JPH11111332A - Nonaqueous electrolyte battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the holding characteristic at a high temperature, and to improve the charge and discharge cycle characteristic having piperazine group included in the nonaqueous electrolyte. SOLUTION: A piperazine group included in the electrolyte is expressed with the formula. In the formula, R1 , R2 are at least one substituent group to be selected from among H, F, Cl, Br, I, CF3 , CCl3 , CBr3 , Cl3 , OCF3 , OCCl3 , OCBr3 and OCl3 . Preferably, 1,4-di-fluoropiperazine, in which R1 , R2 are the same substituent group excluding H, is used. Quantity of the piperazine group included in the electrolyte is set preferably in a range of 0.01-1.5 mol/l. As the solvent for the electrolyte, ethylene carbonate is used. As the electrolyte for the battery electrolyte, at least one kind of LiPF6 , LiBF4 , LiN(C2 F5 SO2 )2 is used preferably.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, and more particularly to a non-aqueous electrolyte having improved storage characteristics at high temperatures. The present invention relates to a non-aqueous electrolyte battery having improved charge / discharge cycle characteristics.

[0002]

2. Description of the Related Art In recent years, non-aqueous electrolyte batteries having a high electromotive force utilizing oxidation and reduction of lithium using a non-aqueous electrolyte have been used as a new type of battery having a high output and a high energy density.

Here, in such a non-aqueous electrolyte battery, as a non-aqueous electrolyte, lithium hexafluorophosphate LiPF ₆ or lithium perchlorate LiCl _{6 is} dissolved in a solvent such as propylene carbonate or dimethyl carbonate.
Obtained by dissolving an electrolyte O ₄ or the like has been generally used.

However, in the case of such a non-aqueous electrolyte battery, the above-mentioned non-aqueous electrolyte reacts with the positive electrode and the negative electrode and is likely to be deteriorated. For example, the non-aqueous electrolyte battery has a problem that storage characteristics at a high temperature are remarkably deteriorated.

For this reason, in recent years, Japanese Patent Laid-Open No. 6-2
As disclosed in Japanese Patent No. 15775, it has been proposed to add a metal salt of an organic anion to a non-aqueous electrolyte to improve the stability of the non-aqueous electrolyte.

[0006] However, as shown in the publication, in the case of a non-aqueous electrolyte battery in which a metal salt of an organic anion is added to a non-aqueous electrolyte, the decrease in discharge capacity when charge and discharge are repeated becomes large. There is a problem that the cycle life of the nonaqueous electrolyte battery is shortened.

[0007]

SUMMARY OF THE INVENTION The present invention provides a positive electrode,
It is an object of the present invention to solve the above-described problems in a nonaqueous electrolyte battery including a negative electrode and a nonaqueous electrolyte, in which the nonaqueous electrolyte reacts with the positive electrode, the negative electrode, and the like to deteriorate. The storage characteristics, especially at high temperatures, are excellent in storage characteristics, and it is also possible to obtain a non-aqueous electrolyte battery excellent in cycle characteristics, in which the discharge capacity is not reduced when charging and discharging are repeated. It is an issue.

[0008]

According to a first aspect of the present invention, there is provided a non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolytic solution. In the electrolyte battery, the piperazine shown in Chemical Formula 1 is contained in the nonaqueous electrolytic solution.

Here, when the piperazine shown in Chemical Formula 1 is contained in the non-aqueous electrolyte solution as in the non-aqueous electrolyte battery according to the present invention, the piperazine becomes lithium in the non-aqueous electrolyte solution. Coordinates by forming a chelate with ions and the like, thereby suppressing the solvent and the like in the non-aqueous electrolyte from coming into contact with lithium ions and the like, and preventing the non-aqueous electrolyte from reacting and deteriorating with the lithium ions and the like. It is thought to prevent.

By preventing the non-aqueous electrolyte from deteriorating by reacting with lithium ions or the like, the storage characteristics of the non-aqueous electrolyte battery are improved, and the discharge capacity is reduced by charging and discharging. Is also suppressed, and the cycle characteristics of the nonaqueous electrolyte battery are improved.

