JP5644732B2 - Nonaqueous electrolyte secondary battery - Google Patents

Description

  The present invention relates to a non-aqueous electrolyte secondary battery.

  In a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, as a safety measure at the time of overcharge, a current interruption mechanism that interrupts current when the battery internal pressure exceeds a predetermined value may be mounted (for example, a patent Reference 1, paragraph 0094). In a nonaqueous electrolyte secondary battery having a current interruption mechanism, an overcharge inhibitor that is oxidized and decomposed to generate protons during overcharge is added to the nonaqueous electrolyte. In such a configuration, at the time of overcharging, the overcharge preventing agent is decomposed to generate protons, and the protons are reduced at the negative electrode to generate hydrogen gas to increase the internal pressure. This is detected and the current is cut off.

Patent Document 1 discloses, as an overcharge inhibitor, in the description of the prior art, biphenyls, alkylbenzenes, alkyl compounds substituted with two aromatic groups, fluorine atom-substituted aromatic compounds, and chlorine atom-substituted biphenyls. (Paragraphs 0009, 0011, and 0014).
Claim 1 of Patent Document 1 includes at least one chlorine atom-substituted fragrance selected from the group consisting of chlorine atom-substituted biphenyl, chlorine atom-substituted naphthalene, chlorine atom-substituted fluorene, and chlorine atom-substituted diphenylmethane as an overcharge inhibitor. Group compounds are mentioned.

JP 2004-087168 A

  In a non-aqueous electrolyte secondary battery equipped with a current interruption mechanism, if the operating pressure of the current interruption mechanism is set low, the internal pressure due to factors other than overcharge to be detected originally, such as internal pressure fluctuations within the normal range or external impacts There is a risk that the current will be cut off by detecting the rise. In order to prevent such malfunction, it is preferable to increase the amount of gas generated during overcharge and to set the operating pressure of the current interrupt mechanism higher.

  Measures for increasing the amount of gas generated during overcharging include increasing the reaction area of the decomposition reaction and proton generation reaction of the overcharge inhibitor, or increasing the amount of addition of the overcharge inhibitor.

In applications such as plug-in hybrid vehicles (PHV) or electric vehicles (EV), high capacity is required for lithium ion secondary batteries.
However, when the above measures are implemented, the battery capacity tends to decrease.

  In order to increase the battery capacity of the lithium ion secondary battery, it is preferable that the specific surface area of the negative electrode active material made of carbon or the like is small. However, when the specific surface area of the negative electrode active material is decreased, the proton reduction performance in the negative electrode is lowered, and the hydrogen gas generation amount tends to be reduced.

  If the specific surface area of the negative electrode active material is increased, protons are easily reduced at the negative electrode, and the amount of hydrogen gas generated can be increased. However, when the specific surface area of the negative electrode active material is increased, the battery capacity tends to decrease.

  As described above, in the conventional nonaqueous electrolyte secondary battery, the battery capacity and the amount of gas generated at the time of overcharging are contradictory characteristics, and it is difficult to achieve both of them.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a non-aqueous electrolyte secondary battery that can increase the amount of gas generated during overcharge without impairing battery performance such as battery capacity. It is what.

The non-aqueous electrolyte secondary battery of the present invention is
A positive electrode, a negative electrode including a negative electrode active material, a non-aqueous electrolyte to which an additive that is oxidatively decomposed and generates protons during overcharge is added, and a current blocking mechanism that blocks current when a battery internal pressure exceeds a predetermined value. A non-aqueous electrolyte secondary battery comprising:
A catalyst having a proton reducing action is supported on the particle surface of the negative electrode active material.

  ADVANTAGE OF THE INVENTION According to this invention, the nonaqueous electrolyte secondary battery which can raise the gas generation amount at the time of overcharge can be provided, without impairing battery performance, such as battery capacity.

1 is an overall view schematically showing a configuration example of a nonaqueous electrolyte secondary battery according to the present invention. It is a fragmentary sectional view of the nonaqueous electrolyte secondary battery of FIG. It is a table | surface which shows the relationship between the particle diameter of a negative electrode active material, a specific surface area, an image figure, battery capacity, and hydrogen gas generation amount in the negative electrode active material of the past and this invention. In [Example], it is a graph which shows the relationship between the specific surface area of a negative electrode active material, and battery capacity. In [Example], it is a graph which shows the relationship between the specific surface area of a negative electrode active material, and a capacity | capacitance maintenance factor. In [Example], it is a graph which shows the relationship between the presence or absence of catalyst loading in the negative electrode active material, the specific surface area of the negative electrode active material, and the amount of gas generated.

