JPH1140194A - Nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte secondary battery with superior cycle characteristic, in which capacity deterioration due to a charging and discharging cycle is low. SOLUTION: This nonaqueous electrolyte secondary battery has a nonaqueous electrolyte made by dissolving electrolyte in organic solvent, and at least one of naphthoquinone, fluorene, epoxide, 1,1-diphenyl-2-picrylhydrozine and hindered- amine (HALS) light stabilizer is added to the nonaqueous electrolyte. In addition, both benzo-triazole and benzo-quinone are added to the nonaqueous electrolyte.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-aqueous electrolyte secondary battery provided with a non-aqueous electrolyte in which an electrolyte is dissolved in an organic solvent, and more particularly to a lithium secondary battery.

[0002]

2. Description of the Related Art Conventionally, there is a non-aqueous electrolyte secondary battery provided with a non-aqueous electrolyte in which an electrolyte is dissolved in an organic solvent such as an ester or an ether. Above all, lithium secondary batteries, in which lithium contributes to the battery reaction, have attracted particular attention as having a high battery capacity, and have been improved in various ways. As one example, a negative electrode composed of a carbon material or oxide capable of inserting and extracting lithium (Japanese Unexamined Patent Publication No. 6-132)
027 publication).

However, in such a non-aqueous electrolyte secondary battery using an organic solvent such as an ester or an ether as a solvent for the non-aqueous electrolyte, the solvent is decomposed on the electrode surface as charging and discharging are repeated, and the charge-discharge cycle is reduced. However, there is a problem that the battery capacity is greatly deteriorated due to the above.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a non-aqueous electrolyte secondary battery having a small capacity deterioration due to a charge / discharge cycle and excellent cycle characteristics. I do.

[0005]

Means for Solving the Problems The present inventors further added at least naphthoquinone, fluorene, epoxide, 1,1-diphenyl-2-picrylhydrazyl, to a non-aqueous electrolyte obtained by dissolving an electrolyte in an organic solvent. When one or more of the HALS-based light stabilizers were added and used in a non-aqueous electrolyte secondary battery, it was found that the capacity deterioration of the battery due to charge / discharge cycles was reduced. In addition, it was found that when both benzotriazole and benzoquinone were added to a non-aqueous electrolyte and used in a non-aqueous electrolyte secondary battery, the capacity deterioration of the battery due to charge / discharge cycles was reduced. The present invention has been made based on these findings.

That is, a non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte secondary battery including a non-aqueous electrolyte in which an electrolyte is dissolved in an organic solvent, wherein the non-aqueous electrolyte includes naphthoquinone. , Fluorene, epoxide, 1,1-diphenyl-2-picrylhydrazyl, and HALS-based light stabilizer.

Another non-aqueous electrolyte secondary battery according to the present invention is a non-aqueous electrolyte secondary battery including a non-aqueous electrolyte in which an electrolyte is dissolved in an organic solvent. Is
It is characterized in that benzotriazole and benzoquinone are added.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The non-aqueous electrolyte secondary battery of the present invention
Both are non-aqueous electrolyte secondary batteries comprising a non-aqueous electrolyte in which an electrolyte is dissolved in an organic solvent.In such a non-aqueous electrolyte, naphthoquinone, fluorene, epoxide,
1,1-diphenyl-2-picrylhydrazyl and HA
It is broadly classified into those in which at least one LS light stabilizer is added (the former) and those in which both benzotriazole and benzoquinone are added (the latter).

Before describing each non-aqueous electrolyte, the overall structure of the battery will be described first. The type of battery is not particularly limited, but a lithium secondary battery is most preferable. Further, the structure of the entire battery is not particularly limited in any of the batteries, and has a cylindrical shape,
A known structure can be used in various forms such as a button type and a square type.

[0010] Each of the batteries constitutes a positive electrode.
The positive electrode active material is not particularly limited,
If it is a lithium secondary battery, LiCoO_Two, LiN
iO _Two, LiMn_TwoO_FourEtc. can be used. Ma
In addition, materials constituting the negative electrode are also particularly limited.
Although it is not, it can be made of carbon material such as graphite
preferable.