When the amount of the piperazine compound is small in the non-aqueous electrolyte, the storage characteristics at high temperatures and the cycle characteristics of the non-aqueous electrolyte battery cannot be sufficiently improved. On the other hand, if the amount is too large, the viscosity of the non-aqueous electrolyte increases, the ionic conductivity deteriorates, and the cycle characteristics of the non-aqueous electrolyte battery deteriorate. Therefore, as shown in claim 2,
It is preferable that the amount of the piperazine to be contained in the non-aqueous electrolyte is in the range of 0.01 to 1.5 mol / l.

[0012] The above-mentioned non-aqueous electrolyte solution contains
Piperazines are also represented by the above formula 1
Where R in formula 1 is₁, R_TwoIs H,
F, Cl, Br, I, CF_Three, CCl_Three, CBr_Three, C
I_Three, OCF_Three, OCCl_Three, OCBr_Three, OCI_ThreeOr
At least one substituent selected from
As shown in claim 4, this R₁And R_TwoAnd the same except H
1,4-difluoropiperazine C having the same substituent_FourN
_TwoH₈F_Two, 1,4-dichloropiperazine C_FourN _TwoH₈
Cl_Two, 1,4-dibromopiperazine C_FourN_TwoH₈Br
_Two, 1,4-Diodopiperazine C_FourN_TwoH₈I_Two,
1,4-di (trifluoromethyl) piperazine C_FourN_Two
H₈(CF_Three)_Two, 1,4-di (trichloromethyl) pi
Perazine C_FourN_TwoH₈(CCl_Three)_Two, 1,4-di (g
Libromomethyl) piperazine C_FourN_TwoH₈(CBr_Three)
_Two, 1,4-di (triiodomethyl) piperazine C_FourN
_TwoH₈(CI_Three)_Two, 1,4-di (trifluoromethoxy)
B) Piperazine C_FourN_TwoH₈(OCF_Three)_Two, 1,4-
Di (trichloromethoxy) piperazine C_FourN_TwoH₈(O
CCl_Three)_Two1,4-di (tribromomethoxy) pipe
Razine C_FourN_TwoH₈(OCBr_Three)_Two, 1,4-di (g
(Liodomethoxy) piperazine C_FourN_TwoH₈(OCCl
_Three)_TwoIt is preferable to use

This is because R ₁ and R ₂ in the above chemical formula ₁ are
When piperazines having the same substituent other than H are used, when a chelate is formed with a lithium ion or the like as described above, a stable chelate is formed,
This is because the contact with lithium ions or the like and the solvent or the like in the non-aqueous electrolyte is more reliably suppressed, and a non-aqueous electrolyte battery having excellent storage characteristics and cycle characteristics at higher temperatures can be obtained. .

The non-aqueous electrolyte battery according to the present invention is characterized in that the piperazine is contained in the non-aqueous electrolyte as described above, and the solvent and the electrolyte in the non-aqueous electrolyte, The material and the like constituting the positive electrode and the negative electrode are not particularly limited, and those conventionally used in nonaqueous electrolyte batteries can be used.

As the solvent in the non-aqueous electrolyte, for example, cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), butylene carbonate (BC), and dimethyl carbonate Chain carbonates such as carbonate (DMC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC), 1,2-diethoxyethane (DEE), 1,2-dimethoxyethane (DM
E) and a solvent such as ethoxymethoxyethane (EME) can be used alone or as a mixture of two or more kinds. Particularly, in order to further improve the cycle characteristics, one or more kinds of cyclic carbonates are used, It is preferable to use a mixed solvent obtained by mixing one or more chain carbonates in a volume ratio of 1: 4 to 4: 1.

In the non-aqueous electrolyte, the electrolyte dissolved in the above-mentioned solvent is, for example, LiPF ₆ , L
iBF ₄ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiAs
F ₆ , LiSbF ₆ , LiBiF ₄ , LiAlF ₄ , L
iGaF ₄ , LiInF ₄ , LiClO ₄ , LiN (C
Lithium compounds such as F ₃ SO ₂ ) ₂ and LiCF ₃ SO ₃ can be used. In particular, in order to further improve the cycle characteristics, LiP
It is preferable to use F ₆ , LiBF ₄ , and LiN (C ₂ F ₅ SO ₂ ) ₂ .

