JP2001057239A - Nonaqueous electrolyte battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To use a stably suppliable positive electrode active material, and reduce degradation even under high-temperature environment. SOLUTION: This nonaqueous electrolyte battery 1 has a positive electrode 2 including manganese oxide or a composite oxide of lithium and manganese as a positive electrode active material; a negative electrode 3 including lithium, a lithium alloy or a material capable of doping and undoping lithium as a negative electrode active material; and a nonaquecrus electrolytic solution formed by dissolving an electrolyte in a nonaqueous solvent. The nonaqueous electrolytic solution contains an organic compound represented by the formula as the nonaqueous solvent. In the formula, X is a halogen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a non-aqueous electrolyte battery. More specifically, the present invention relates to a non-aqueous electrolyte battery having improved cycle characteristics by including a specific compound in the non-aqueous electrolyte.

[0002]

2. Description of the Related Art In recent years, many portable electronic devices such as a camera-integrated video tape recorder, a mobile phone, and a portable computer have appeared and their size and weight have been reduced. Researches have been made to improve the energy density of batteries that are portable power sources for these electronic devices, particularly secondary batteries. Among secondary batteries, lithium-ion batteries are expected to have higher energy density than lead batteries and nickel-cadmium batteries, which are secondary batteries using conventional aqueous electrolytes. It is being advanced.

As a non-aqueous electrolyte used for a lithium or lithium ion secondary battery, one obtained by dissolving LiPF ₆ as an electrolyte in a carbonate-based non-aqueous solvent such as propylene carbonate or diethyl carbonate has a relatively high conductivity. Also high,
It is widely used because it is stable in potential.

Further, as a positive electrode active material of a lithium ion secondary battery, Li _x Mn ₂ O ₄ , Li _x having a high discharge potential are used.
M _y O ₂ (M is Ni or Co. The value of x changes with charge and discharge, but usually x {1, y} during synthesis.
It is one. ) Etc. are known. Then, a lithium ion secondary battery using LiCo _y O ₂ known as a positive electrode active material having a high discharge potential and a high energy density has been put to practical use.

[0005] However, cobalt, which is a raw material of this composite oxide, is scarce in terms of resources, and commercially available mineral deposits are unevenly distributed in a few countries. In the future, supply will be uncertain.

Therefore, in order to promote the widespread use of such non-aqueous electrolyte secondary batteries, a positive electrode active material which can be made of less expensive, resource-rich raw materials and which is not inferior in performance is required. Is desired.

As a solution to the above problem, LiCo _y O ₂
Li with discharge potential and practical energy density almost equivalent to
_x NiO ₂ or Li _x Mn ₂ O ₄ has been proposed.

Although nickel is an inexpensive material as compared with cobalt, it goes without saying that it is more desirable to manufacture a positive electrode active material using a raw material that is less expensive and has less supply concerns. Manganese is cheaper than cobalt and nickel, and is rich in resources. In addition, manganese dioxide as a material for manganese dry batteries, alkaline manganese dry batteries, and lithium primary batteries is distributed in large quantities, and is a material with little concern in terms of material supply. Therefore, research on a positive electrode active material of a non-aqueous electrolyte secondary battery using manganese as a raw material has been actively conducted in recent years.

[0009] The various manganese raw material and a lithium-manganese composite oxide is synthesized from lithium compounds have been reported various things, _{but, Li x Mn y O 4 (} x ≒ 1, y with these example spinel structure # 1) is a material having a potential of 3 V or more with respect to lithium by electrochemical oxidation and having a theoretical charge / discharge capacity of 148 mAh / g.

[0010]

On the other hand, in recent years, large-scale non-aqueous electrolyte secondary batteries have been developed in various fields for use in electric vehicles or road leveling. Since it is required in large quantities, it is important for its widespread use that it can be made of inexpensive and resource-rich raw materials. Therefore, in a large nonaqueous electrolyte secondary battery, the above-mentioned spinel-type lithium manganese oxide is considered to be promising as a positive electrode active material.

