JP2005222744A - Nonaqueous electrolyte battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte battery capable of well keeping a charge-discharge characteristic, and improved in battery life performance and thermal stability. <P>SOLUTION: A negative electrode plate 4 having, on one surface, a first negative electrode mix layer containing a non-fluorine-based binder of a mixture or the like of styrene-butadiene-based rubber and a cellulose-based compound and having, on the other surface, a second negative mix layer containing a fluorine-based binder of a polyvinylidene fluoride-based substance or the like and a positive electrode plate 3 are stacked by interposing a separator 5 so that the first negative electrode mix layer is set closest to the outside periphery. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a non-aqueous electrolyte battery including a power generation element in which a negative electrode plate having a negative electrode mixture layer and a positive electrode plate are laminated via a separator.

  In recent years, portable electronic devices such as mobile phones, notebook personal computers, and video cameras have been improved in performance, size, and weight. Lithium ion secondary batteries are used as high energy density secondary batteries used in these electronic devices. The use of secondary batteries is expanding. In a lithium ion secondary battery, for example, a power generation element in which a sheet-like or foil-like positive electrode plate and a negative electrode plate are wound via a separator (separator) is housed in a battery case.

  The binder (binder) of the negative electrode plate of the lithium ion secondary battery is represented by a fluorine-based polymer material typified by polyvinylidene fluoride-based material or a mixture of styrene-butadiene rubber and carboxymethyl cellulose. Various materials such as non-fluorine polymer materials are used. However, when a non-fluorinated polymer material such as a mixture of styrene / butadiene rubber and carboxymethyl cellulose is used, the adhesive strength between the negative electrode mixture layer and the negative electrode current collector is low, and the negative electrode plate expands and contracts due to repeated charge and discharge. When is repeated, the negative electrode mixture layer is likely to be peeled off, so that there is a problem in that the battery life performance is likely to deteriorate early.

On the other hand, when a fluorine-based polymer material such as polyvinylidene fluoride is used, the battery life performance is higher than that of non-fluorine-based polymer materials because the adhesive strength between the negative electrode mixture layer and the negative electrode current collector is high. Is good. However, since a negative electrode (such as a lithium-carbon composite compound) in a charged state tends to easily generate an exothermic reaction with a fluorine compound in a high temperature region, a non-fluorine polymer material and In comparison, there is a problem that liquid leakage or smoke generation due to heat generation is likely to occur (see, for example, Patent Document 1).
Japanese Patent Laid-Open No. 6-163031

  As a method for solving these problems, a manufacturing method in which a slurry in which a non-fluorine binder and a fluorine binder are mixed is applied to a current collector, and the respective advantages are utilized. However, in most cases, the solvent in which the different types of polymers are dispersed or dissolved is different, and the different types of polymers generally have poor compatibility.

  In addition, when the positive electrode plate and the negative electrode plate are short-circuited due to a metal nail pierced into the battery case, a large current flows through the short-circuited portion to locally generate heat, and the temperature rises to increase the positive electrode active material or When the negative electrode active material undergoes thermal runaway, the entire battery may generate heat, causing leakage or fuming. As a countermeasure for this problem, in the power generation element, the positive electrode active material used for the positive electrode mixture layer on the outermost surface of the positive electrode plate, which is the outermost side, is more differentially scanned than the positive electrode active material used for the positive electrode mixture layer on the other surface There has been proposed a method using a calorimeter (DSC method) having a high heat generation starting temperature. However, this method has a problem in charge / discharge characteristics such that charge / discharge tends to become unstable because the positive electrode active material contained in the positive electrode mixture layer on each surface of the positive electrode plate is different.

  This invention is made | formed in view of such a situation, and it aims at providing the non-aqueous electrolyte battery which maintained charging / discharging characteristics favorably and improved battery life performance and thermal stability.

  Another object of the present invention is to provide a non-aqueous electrolyte battery having improved thermal stability when a metal nail or the like enters from the outside to cause a short circuit between the positive electrode and the negative electrode.

  A non-aqueous electrolyte battery according to a first aspect of the present invention is a non-aqueous electrolyte battery comprising a power generating element in which a negative electrode plate having a negative electrode mixture layer and a positive electrode plate are laminated via a separator, It has the 1st negative electrode mixture layer containing a non-fluorine-type binder on this surface, and has the 2nd negative electrode mixture layer containing a fluorine-type binder on the other surface.