In the non-aqueous electrolyte battery of the present invention, the positive electrode material constituting the positive electrode includes, for example, manganese dioxide, lithium-containing manganese oxide, lithium-containing cobalt oxide, lithium-containing vanadium oxide,
Lithium-containing nickel oxide, lithium-containing iron oxide,
Lithium-containing chromium oxide, lithium-containing titanium oxide and the like are used.

Further, in the non-aqueous electrolyte battery according to the present invention,
As the negative electrode material constituting the negative electrode, metal lithium is used.
, Li-Al, Li-In, Li-Sn, Li-P
b, Li-Bi, Li-Ga, Li-Sr, Li-S
i, Li-Zn, Li-Cd, Li-Ca, Li-Ba
Can absorb and release lithium alloys and lithium ions
Materials such as pure graphite, coke, and fired organic materials, SnO
_Two, SnO, TiO_Two, Nb _TwoO_ThreeEquivalent potential is positive electrode material
A lower metal oxide or the like is used.

[0019]

EXAMPLES Hereinafter, the nonaqueous electrolyte battery according to the present invention will be described in detail with reference to examples. In the nonaqueous electrolyte battery of this example, the storage characteristics at high temperatures and the cycle characteristics are improved. This will be clarified with reference to comparative examples. The nonaqueous electrolyte battery according to the present invention is not limited to those shown in the following examples, but can be implemented by appropriately changing the scope of the invention without changing its gist.

(Examples 1 to 15) In these examples, a positive electrode and a negative electrode were produced as follows.
A non-aqueous electrolyte solution was prepared as described below to produce a cylindrical non-aqueous electrolyte secondary battery as shown in FIG.

[Preparation of Positive Electrode] In preparing a positive electrode, LiCoO ₂ powder was used as a positive electrode material.
O ₂ powder, artificial graphite powder and polyvinylidene fluoride are 9
At a weight ratio of 0: 5: 5, artificial graphite powder and a solution of polyvinylidene fluoride in N-methyl-2-pyrrolidone (NMP) were added to LiCoO ₂ powder, and these were mixed to prepare a slurry. . Then, this slurry was applied to both surfaces of a positive electrode current collector made of aluminum foil by a doctor blade method, and this was vacuum-dried at 150 ° C. for 2 hours to produce a positive electrode.

[Preparation of Negative Electrode] In preparing the negative electrode, natural graphite was used as a negative electrode material, and the weight ratio of the natural graphite to polyvinylidene fluoride was 90: 5. An NMP solution of vinylidene was added, and these were mixed to prepare a slurry. The slurry was applied to both surfaces of a copper foil as a negative electrode current collector by a doctor blade method. Was prepared.

[Preparation of non-aqueous electrolyte] A non-aqueous electrolyte was prepared.
In the production, ethylene carbonate and diethyl
Mixed solvent obtained by mixing carbonate and carbonate at a volume ratio of 1: 1
And lithium hexafluorophosphate LiP as electrolyte
F₆Was dissolved at a rate of 0.5 mol / l, and further pipetted.
As azines, as shown in Table 1 below,
Is 1,4-difluoropiperazine C_FourN_TwoH₈F_TwoTo
In Example 2, 1,4-dichloropiperazine C_FourN_TwoH₈
Cl_TwoIn Example 3, 1,4-dibromopiperazine C
_FourN_TwoH₈Br _TwoIn Example 4, 1,4-diodopypi
Perazine C_FourN_TwoH₈I_TwoIn Example 5, 1,4-di
(Trifluoromethyl) piperazine C_FourN_TwoH₈(CF
_Three)_TwoIn Example 6, 1,4-di (trichloromethyl)
Piperazine C_FourN_TwoH₈(CCl _Three)_TwoIn Example 7
Is 1,4-di (tribromomethyl) piperazine C_FourN_Two
H ₈(CBr_Three)_TwoIn Example 8, 1,4-di (tri
Iodomethyl) piperazine C_FourN_TwoH₈(CI_Three)
_TwoIn Example 9, 1,4-di (trifluoromethoxy)
B) Piperazine C_FourN_TwoH₈(OCF_Three)_TwoThe example
10 is 1,4-di (trichloromethoxy) piperazine
C_FourN_TwoH₈(OCCl_Three)_TwoIn the eleventh embodiment,
4-di (tribromomethoxy) piperazine C_FourN_TwoH₈
(OCBr_Three)_TwoIn Example 12, 1,4-di (tri
Iodomethoxy) piperazine C_FourN_TwoH₈(OCC
I_Three)_TwoIn Example 13, 1-fluoropiperazine C
_FourN_TwoH₉F, in Example 14, 1-chloro-4-fluoro
Lopiperazine C_FourN_TwoH₈ClF, pipette in Example 15
Razine C_FourN_TwoH_TenAt a rate of 0.5 mol / l each
To prepare each non-aqueous electrolyte solution.