Next, the non-aqueous electrolyte will be described. The organic solvent and the electrolyte are not particularly limited in any of the nonaqueous electrolyte secondary batteries, and known ones can be used. For the organic solvent, ethylene carbonate, propylene carbonate,
Butylene carbonate, γ-butyrolactone, 1,2-
Esters and ethers such as dimethoxyethane, dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate can be used, and it is preferable to use a mixed organic solvent in which a plurality of these are selected and mixed at an appropriate ratio. For the electrolyte, LiPF ₆ , LiB
F ₄ , LiClO ₄ , LiCF ₃ SO ₃ or the like can be used. The dissolution amount is 0.5 to 1.5 mol.
/ L is preferred.

In the former battery, an electrolyte is dissolved in an organic solvent, and at least one of naphthoquinone, fluorene, epoxide, 1,1-diphenyl-2-picrylhydrazyl and a HALS-based light stabilizer is added to the solution. To prepare a non-aqueous electrolyte. Here, the epoxide is not particularly limited, but 1,2-
It is desirably at least one of epoxy-3-phenoxypropane, 3,4-epoxycyclohexanecarboxylic acid, and 3,4-epoxycyclohexylmethyl. By selectively including these substances,
The cycle characteristics of the battery can be further improved.

The HALS-based light stabilizer is not particularly limited, but is preferably bis- (2,2,6,6-
Tetramethyl-4-piperidyl) separate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) separate, [dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2 succinate] , 6,6-tetramethylpiperidine] condensate, poly {[6- (1,
1,3,3-tetramethylbutyl) imino] -1,3
5-triazine-2,4-diyl [(2,2,6,6-
Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) iminol]}, tetragis (2,2,6,6-tetramethyl-4-piperidyl) 1 , 2,3,4-butanetetracarboxylate, and 1,2,2,6,6-
Pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,
It is desirably at least one of ester compounds of 4,8,10-tetrasubiro [5,5] undecane and butanetetracarboxylic acid. By selectively including these substances, the cycle characteristics of the battery can be further improved.

The non-aqueous electrolyte is naphthoquinone,
It is desirable to contain 1 to 0.0001 mol / L of at least one of fluorene, epoxide, 1,1-diphenyl-2-picrylhydrazyl and HALS-based light stabilizer. When the content is less than 0.0001 mol / L, the content is too small, and the cycle characteristics cannot be sufficiently improved. On the other hand, when the content exceeds 1 mol / L, the content is too large, and the functions of the organic solvent and the electrolyte are inhibited, so that the characteristics of the battery may be deteriorated.

Further, the non-aqueous electrolyte may contain benzotriazole and benzoquinone, in addition to at least one of naphthoquinone, fluorene, epoxide, 1,1-diphenyl-2-picrylhydrazyl and HALS-based light stabilizer. It is desirable to include any of them. The addition amount at this time is also preferably 1 to 0.0001 mol per liter of the non-aqueous electrolyte. By further including benzotriazole and benzoquinone in the non-aqueous electrolyte, the cycle characteristics of the battery can be further improved.

On the other hand, the latter battery can be prepared by dissolving an electrolyte in an organic solvent and adding both benzotriazole and benzoquinone to the solution when preparing the non-aqueous electrolyte. At this time, the amount of addition of both is not particularly limited. The order of addition is not particularly limited. The above naphthoquinone,
At least one of fluorene, epoxide, 1,1-diphenyl-2-picrylhydrazyl and a HALS-based light stabilizer, and additives of benzotriazole and benzoquinone, all of which have high purity and contain little water are used. Is preferred. This is because if water is mixed into the non-aqueous electrolyte through these additives, the characteristics of the battery may be deteriorated.

[0017]

The non-aqueous electrolyte secondary battery of the present invention is particularly excellent in cycle characteristics as compared with conventional batteries. This is based on naphthoquinone, fluorene, epoxide,
1,1-diphenyl-2-picrylhydrazyl and HA
This is because at least one of the LS light stabilizers, or benzotriazole and benzoquinone improve the cycle characteristics of the battery.