  In the first invention, a negative electrode having a first negative electrode mixture layer containing a non-fluorine binder on one side and a second negative electrode mixture layer containing a fluorine binder on the other side The plate and the positive electrode plate are laminated via a separator. The negative electrode plate forms, for example, a first negative electrode mixture layer on one surface of a foil-like negative electrode current collector and a second negative electrode mixture layer on the other surface. The non-fluorine-based binder contained in the first negative electrode mixture layer on one surface of the negative electrode plate has better thermal stability than the fluorine-based binder, and the second surface on the other surface of the negative electrode plate. The fluorine-based binder contained in the negative electrode mixture layer has better battery life performance than the non-fluorinated binder, and the present invention has the advantages of both the non-fluorinated binder and the fluorine-based binder. Will be provided. Moreover, although an electrode plate has two types of mixture layers, since the binder of each mixture layer differs, but an active material does not differ, charging / discharging characteristics are maintained favorable.

  A non-aqueous electrolyte battery according to a second aspect of the present invention is a non-aqueous electrolyte battery comprising a power generating element in which a negative electrode plate having a negative electrode mixture layer and a positive electrode plate are laminated via a separator, wherein the negative electrode plate is made of fluorine It has the 2nd negative mix layer containing a type | system | group binder, and the 1st negative mix layer containing the non-fluorine type binder laminated | stacked on this 2nd negative mix layer.

  In the second invention, a second negative electrode mixture layer containing a fluorine-based binder, and a first negative electrode mixture layer containing a non-fluorine-based binder laminated on the second negative electrode mixture layer are provided. The negative electrode plate and the positive electrode plate are stacked via a separator. In the negative electrode plate, for example, a second negative electrode mixture layer is formed on both surfaces or one surface of a foil-shaped negative electrode current collector, and a first negative electrode mixture layer is formed on the formed second negative electrode mixture layer. The fluorine-based binder contained in the second negative electrode mixture layer has better battery life performance than the non-fluorine binder, and the first negative electrode mixture layer laminated on the second negative electrode mixture layer has The contained non-fluorinated binder has better thermal stability than the fluorine-based binder, and the present invention has the advantages of both the non-fluorinated binder and the fluorine-based binder. Moreover, although an electrode plate has two types of mixture layers, since the binder of each mixture layer differs, but an active material does not differ, charging / discharging characteristics are maintained favorable.

  A nonaqueous electrolyte battery according to a third invention is the non-aqueous electrolyte battery according to the first or second invention, wherein the power generation element is laminated such that the negative electrode mixture layer facing the positive electrode plate and closest to the outer periphery is the first negative electrode mixture layer. Is carried out.

  In the third invention, the negative electrode plate, the positive electrode plate, and the separation plate are arranged so that the negative electrode mixture layer facing the positive electrode plate and closest to the outer periphery is the first negative electrode mixture layer containing a non-fluorine binder. Laminate the body. When a metal nail or the like enters the power generation element thus laminated from the outside, a short circuit between the positive electrode and the negative electrode is first performed on the first negative electrode mixture layer side facing the positive electrode plate and closest to the outer periphery. To happen. Although current flows through the short-circuited part and heat is locally generated, the thermal stability of the negative electrode in the charged state is superior to non-fluorinated binders than fluorine-based binders. The short circuit occurs on the first negative electrode mixture layer side containing the non-fluorine binder rather than the short circuit occurs on the second negative electrode mixture layer side containing the adhesive material. Is suppressed.

  The nonaqueous electrolyte battery according to a fourth invention is any one of the first to third inventions, wherein the non-fluorine binder is a mixture of a styrene / butadiene rubber and a cellulose compound. .

  In the fourth invention, a mixture of a styrene / butadiene rubber and a cellulose compound is used as the non-fluorine binder contained in the first negative electrode mixture layer. By using a mixture of a general styrene / butadiene rubber and a cellulose compound as the non-fluorinated binder, the first negative electrode mixture layer can be easily formed.

  The nonaqueous electrolyte battery according to a fifth aspect of the present invention is characterized in that, in any one of the first to third aspects, the fluorine-based binder is a polyvinylidene fluoride-based substance.