There are many possible non-aqueous electrolytes to be combined with the electrolyte. Among them, an electrolyte obtained by dissolving LiPF ₆ as an electrolyte in a carbonate-based non-aqueous solvent such as propylene carbonate or diethyl carbonate is used. Since it shows good battery characteristics when used, it is considered as one promising candidate.

However, LiPF ₆ is a relatively expensive material and must be used in large quantities in large batteries, which may hinder widespread use of large non-aqueous electrolyte secondary batteries. There was a problem. LiPF ₆ has relatively good battery characteristics, but continuous charging characteristics are somewhat inferior. The continuous charging characteristic is to supply a small current to the battery and always keep the battery in a charged state in order to compensate for a capacity loss due to self-discharge of the battery. In this way,
When continuous charging is performed for a long time, Mn of the positive electrode elutes and precipitates on the surface of the negative electrode, so that a minute internal short circuit occurs and the charging current increases. That is, it can be said that the longer the time until the charging current increases, the better the battery.

Therefore, LiBF ₄ is considered as a promising electrolyte alternative to LiPF _{6. An} electrolyte is prepared using this electrolyte, and a secondary battery using the same is used in an environment above room temperature. Deterioration by LiPF
There was a drawback that it was larger than when ₆ was used.

As the size of the battery increases, such as for electric vehicles or road leveling, the internal heat generation during use becomes not negligible, and the temperature inside the battery can be relatively high even when the ambient temperature is around room temperature. Sex is increased. In addition, even if a relatively small battery used as a small portable device or the like is used in a high-temperature environment such as a cabin of a car in midsummer, deterioration of the battery in an environment above room temperature is considered. It can be said that less is more desirable.

The present invention has been proposed in view of such conventional circumstances, and provides a non-aqueous electrolyte battery that uses a positive electrode active material that can be stably supplied and has little deterioration even in a high temperature environment. The purpose is to:

[0016]

A nonaqueous electrolyte battery according to the present invention comprises a positive electrode having an oxide of manganese or a composite oxide of lithium and manganese as a positive electrode active material, a lithium metal, a lithium alloy or lithium doped. A negative electrode having a material capable of being undoped as a negative electrode active material, and a non-aqueous electrolyte obtained by dissolving an electrolyte in a non-aqueous solvent, wherein the non-aqueous electrolyte is an organic compound represented by Chemical Formula 2 It is characterized by containing as a non-aqueous solvent.

[0017]

Embedded image

Since the non-aqueous electrolyte battery according to the present invention as described above contains the organic compound represented by the above formula (2) as a non-aqueous solvent of the non-aqueous electrolyte, it is caused by repeated charge and discharge. Thus, the formation of a film on the electrode surface due to the product of the chemical reaction of the non-aqueous electrolyte is suppressed, and the characteristic deterioration is suppressed.

[0019]

Embodiments of the present invention will be described below.

FIG. 1 is a longitudinal sectional view showing one configuration example of the nonaqueous electrolyte battery according to the present invention. This non-aqueous electrolyte battery 1
Is a film-shaped positive electrode 2 and a film-shaped negative electrode 3,
The wound layer body wound in close contact with the separator 4 interposed therebetween,
It is mounted inside the battery can 5.

The positive electrode 2 is manufactured by applying a positive electrode mixture containing a positive electrode active material and a binder on a current collector and drying the mixture. A metal foil such as an aluminum foil is used for the current collector.

As the positive electrode active material, a metal oxide, a metal sulfide, or a specific polymer can be used depending on the type of the intended battery.

For example, when forming a lithium primary battery, TiS ₂ , MnO ₂ , graphite, F
eS ₂ or the like can be used. When a lithium secondary battery is configured, TiS ₂ ,
Metal sulfides or oxides such as MoS ₂ , NbSe ₂ , and V ₂ O ₅ can be used. Further, a lithium composite oxide mainly composed of LiM _x O ₂ (where M represents one or more transition metals and x varies depending on the charge / discharge state of the battery and is usually 0.05 or more and 1.10 or less). Things and the like can be used. As the transition metal M constituting the lithium composite oxide, Co, Ni, Mn, or the like is preferable. A specific example of such a lithium composite oxide is LiCo.
O ₂ , LiNiO ₂ , LiNiyCo _1-y O ₂ (where 0 <
y <1. ), LiMn ₂ O _{4 and the} like. These lithium composite oxides can generate a high voltage and become positive electrode active materials excellent in energy density. In particular, from the viewpoint that a large capacity can be obtained, it is preferable to use a manganese oxide or a lithium manganese composite oxide having a spinel crystal structure as the positive electrode active material. Positive electrode 2
, A plurality of these positive electrode active materials may be used together.