Although the cause of the improvement in the cycle characteristics of the battery is not clearly understood at present, these additives prevent the oxidation and reduction of the non-aqueous electrolyte and the polymerization during charging and discharging of the battery. It is considered that the non-aqueous electrolyte is prevented from decomposing and deteriorating by acting to suppress acid, trap a decomposed product of the solvent and radicals on the electrode surface, and the like. The effect of preventing the decomposition and deterioration of the non-aqueous electrolyte may involve an additive film formed by depositing the additive on the electrode surface.

[0019]

The present invention will be described below in detail with reference to examples. (Example 1) The nonaqueous electrolyte secondary battery of this example is a prismatic lithium secondary battery as schematically shown in FIG. In this battery 1, an electrode body 2 is immersed in a non-aqueous electrolyte (not shown) and fixedly arranged in a case 4. The electrode body 2 is formed by laminating a square plate-shaped positive electrode 22 and a negative electrode 24 with a separator 26 interposed therebetween.

As for the positive electrode 22, LiC is used as the positive electrode active material.
oO ₂ is used, and the LiCoO ₂ , the carbon material as the conductive material, and the polyvinylidene fluoride as the binder are mixed in 9%.
After mixing in a weight ratio of 4: 4: 2 and dispersing in n-methyl-2-pyrrolidone to prepare a slurry, the slurry was applied to an aluminum foil as a positive electrode current collector, and then pressed to increase the density. What was produced by using it was used.

For the negative electrode 24, a carbon material (graphite) having a d value (d _{0 2} ) of 0.337 nm or less on the lattice plane (002) plane is used as the negative electrode material. 9 with polyvinylidene fluoride
After mixing at a weight ratio of 2.5: 7.5 and dispersing in n-methyl-2-pyrrolidone to prepare a slurry, the slurry was applied to a copper foil serving as a negative electrode current collector, and then to increase the density. What was produced by pressing was used.

As the separator 26, a microporous film made of polyethylene was used. For non-aqueous electrolytes, ethylene carbonate (EC) and diethyl carbonate (D
EC), dimethyl carbonate (DMC) and ethyl methyl carbonate (EMC) in a volume ratio of 25:20:
1 mol / L of an electrolyte of LiPF ₆ was dissolved in a mixed organic solvent mixed at 15:40, and a solution obtained by adding 0.001 mol / L of naphthoquinone to this solution was used. (Example 2) In this example, except that 0.01 mol / L of fluorene was added instead of naphthoquinone,
A non-aqueous electrolyte was prepared in the same manner as described above. Using this non-aqueous electrolyte, a lithium secondary battery having the same configuration as the battery of Example 1 was produced. Comparative Example 1 In this comparative example, a solution of a mixed organic solvent and an electrolyte was prepared in the same manner as in Example 1, but no additive such as naphthoquinone was added to this solution. Using this solution as a non-aqueous electrolyte, a lithium secondary battery having the same configuration as in Example 1 was produced. [Evaluation of Cycle Characteristics] A charge / discharge test was performed using each of the batteries of Example 1, Example 2, and Comparative Example 1, and the cycle characteristics of each battery were evaluated.

In this charge / discharge test, the current density with respect to the area of the positive electrode was set to 3.1 mA / cm ² , and charging was first performed at a voltage of 4.
A series of charging / discharging was repeated for 30 cycles, in which the charging was performed at 2 V, and then the discharging was performed at a voltage of 3.0 V. Next, the current density with respect to the area of the positive electrode was changed to 0.62 mA / cm ² , charge / discharge was performed for one cycle at the same voltage as before, and the discharge capacity at this time was measured. These 31 cycles of charge / discharge were measured as a basic pattern.

With respect to each of the batteries of Examples 1 and 2, and Comparative Example 1, the above-mentioned basic pattern of charge and discharge was repeated 10 times, and the discharge capacity was measured. At that time, the discharge capacity ratio when the current density was 0.62 mA / cm ^{2 with} respect to the positive electrode area was plotted. FIG. 2 shows the measurement results. The graph of FIG. 2 shows the relationship between the number of charge / discharge cycles and the discharge capacity, and the magnitude of the discharge capacity was represented by a ratio (discharge capacity ratio) where the initial discharge capacity was 1.