[Preparation of Battery] In preparing the battery, as shown in FIG. 1, a porous film made of polypropylene as a separator 3 was interposed between the positive electrode 1 and the negative electrode 2 prepared as described above. These were wound in a spiral shape and accommodated in each battery can 4, and then each non-aqueous electrolyte prepared as described above was injected into each battery can 4 and sealed. The positive electrode 1 is connected to a positive electrode external terminal 6 via a positive electrode lead 5, and the negative electrode 2 is connected to a battery can 4 via a negative electrode lead 7. Electrically separated by insulating packing 8,
Each non-aqueous electrolyte secondary battery having an outer diameter of 14 mm and a height of 50 mm was obtained.

(Comparative Examples 1 and 2) In these comparative examples, in the preparation of the non-aqueous electrolyte solution in Examples 1 to 15 described above, in Comparative Example 1, piperazines were added to the non-aqueous electrolyte solution. In the case of no addition, and in the case of Comparative Example 2, in place of piperazine, lithium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate LiTFFPB was added in a non-aqueous electrolyte at a rate of 0.5 mol / l. Other than that, a non-aqueous electrolyte secondary battery was manufactured in the same manner as in Examples 1 to 15 described above.

Next, Example 1 manufactured as described above was used.
Using each of the nonaqueous electrolyte secondary batteries of Comparative Examples 1 to 15 and Comparative Examples 1 and 2, at room temperature (25 ° C.), each battery was charged to 4.2 V at a constant current of 200 mA, and then discharged to 2.75 V at a constant current of 200 mA. The charge and discharge were repeated as one cycle, and the discharge capacity at the initial stage and after 500 cycles was obtained, and the remaining capacity after 500 cycles was obtained. The results are shown in Table 1 below.

[0027]

[Table 1]

As is apparent from the results, each of the non-aqueous electrolyte secondary batteries of Examples 1 to 15 in which piperazine was added to the non-aqueous electrolyte did not add piperazine to the non-aqueous electrolyte. Compared to the non-aqueous electrolyte secondary battery of Comparative Example 1 and the non-aqueous electrolyte secondary battery of Comparative Example 2 in which LiTFFP was added to the non-aqueous electrolyte solution instead of piperazine, the capacity retention rate after 500 cycles was higher. Cycle characteristics were improved.

The non-aqueous electrolyte secondary batteries of Examples 1 to 15
When comparing ponds, piperazi added to non-aqueous electrolyte
As the substituents, the substituent R represented by the above formula 1₁, R
_TwoIs F, Cl, Br, I, CF_Three, CCl_Three, CBr
_Three, CI_Three, OCF_Three, OCCl _Three, OCBr_Three, OC
I_ThreeAnd R₁And R_TwoPipette with the same substituent as
Non-aqueous electrolyte secondary batteries of Examples 1 to 12 to which azines were added
The pond has the substituent R shown in the above chemical formula 1.₁, R_TwoIs different
-Aqueous electrolysis of Examples 13 and 14 to which added piperazines were added
Secondary battery and the substituent R₁, R_TwoAre made of H
In the non-aqueous electrolyte secondary battery of Example 15 to which perazine was added
In comparison, the capacity remaining rate after 500 cycles is higher.
Thus, the cycle characteristics were further improved.

