JP2002042864A - Nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte secondary battery with improved high temperature retaining characteristic after charged and a charge-discharge cycle characteristic. SOLUTION: This nonaqueous electrolyte secondary battery comprises a positive electrode and a negative electrode reversible in relation to charge and discharge, and a nonaqueous electrolyte containing an electrolyte and a silane coupling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-aqueous electrolyte secondary battery having a high energy density and a method for manufacturing the same.

[0002]

2. Description of the Related Art Lithium (Li) or sodium (N)
A non-aqueous electrolyte secondary battery using an alkali metal such as a) for the negative electrode has a high electromotive force and is expected to have a higher energy density than conventional nickel cadmium storage batteries and lead storage batteries. Above all, many studies have been made especially on non-aqueous electrolyte secondary batteries using Li for the negative electrode.However, if a single alkali metal is used for the negative electrode, dendrites are generated during charging, short-circuits are likely to occur, and reliability is high. There is a problem that the battery becomes low. On the other hand, use of an alloy of Li and aluminum (Al) or lead (Pb) for the negative electrode has been studied. When these alloys are used for the negative electrode, Li is occluded in the alloy of the negative electrode during charging, so that dendrite does not occur and a highly reliable battery is obtained. However, since the discharge potential of these alloys is about 0.5 V more noble than that of metal Li, the voltage of the obtained battery is also about 0.5 V.
There is a problem that V decreases and the energy density also decreases.

On the other hand, a negative electrode active material comprising an intercalation compound of carbon (C) and Li such as graphite has also been studied, and a battery using the same has been put to practical use under the name of "lithium ion secondary battery". . In this battery, even in the negative electrode using the above-mentioned intercalation compound, dendrite does not occur because Li enters the C layer by charging. Further, this negative electrode has a discharge potential of about 0.1 V as compared with metal Li.
Since it is only noble and the decrease in the voltage of the obtained battery is small, it can be said that the negative electrode is more preferable. However, when charging
In the case of graphite, the maximum amount of Li that can enter between layers is theoretically an amount capable of forming C ₆ Li, and the electric capacity at that time is 372 Ah / kg. Therefore, materials that can provide a high capacity exceeding the above-mentioned theoretical value using carbon having lower crystallinity than graphite, various alloys, metal oxides, and the like have been successively proposed.

[0004] Further, as the performance of non-aqueous electrolyte secondary batteries is typified by higher capacities, the dispersibility of electrode mixture slurries is improved, and a decrease in battery capacity due to charge / discharge cycles is suppressed. A technique for pretreating a positive electrode active material or a negative electrode active material with a silane coupling agent has been proposed (for example,
JP-A-10-125307, JP-A-09-50869
And JP-A-11-354104. Further, for the purpose of increasing the adhesiveness between the current collector plate and the active material mixture, a technique has been proposed in which a coupling agent layer is provided between the current collector surface and the active material layer, or a coupling agent is mixed with a coating liquid. (For example, JP-A-09-237625, JP-A-200
0-30694 and JP-A-09-306472.

[0005]

The emergence of a negative electrode material having a higher capacity than a carbon material such as graphite as described above has realized a nonaqueous electrolyte secondary battery having a large discharge capacity. As a result, the electrode can store a large amount of electricity per unit weight or unit volume, and as the charge / discharge cycle progresses, the non-aqueous electrolyte is decomposed on the negative electrode or the positive electrode, and the discharge capacity gradually decreases. The problem is that it does. In addition, if the battery becomes high voltage while the battery is stored in a charged state, a decomposition reaction of the non-aqueous electrolyte occurs on the negative electrode or the positive electrode particularly at a high temperature. Further, there is a problem that the capacity is deteriorated due to the elution of transition metal ions constituting the positive electrode active material, and the non-aqueous electrolyte itself is deteriorated due to a thermal reaction, thereby deteriorating battery characteristics. Therefore, the present invention
By electrochemically stabilizing the non-aqueous electrolyte, side reactions between the non-aqueous electrolyte and the negative electrode or the positive electrode are suppressed, and furthermore, the deterioration due to the thermal reaction of the non-aqueous electrolyte and the battery accompanying the charge / discharge cycle It is an object of the present invention to provide a non-aqueous electrolyte secondary battery in which a decrease in discharge capacity and a decrease in battery characteristics due to deterioration of a positive electrode active material and a negative electrode active material during storage at a high temperature are suppressed.