FIG. 2 shows that all the batteries have the same initial discharge capacity. In addition, in the batteries of Example 1 and Example 2, the decrease in the discharge capacity ratio with the increase in the number of charge / discharge cycles is lower than that of the battery of Comparative Example 1. Therefore, from the results of this charge / discharge test, in a non-aqueous electrolyte secondary battery including a non-aqueous electrolyte in which an electrolyte is dissolved in an organic solvent, by adding naphthoquinone or fluorene to the non-aqueous electrolyte, It became clear that the charge-discharge cycle characteristics were improved without a decrease in the discharge capacity.

The reason why the addition of naphthoquinone to the non-aqueous electrolyte improves the charge / discharge cycle characteristics is not clearly understood. However, naphthoquinone traps radicals generated in the non-aqueous electrolyte to remove the radicals. It is considered that the cause is that the progress of the decomposition of the solvent is suppressed.
On the other hand, the cause of the improvement of the charge-discharge cycle characteristics by adding fluorene to the non-aqueous electrolyte is not clearly understood, but this additive dissolved in the non-aqueous electrolyte precipitates on the electrode surface. This is considered to be due to the fact that the formation of the film by the coating suppresses the decomposition of the solvent. (Example 3) In this example, nonaqueous electrolysis was performed in the same manner as in Example 1 except that 0.01 mol / L of 1,2-epoxy-3-phenoxypropane, which is a kind of epoxide, was added instead of naphthoquinone. A liquid was prepared. Using this non-aqueous electrolyte, a lithium secondary battery having the same configuration as the battery of Example 1 was produced. Example 4 In this example, 1,1-diphenyl-2-picrylhydrazyl was used in place of naphthoquinone for 0.0%.
A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that 1 mol / L was added. Example 1 using this non-aqueous electrolyte
A lithium secondary battery having the same configuration as the above battery was manufactured. (Embodiment 5) In this embodiment, H is used instead of naphthoquinone.
Poly {[6- (1,1,1) which is a kind of ALS light stabilizer
3,3-Tetramethylbutyl) imino] -1,3,5-
Triazine-2,4-diyl [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)
Iminol]｝ (hereinafter referred to as compound A) 3.94
A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that g / L (about 0.001 to 0.0001 mol / L) was added. Using this non-aqueous electrolyte, a lithium secondary battery having the same configuration as the battery of Example 1 was produced. [Evaluation of Cycle Characteristics] Each of the batteries of Examples 3 to 5 was subjected to the same charge / discharge test as the charge / discharge test of the battery of Example 1 described above. In this test, the basic pattern of charge and discharge was performed once, and the discharge capacity was measured. Table 1 shows the measurement results. For comparison, the measurement results of the battery of Comparative Example 1 are also shown in Table 1. In Table 1, the magnitude of the discharge capacity was represented by a ratio (discharge capacity ratio) when the initial discharge capacity was 1.

[0027]

[Table 1] Table 1 shows that in each of the batteries of Examples 3 to 5, the decrease in the discharge capacity ratio at the 31st charge / discharge cycle was lower than that of the battery of Comparative Example 1. Although not shown here, all the batteries had the same initial discharge capacity.

Therefore, according to the results of the charge / discharge test, in the non-aqueous electrolyte secondary battery including the non-aqueous electrolyte in which the electrolyte was dissolved in an organic solvent, 1,2-epoxy-3- Phenoxypropane, 1,1-diphenyl-2
-It became clear that the addition of either picrylhydrazyl or compound A improved the charge-discharge cycle characteristics without lowering the initial discharge capacity.

Although the cause of improving the charge-discharge cycle characteristics of the battery by adding 1,2-epoxy-3-phenoxypropane to the non-aqueous electrolyte is not clearly understood, this additive does not improve the charge-discharge cycle. It is considered that the cycle characteristics are improved by trapping impurities such as acid generated in the non-aqueous electrolytic solution. On the other hand, by adding 1,1-diphenyl-2-picrylhydrazyl,
Although the cause of the improvement in the charge / discharge cycle characteristics is not clearly understood, the same cause as when 1,2-epoxy-3-phenoxypropane is added is considered.

