 37, in which iron disulfide (FeS ₂ ) is used for the positive electrode and an electrolyte containing 2-sulfolene represented by Formula (4) is used as the compound having a sulfone group, When the content of 2-sulfolene represented by 4) is smaller than 0.01 wt%, the effect of containing 2-sulfolene represented by formula (4) is small, and the retention rate after storage is low. . Moreover, when the content of 2-sulfolene represented by the formula (4) is 0.5 wt% or more, the effect of containing the 2-sulfolene represented by the formula (4) is large, and the retention rate after storage is more It became high. Furthermore, when the content of 2-sulfolene represented by the formula (4) exceeds 2.5 wt%, the positive electrode is considered to be deteriorated, so that the discharge performance is remarkably deteriorated and the maintenance rate after storage is also lowered. It was. Furthermore, when the content of 2-sulfolene represented by the formula (4) exceeds 5 wt%, the retention rate after storage further decreases.

Further, in Examples 38 to 44 using iron disulfide (FeS ₂ ) for the positive electrode and using an electrolyte containing propene sultone represented by Formula (5) as the compound having a sulfone group, Formula (5) When the content of propene sultone represented by () is smaller than 0.01 wt%, the effect of containing propene sultone represented by formula (5) was small, and the retention rate after storage was low. Moreover, when the content of propene sultone represented by the formula (5) is 0.5 wt% or more, the effect of containing the propene sultone represented by the formula (5) is large, and the maintenance rate after storage becomes higher. It was. Furthermore, when the content of propene sultone represented by the formula (5) exceeds 2.5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated and the maintenance rate after storage is also lowered. . Furthermore, when the content of propene sultone represented by the formula (5) exceeds 5 wt%, the retention rate after storage further decreased.

Furthermore, using the iron disulfide (FeS ₂₎ in the positive electrode, as a compound having a sulfonic group, in Example 45 to Example 51 using the electrolytic solution containing propane sultone represented by Formula (6), equation (6 When the content of propane sultone represented by) is smaller than 0.01 wt%, the effect of containing propane sultone represented by formula (6) was small, and the retention rate after storage was low. Moreover, when the content of propane sultone represented by the formula (6) is 0.5 wt% or more, the effect of containing the propane sultone represented by the formula (6) is large, and the maintenance rate after storage becomes higher. It was. Furthermore, when the content of propane sultone represented by the formula (6) exceeds 2.5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated and the maintenance rate after storage is also lowered. . Furthermore, when the content of propane sultone represented by the formula (6) exceeds 5 wt%, the retention rate after storage further decreases.

  Furthermore, Examples 38 to 44 using an electrolytic solution containing propene sultone represented by Formula (5) and Examples 45 to 45 using an electrolytic solution containing propane sultone represented by Formula (6) According to comparison with Example 51, Examples 38 to 44 using the electrolytic solution containing propene sultone represented by the formula (5) showed more excellent effects. That is, in the cyclic sulfone, the compound having an unsaturated group showed a more excellent effect.

As shown in Table 5, in Examples 52 to 56 using manganese dioxide (MnO ₂ ) for the positive electrode and using an electrolyte containing vinyl sulfone represented by the formula (1) as a compound having a sulfone group, When the content of the vinyl sulfone represented by the formula (1) is less than 0.01 wt%, the effect of containing the vinyl sulfone represented by the formula (1) is small, and the retention rate after storage is low. It was. Moreover, when the content of the vinyl sulfone represented by the formula (1) is 0.5 wt% or more, the effect of containing the vinyl sulfone represented by the formula (1) is large, and the retention rate after storage becomes higher. It was. Furthermore, when the content of the vinyl sulfone represented by the formula (1) exceeds 5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated and the maintenance rate after storage is remarkably lowered.

Further, using the positive electrode of manganese dioxide (MnO _2), as a compound having a sulfonic group, in Example 57 to Example 61 using the electrolytic solution containing divinyl sulfone represented by the formula (2), Equation (2) When the content of divinyl sulfone represented by the formula (2) is smaller than 0.01 wt%, the effect of containing the divinyl sulfone represented by the formula (2) is small, and the retention rate after storage is low. Moreover, when the content of divinyl sulfone represented by the formula (2) is 0.5 wt% or more, the effect of containing the divinyl sulfone represented by the formula (2) is large, and the retention rate after storage becomes higher. It was. Furthermore, if it exceeds 5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated, and the maintenance ratio after storage is remarkably lowered.