  In the fifth invention, a polyvinylidene fluoride-based material is used as the fluorine-based binder contained in the second negative electrode mixture layer. By using a general polyvinylidene fluoride-based substance as the fluorine-based binder, the second negative electrode mixture layer can be easily formed.

  According to the first, second, fourth, and fifth inventions, the negative electrode mixture layer is excellent in the first negative electrode mixture layer containing a non-fluorinated binder having excellent thermal stability and the battery life performance. Battery life performance and thermal stability can be improved by forming both layers of the second negative electrode mixture layer containing a fluorine-based binder. Moreover, although an electrode plate has two types of mixture layers, since the binder of each mixture layer differs, but an active material does not differ, charging / discharging characteristics are maintained favorable.

  According to the third, fourth, and fifth inventions, the first negative electrode mixture layer containing a non-fluorine binder that has better thermal stability than the fluorine binder is opposed to the positive electrode plate, The first negative electrode mixture layer side having excellent thermal stability when a metal nail or the like is stuck from the outside by laminating the positive electrode plate, the negative electrode plate, and the separator so as to be the closest negative electrode mixture layer to Since a short circuit with the positive electrode occurs first, heat generation and leakage or smoke generation due to heat generation can be suppressed.

Hereinafter, the present invention will be specifically described with reference to the drawings showing embodiments thereof.
(Example 1)
A schematic cross-sectional view of a square lithium ion secondary battery (nonaqueous electrolyte battery) according to the present invention is shown in FIG. FIG. 2 is an enlarged cross-sectional view of a portion X in FIG. In FIG. 1, 1 is a rectangular lithium ion secondary battery, 2 is a wound-type power generation element, 3 is a positive electrode plate, 4 is a negative electrode plate, 5 is a separator (separator), and 6 is a battery also serving as a positive electrode terminal. Case, 7 is a battery cover, 8 is a safety valve, 9 is a negative terminal, 10 is a positive lead, and 11 is a negative lead.

  The lithium ion secondary battery 1 includes a positive electrode plate 3 in which a positive electrode mixture layer 22 containing a positive electrode active material is formed on a positive electrode current collector 21, and a negative electrode mixture layer 24 containing a negative electrode active material (described later). The negative electrode plate 4 formed by forming the first negative electrode mixture layer 24 </ b> A and the second negative electrode mixture layer 24 </ b> B) on the negative electrode current collector 23 is wound through a separator 5 into which a nonaqueous electrolyte is injected. 2 is accommodated in a battery case (thickness 5 mm) 6 having a bottom and a side wall surrounding the bottom. Further, a battery lid 7 having a safety valve 8 is attached to the opening of the battery case 6 by laser welding. The positive electrode plate 3 is in contact with the inner wall of the battery case 6 and is connected to the battery lid 7 via the positive electrode lead 10. The negative electrode plate 4 is connected to the negative electrode terminal 9 of the battery lid 7 via the negative electrode lead 11.

For the positive electrode plate 3, first and LiCoO ₂ 90 wt% of the positive electrode active material, acetylene black 5 wt% of a conductive agent, a binder was mixed with polyvinylidene fluoride 5 wt% of a (binder) the positive electrode mixture, N A slurry was prepared by dispersing in -methyl-2-pyrrolidone (NMP). This slurry was uniformly applied to a positive electrode current collector 21 made of aluminum foil having a thickness of 15 μm to form a positive electrode mixture layer 22, dried, and then compression-molded by a roll press to prepare a positive electrode plate 3.

  Regarding the negative electrode mixture layer 24 of the negative electrode plate 4, the first negative electrode mixture layer 24 </ b> A is formed on one surface of the negative electrode current collector 23, and the second negative electrode mixture layer 24 </ b> B is formed on the other surface. Regarding the first negative electrode mixture layer 24A, the graphite powder 97 wt% was adjusted so that the styrene / butadiene copolymer as a binder (binder) was 1.5 wt% and the carboxymethyl cellulose was 1.5 wt%. Water was added and mixed to prepare a negative electrode slurry. Regarding the second negative electrode mixture layer 24B, NMP was added to and mixed with 95 wt% of graphite powder so that polyvinylidene fluoride as a binder was 5 wt% to prepare a negative electrode slurry. Then, the negative electrode slurry for the first negative electrode mixture layer is fed to the negative electrode current collector 23 made of copper foil having a thickness of 10 μm, using a roll coater, at a feed rate of 0.50 m / min, a drying temperature of 125 ° C., and an air flow rate of 10 Then, 200 mm is applied under the condition of 0.0 m / s, and then the negative electrode slurry for the second negative electrode mixture layer is applied under the same conditions as the above on the opposite surface of the copper foil to form a coating film having a film thickness of 200 to 240 μm. The negative electrode plate 4 was produced by compression molding with a roll press.