Although the cause of the improvement of the charge / discharge cycle characteristics by adding the compound A to the non-aqueous electrolyte is not clearly understood, the additive traps the radicals generated by the decomposition of the solvent. This is considered to be caused by suppressing the progress of the decomposition of the solvent. In Example 3, 1,2-epoxy-3-phenoxypropane was used as an additive, but the same action and effect can be obtained by using 3,4-epoxycyclohexanecarboxylic acid or 3,4-epoxycyclohexylmethyl. There is. (Example 6) EC, DEC and DMC were mixed at a volume ratio of 3
LiPF ₆ was added to the mixed organic solvent mixed at 5:45:20.
Was dissolved in 1 mol / L, and 0.0005 mol / L of naphthoquinone was added to this solution, and 0.005 mol / L of benzotriazole was further added to prepare a non-aqueous electrolyte. Using this non-aqueous electrolyte, a lithium secondary battery having the same configuration as the battery of Example 1 was produced. Example 7 In this example, benzoquinone was used in place of naphthoquinone, except that 0.005 mol / L of benzoquinone was used.
A non-aqueous electrolyte was prepared in the same manner as described above. That is, both benzoquinone and benzotriazole are added to this non-aqueous electrolyte. Using this non-aqueous electrolyte, a lithium secondary battery having the same configuration as the battery of Example 1 was produced. Comparative Example 2 In this comparative example, a solution of a mixed organic solvent and an electrolyte was prepared in the same manner as in Example 6, but no additive such as naphthoquinone was added to this solution. Using this solution as a non-aqueous electrolyte, a lithium secondary battery having the same configuration as in Example 1 was produced. Comparative Example 3 In this comparative example, a non-aqueous electrolyte was prepared in the same manner as in Example 6, except that 0.005 mol / L of benzotriazole alone was added without adding naphthoquinone.
Using this non-aqueous electrolyte, a lithium secondary battery having the same configuration as the battery of Example 1 was produced. (Comparative Example 4) In this comparative example, only benzoquinone was used in place of naphthoquinone and benzotriazole by 0.005 m.
A non-aqueous electrolyte was prepared in the same manner as in Example 6, except that ol / L was added. Using this non-aqueous electrolyte, a lithium secondary battery having the same configuration as the battery of Example 1 was produced. [Evaluation of Cycle Characteristics] The batteries of Examples 6 and 7 and Comparative Examples 2 to 4 were subjected to the same charge / discharge test as the charge / discharge test of the batteries of Example 1 described above. In this test, the basic pattern of charging and discharging was repeated seven times (21 times).
7 cycles) to measure the discharge capacity. Table 2 shows the measurement results. For comparison, the measurement results of the battery of Comparative Example 1 are also shown in Table 2. In Table 2, the magnitude of the discharge capacity was represented by a ratio (discharge capacity ratio) where the initial discharge capacity was 1.

[0031]

[Table 2] From Table 2, in each of the batteries of Example 6 and Example 7, the decrease in the discharge capacity ratio at the 217th charge / discharge cycle was lower than that of the batteries of Comparative Examples 2 to 4 Comparative Example. Recognize.

Therefore, from the results of this charge / discharge test, in a non-aqueous electrolyte secondary battery provided with a non-aqueous electrolyte in which an electrolyte was dissolved in an organic solvent, both naphthoquinone and benzotriazole were added to the non-aqueous electrolyte. It was clarified that the charge / discharge cycle characteristics were improved without decreasing the initial discharge capacity by adding benzoquinone and benzotriazole.

The cause of improving the charge / discharge cycle characteristics of the battery by adding both naphthoquinone and benzotriazole to the non-aqueous electrolyte is not clearly understood, but the following two causes are considered. . One is that naphthoquinone and benzotriazole both adhere to the electrode surface to form a mechanically strong film on the electrode surface, thereby inhibiting the dendrite deposition of metallic lithium. The other is that these additives dissolved in the non-aqueous electrolyte trap radicals generated by the decomposition of the solvent, thereby suppressing the decomposition of the solvent. Although neither idea has been clearly proved yet, it is considered that at least naphthoquinone and benzotriazole cooperate to improve the charge / discharge cycle characteristics.