(Examples 16 to 21) In these examples, in the preparation of the non-aqueous electrolyte in Examples 1 to 15, the piperazines added to the non-aqueous electrolyte were the same as those in Example 1 described above. The same 1,4-difluoropiperazine C ₄ N ₂ H ₈ F _{2 as in the case of} was used. Then, the amount of the 1,4-difluoro piperazine _{C 4 N 2 H 8 F 2} , as shown in Table 2 below 0.001～2Mol /
1 in the range of 1 to 15
A non-aqueous electrolyte secondary battery was produced in the same manner as in the above case.

Then, the embodiment 1 manufactured as described above is prepared.
For each of the nonaqueous electrolyte secondary batteries of Nos. 6 to 21, the discharge capacity at the initial stage and after 500 cycles was obtained in the same manner as described above, and the residual capacity ratio after 500 cycles was obtained. 2 is shown.

[0032]

[Table 2]

As a result, when 1,4-difluoropiperazine C ₄ N ₂ H ₈ F ₂ was added to the non-aqueous electrolyte, the amount of addition was set in the range of 0.01 to 1.5 mol / l. After 500 cycles, the residual capacity ratio was increased, and the cycle characteristics were improved. In particular, when the addition amount was 0.5 mol / l, the residual capacity ratio after 500 cycles was further increased, and a nonaqueous electrolyte secondary battery having more excellent cycle characteristics was obtained. Similar results were obtained when the piperazines used in Examples 2 to 15 were used as the piperazines contained in the non-aqueous electrolyte.

(Examples 22 to 28) In these examples, ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1 in the preparation of the non-aqueous electrolyte in Examples 1 to 15 described above. The type of electrolyte dissolved in the mixed solvent was changed as shown in Table 3 below,
In Example 22, LiBF ₄ was used, and in Example 23, LiN
(C ₂ F ₅ SO ₂ ) ₂ , and in Example 24, LiAsF ₆
In Example 25, LiSbF ₆ was used, and in Example 26, LSbF ₆ was used.
0.5 m each of iAlF ₄ , LiClO ₄ in Example 27, and LiN (CF ₃ SO ₂ ) ₂ in Example 28
ol / l, and 1,4-difluoropiperazine C ₄ N _{2 in the same} manner as in Example 1 above.
Each non-aqueous electrolyte solution was prepared by adding 0.5 mol / l of H ₈ F ₂ , and each non-aqueous electrolyte secondary battery was produced in the same manner as in Examples 1 to 15 except for the above.

The embodiment 2 thus manufactured
Regarding each of the non-aqueous electrolyte secondary batteries 2 to 28, the discharge capacity at the initial stage and after 500 cycles was obtained in the same manner as in the above case, and the capacity remaining rate after 500 cycles was obtained. 3 is shown.

[0036]

[Table 3]

As a result, LiP was added to the electrolyte of the non-aqueous electrolyte.
F₆, LiBF_Four, LiN (C_TwoF _FiveSO_Two)_TwoUsing
The non-aqueous electrolyte secondary batteries of Examples 1, 22, 23
Non-aqueous electrolyte secondary batteries of Examples 24 to 28 using
The capacity remaining rate after 500 cycles is higher than that of the pond
Non-aqueous electrolyte secondary battery with excellent cycle characteristics
Obtained. The piperazine contained in the non-aqueous electrolyte
As a class, each pin used in the above Examples 2 to 15 was used.
Similar results were obtained with perazines.
Was.

With respect to each of the non-aqueous electrolyte secondary batteries of Examples 1 to 28 and Comparative Examples 1 and 2, charge / discharge was performed in the same manner as in the above case, and the relationship between the number of charge / discharge cycles and discharge capacity. And the results are shown in FIG.

As a result, in each of the non-aqueous electrolyte secondary batteries of Examples 1 to 28, compared with each of the non-aqueous electrolyte secondary batteries of Comparative Examples 1 and 2, the non-aqueous electrolyte secondary batteries had a lower discharge capacity with an increase in the number of charge / discharge cycles. Was decreasing.