Hereinafter, the present invention will be described in detail.
The non-aqueous electrolyte secondary battery of the present invention includes a positive electrode, a negative electrode containing a negative electrode active material, a non-aqueous electrolyte to which an additive that is oxidized and decomposed during overcharge to generate protons, and the internal pressure of the battery is equal to or higher than a predetermined value. Then, a current interrupting mechanism for interrupting the current is provided, and a catalyst having a proton reducing action is supported on the particle surface of the negative electrode active material.

  Hereinafter, an additive that is oxidatively decomposed to generate protons during overcharge is referred to as an “overcharge inhibitor”.

  FIG. 1 and FIG. 2 schematically show a configuration example of a nonaqueous electrolyte secondary battery. 1 is an overall view, and FIG. 2 is a partial cross-sectional view. Both are schematic diagrams.

A non-aqueous electrolyte secondary battery 1 shown in FIG. 1 is a battery in which a laminate 20 shown in FIG. 2 and a non-aqueous electrolyte (reference numeral omitted) to which an overcharge preventing agent is added are accommodated in an exterior body 11. is there.
The laminate 20 includes a positive electrode 21 in which a particulate positive electrode active material is applied on a current collector, a negative electrode 22 in which a particulate negative electrode active material is applied on a current collector, and a resin separator 23. It has been done.

  The nonaqueous electrolyte secondary battery 1 is provided with a current interruption mechanism 13 that interrupts current when the internal pressure of the battery becomes a predetermined value or more in the exterior body 11. The installation location of the current interruption mechanism 13 is designed according to the current interruption action.

  In the nonaqueous electrolyte secondary battery provided with the current interruption mechanism 13, an overcharge inhibitor that is oxidized and decomposed during overcharge to generate protons is added to the nonaqueous electrolyte. In such a configuration, during overcharging, the overcharge inhibitor in the non-aqueous electrolyte is decomposed to generate protons, and the protons are reduced at the negative electrode to generate hydrogen gas. The internal pressure of the battery rises due to this gas generation, and the current is interrupted by the current interrupt mechanism 13.

A known mechanism can be adopted as the current interrupt mechanism 13.
The current interrupting mechanism 13 includes a structure that is deformed by increasing the battery internal pressure and cuts the contact point of the charging current, an external circuit that detects the battery internal pressure by the sensor and stops charging, and the battery deformation due to the battery internal pressure is detected by the sensor. Examples include an external circuit that detects and stops charging, and a structure that deforms when the battery internal pressure rises to short-circuit the positive electrode and the negative electrode.
For example, a structure that is deformed by cutting the contact point of the charging current by increasing the battery internal pressure is preferable because it has a simple structure and a high current blocking effect.

  Two terminals (a plus terminal and a minus terminal) 12 for external connection are provided on the outer surface of the exterior body 11.

Examples of the non-aqueous electrolyte secondary battery include a lithium ion secondary battery.
Hereinafter, the main components of the nonaqueous electrolyte secondary battery will be described by taking a lithium ion secondary battery as an example.

<Positive electrode>
The positive electrode can be manufactured by applying a positive electrode active material to a positive electrode current collector such as an aluminum foil by a known method.
Known no particular limitation on the positive electrode active material, for _{example, LiCoO 2, LiMnO 2, LiMn} 2 O 4, LiNiO 2, LiNi x Co (1-x) O 2, and _{LiNi x Co y Mn (1-} x-y _And lithium-containing composite oxides such as O ₂ (where 0 <x <1, 0 <y <1).

For example, using a dispersant such as N-methyl-2-pyrrolidone, the above positive electrode active material, a conductive agent such as carbon powder, and a binder such as polyvinylidene fluoride (PVDF) are mixed to form a slurry. The slurry can be applied onto a current collector such as an aluminum foil, dried, and pressed to obtain a positive electrode.
The basis weight of the positive electrode is not particularly limited and is preferably 1.5 to 15 mg / cm ² . If the basis weight of the positive electrode is too small, uniform application is difficult, and if it is too large, there is a risk of peeling from the current collector.