[0006]

According to the present invention, there is provided a chargeable / dischargeable positive electrode, a nonaqueous electrolyte, and a chargeable / dischargeable negative electrode, wherein the nonaqueous electrolyte contains a silane coupling agent. Non-aqueous electrolyte secondary battery. The silane coupling agent may be N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β
-(Aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-
It is effective that at least one selected from the group consisting of aminopropyltrimethoxysilane and bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane.

Further, it is effective that the non-aqueous electrolyte comprises a non-aqueous solvent containing a cyclic carbonate and a chain carbonate, and a Li salt. It is effective that the weight ratio of the silane coupling agent in the nonaqueous electrolyte is 0.1 to 10% by weight. Further, the positive electrode is made of LiCoO ₂ , Li
It is effective to include at least one active material selected from the group consisting of Mn ₂ O ₄ , LiNiO ₂ and LiFeO ₂ . The negative electrode is a Li-based alloy including at least one selected from the group consisting of Sn, Si, Al and In, and at least one selected from the group consisting of a Li-based compound, carbon, carbon, and metal Li. It is effective to include some active materials.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present inventors have been studying to obtain an electrochemically stable non-aqueous electrolyte solution to solve the above-mentioned problems. It has been known that a technique for pretreating a positive electrode active material or a negative electrode active material with a silane coupling agent has been proposed (for example, JP-A-10-125307). However, for example, JP-A-10-125307 does not positively describe the electrochemical stability of a non-aqueous electrolyte by adding various silane coupling agents to the non-aqueous electrolyte, In particular, it does not describe the reactivity of the nonaqueous electrolyte with the positive electrode active material or the negative electrode active material during storage of the battery at a high temperature, and the deterioration of the positive electrode active material or the negative electrode active material.

The inventors of the present invention have conducted intensive experiments on including a silane coupling agent in a non-aqueous electrolytic solution. As a result, if the silane coupling agent is contained in the non-aqueous electrolytic solution, The present inventors have found that electrochemical stabilization can be achieved and that a side reaction between a nonaqueous electrolyte and a negative electrode or a positive electrode can be suppressed, and the present invention has been completed. That is, the nonaqueous electrolyte secondary battery of the present invention includes a chargeable / dischargeable positive electrode, a nonaqueous electrolyte containing an electrolyte, and a chargeable / dischargeable negative electrode, and the nonaqueous electrolyte uses a silane coupling agent. It is characterized by including. First, the non-aqueous electrolyte which is the most significant feature of the present invention will be described. The non-aqueous electrolyte of the present invention contains a solvent and an electrolyte as well as a normal non-aqueous electrolyte, and also contains a silane coupling agent.

Various examples of such silane coupling agents include, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane,
β- (3,4 epoxycyclohexyl) ethyltrimethylsilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxymethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane , Γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (Aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β-
(Aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane and the like can be mentioned.

These can be used alone or in any combination as long as the effects of the present invention are not impaired. Above all, N-β- is preferred because of its high electrochemical stability when contained in the electrolyte.
(Aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxy Using at least one selected from the group consisting of silane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane Is preferred.