Next, each of the non-aqueous electrolyte secondary batteries of Examples 1 to 28 and Comparative Examples 1 and 2 was manufactured, charged and discharged in one cycle, and charged to 4.2 V. The sample was stored in an atmosphere at a temperature of 60 ° C. for 60 days, and changes in the internal resistance of each nonaqueous electrolyte secondary battery were examined every 10 days.

As a result, in each of the non-aqueous electrolyte secondary batteries of Examples 1 to 28, the increase in internal resistance when stored at a high temperature was smaller than that of each of the non-aqueous electrolyte secondary batteries of Comparative Examples 1 and 2. The storage characteristics at high temperatures were also improved.

After each of the non-aqueous electrolyte secondary batteries of Examples 1 to 28 and Comparative Examples 1 and 2 was manufactured, one cycle of charge / discharge was performed in the same manner as in the above case to 4.2 V. After charging, 60
After storing for 10 days, the open circuit voltage of each nonaqueous electrolyte secondary battery was examined every 10 days, and the results are shown in FIG.

As a result, each of the non-aqueous electrolyte secondary batteries of Examples 1 to 28 has a smaller open-circuit voltage drop when stored at a high temperature than the non-aqueous electrolyte secondary batteries of Comparative Examples 1 and 2. It has been found that the addition of piperazines to the non-aqueous electrolyte also suppresses the drop in open circuit voltage during storage at high temperatures.

[0044]

As described above in detail, in the non-aqueous electrolyte battery according to the present invention, the above-mentioned compound 1 is contained in the non-aqueous electrolyte.
Since the piperazine shown in (1) was contained, decomposition of the non-aqueous electrolyte solution at high temperature or during charge and discharge was suppressed by the piperazine, and a non-aqueous electrolyte battery having excellent storage characteristics and cycle characteristics at high temperatures was obtained. .

[Brief description of the drawings]

FIG. 1 is an explanatory cross-sectional view showing an internal structure of a nonaqueous electrolyte secondary battery produced in an example of the present invention and a comparative example.

FIG. 2 is a diagram showing the relationship between the number of charge / discharge cycles and the discharge capacity when each of the non-aqueous electrolyte secondary batteries of Examples and Comparative Examples of the present invention was charged and discharged.

FIG. 3 shows the relationship between the storage period and the internal resistance of each non-aqueous electrolyte secondary battery when the non-aqueous electrolyte secondary batteries of the examples and comparative examples of the present invention are stored in an atmosphere at 80 ° C. FIG.

FIG. 4 shows the relationship between the storage period and the open-circuit voltage of each non-aqueous electrolyte secondary battery when the non-aqueous electrolyte secondary batteries of Examples and Comparative Examples of the present invention are stored in an atmosphere at 80 ° C. FIG.

[Explanation of symbols]

 1 Positive electrode 2 Negative electrode

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiyuki Noma 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Koji Nishio 2-chome, Keihanhondori, Moriguchi-shi, Osaka No. 5-5 in Sanyo Electric Co., Ltd.

Claims (4)

[Claims] 1. A non-aqueous electrolyte battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the non-aqueous electrolyte contains a piperazine represented by the following Chemical Formula 1. Non-aqueous electrolyte battery. Embedded image (Wherein R ₁ and R ₂ are H, F, Cl, Br, I, C
F ₃ , CCl ₃ , CBr ₃ , CI ₃ , OCF ₃ , OCC
at least one substituent selected from the group consisting of l ₃ , OCBr ₃ and OCI ₃ , wherein R ₁ and R ₂ may be the same or different. ) 2. The non-aqueous electrolyte battery according to claim 1, wherein the piperazine is contained in the non-aqueous electrolyte in a range of 0.01 to 1.5 mol / l. Item 2. The non-aqueous electrolyte battery according to Item 1. 3. The non-aqueous electrolyte battery according to claim 1, wherein the non-aqueous electrolyte contains LiPF ₆ , Li
A non-aqueous electrolyte battery comprising at least one electrolyte selected from BF ₄ and LiN (C ₂ F ₅ SO ₂ ) ₂ . 4. The non-aqueous electrolyte battery according to claim 1, wherein R ₁ and R ₂ are the same substituents other than H in the piperazines represented by Chemical Formula ₁ . Non-aqueous electrolyte battery characterized by the above-mentioned.