Furthermore, in Example 62 to Example 66 using manganese dioxide (MnO ₂ ) for the positive electrode and using an electrolyte containing 3-sulfolene represented by the formula (3) as the compound having a sulfone group, the formula (3 When the content of 3-sulfolene represented by the formula (3) is smaller than 0.01 wt%, the effect of containing 3-sulfolene represented by the formula (3) was small, and the retention rate after storage was low. Moreover, when the content of 3-sulfolene represented by the formula (3) is 0.5 wt% or more, the effect of containing the 3-sulfolene represented by the formula (3) is large, and the retention rate after storage is more It became high. Furthermore, if it exceeds 5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated, and the maintenance ratio after storage is remarkably lowered.

Further, in Examples 67 to 71 using manganese dioxide (MnO ₂ ) for the positive electrode and using an electrolyte containing 2-sulfolene represented by the formula (4) as a compound having a sulfone group, the formula (4 When the content of 2-sulfolene represented by) is smaller than 0.01 wt%, the effect of incorporating 2-sulfolene represented by formula (4) was small, and the retention rate after storage was low. Moreover, when the content of 2-sulfolene represented by the formula (4) is 0.5 wt% or more, the effect of containing the 2-sulfolene represented by the formula (4) is large, and the retention rate after storage is more It became high. Furthermore, if it exceeds 5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated, and the maintenance ratio after storage is remarkably lowered.

  As shown in Table 6, in Examples 72 to 76 using copper oxide (CuO) for the positive electrode and using an electrolyte containing vinyl sulfone represented by the formula (1) as a compound having a sulfone group, When the content of the vinyl sulfone represented by the formula (1) is smaller than 0.01 wt%, the effect of containing the vinyl sulfone represented by the formula (1) is small, and the retention rate after storage is low. . Moreover, when the content of the vinyl sulfone represented by the formula (1) is 0.5 wt% or more, the effect of containing the vinyl sulfone represented by the formula (1) is large, and the retention rate after storage becomes higher. It was. Furthermore, if it exceeds 5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated, and the maintenance ratio after storage is remarkably lowered.

  Moreover, in Example 77-Example 81 using the electrolytic solution containing the divinyl sulfone represented by Formula (2) as a compound which uses a copper oxide (CuO) for a positive electrode and has a sulfone group, it is Formula (2). When the content of the divinyl sulfone represented is smaller than 0.01 wt%, the effect of containing the divinyl sulfone represented by the formula (2) was small, and the retention rate after storage was low. Moreover, when the content of divinyl sulfone represented by the formula (2) is 0.5 wt% or more, the effect of containing the divinyl sulfone represented by the formula (2) is large, and the retention rate after storage becomes higher. It was. Furthermore, if it exceeds 5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated, and the maintenance ratio after storage is remarkably lowered.

  Further, in Examples 82 to 86 using copper oxide (CuO) for the positive electrode and using an electrolyte containing 3-sulfolene represented by Formula (3) as a compound having a sulfone group, Formula (3) When the content of 3-sulfolene represented by the formula (3) is smaller than 0.01 wt%, the effect of containing 3-sulfolene represented by the formula (3) is small, and the retention rate after storage is low. Moreover, when the content of 3-sulfolene represented by the formula (3) is 0.5 wt% or more, the effect of containing the 3-sulfolene represented by the formula (3) is large, and the retention rate after storage is more It became high. Furthermore, if it exceeds 5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated, and the maintenance ratio after storage is remarkably lowered.

  Further, in Examples 87 to 91 using copper oxide (CuO) for the positive electrode and an electrolyte containing 2-sulfolene represented by the formula (4) as the compound having a sulfone group, the formula (4) When the content of 2-sulfolene represented by the formula is smaller than 0.01 wt%, the effect of containing 2-sulfolene represented by the formula (4) was small, and the retention rate after storage was low. Moreover, when the content of 2-sulfolene represented by the formula (4) is 0.5 wt% or more, the effect of containing the 2-sulfolene represented by the formula (4) is large, and the retention rate after storage is more It became high. Furthermore, if it exceeds 5 wt%, it is considered that the positive electrode is deteriorated, so that the discharge performance is remarkably deteriorated, and the maintenance ratio after storage is remarkably lowered.