As the binder for the above-mentioned positive electrode mixture, a known binder which is usually used for a positive electrode mixture of a battery can be used. Can be added.

The negative electrode 3 is manufactured by applying a negative electrode mixture containing a negative electrode active material and a binder on a current collector and drying the mixture. For the current collector, for example, a metal foil such as a copper foil is used.

When forming a lithium primary battery or a lithium secondary battery, it is preferable to use lithium, a lithium alloy, or a material capable of doping or undoping lithium as a negative electrode material. As a material that can be doped and de-doped with lithium, for example, a carbon material such as a non-graphitizable carbon-based material and a graphite-based material can be used. Specifically, carbon materials such as pyrolytic carbons, cokes, graphites, glassy carbon fibers, organic polymer compound fired bodies, carbon fibers, and activated carbon can be used. Examples of the coke include pitch coke, needle coke, and petroleum coke. The fired organic polymer compound is obtained by firing a phenol resin, a furan resin or the like at an appropriate temperature and carbonizing the same.

In addition to the above-mentioned carbon materials, polymers such as polyacetylene and polypyrrole and oxides such as SnO ₂ can also be used as materials capable of doping and undoping lithium. Further, as the lithium alloy, a lithium-aluminum alloy or the like can be used.

As the binder of the above-mentioned negative electrode mixture, a known binder which is usually used for a negative electrode mixture of a lithium ion battery can be used, and a known additive of the above-mentioned negative electrode mixture can be used. Etc. can be added.

The separator 4 is disposed between the positive electrode 2 and the negative electrode 3 to prevent a short circuit due to physical contact between the positive electrode 2 and the negative electrode 3. As the separator 4, a microporous polyolefin film such as a polyethylene film and a polypropylene film is used.

The non-aqueous electrolyte is prepared by dissolving an electrolyte in a non-aqueous solvent.

As the electrolyte, a known electrolyte usually used for a battery electrolyte can be used. Specifically, LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiC
10 ₄ , LiCF ₃ SO ₃ , LiN (SO ₂ CF ₃ ) ₂ , Li
Lithium salts such as C (SO ₂ CF ₃ ) ₃ , LiAlCl ₄ , and LiSiF ₆ can be given.

Among the above lithium salts, LiPF
₆ is desirable from the viewpoint of oxidation stability. However, since LiPF ₆ is a relatively expensive material and must be used in large quantities in large batteries, LiBF ₄ is considered as a promising electrolyte alternative to LiPF ₆ . This LiBF ₄ has an advantage that the continuous charging characteristics are superior to LiPF ₆ .

Such an electrolyte is contained in a non-aqueous solvent at a concentration of 0.1%.
Preferably, it is dissolved at a concentration of from mol / l to 3.0 mol / l. More preferably, 0.5 mol / l
２．０2.0 mol / l.

As the non-aqueous solvent, various non-aqueous solvents conventionally used for non-aqueous electrolytes can be used. For example, propylene carbonate, cyclic carbonates such as ethylene carbonate, chain carbonates such as diethyl carbonate and dimethyl carbonate, carboxylate esters such as methyl propionate and methyl butyrate, γ-butyl lactone, sulfolane, 2-methyltetrahydrofuran Ethers such as dimethoxyethane can be used. These non-aqueous solvents may be used alone or in combination of two or more. Among them, especially from the viewpoint of oxidation stability,
It is preferable to use a carbonate ester.