<Negative electrode>
The negative electrode can be produced by applying a negative electrode active material to a negative electrode current collector such as a copper foil by a known method.
The negative electrode active material is not particularly limited, and a material having a lithium storage capacity of 2.0 V or less on the basis of Li / Li + is preferably used. As the negative electrode active material, carbon such as graphite, metallic lithium, lithium alloy, transition metal oxide / transition metal nitride / transition metal sulfide capable of doping / dedoping lithium ions, and these A combination etc. are mentioned.

For example, using a dispersant such as water, the negative electrode active material described above, a binder such as a modified styrene-butadiene copolymer latex, and a thickener such as carboxymethyl cellulose Na salt (CMC) as necessary. Mixing is performed to obtain a slurry, and this slurry is applied onto a negative electrode current collector such as a copper foil, dried, and pressed to obtain a negative electrode.
The basis weight of the negative electrode is not particularly limited and is preferably 1.5 to 15 mg / cm ² . If the basis weight of the negative electrode is too small, uniform application is difficult, and if it is too large, there is a risk of peeling from the current collector.

  In a lithium ion secondary battery, a carbon material capable of inserting and extracting lithium is widely used as a negative electrode active material. In particular, highly crystalline carbon such as graphite has characteristics such as a flat discharge potential, high true density, and good fillability. Therefore, many negative electrode actives of commercially available lithium ion secondary batteries are used. It is used as a substance. Accordingly, graphite and the like are particularly preferable as the negative electrode active material.

In the nonaqueous electrolyte secondary battery of the present invention, at least one type of catalyst having a proton reducing action is supported on the surface of the negative electrode active material particles.
Any catalyst may be used as long as it has a proton reducing action. At least one selected from the group consisting of Pt, Ru, Rh, Pd, Au, and Ag, a metal compound containing these, and a combination thereof Etc. are preferred.

The method for supporting the catalyst on the particle surface of the negative electrode active material is not particularly limited.
For example, when a Pt catalyst is used, an aqueous solution of H ₂ PtCl ₆ (hexachloroplatinic acid) and a negative electrode active material such as graphite are mixed, and this is heated and reduced to support the Pt catalyst on the particle surface of the negative electrode active material. Can be made.
The amount of the catalyst supported is not particularly limited, and can be supported up to 30 to 40% by mass with respect to the negative electrode active material. The supported amount of the catalyst is preferably 2 to 10% by mass with respect to the negative electrode active material.

As described in the section “Problems to be Solved by the Invention”, the prior art has the following problems.
In order to increase the amount of gas generated during overcharge, if the reaction area of the decomposition reaction and proton generation reaction of the overcharge inhibitor is increased or the amount of addition of the overcharge inhibitor is increased, the battery capacity tends to decrease. is there.
In order to increase the battery capacity, it is preferable that the specific surface area of the negative electrode active material is small. However, if the specific surface area of the negative electrode active material is decreased by increasing the particle size of the negative electrode active material, the proton reduction performance in the negative electrode is reduced. Therefore, the hydrogen gas generation amount tends to decrease.
If the specific surface area is increased by reducing the particle size of the negative electrode active material, the amount of hydrogen gas generated can be increased, but the battery capacity tends to decrease.

In the present invention, a catalyst having a proton reducing action is supported on the particle surface of the negative electrode active material, thereby reducing the particle size of the negative electrode active material and increasing the specific surface area of the negative electrode active material. Reduction performance can be improved and the amount of hydrogen gas generation can be increased.
In the present invention, since it is not necessary to increase the specific surface area of the negative electrode active material, the effect of increasing the amount of hydrogen gas generated can be obtained without reducing the battery capacity.

  Regardless of whether or not the catalyst is supported, generally, the smaller the specific surface area of the negative electrode active material, the lower the lithium deposition resistance when charging and discharging are repeated, and the capacity retention rate tends to decrease (see FIG. 5). ). Further, as the specific surface area of the negative electrode active material increases, the irreversible capacity of the negative electrode active material made of graphite or the like increases and the battery capacity tends to decrease (see FIG. 4).