As the separator 5, a microporous polyethylene film having a thickness of about 25 μm was used. In addition, an electrolytic solution in which 1 mol of LiPF ₆ was dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate (volume ratio 1: 2) was used.

  As shown in FIG. 2, the power generating element 2 is wound so that the positive electrode plate 3 becomes the outer periphery and the outer peripheral side of the negative electrode plate 4 becomes the first negative electrode mixture layer 24 </ b> A. The power generation element 2 has a battery case 6, a positive electrode plate 3, a separator 5, a negative electrode plate 4, a separator 5, a positive electrode plate 3,... From the outer periphery toward the winding center (from left to right in FIG. 2). They are stacked in order. Further, a first negative electrode mixture layer 24A is formed on the outer peripheral surface (the left surface in FIG. 2) of the negative electrode plate 4, and the second central electrode surface (the right surface in FIG. 2) is the second. A negative electrode mixture layer 24B is formed. The negative electrode mixture layer 24 that faces the positive electrode plate 3 and is on the outermost side is a first negative electrode mixture layer 24A.

(Example 2)
Regarding the second negative electrode mixture layer 24B, a copolymer of vinylidene fluoride and hexafluoropropylene as a binder is adjusted to 5 wt% with respect to 95 wt% of the graphite powder, and NMP is added and mixed to mix the negative electrode slurry. A lithium ion secondary battery was produced in the same manner as in Example 1 except that it was prepared and applied to the negative electrode current collector 23.

(Example 3)
Regarding the first negative electrode mixture layer 24A, with respect to 97 wt% of graphite powder, acrylonitrile-butadiene copolymer as a binder is adjusted to 1.5 wt% and carboxymethylcellulose is 1.5 wt%, and water is added and mixed. A lithium ion secondary battery was produced in the same manner as in Example 1 except that a negative electrode slurry was prepared and applied to the negative electrode current collector 23.

Example 4
Regarding the first negative electrode mixture layer 24A, a polyimide as a binder was adjusted to 5 wt% with respect to 95 wt% of the graphite powder, and NMP was added and mixed to prepare a negative electrode slurry, which was applied to the negative electrode current collector 23. A lithium ion secondary battery was produced in the same manner as in Example 1 except that.

(Example 5)
Regarding the first negative electrode mixture layer 24A, a polyamide imide as a binder is adjusted to 5 wt% with respect to 95 wt% of the graphite powder, and NMP is added and mixed to prepare a negative electrode slurry, which is applied to the negative electrode current collector 23 A lithium ion secondary battery was produced in the same manner as in Example 1 except that.

(Example 6)
Regarding the first negative electrode mixture layer 24A, the graphite powder 95 wt% is adjusted to 5 wt% polyvinylidene fluoride as a binder, NMP is added and mixed to prepare a negative electrode slurry, and the second negative electrode mixture layer is further mixed. With respect to the agent layer 24B, the graphite powder 97 wt% is adjusted so that the styrene-butadiene copolymer as a binder is 1.5 wt% and the carboxymethyl cellulose is 1.5 wt%, and water is added and mixed to prepare a negative electrode slurry. A lithium ion secondary battery was produced in the same manner as in Example 1 except that it was prepared and applied to the negative electrode current collector 23.

(Comparative Example 1)
Regarding the second negative electrode mixture layer 24B, with respect to 97 wt% of the graphite powder, the styrene / butadiene copolymer as a binder is adjusted to 1.5 wt% and the carboxymethyl cellulose is 1.5 wt%, and water is added and mixed. A lithium ion secondary battery was produced in the same manner as in Example 1 except that a negative electrode slurry was prepared and applied to the negative electrode current collector 23.

(Comparative Example 2)
For both the first negative electrode mixture layer 24A and the second negative electrode mixture layer 24B, the polyimide resin as the binder is adjusted to 5 wt% with respect to the graphite powder 95 wt%, and NMP is added and mixed to mix the negative electrode slurry. A lithium ion secondary battery was produced in the same manner as in Example 1 except that it was prepared and applied to the negative electrode current collector 23.