In the non-aqueous electrolyte battery according to the present invention, the non-aqueous electrolyte contains an organic compound represented by Chemical Formula 3 as a non-aqueous solvent. The coating on the electrode surface by the product of the chemical reaction of the non-aqueous electrolyte caused by repeating the charge and discharge by including the organic compound represented by the chemical formula 3 as a non-aqueous solvent in the non-aqueous electrolyte. Generation can be suppressed. This improves the cycle characteristics of the nonaqueous electrolyte battery 1 at high temperatures.

[0036]

Embedded image

The organic compound represented by the above formula 3 includes:
For example, 1,4-dimethoxy-2-fluorobenzene,
1,3-dimethoxy-5-chlorobenzene, 3,5-dimethoxy-1-fluorobenzene, 1,2-dimethoxy-4-fluorobenzene, 1,2-dimethoxy-4-bromobenzene, 1,3-dimethoxy-4 -Bromobenzene, 2,5-dimethoxy-1-bromobenzene and the like.

In the non-aqueous electrolyte battery 1, the organic compound represented by Chemical Formula 3 described above is contained in the non-aqueous solvent in a range of 0.5% by volume or more and 5% by volume or less. I have. The amount of the organic compound represented by Chemical formula 3 is 0.1% of the non-aqueous solvent.
If it is less than 5% by volume, the effect of improving the cycle characteristics cannot be sufficiently obtained. On the other hand, if the amount of the organic compound represented by Chemical Formula 3 is more than 5% by volume of the non-aqueous solvent, the battery characteristics other than the cycle characteristics may be adversely affected.

Therefore, in the non-aqueous electrolyte, 0.5% by volume or more of an organic compound represented by Chemical Formula 3 as a non-aqueous solvent is used.
Non-aqueous electrolyte battery 1 containing 5% by volume or less
Has excellent high-temperature cycle characteristics without deteriorating other battery characteristics.

And such a non-aqueous electrolyte battery 1 is
It is manufactured as follows.

The positive electrode 2 is uniformly coated with a positive electrode mixture containing a positive electrode active material and a binder on a metal foil such as an aluminum foil, which serves as a positive electrode current collector, and dried to form a positive electrode active material layer. It is produced by forming. Known binders can be used as the binder of the positive electrode mixture, and known additives and the like can be added to the positive electrode mixture.

The negative electrode 3 is formed by uniformly applying a negative electrode mixture containing a negative electrode active material and a binder on a metal foil such as a copper foil serving as a negative electrode current collector and drying the same to form a negative electrode active material layer. It is produced by forming. As the binder of the negative electrode mixture, a known binder can be used, and a known additive or the like can be added to the negative electrode mixture.

The positive electrode 2 and the negative electrode 3 obtained as described above are brought into close contact with each other via a separator 4 made of, for example, a microporous polypropylene film, and wound in a spiral form many times to form a wound layer body. Is done.

Next, the insulating plate 6 is inserted into the bottom of the nickel-plated iron battery can 5 and the wound body is further housed. Then, in order to collect the current of the negative electrode, one end of a negative electrode lead 7 made of, for example, nickel is pressed against the negative electrode 3 and the other end is welded to the battery can 5. Thereby, the battery can 5
Has conductivity with the negative electrode 3 and becomes an external negative electrode of the nonaqueous electrolyte battery 1. In order to collect the current of the positive electrode 2, one end of a positive electrode lead 8 made of, for example, aluminum is connected to the positive electrode 2.
To the battery cover 1 at the other end via a current interrupting thin plate 9.
0 is electrically connected. The current interrupting thin plate 9 interrupts the current in accordance with the internal pressure of the battery. This allows
The battery lid 10 has conductivity with the positive electrode 2, and serves as an external positive electrode of the nonaqueous electrolyte battery 1.

Next, a non-aqueous electrolyte is injected into the battery can 5. This non-aqueous electrolyte is prepared by dissolving an electrolyte in a non-aqueous solvent. Here, in the non-aqueous electrolyte battery 1 according to the present invention, the non-aqueous electrolyte contains an organic compound represented by Chemical Formula 3 in a range of 0.5% by volume or more and 5% by volume or less. I have.