Conventionally, in a lithium ion secondary battery or the like mounted on a plug-in hybrid vehicle (PHV) or an electric vehicle (EV), the specific surface area of a negative electrode active material such as graphite is generally 2.5 to 5.0 m ² / It is used within the range of g.
In the present invention, the specific surface area of the negative electrode active material is preferably 2.0 to 3.5 m ² / g. Within such a range, it is possible to provide a nonaqueous electrolyte secondary battery in which both the battery capacity and the capacity retention rate upon repeated charge / discharge are good.
In the present invention, since the catalyst is supported on the surface of the negative electrode active material, the reducing action at the negative electrode works effectively not only during overcharge but also during normal use. Therefore, even if the specific surface area of the negative electrode active material is set lower than before, good characteristics can be obtained.

  FIG. 3 shows a particle size, specific surface area, and image diagram of the negative electrode active material, and a table showing the relative relationship between the battery capacity and the amount of hydrogen gas generation in the conventional and the negative electrode active materials of the present invention. “Large”, “small”, “many”, and “small” in the table indicate relative relationships. In the drawing, reference numeral 31 denotes particles of the negative electrode active material, and reference numeral 32 denotes a catalyst.

In the figure, “Conventional 1” is one in which the diameter of the negative electrode active material is relatively small, the specific surface area is relatively large, 3.5 m ² / g or more, and no catalyst is supported. In the lithium ion secondary battery using this negative electrode active material, the amount of hydrogen gas generated is relatively large, but the battery capacity is relatively small.
“Conventional 2” has a negative electrode active material having a relatively large diameter, a relatively small specific surface area, 2.0 to 3.5 m ² / g, and no catalyst supported. In the lithium ion secondary battery using this negative electrode active material, the battery capacity is relatively large, but the hydrogen gas generation amount is relatively small.
In the present invention, the negative electrode active material has a relatively large diameter, a relatively small specific surface area, 2.0 to 3.5 m ² / g, and a catalyst supported. In a lithium ion secondary battery using this negative electrode active material, the battery capacity is relatively large and the amount of hydrogen gas generated is relatively large. In other words, the “present invention” covers both the disadvantages of “Conventional 1” and “Conventional 2” and has good characteristics.

  Refer to FIG. 6 for an example of the relationship between the presence or absence of catalyst loading in the negative electrode active material, the specific surface area of the negative electrode active material, and the amount of hydrogen gas generated.

<Nonaqueous electrolyte>
As the non-aqueous electrolyte, known ones can be used, and liquid, gel-like or solid non-aqueous electrolytes can be used.
For example, a lithium-containing electrolyte is dissolved in a mixed solvent of a high dielectric constant carbonate solvent such as propylene carbonate or ethylene carbonate and a low viscosity carbonate solvent such as diethyl carbonate, methyl ethyl carbonate, or dimethyl carbonate. A water electrolysis solution is preferably used.

As the mixed solvent, for example, a mixed solvent of ethylene carbonate (EC) / dimethyl carbonate (DMC) / ethyl methyl carbonate (EMC) is preferably used.
Examples of the lithium-containing electrolyte include LiPF ₆ , LiBF ₄ , LiClO ₄ , LiAsF ₆ , Li ₂ SiF ₆ , LiOSO ₂ C _k F _{(2k + 1)} (k = 1 to 8), LiPF _n {C _k F _{(2k + 1) )} (6-n) (} n = 1~5 integer, k = 1 to 8 integer) lithium salts such as, and combinations thereof.

  As the overcharge inhibitor that decomposes during overcharge and generates protons, known ones can be used. For example, one or more of the overcharge inhibitors described in Patent Document 1 listed in the “Background Art” section can be used. Seeds can be used.

Patent Document 1 discloses, as an overcharge inhibitor, in the description of the prior art, biphenyls, alkylbenzenes, alkyl compounds substituted with two aromatic groups, fluorine atom-substituted aromatic compounds, and chlorine atom-substituted biphenyls. (Paragraphs 0009, 0011, and 0014).
Claim 1 of Patent Document 1 includes at least one chlorine atom-substituted fragrance selected from the group consisting of chlorine atom-substituted biphenyl, chlorine atom-substituted naphthalene, chlorine atom-substituted fluorene, and chlorine atom-substituted diphenylmethane as an overcharge inhibitor. Group compounds are mentioned.

<Separator>
The separator may be a film that electrically insulates the positive electrode and the negative electrode and is permeable to lithium ions, and a porous polymer film is preferably used.
As the separator, for example, a porous film made of polyolefin such as a porous film made of PP (polypropylene), a porous film made of PE (polyethylene), or a laminated porous film of PP (polypropylene) -PE (polyethylene) is preferably used. It is done.