(Comparative Example 3)
Regarding the first negative electrode mixture layer 24A, a polyvinylidene fluoride as a binder is adjusted to 5 wt% with respect to 95 wt% of the graphite powder, and NMP is added and mixed to prepare a negative electrode slurry. A lithium ion secondary battery was produced in the same manner as in Example 1 except that it was applied.

(Comparative Example 4)
For both the first negative electrode mixture layer 24A and the second negative electrode mixture layer 24B, the copolymer of vinylidene fluoride and hexafluoropropylene as a binder is adjusted to 5 wt% with respect to 95 wt% of the graphite powder. , NMP was added and mixed to prepare a negative electrode slurry, and a lithium ion secondary battery was fabricated in the same manner as in Example 1, except that the negative electrode current collector 23 was applied.

  A nail penetration test was performed on the lithium ion secondary batteries of Examples 1 to 6 and Comparative Examples 1 to 4 described above. When the metal nail 30 is pierced into the battery case 6, as shown in FIG. 2, the tip of the nail 30 first breaks through the battery case 6 that is electrically connected to the positive electrode plate 3 to reach the positive electrode plate 3. ((A) of FIG. 2). At this time, since the battery case 6 and the positive electrode plate 3 in contact with the nail 30 have the same potential, no current flows through the nail 30. When the nail 30 further enters the power generation element 2, the separator 5 is broken through and reaches the first negative electrode mixture layer 24A on the outer peripheral side of the negative electrode plate 4 ((B) of FIG. 2). At this time, the positive electrode (positive electrode plate 3) and the negative electrode plate 4 are short-circuited by the nail 30, and a large current flows. When a large current flows in the short-circuit portion and locally generates heat, abnormalities such as leakage or smoke may occur.

  In the nail penetration test, a steel nail having a diameter of 3 mm was pierced so as to penetrate the battery case 6, and the presence or absence of leakage or smoke generation was confirmed. The number of tests was 10 for each example and each comparative example.

  Moreover, about the lithium ion secondary battery of Examples 1-6 and Comparative Examples 1-4, the initial stage discharge capacity and the discharge capacity after repeating 500 times charge / discharge were measured, and a lifetime characteristic (100x "initial stage Discharge capacity "/" discharge capacity after 500 charge / discharge cycles "[%]). The number of tests for measuring the discharge capacity was set to 3 for each example and each comparative example, and the average value of the measured values was obtained. Test results and measurement results are shown in Table 1.

  From Table 1, in Examples 1-5 in which the first negative electrode mixture layer 24A contains a non-fluorine binder and the second negative electrode mixture layer 24B contains a fluorine binder, no abnormality occurred in the nail penetration test. Moreover, the life characteristics are 80% or more.

  Further, in Example 6 in which the first negative electrode mixture layer 24A is a fluorine-based binder and the second negative electrode mixture layer 24B is a non-fluorine-based binder, the life characteristics are 80% or more, and there is no battery that generates smoke. However, since there is a leaked battery, the first negative electrode mixture layer 24A is preferably made of a non-fluorine binder and is closer to the outer periphery than the second negative electrode mixture layer 24B (fluorine binder).

  Further, in Comparative Examples 1 and 2 in which the first negative electrode mixture layer 24A and the second negative electrode mixture layer 24B are non-fluorine binders, no abnormality occurred in the nail penetration test, but the life characteristics were 65 to 65. 70%, which is inferior to Examples 1-6.

  On the other hand, in Comparative Examples 3 and 4 in which the first negative electrode mixture layer 24 </ b> A and the second negative electrode mixture layer 24 </ b> B are fluorine-based binders, liquid leakage or smoke generation occurs in the nail penetration test.

  By using the first negative electrode mixture layer 24A containing a non-fluorine binder and the second negative electrode mixture layer 24B containing a fluorine binder as the negative electrode mixture layer 24, the battery life performance of the fluorine binder can be improved. The advantages of both the excellent characteristics and the excellent thermal stability of the non-fluorinated binder can be utilized. Moreover, although two types of mixture layers are formed on the current collector, the binder of each mixture layer is different, but since the active material is not different, the charge / discharge characteristics are maintained well.