The weight ratio of the silane coupling agent in the non-aqueous electrolyte is preferably 0.1 to 10% by weight. If the content is less than 0.1% by weight, the effect of suppressing the decomposition of the nonaqueous electrolyte on the negative electrode or the positive electrode and the deterioration of the nonaqueous electrolyte itself due to the thermal reaction cannot be obtained sufficiently, and
This is because, when it exceeds, the ionic conductivity of the non-aqueous electrolyte is easily damaged. Further, the weight ratio of the silane coupling agent in the nonaqueous electrolyte is 0.5 to 5% by weight because the effect of the present invention can be maximized without adversely affecting various characteristics of the battery. It is preferred that

The solvent constituting the non-aqueous electrolyte of the present invention may be any known solvent, such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 2-dimethoxyethane, γ-butyrolactone, tetrahydrofuran, 2
-Methyltetrahydrofuran, dimethylsulfoxide, dioxolan, 1,3-dioxolan, formamide, dimethylformamide, nitromethane, acetonitrile, methyl formate, methyl acetate, methyl propionate,
Examples include trimethoxymethane, dioxolane derivatives, sulfolane, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, diethyl ether and 1,3-propanesultone. These can be used alone or in any combination as long as the effects of the present invention are not impaired.

Among them, it is preferable to use a mixture of two or more kinds of cyclic carbonates such as ethylene carbonate and propylene carbonate and chain carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate. The weight ratio of the solvent in the non-aqueous electrolyte is not particularly limited as long as the effect of the present invention is not impaired, but may be, for example, 80 to 95% by weight.

As the electrolyte contained in the non-aqueous electrolyte of the present invention, conventionally known electrolytes can be used.
iClO ₄ , LiBF ₄ , LiPF ₆ , LiCF ₃ SO ₃ ,
_{LiCF 3 CO 2, LiAsF 6,} LiSbF 6, LiB 10
Cl ₁₀ , lithium lower aliphatic carboxylate, LiAlCl
₄ , Li salts such as LiCl, LiBr, LiI, lithium chloroborane and lithium tetraphenylborate are useful. These can be used alone or in any combination as long as the effects of the present invention are not impaired. In addition to the Li salt, a sodium-containing salt, a magnesium-containing salt, an aluminum-containing salt, a potassium-containing salt, a rubidium-containing salt, a calcium-containing salt, and the like can be used. The weight ratio of the electrolyte in the non-aqueous electrolyte is not particularly limited as long as the effect of the present invention is not impaired. However, for example, 5% is preferable because sufficient conductivity can be obtained as the electrolyte. It may be -20% by weight.

Next, as the chargeable / dischargeable positive electrode according to the present invention, a conventionally known positive electrode can be used. Among them, LiCoO 2 is preferred because of its high energy density and small deterioration of the structure due to charge / discharge. ₂ , LiMn
_It preferably contains at least one active material selected from the group consisting of ₂ O ₄ , LiNiO ₂ and LiFeO ₂ .
As the positive electrode, for example, a positive electrode plate obtained by applying a positive electrode mixture composed of an active material, a conductive agent and a binder to a current collector plate is used.

As the chargeable / dischargeable negative electrode according to the present invention, a conventionally known negative electrode can be used. Among them, Sn and Si are particularly preferred because of their extremely low discharge potential and high energy density. , A Li-based alloy containing at least one selected from the group consisting of Al and In, and a negative electrode containing at least one active material selected from the group consisting of a Li-based compound, carbon, and metal Li. Is preferred. Examples of the Li-based alloy include lithium-
Tin alloys and lithium-silicon alloys,
Examples of the Li-based compound include lithium-tin oxide and lithium-silicon oxide. As the negative electrode, for example, a negative electrode plate obtained by applying a negative electrode mixture including an active material, a conductive agent, and a binder to a current collector plate is used.

As the conductive agent used for the positive electrode mixture and the negative electrode mixture for producing the positive electrode and the negative electrode, an electron conductive material which does not adversely affect the battery performance can be used without any particular limitation. For example, a carbon material containing other elements such as B, P, N, S, H, and F in addition to graphite and low-crystalline carbon can be used. Examples of the binder include polyacrylic acid, carboxymethyl cellulose, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl alcohol, starch, diacetyl cellulose, hydroxypropyl cellulose, and polyvinyl chloride. , Polyvinylpyrrolidone, polyethylene, polypropylene, SBR (styrene-butadiene copolymer rubber), EPDM (ethylene-propylene-diene copolymer rubber), sulfonated EPDM, fluorine rubber,
And polybutadiene and polyethylene oxide. These can be used alone or in any combination as long as the effects of the present invention are not impaired.