<Exterior body>
A well-known thing can be used as an exterior body.
As a type of the secondary battery, there are a cylindrical type, a coin type, a square type, a film type (laminate type), and the like, and an exterior body can be selected according to a desired type.

  ADVANTAGE OF THE INVENTION According to this invention, the nonaqueous electrolyte secondary battery which can raise the gas generation amount at the time of overcharge can be provided, without impairing battery performance, such as battery capacity.

  Examples and comparative examples according to the present invention will be described.

[Preliminary experiment]
<Positive electrode active material>
As the positive electrode active material, a ternary lithium composite oxide represented by the following formula was used.
LiMn _1/3 Co _1/3 Ni _1/3 O ₂

<Production of positive electrode>
Using N-methyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersant, the above positive electrode active material and acetylene black as a conductive agent (HS-100, manufactured by Denki Kagaku Kogyo Co., Ltd.) And PVDF (KF polymer # 1120 manufactured by Kureha Co., Ltd.) as a binder were mixed at 90/6/4 (mass ratio) to obtain a slurry.
The slurry was applied onto an aluminum foil as a current collector by a doctor blade method, dried at 150 ° C. for 30 minutes, and pressed using a press machine to obtain a positive electrode. The positive electrode had a basis weight of 15 mg / cm ² and a thickness of 70 μm.

<Negative electrode>
As the negative electrode active material, the following graphites having different specific surface areas (all without catalyst support) were used.
Graphite with a specific surface area of 1.5 m ² / g,
Graphite with a specific surface area of 2.0 m ² / g,
Graphite with a specific surface area of 3.0 m ² / g,
Graphite with a specific surface area of 4.0 m ² / g.

Using water as a dispersant, the negative electrode active material, a modified styrene-butadiene copolymer latex (SBR) as a binder, and a carboxymethyl cellulose Na salt (CMC) as a thickener are 98/1 / 1 (mass ratio) was mixed to obtain a slurry.
The slurry was applied onto a copper foil as a current collector by a doctor blade method, dried at 150 ° C. for 30 minutes, and pressed using a press machine to obtain a negative electrode. The negative electrode had a basis weight of 8 mg / cm ² and a thickness of 70 μm.

<Separator>
A commercially available separator made of a PE (polyethylene) porous film was prepared.

<Nonaqueous electrolyte>
A mixed solution of ethylene carbonate (EC) / dimethyl carbonate (DMC) / ethyl methyl carbonate = 3/3/4 (volume ratio) is used as a solvent, and LiPF ₆ which is a lithium salt as an electrolyte is dissolved at a concentration of 1 mol / L. Furthermore, 2 mass% of cyclohexylbenzene (CHB) was dissolved as an overcharge inhibitor to prepare a non-aqueous electric field solution.

<Manufacture of lithium ion secondary batteries>
A film-type (laminate-type) lithium ion secondary battery was manufactured by a known method using the positive electrode, the negative electrode, the separator, the non-aqueous electrolyte, and the film outer package.

<Charge / discharge test>
A charge / discharge test was performed on each lithium ion secondary battery obtained in the preliminary experiment.
At 25 ° C., one cycle of charge / discharge was performed under the conditions of a charge voltage of 4.1 V (vs. Li / Li +), a discharge voltage of 3.0 V (vs. Li / Li +), and a current density of 1 C. The CCCV capacity at this time was determined as the battery capacity.
In addition, 10,000 cycles of charging / discharging were performed at −30 ° C. under the conditions of SOC 60%, 4C, and then discharging. The capacity retention rate at this time was determined.

4 and 5 show the relationship between the specific surface area of the negative electrode active material and the battery capacity, and the relationship between the specific surface area of the negative electrode active material and the capacity retention rate, respectively. These figures are obtained when the data of the specific surface area of the negative electrode active material being 4.0 m ² / g is 100%.

It was shown that when the catalyst is not supported, the battery capacity tends to decrease as the specific surface area of the negative electrode active material increases. Considering the battery capacity, it was shown that the specific surface area of the negative electrode active material is preferably 3.5 m ² / g or less.
It was shown that when the catalyst is not supported, the capacity retention rate (Li precipitation resistance) tends to decrease as the specific surface area of the negative electrode active material decreases. Considering the capacity retention rate, it was shown that the specific surface area of the negative electrode active material is preferably 2.0 m ² / g or more.
The specific surface area of the preferred negative electrode active material is the same regardless of whether or not the catalyst is supported on the negative electrode active material.