On the other hand, the reason why the addition of both benzoquinone and benzotriazole to the non-aqueous electrolyte improves the charge / discharge cycle characteristics of the battery is not clearly understood. The same cause is considered as when both of the triazoles are added to the non-aqueous electrolyte. In Example 6, both naphthoquinone and benzotriazole were used as additives. Although not specifically exemplified here, it is clear that the cycle characteristics can be improved by using both naphthoquinone and benzoquinone. . The cause may be the same as the case where both naphthoquinone and benzotriazole are added to the non-aqueous electrolyte.

[0035]

According to the non-aqueous electrolyte secondary battery of the present invention, naphthoquinone, fluorene, epoxide, 1,
1-diphenyl-2-picrylhydrazyl and HALS
Because at least one of the light stabilizers, or both benzotriazole and benzoquinone are added,
It is difficult for the electrolyte to decompose and deteriorate during charging and discharging. As a result,
Excellent in charge / discharge cycle characteristics.

Therefore, the non-aqueous electrolyte secondary battery of the present invention is most suitable for applications where a long-life secondary battery is particularly required. For example, when the battery is used for a battery of an electronic device that is frequently used and is frequently charged and discharged, such as a mobile phone and a portable notebook personal computer, the electronic device can normally operate with one battery for a long period of time. This leads to a reduction in the number of times of replacement of the battery, which not only saves the user the trouble of replacement but also reduces the cost of replacement, which is very convenient economically.

[Brief description of the drawings]

FIG. 1 is a partial sectional view of a battery schematically illustrating a non-aqueous electrolyte secondary battery of Example 1. FIG.

FIG. 2 is a graph showing the charge / discharge cycle characteristics of each battery of Example 1, Example 2, and Comparative Example 1.

[Explanation of symbols]

1: Battery, 2: Electrode body 3: Case 22: Positive electrode 2
4: Negative electrode 26: Separator

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Masaru Urushihara 1-1-1, Showa-cho, Kariya-shi, Aichi Pref. Denso Corporation

Claims (7)

[Claims] 1. A non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte in which an electrolyte is dissolved in an organic solvent, wherein the non-aqueous electrolyte includes naphthoquinone, fluorene, epoxide, 1,1-diphenyl-2. -A non-aqueous electrolyte secondary battery to which at least one of picryl hydrazyl and hindered amine (HALS) light stabilizer is added. 2. The method according to claim 1, wherein said epoxide is 1,2-epoxy-3.
The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte secondary battery is at least one of phenoxypropane, 3,4-epoxycyclohexanecarboxylic acid, and 3,4-epoxycyclohexylmethyl. 3. The HALS-based light stabilizer comprises bis- (2,2).
2,6,6-tetramethyl-4-piperidyl) separate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) separate, [dimethyl-1- (2-succinate)
-Hydroxyethyl) -4-hydroxy-2,2,6
6-tetramethylpiperidine] condensate, poly {[6-
(1,1,3,3-tetramethylbutyl) imino]-
1,3,5-triazine-2,4-diyl [(2,2,
6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) iminol]} tetragis (2,2,6,6
-Tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate and 1,2,2,6
6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,
The non-aqueous electrolyte secondary battery according to claim 1, which is at least one of ester compounds of 4,8,10-tetrasubiro [5,5] undecane and butanetetracarboxylic acid. 4. The non-aqueous electrolyte contains at least one of naphthoquinone, fluorene, epoxide, 1,1-diphenyl-2-picrylhydrazyl and HALS-based light stabilizer in an amount of 1 to 0.0001 mol / L. The non-aqueous electrolyte secondary battery according to claim 1, wherein the secondary battery is added. 5. The non-aqueous electrolyte further comprises at least one of naphthoquinone, fluorene, epoxide, 1,1-diphenyl-2-picrylhydrazyl, HALS-based light stabilizer, benzotriazole and benzotriazole. The non-aqueous electrolyte secondary battery according to claim 1, wherein any one of benzoquinone is added. 6. A non-aqueous electrolyte secondary battery comprising a non-aqueous electrolyte in which an electrolyte is dissolved in an organic solvent, wherein benzotriazole and benzoquinone are added to the non-aqueous electrolyte. Non-aqueous electrolyte secondary battery. 7. The method according to claim 1, wherein the negative electrode is made of a carbon material.
7. The non-aqueous electrolyte secondary battery according to any one of 6.