Of these, polyacrylic acid, carboxymethylcellulose, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoro is preferred because of good adhesion to the active material and the current collector and no side reaction accompanying charge / discharge. Preferred are propylene copolymer, polytetrafluoroethylene and styrene-butadiene rubber. As the current collector plate used for the positive electrode, for example, aluminum, stainless steel, nickel, titanium, and alloys thereof can be used.
Expanded metal, punched metal, wire mesh, and the like are preferable. In particular, an aluminum foil is suitable as a current collector for a positive electrode. On the other hand, as a current collector plate used for the negative electrode,
Copper, stainless steel, nickel, titanium, and alloys thereof can be used, and the form is preferably the same as that of the positive electrode. In particular, copper foil is suitable as a current collecting plate for a negative electrode.

FIG. 1 is a schematic longitudinal sectional view of a cylindrical non-aqueous electrolyte secondary battery which is an example of the non-aqueous electrolyte secondary battery of the present invention. This battery has a positive electrode plate 1 having a positive electrode lead plate 4 of the same material as the core material attached by spot welding, a negative electrode plate 2 having a negative electrode lead plate 5 of the same material as the core material attached by spot welding, An electrode body wound entirely in a spiral shape comprising a strip-shaped microporous polypropylene separator 3 wider than the bipolar plates provided between the bipolar plates, and polypropylene insulating plates 6 disposed on the upper and lower sides of the electrode body, respectively; And 7 and a battery case 8 having a step formed on the upper part after the electrode body is inserted. The battery is charged with a non-aqueous electrolyte in a battery case 8, charged and discharged for one cycle in a state where the upper part of the battery case is opened, and after releasing a reaction product gas, the battery is sealed with a sealing plate 9 having a positive electrode terminal 10. Is done.

[0021]

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. First, a method for evaluating batteries manufactured in the following Examples and Comparative Examples will be described. (1) Charge / discharge cycle test The batteries obtained in each of the examples and comparative examples were subjected to 50 ° C at 20 ° C.
A charge / discharge cycle of charging to 4.1, 4.15 or 4.2 V with a constant current of mA and then discharging to 3 V is repeated. Then, the discharge capacity at the first cycle and the 100th cycle is measured. From the measured values, the formula: Capacity maintenance rate at 100th cycle (%) = 100 × (100
The discharge capacity at the 100th cycle is determined according to (discharge capacity at the cycle / discharge capacity at the first cycle).

(2) High-Temperature Storage Test The batteries obtained in each of the examples and comparative examples were tested at 20 ° C. for 50 days.
A charge / discharge cycle in which the battery is charged to 4.1, 4.15 or 4.2 V at a constant current of mA, and then discharged to 3 V is 10 cycles.
Perform a cycle. And after the eleventh charge is over,
The batteries are stored at 85 ° C. for one week. Next, the battery after storage was returned to a temperature of 20 ° C., the discharge capacity when the battery was discharged to 3 V (discharge capacity at the eleventh cycle) was measured, and the battery was charged to 4.2 V and then discharged to 3 V. The discharge capacity at that time (discharge capacity at the 12th cycle) is measured. From the measured values, the capacity retention rate after high-temperature storage is determined according to the formula: capacity retention rate after high-temperature storage (%) = 100 × (discharge capacity at 11th cycle / 10th discharge capacity at 10th cycle). Also,
The capacity recovery rate is calculated according to the following formula: capacity recovery rate (%) = 100 × (discharge capacity at the 12th cycle / 10 discharge capacity at the 10th cycle).