Example 1
As the negative electrode active material, a graphite having a specific surface area of 2 m ² / g and carrying a Pt catalyst was used.
An aqueous solution of H ₂ PtCl ₆ (hexachloroplatinic acid) and graphite were mixed at 90:10 (solid content mass ratio), and this was heated and reduced at 120 ° C. for 15 hours, so that a Pt catalyst was formed on the particle surface of the negative electrode active material. Was supported. The amount of Pt catalyst supported was 10% by mass with respect to graphite. Using this as a negative electrode active material, a lithium ion secondary battery was produced in the same manner as in the preliminary experiment.

<Overcharge test>
An overcharge test was performed on the lithium ion secondary battery obtained in the preliminary experiment and Example 1.
The amount of gas generated when the battery was once overcharged under the conditions of SOC 150%, 4C at 25 ° C. was determined by the buoyancy method (Archimedes method). Before and after overcharging, a film type (laminate type) lithium ion secondary battery was immersed in water, the volume was determined from buoyancy, and the volume change before and after overcharging was determined as the amount of gas generated. This gas generation amount can be regarded as the hydrogen gas generation amount.

In a preliminary experiment, a lithium ion secondary battery obtained using graphite having a specific surface area of 4.0 m ² / g (no catalyst supported) as a negative electrode active material was used as Comparative Example 1.
In a preliminary experiment, a lithium ion secondary battery obtained using graphite (no catalyst support) having a specific surface area of 2.0 m ² / g as a negative electrode active material was used as Comparative Example 2.

The results are shown in FIG.
FIG. 6 is data when the gas generation amount in Comparative Example 1 is 100%.
As shown in the figure, in Example 1 in which a catalyst was supported on graphite, the amount of hydrogen gas generated could be significantly increased compared to Comparative Example 2 using graphite having the same specific surface area and no catalyst. Further, in Example 1 in which the catalyst was supported on graphite, the amount of hydrogen gas generated could be increased compared to Comparative Example 1 in which graphite having a large specific surface area and no catalyst was supported. From these results, it was shown that by supporting the catalyst on the surface of the negative electrode active material, the amount of hydrogen gas generated can be increased without increasing the specific surface area of the negative electrode active material.

  The nonaqueous electrolyte secondary battery of the present invention can be preferably applied to a lithium ion secondary battery mounted on a plug-in hybrid vehicle (PHV) or an electric vehicle (EV).

DESCRIPTION OF SYMBOLS 1 Nonaqueous electrolyte secondary battery 11 Exterior body 12 Terminal 13 Current interruption | blocking mechanism 20 Laminated body 21 Positive electrode 22 Negative electrode 23 Resin separator 31 Negative electrode active material 32 Catalyst

Claims (6)

A positive electrode, a negative electrode containing a negative electrode active material, a non-aqueous electrolyte to which an overcharge inhibitor that is oxidatively decomposed and generates protons during overcharge, and a current interruption mechanism that cuts off current when the battery internal pressure exceeds a predetermined value A non-aqueous electrolyte secondary battery comprising:
The overcharge inhibitor is a chlorine atom-substituted aromatic compound and / or a fluorine atom-substituted aromatic compound ,
A non-aqueous electrolyte secondary battery in which a catalyst having a proton reducing action is supported on the surface of particles of the negative electrode active material. 2. The overcharge inhibitor is at least one chlorine atom-substituted aromatic compound selected from the group consisting of chlorine atom-substituted biphenyl, chlorine atom-substituted naphthalene, chlorine atom-substituted fluorene, and chlorine atom-substituted diphenylmethane. The nonaqueous electrolyte secondary battery as described.

The non-aqueous electrolyte secondary battery according to claim 1 , wherein the negative electrode active material has a specific surface area of 2.0 to 3.5 m ² / g. The non-aqueous electrolyte secondary battery according to claim 1 , wherein the catalyst includes at least one selected from the group consisting of Pt, Ru, Rh, Pd, Au, and Ag. The non-aqueous electrolyte secondary battery according to claim 1 , wherein the negative electrode active material is graphite. It is a lithium ion secondary battery, The nonaqueous electrolyte secondary battery in any one of Claims 1-5 .

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