  In addition, by arranging the first negative electrode mixture layer 24A containing a non-fluorine binder on the side closer to the outer periphery, when a metal nail 30 or the like enters the power generation element 2 from the outside, the first short circuit is first performed. Since the negative electrode mixture layer 24 of the portion becomes the first negative electrode mixture layer 24A containing a non-fluorine binder that has a thermal stability with respect to the negative electrode in a charged state better than the fluorine binder, heat generation due to a short circuit, and The occurrence of leakage or smoke due to heat generation is suppressed, and safety is improved.

  In each of the above-described embodiments, the first negative electrode mixture layer 24A is formed on one surface of the negative electrode plate 4, and the second negative electrode mixture layer 24B is formed on the other surface, but the lithium ion secondary battery shown in FIG. 2B, the second negative electrode mixture layer 24B is formed on both surfaces (or one surface) of the negative electrode plate 4, and the first negative electrode mixture layer 24A is formed on the formed second negative electrode mixture layer 24B. It is also possible.

(Example 7)
In the lithium ion secondary battery of Example 1 described above, the formation state of the negative electrode mixture layer 24 (first negative electrode mixture layer 24A and second negative electrode mixture layer 24B) is shown in FIG. It changed into the state which laminated | stacked the different negative mix layer on both surfaces shown in FIG. 3 from the state from which a layer differs. That is, as shown in FIG. 3, a second negative electrode mixture layer (polyvinylidene fluoride as a binder is 5 wt% with respect to 95 wt% of graphite powder) 24B is formed on both surfaces of the negative electrode current collector 23 to form the second On the negative electrode mixture layer 24B, a first negative electrode mixture layer 24A (1.5 wt% of styrene-butadiene copolymer as a binder and 1.5 wt% of carboxymethylcellulose with respect to 97 wt% of graphite powder) is formed, A lithium ion secondary battery was produced. Moreover, the nail penetration test similar to Examples 1-6 and Comparative Examples 1-4 was implemented, and the lifetime characteristic was calculated | required. Test results and measurement results are shown in Table 1, and the same effects as in Examples 1 to 5 are obtained.

  In the above-described embodiment, the positive electrode plate, the negative electrode plate, and the separator are stacked by winding one positive electrode plate, the negative electrode plate, and the separator. For example, a plurality of positive electrode plates, negative electrode plates, and It is also possible to sequentially stack the separators.

It is a schematic sectional drawing of the square-shaped lithium ion secondary battery (nonaqueous electrolyte battery) which concerns on this invention. It is an expanded sectional view of the X section of FIG. It is an expanded sectional view of the lithium ion secondary battery which concerns on another Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Lithium ion secondary battery 2 Power generation element 3 Positive electrode plate 4 Negative electrode plate 5 Separator 6 Battery case 7 Battery lid 8 Safety valve 9 Negative electrode terminal 10 Positive electrode lead 11 Negative electrode lead 21 Positive electrode collector 22 Positive electrode mixture layer 23 Negative electrode collector 24 Negative electrode mixture layer 24A First negative electrode mixture layer 24B Second negative electrode mixture layer 30 Nail

Claims (5)

In a non-aqueous electrolyte battery comprising a power generation element in which a negative electrode plate having a negative electrode mixture layer and a positive electrode plate are laminated via a separator,
The negative electrode plate has a first negative electrode mixture layer containing a non-fluorine binder on one side and a second negative electrode mixture layer containing a fluorine binder on the other side. Non-aqueous electrolyte battery characterized. In a non-aqueous electrolyte battery comprising a power generation element in which a negative electrode plate having a negative electrode mixture layer and a positive electrode plate are laminated via a separator,
The negative electrode plate has a second negative electrode mixture layer containing a fluorine-based binder, and a first negative electrode mixture layer containing a non-fluorine-based binder laminated on the second negative electrode mixture layer. The nonaqueous electrolyte battery characterized by the above-mentioned.   3. The non-aqueous composition according to claim 1, wherein the power generation element is laminated such that the negative electrode mixture layer facing the positive electrode plate and closest to the outer periphery becomes the first negative electrode mixture layer. Electrolyte battery.   4. The nonaqueous electrolyte battery according to claim 1, wherein the non-fluorine binder is a mixture of a styrene / butadiene rubber and a cellulose compound.   The non-aqueous electrolyte battery according to claim 1, wherein the fluorine-based binder is a polyvinylidene fluoride-based substance.

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