Examples 1 to 7 100 g of carbon powder as a negative electrode active material and styrene-butadiene rubber 5 as a binder
g were mixed, a petroleum solvent was further added, and the mixture was sufficiently stirred to obtain a paste. This paste was applied to a copper core, dried at 120 ° C., rolled and cut to obtain a negative electrode plate containing 2.5 g of carbon powder. The discharge capacity of the carbon powder was 350 mAh per gram. next,
LiCoO ₂ as a positive electrode active material was synthesized by mixing lithium carbonate and cobalt carbonate at a predetermined molar ratio and heating the mixture at 900 ° C. This was classified into 100 mesh or less, 100 g of LiCoO ₂ , 5 g of carbon powder as a conductive agent, and 8 g of polytetrafluoroethylene as a binder.
Were mixed, and a petroleum-based solvent was further added, followed by sufficient stirring to obtain a paste. This paste was applied to a titanium core material, dried, rolled and cut to obtain a positive electrode plate containing 5 g of a positive electrode active material.

Further, lithium hexafluorophosphate was dissolved in a mixed solution of ethylene carbonate and diethyl carbonate having the same volume ratio so as to be 1 mol / liter, and the silane coupling shown in Table 1 was added thereto. ,
With sufficient stirring, the weight ratio of the silane coupling agent becomes 1
Seven types of non-aqueous electrolytes were obtained in a weight%. Using the negative electrode plate, positive electrode plate and various non-aqueous electrolytes, seven types of cylindrical non-aqueous electrolyte secondary batteries of the present invention shown in FIG. 1 were assembled. In addition, 2.6 ml of the non-aqueous electrolyte was injected. Table 1 shows the results of the charge / discharge cycle test and the high-temperature storage test of each battery. The evaluation was performed with a charging voltage of 4.1 V.

Comparative Example 1 A non-aqueous electrolyte secondary battery was assembled in the same manner as in Example 1 except that the silane coupling agent was not contained in the non-aqueous electrolyte. Table 1 shows the results of the charge / discharge cycle test and the high-temperature storage test.

[0026]

[Table 1]

From Table 1, it can be seen that the battery obtained by adding the silane coupling agent to the non-aqueous electrolyte has a capacity retention ratio at the 100th cycle,
The capacity retention rate and capacity recovery rate after high-temperature storage are dramatically improved compared to batteries in which the silane coupling agent was not added to the non-aqueous electrolyte, and the silane coupling agent suppresses the capacity reduction. It turns out that there is an effect. This is because the addition of the silane coupling agent improves the electrochemical stability of the non-aqueous electrolyte, and the silane coupling agent is adsorbed on the positive and negative electrode surfaces, and the non-aqueous electrolyte and the charged state This is probably because the reaction with the positive electrode and the negative electrode was suppressed, and the deterioration of the active material was suppressed.

<< Embodiments 8 and 9 >> N as a non-aqueous electrolyte
-Β- (aminoethyl) γ-aminopropyltriethoxysilane or bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane in the same manner as in Example 1 except that A secondary battery was manufactured. Then, the charging voltages are set to 4.1, 4.15 and 4.2.
V and stored at high temperature under the same conditions as in Example 1 for evaluation. Table 2 shows the results of the charge / discharge cycle test and the high-temperature storage test.

Comparative Example 2 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 7, except that the silane coupling agent was not used in the non-aqueous electrolyte. Table 2 shows the results of the charge / discharge cycle test and the high-temperature storage test.

[0030]

[Table 2]

From Table 2, it can be seen that the battery in which the silane coupling agent was added to the non-aqueous electrolyte had a charging voltage of 4.1 V to 4.15.
V, and 4.15 to 4.2 V, the capacity retention rate and capacity recovery rate after high-temperature storage are dramatically improved as compared to a battery in which the silane coupling agent was not added to the nonaqueous electrolyte. It can be seen that the silane coupling agent has an effect of suppressing a decrease in capacity. This is considered to be because the silane coupling agent in the non-aqueous electrolyte improved the electrochemical stability of the non-aqueous electrolyte by adding the silane coupling agent, and suppressed deterioration of the active material. . In addition,
Similar effects were obtained with silane coupling agents other than the above-mentioned N-β- (aminoethyl) γ-aminopropyltriethoxysilane or bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane.