As described above, Lewis acid salts, cyclic ethers and chain ethers are used for the positive electrode using sulfides such as iron disulfide (FeS ₂ ), 3d transition metal oxides such as manganese dioxide (MnO ₂ ) and copper oxide (CuO). It was found that the heavy load characteristics after storage can be improved by adding a compound having a sulfone group to the electrolyte solution containing. In addition, when an electrolytic solution containing propylene carbonate (PC), which is a carbonate-based solvent, was used, a significant effect was not observed when a compound having a sulfone group was contained. It was found that the heavy load characteristics after storage were greatly improved when an ether-based solvent such as ethereal ether was used.

When an ether solvent such as cyclic ether or chain ether is used, the effect of containing a compound having a sulfone group is large because lithium hexafluorophosphate (LiPF ₆ ) is used as a Lewis acid salt. In such a case, the PF ₆ anion is unstable in ether having a low degree of ionic dissociation, and LiF and PF ₅ are likely to be generated. Therefore, the formation of LiF and PF ₅ by adding a compound having a sulfone group is prevented. It is thought that the suppression effect is great.

Further, in the examples, lithium hexafluorophosphate (LiPF ₆ ) was used as the Lewis acid salt, but lithium perchlorate (LiClO ₄ ), tetrafluoride other than lithium hexafluorophosphate (LiPF ₆ ) Similarly, when a Lewis acidic salt such as lithium borate (LiBF ₄ ), lithium trifluoromethanesulfonate (LiCF ₃ SO ₃ ) or lithium hexafluoroarsenate (LiAsF ₆ ) is used, a compound having a sulfone group is also used. There exists a tendency for the effect to contain to be acquired.

  Furthermore, the content of the compound having a sulfone group is preferably 0.01 wt% to 5 wt% from the viewpoint of obtaining a more excellent heavy load characteristic after storage, and further has an excellent heavy load characteristic and more excellent discharge performance. From the obtained point, it turned out that 0.5 wt%-2.5 wt% are more preferable.

  Furthermore, in Table 4, when comparing Example 38 to Example 44 with Example 45 to Example 51, it was found that the cyclic sulfone preferably has an unsaturated group.

Furthermore, in Tables 1 to 6, when focusing on the positive electrode active material, the sulfone group is obtained when iron disulfide (FeS ₂ ) is used rather than when copper oxide (CuO) or manganese dioxide (MnO ₂ ) is used. It has been found that the effect of adding a compound having a large amount is great. From this, it is considered that the compound having a sulfone group has an effect such as protecting the positive electrode as a positive electrode film, and this film can exist particularly stably on iron disulfide (FeS ₂ ).

Further, in the examples, the concentration of lithium hexafluorophosphate (LiPF ₆ ) was adjusted to 1.0 mol / kg. However, the effect of containing a compound having a sulfone group is that of 6 fluorine which can maintain basic battery performance. The same effect tends to be obtained at a concentration of lithium phosphate (LiPF ₆ ) of 0.25 mol / kg to 1.5 mol / kg.

  The present invention is not limited to the embodiments and examples of the present invention described above, and various modifications and applications can be made without departing from the gist of the present invention. For example, the battery shape can be applied to a cylindrical shape, a button shape, a square shape, etc. in addition to a coin shape. Further, the present invention is not limited to the primary battery and can be similarly applied to other batteries such as a secondary battery.

It is sectional drawing which shows the structure of the nonaqueous electrolyte battery by one Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Positive electrode 2 ... Negative electrode 3 ... Separator 4 ... Positive electrode collector 5 ... Negative electrode collector 6 ... Positive electrode battery can 7 ... Negative electrode battery can 8 ... Gasket

Claims (30)

A nonaqueous electrolytic solution comprising a cyclic ether and a chain ether, a Lewis acid salt, and a compound having a sulfone group. The non-aqueous electrolyte according to claim 1, wherein the compound having a sulfone group is an unsaturated chain sulfone. The non-aqueous electrolysis according to claim 2, wherein the unsaturated chain sulfone is at least one of a vinyl sulfone represented by the formula (1) and a divinyl sulfone represented by the formula (2). liquid.

The non-aqueous electrolyte according to claim 1, wherein the compound having a sulfone group is a cyclic sulfone. The cyclic sulfone includes 3-sulfolene represented by formula (3), 2-sulfolene represented by formula (4), propene sultone represented by formula (5), and propane sultone represented by formula (6). The nonaqueous electrolytic solution according to claim 4, wherein the nonaqueous electrolytic solution is at least one selected from the group consisting of:

The nonaqueous electrolytic solution according to claim 1, wherein the compound having a sulfone group is an unsaturated cyclic sulfone. The unsaturated cyclic sulfone is at least one of 3-sulfolene represented by formula (3), 2-sulfolene represented by formula (4), and propene sultone represented by formula (5). The non-aqueous electrolyte according to claim 6.