Next, the battery lid 5 is fixed by caulking the battery can 5 via the insulating sealing gasket 11 coated with asphalt, and the cylindrical nonaqueous electrolyte battery 1 is manufactured.

In this non-aqueous electrolyte battery 1,
As shown in FIG. 1, a center pin 12 connected to the negative electrode lead 7 and the positive electrode lead 8 is provided, and a safety valve device for bleeding gas when the pressure inside the battery becomes higher than a predetermined value. 13 and a PTC element 14 for preventing a rise in temperature inside the battery.

In the above embodiment, a non-aqueous electrolyte battery using a non-aqueous electrolyte has been described as an example. However, the present invention is not limited to this. The present invention is also applicable to a solid electrolyte battery using a polymer solid electrolyte containing a simple substance or a mixture thereof, and a gel electrolyte battery using a gel solid electrolyte containing a swelling solvent.

Further, in the above-described embodiment, the description has been given by taking the secondary battery as an example. However, the present invention is not limited to this, and can be applied to a primary battery. In addition, the battery of the present invention has a cylindrical shape, a square shape, a coin shape, a button shape, and the like, and its shape is not particularly limited,
In addition, various sizes such as a thin type and a large size can be used.

[0050]

EXAMPLES A non-aqueous electrolyte battery as described above was manufactured and its characteristics were evaluated.

<Example 1> First, a negative electrode was manufactured as follows.

Using petroleum pitch as a starting material, the mixture was calcined at 1000 ° C. in an inert gas stream to obtain a non-graphitizable carbon material having properties similar to glassy carbon. When an X-ray diffraction measurement was performed on the obtained material, the (002) plane spacing was 3.
76 Angstroms, true specific gravity 1.58 g / c
m ³ . This non-graphitizable carbon material was pulverized to obtain a carbon material powder having an average particle size of 10 μm.

Next, 90 parts by weight of the carbon material powder was added.
A negative electrode mixture was prepared by mixing 10 parts by weight of polyvinylidene fluoride as a binder.

Next, the obtained negative electrode mixture was mixed with N-methyl-2.
-Dispersed in pyrrolidone to form a slurry. And
This slurry was uniformly coated on both sides of a 10 μm-thick strip-shaped copper foil as a negative electrode current collector, dried to form a negative electrode active material layer, and then compression-molded with a roll press to produce a negative electrode.

Next, a positive electrode was produced as follows.

First, lithium carbonate (Li ₂ CO ₃ ) powder and manganese carbonate (MnCO ₃ ) powder were mixed in a molar ratio of Li / M
It mixed so that it might become n = 1/2, and baked at 800 degreeC in air, and obtained the lithium manganese composite oxide used as a positive electrode active material. When this sample was analyzed by powder X-ray diffraction, I
It almost coincided with LiMn ₂ O ₄ described in SDD card 35-782.

Next, 91 parts by weight of the obtained lithium manganese composite oxide, 6 parts by weight of graphite as a conductive agent, and 3 parts by weight of polyvinylidene fluoride as a binder were mixed to prepare a positive electrode mixture. Prepared.

Next, the obtained positive electrode mixture was mixed with N-methyl-
It was dispersed in 2-pyrrolidone to form a slurry. And
This slurry was uniformly coated on both sides of a 20 μm-thick aluminum foil serving as a positive electrode current collector, dried to form a positive electrode active material layer, and then compression-molded with a roll press to produce a positive electrode.

The positive electrode obtained as described above and the negative electrode are brought into close contact with each other via a separator made of a microporous polypropylene film having a thickness of 25 μm, and are wound in a spiral form many times to form a wound body. did.

Next, an insulating plate was inserted into the bottom of a nickel-plated iron battery can, and the wound body was further housed. Then, in order to collect the current of the negative electrode, one end of a nickel negative electrode lead was pressed against the negative electrode, and the other end was welded to the battery can. Further, in order to collect the current of the positive electrode, one end of an aluminum positive electrode lead was attached to the positive electrode, and the other end was electrically connected to the battery lid via a current interrupting thin plate. The current interrupting thin plate interrupts the current according to the internal pressure of the battery.