Examples 10 to 16 N- in a non-aqueous electrolyte
The weight ratio of β- (aminoethyl) γ-aminopropyltriethoxysilane is 0.05 to 20% by weight (see Table 3).
A non-aqueous electrolyte secondary battery of the present invention was prepared in the same manner as in Example 1 except that the charging voltage was set to 4.2 V and evaluated. Table 3 shows the results of the charge / discharge cycle test and the high-temperature storage test.

[0033]

[Table 3]

From Table 3, when the weight ratio of N-β- (aminoethyl) γ-aminopropyltriethoxysilane in the nonaqueous electrolyte is 0.1 to 10% by weight, the capacity maintenance ratio at the 100th cycle and the high temperature It can be seen that the capacity retention rate and the capacity recovery rate after storage are high. This means that the weight ratio is 0.1% by weight
When it is lower, the effect of suppressing the reaction between the nonaqueous electrolyte and the charged positive electrode and the negative electrode and the effect of improving the electrochemical stability of the nonaqueous electrolyte are reduced, and the weight ratio is 2%.
It is considered that when the content is more than 0% by weight, the ionic conductivity of the non-aqueous electrolyte is impaired. Although LiCoO ₂ was used as the positive electrode active material and carbon powder was used as the negative electrode active material in the above examples, the present invention is not particularly limited to this.

[0035]

According to the present invention, at a high energy density,
It is possible to obtain a nonaqueous electrolyte secondary battery in which a decrease in discharge capacity due to a charge / discharge cycle and a decrease in characteristics due to storage at a high temperature are suppressed, and its industrial significance is large.

[Brief description of the drawings]

FIG. 1 is a schematic longitudinal sectional view of a cylindrical non-aqueous electrolyte secondary battery which is an example of the non-aqueous electrolyte secondary battery of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Positive electrode lead plate 5 Negative electrode lead plate 6 Upper insulating plate 7 Lower insulating plate 8 Battery case 9 Sealing plate 10 Positive terminal

[Procedure amendment]

[Submission Date] August 25, 2000 (2008.2.
5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

[0026]

[Table 1]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0030

[Correction method] Change

[Correction contents]

[0030]

[Table 2]

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

[0033]

[Table 3]

Continued on the front page (72) Inventor Yoshiaki Nitta 1006 Kadoma, Kazuma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. F-term (reference) 5H029 AJ04 AJ05 AK03 AL02 AL06 AL12 AM02 AM03 AM04 AM05 AM07 BJ02 BJ14 DJ09 HJ01

Claims (6)

[Claims] 1. A non-aqueous electrolyte secondary battery comprising a chargeable / dischargeable positive electrode, a nonaqueous electrolyte, and a chargeable / dischargeable negative electrode, wherein the nonaqueous electrolyte contains a silane coupling agent. 2. The method according to claim 1, wherein the silane coupling agent is N-β-
(Aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxy Be at least one selected from the group consisting of silane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane The non-aqueous electrolyte secondary battery according to claim 1, wherein: 3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte comprises a non-aqueous solvent containing a cyclic carbonate and a chain carbonate, and a Li salt. 4. The non-aqueous electrolyte secondary according to claim 1, wherein a weight ratio of the silane coupling agent in the non-aqueous electrolyte is 0.1 to 10% by weight. battery. 5. The method according to claim 1, wherein the positive electrode is LiCoO ₂ , LiMn ₂ O
_4, LiNiO non-aqueous electrolyte secondary battery according to any one of claims 1 to 4, characterized in that it comprises ₂ and at least one active material selected from the group consisting of LiFeO _2. 6. The method according to claim 1, wherein the negative electrode comprises Sn, Si, Al and I.
Li containing at least one member selected from the group consisting of
The non-aqueous solution according to any one of claims 1 to 5, wherein the non-aqueous solution contains at least one active material selected from the group consisting of a lithium alloy, a lithium compound, carbon, carbon, and metal Li. Electrolyte secondary battery.