2. The non-aqueous electrolyte according to claim 1, wherein the content of the compound having a sulfone group is 0.01 wt% to 5 wt%. The non-aqueous electrolysis according to claim 1, wherein the cyclic ether is at least one selected from the group consisting of 1,3-dioxolane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, and derivatives thereof. liquid. The non-aqueous electrolyte according to claim 1, wherein the chain ether is at least one selected from the group consisting of 1,2-dimethoxyethane and derivatives thereof. The non-aqueous electrolyte according to claim 1, wherein the Lewis acid salt is lithium hexafluorophosphate (LiPF ₆ ). The nonaqueous electrolytic solution according to claim 11, wherein a concentration of the lithium hexafluorophosphate (LiPF ₆ ) is 0.25 mol / kg to 1.5 mol / kg with respect to the nonaqueous electrolytic solution. . The nonaqueous electrolytic solution according to claim 1, wherein the nonaqueous electrolytic solution is for a lithium battery using lithium or a lithium alloy as a negative electrode. One or more selected from the group consisting of iron disulfide (FeS ₂ ), manganese dioxide (MnO ₂ ) and copper oxide (CuO) is used for the positive electrode,
The nonaqueous electrolytic solution according to claim 1, wherein the nonaqueous electrolytic solution is for a lithium battery using lithium or a lithium alloy as a negative electrode. Using iron disulfide (FeS ₂ ) for the positive electrode,
2. The non-aqueous electrolyte according to claim 1, wherein the non-aqueous electrolyte is for a lithium iron disulfide battery using lithium or a lithium alloy as the negative electrode. Having a positive electrode and a negative electrode, and a non-aqueous electrolyte,
The non-aqueous electrolyte battery includes a cyclic ether and a chain ether, a Lewis acid salt, and a compound having a sulfone group. The nonaqueous electrolyte battery according to claim 16, wherein the compound having a sulfone group is an unsaturated chain sulfone. The non-aqueous electrolysis according to claim 17, wherein the unsaturated chain sulfone is at least one of a vinyl sulfone represented by the formula (1) and a divinyl sulfone represented by the formula (2). Liquid battery.

The non-aqueous electrolyte battery according to claim 16, wherein the compound having a sulfone group is a cyclic sulfone. The cyclic sulfone includes 3-sulfolene represented by formula (3), 2-sulfolene represented by formula (4), propene sultone represented by formula (5), and propane sultone represented by formula (6). The nonaqueous electrolyte battery according to claim 19, wherein the battery is at least one selected from the group consisting of:

The non-aqueous electrolyte battery according to claim 16, wherein the compound having a sulfone group is an unsaturated cyclic sulfone. The unsaturated cyclic sulfone is at least one of 3-sulfolene represented by formula (3), 2-sulfolene represented by formula (4), and propene sultone represented by formula (5). The non-aqueous electrolyte battery according to claim 21.

The nonaqueous electrolyte battery according to claim 16, wherein the content of the compound having a sulfone group is 0.01 wt% to 5 wt% with respect to the nonaqueous electrolyte. The non-aqueous electrolysis according to claim 16, wherein the cyclic ether is at least one selected from the group consisting of 1,3-dioxolane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, and derivatives thereof. Liquid battery. The non-aqueous electrolyte battery according to claim 16, wherein the chain ether is at least one selected from the group consisting of 1,2-dimethoxyethane and derivatives thereof. The non-aqueous electrolyte battery according to claim 16, wherein the Lewis acid salt is lithium hexafluorophosphate (LiPF ₆ ). 27. The non-aqueous electrolysis according to claim 26, wherein a concentration of the lithium hexafluorophosphate (LiPF ₆ ) is 0.25 mol / kg to 1.5 mol / kg with respect to the non-aqueous electrolyte. Liquid battery. The nonaqueous electrolyte battery according to claim 16, which is a lithium battery using lithium or a lithium alloy as the negative electrode. Using at least one selected from the group consisting of iron disulfide (FeS ₂ ), manganese dioxide (MnO ₂ ), and copper oxide (CuO) for the positive electrode,
The nonaqueous electrolyte battery according to claim 16, which is a lithium battery using lithium or a lithium alloy as the negative electrode. Using iron disulfide (FeS ₂ ) for the positive electrode,
The nonaqueous electrolyte battery according to claim 16, which is a lithium iron disulfide battery using lithium or a lithium alloy as the negative electrode.

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