Then, a non-aqueous electrolyte was injected into the battery can. This non-aqueous electrolyte contained 49.9% by volume of propylene carbonate, 49.9% by volume of dimethyl carbonate,
In a mixed solvent of 1,2-dimethoxy-4-bromobenzene and 0.2% by volume, 1.5 parts of LiBF ₄ was used as an electrolyte.
It was prepared by dissolving at a concentration of mol / l.

Finally, the battery cover is fixed by caulking the battery can through an insulating sealing gasket coated with asphalt, and a cylindrical non-aqueous electrolyte battery having a diameter of about 18 mm and a height of about 65 mm is obtained. Produced.

Example 2 The composition of the mixed solvent of the non-aqueous electrolyte was 49.75% by volume of propylene carbonate, 49.75% by volume of dimethyl carbonate, and 1,2-dimethoxy-4-bromobenzene. A non-aqueous electrolyte battery was produced in the same manner as in Example 1, except that the volume was 0.5% by volume.

Example 3 The composition of the mixed solvent of the non-aqueous electrolyte was as follows: propylene carbonate was 49% by volume, dimethyl carbonate was 49% by volume, and 1,2-dimethoxy-4-bromobenzene was 2% by volume. A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1 except for the above.

Example 4 The composition of the mixed solvent of the non-aqueous electrolyte was propylene carbonate 47.5% by volume, dimethyl carbonate 47.5% by volume, 1,2-dimethoxy-4
A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1, except that 5% by volume of -bromobenzene was used.

Example 5 The composition of the mixed solvent of the nonaqueous electrolyte was as follows: propylene carbonate was 47% by volume, dimethyl carbonate was 47% by volume, and 1,2-dimethoxy-4-bromobenzene was 6% by volume. A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1 except for the above.

Example 6 The composition of the mixed solvent of the non-aqueous electrolyte was propylene carbonate 49.9% by volume, dimethyl carbonate 49.9% by volume, 1,4-dimethoxy-2
-Except that the fluorobenzene was 0.2% by volume
A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1.

Example 7 The composition of the mixed solvent of the non-aqueous electrolyte was 49.75% by volume of propylene carbonate, 49.75% by volume of dimethyl carbonate, and 1,4-dimethoxy-2-fluorobenzene. A non-aqueous electrolyte battery was produced in the same manner as in Example 1, except that the volume was 0.5% by volume.

Example 8 The composition of the mixed solvent of the non-aqueous electrolyte was as follows: propylene carbonate: 47.5% by volume, dimethyl carbonate: 47.5% by volume, 1,4-dimethoxy-2
A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1, except that 5% by volume of fluorobenzene was used.

Example 9 The composition of the mixed solvent of the non-aqueous electrolyte was 47 volume% of propylene carbonate, 47 volume% of dimethyl carbonate, and 6 volume% of 1,4-dimethoxy-2-fluorobenzene. A non-aqueous electrolyte battery was manufactured in the same manner as in Example 1 except for the above.

Comparative Example The composition of the mixed solvent of the nonaqueous electrolyte was propylene carbonate at 50% by volume, dimethyl carbonate at 50% by volume, and 1,2-dimethoxy-4-bromobenzene or 1,4-dimethoxy. A non-aqueous electrolyte battery was produced in the same manner as in Example 1, except that -2-fluorobenzene was not contained.

The batteries manufactured as described above were subjected to an evaluation experiment on the discharge capacity and the high-temperature cycle characteristics.

First, in an atmosphere of 23 ° C., each battery was charged at a constant current and a constant voltage of 1 A to an upper limit of 4.1 V. Next, a constant current discharge of 1000 mA was performed to a final voltage of 2.5 V to determine a discharge capacity.

The high-temperature cycle characteristic is 60 ° C.
Under the atmosphere described above, each battery was charged at a constant current and a constant voltage of 1 A up to an upper limit of 4.1 V, and then discharged at a constant current of 1000 mA to a final voltage of 2.5 V. The above process was defined as one cycle, and this cycle was repeated 100 times. Then, 100 with respect to the discharge capacity (C1) in the first cycle.
Ratio of discharge capacity at cycle (C2) ((C2 / C1)
× 100) was obtained as a discharge capacity retention ratio (%).

Table 1 shows the evaluation results of the discharge capacity and the discharge capacity retention rate of the batteries of Examples 1 to 9 and Comparative Example.
Shown in

[0076]

[Table 1]

As is clear from Table 1, 1, 1
In the batteries of Examples 1 to 9 to which 2-dimethoxy-4-bromobenzene or 1,4-dimethoxy-2-fluorobenzene was added, 1,2-dimethoxy-4 was contained in the electrolyte.
It was found that the battery had excellent high-temperature cycle characteristics as compared with the battery of Comparative Example in which -bromobenzene or 1,4-dimethoxy-2-fluorobenzene was not added.

This effect is not limited to 1,2-dimethoxy-4-bromobenzene or 1,4-dimethoxy-2-fluorobenzene, and the same effect can be obtained if the compound is represented by the above formula (3). Can be obtained.

However, the content of the compound in a non-aqueous solvent is 0.1%.
In the batteries of Example 1 and Example 6 less than 5% by volume, the effect of improving the capacity retention rate cannot be said to be sufficient. Also,
Example 5 in which the content of the compound exceeds 5% by volume in the non-aqueous solvent
And the battery of Example 9 has a higher capacity retention rate,
On the other hand, the capacity itself has decreased.

On the other hand, the content of the compound was adjusted to 0.5 in a non-aqueous solvent.
In the batteries of Examples 2 to 4, Example 7, and Example 8 in the range of not less than 5% by volume and not more than 5% by volume, good characteristics are obtained.

Accordingly, the content of the compound in a non-aqueous solvent is adjusted to 0.1.
It has been found that a non-aqueous electrolyte battery having particularly good characteristics can be obtained by setting the content to 5% by volume or more and 5% by volume or less.

[0082]

According to the present invention, the organic compound represented by the above formula (3) is contained as a non-aqueous solvent in a non-aqueous electrolyte solution.
A non-aqueous electrolyte battery having excellent cycle characteristics at high temperatures can be realized.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing one configuration example of a nonaqueous electrolyte battery according to the present invention.

[Explanation of symbols]

1 Non-aqueous electrolyte battery, 2 Positive electrode, 3 Negative electrode, 4
Separator, 5 Battery can, 10 Battery lid

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) H01M 6/16 H01M 6/16 A F term (reference) 5H003 AA04 BB01 BB02 BB04 BB05 BB12 BD03 5H014 AA02 EE05 EE08 EE10 HH01 5H024 AA02 AA03 AA12 CC02 CC12 FF11 FF14 FF18 FF19 FF32 HH01 5H029 AJ05 AJ07 AK02 AK03 AK05 AK16 AL02 AL06 AL07 AL12 AL16 AM00 AM01 AM02 AM03 AM04 AM05 AM07 AM16 BJ02 BJ03 HJ04 BJ14 DJ14

Claims (5)

[Claims] 1. A positive electrode having a manganese oxide or a composite oxide of lithium and manganese as a positive electrode active material; and a negative electrode having a lithium metal, a lithium alloy or a material capable of doping / dedoping lithium as a negative electrode active material. A non-aqueous electrolyte in which an electrolyte is dissolved in a non-aqueous solvent, wherein the non-aqueous electrolyte contains an organic compound represented by Chemical Formula 1 as the non-aqueous solvent. Electrolyte battery. Embedded image 2. The non-aqueous electrolyte according to claim 1, wherein the non-aqueous electrolyte contains the organic compound represented by Chemical Formula 1 in a range of 0.5% by volume or more and 5% by volume or less. Electrolyte battery. 3. The method according to claim 1, wherein the non-aqueous electrolyte is L
Non-aqueous electrolyte battery according to claim 1, wherein the containing iBF _4. 4. The non-aqueous electrolyte battery according to claim 1, wherein the composite oxide of lithium and manganese has a spinel-type crystal structure. 5. The non-aqueous electrolyte battery according to claim 1, wherein the material capable of doping / dedoping lithium is a carbon material.