JP2011040410A - Nonaqueous electrolyte secondary battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve various battery characteristics, such as low-temperature load characteristics and cycle characteristics. <P>SOLUTION: A battery includes: a positive electrode material 2 containing a positive electrode active material in which 10 to 80 wt.% lithium-manganese composite oxide and 90 to 20 wt.% lithium-nickel composite oxide are mixed and in which a positive electrode mix layer 8 having a thickness of 80 to 250 μm is formed; a negative electrode material 3 in which a negative electrode mix layer 11 containing at least one or more materials capable of occluding, removing, and attaching a lithium metal, lithium alloy, or lithium as a negative electrode active material and having a thickness of 80 to 250 μm is formed; and a nonaqueous electrolyte. In these positive electrode material 2 and negative electrode material 3, the positive electrode mix layer 8 and the negative electrode mix layer 11 are formed with a ratio A/B between a total thickness A of the positive electrode mix layer 8 and a total thickness B of the negative electrode mix layer 11 being in a range of 0.4≤A/B≤1.0 and a sum A+B of the total thickness A of the positive electrode mix layer 8 and the total thickness B of the negative electrode mix layer 11 being in a range of 230≤A+B≤450 μm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a non-aqueous electrolyte secondary battery using a mixed material of a lithium / nickel composite oxide and a lithium / manganese composite oxide as a positive electrode active material.

  2. Description of the Related Art In recent years, research on secondary batteries that can be repeatedly charged and discharged has been promoted as a power source that can be used conveniently and economically for a long time along with dramatic progress of various electronic devices. As typical secondary batteries, lead storage batteries, alkaline storage batteries, non-aqueous electrolyte secondary batteries, and the like are known.

  Among the secondary batteries as described above, a lithium ion secondary battery that is a non-aqueous electrolyte secondary battery has advantages such as high output and high energy density.

  A lithium ion secondary battery is composed of at least a positive electrode and a negative electrode having an active material capable of reversibly removing and inserting lithium ions, and a non-aqueous electrolyte. In the negative electrode, lithium ions are intercalated in the negative electrode active material. Conversely, when discharging, the reverse reaction proceeds and lithium ions intercalate at the positive electrode. That is, charge / discharge can be repeated by repeating the reaction in which lithium ions from the positive electrode enter and exit the negative electrode active material.

Currently, LiCoO ₂ , LiNiO ₂ , LiMn ₂ O _{4 and the} like are used as the positive electrode active material of the lithium ion secondary battery because it has a high energy density and high voltage, and the negative electrode active material is a carbonaceous material. Is used.

Among the positive electrode active materials described above, lithium-cobalt composite oxides such as LiCoO ₂ have the best balance in terms of battery capacity, manufacturing cost, thermal stability, etc., but lithium such as LiMn ₂ O ₄・ Manganese composite oxides have drawbacks such as low battery capacity and slightly high-temperature storage characteristics. Lithium / nickel composite oxides such as LiNiO ₂ have high battery capacity but low thermal stability. There is. However, these lithium / manganese composite oxides and lithium / nickel composite oxides are excellent in terms of the price and stable supply of raw materials, and researches are underway for future utilization.

  Therefore, the present invention has been made in view of the above-described problems, and uses this positive electrode active material together with a novel positive electrode active material that utilizes a lithium / manganese composite oxide and a lithium / nickel composite oxide. An object of the present invention is to provide a non-aqueous electrolyte secondary battery excellent in various battery characteristics such as low-temperature load characteristics and cycle characteristics.

The non-aqueous electrolyte secondary battery according to the present invention that achieves the above-described object has a general formula Li _x Mn _2−y M ′ _y O ₄ (wherein x is 0.9 ≦ x, y) as a positive electrode active material. The value is in the range of 0.01 ≦ y ≦ 0.5, and M ′ is Fe, Co, Ni, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, And a lithium-manganese composite oxide represented by the general formula LiNi _1-z M ″ _z O ₂ (provided that the value of z is 0.01 ≦ z ≦ The range is 0.5, and M ″ is one of Fe, Co, Mn, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, and Ge. Or a lithium / nickel composite oxide represented by a mass ratio of 10 wt% to 80 wt% of lithium / manganese composite oxide. A positive electrode comprising a mixed material mixed so as to be 90 wt% to 20 wt% of a um / nickel composite oxide, and comprising a positive electrode mixture layer applied and formed on at least one surface of a positive electrode current collector;
A negative electrode active material containing at least one of lithium metal, a lithium alloy, or a material capable of occluding and releasing lithium as a negative electrode active material, and having a negative electrode mixture layer formed by coating on at least one surface of the negative electrode current collector A negative electrode,
With a non-aqueous electrolyte,
The total thickness A, which is the total thickness of the positive electrode mixture layer formed on at least one surface of the positive electrode current collector, and the total thickness of the negative electrode mixture layer formed on at least one surface of the negative electrode current collector The total thickness B is in the range of 80 μm to 250 μm, the ratio A / B of the total thickness A to the total thickness B is in the range of 0.4 ≦ A / B ≦ 1.0, and the total thickness A and the total thickness The sum A + B with B is in the range of 230 μm ≦ A + B ≦ 450 μm.

  According to the nonaqueous electrolyte secondary battery according to the present invention having the above-described configuration, the positive electrode active layer contained in the positive electrode mixture layer in the positive electrode mixture layer and the negative electrode mixture layer formed in a predetermined thickness range. Using a mixed material of lithium / manganese composite oxide and lithium / nickel composite oxide as the substance, the ratio of the thickness of the positive electrode mixture layer to the negative electrode mixture layer, and the ratio between the positive electrode mixture layer and the negative electrode mixture layer The total thickness is in a certain range, specifically, the ratio of the thickness of the positive electrode mixture layer to the negative electrode mixture layer is in the range of 0.4 to 1.0, and the positive electrode mixture layer and the negative electrode mixture layer By regulating the total thickness within the range of 230 μm or more and 450 μm or less, the initial capacity, low temperature load characteristics, and cycle characteristics under high temperature heavy loads can be improved.

  According to the present invention, in the positive electrode mixture layer and the negative electrode mixture layer formed in a predetermined range of thickness, lithium-manganese composite oxide and lithium-nickel composite are used as the positive electrode active material contained in the positive electrode mixture layer. Using a mixed material with oxide, the ratio of the thickness of the positive electrode mixture layer to the negative electrode mixture layer and the total thickness of the positive electrode mixture layer and the negative electrode mixture layer are within a certain range, specifically the positive electrode The ratio of the thickness of the mixture layer to the negative electrode mixture layer is regulated in the range of 0.4 to 1.0, and the total thickness of the positive electrode mixture layer and the negative electrode mixture layer is regulated in the range of 230 μm to 450 μm. By doing so, it is possible to improve the initial capacity, the low temperature load characteristics, and the cycle characteristics under high temperature heavy loads. Especially, the low temperature load characteristic can be remarkably improved.

It is sectional drawing of the non-aqueous electrolyte secondary battery which concerns on embodiment of this invention. It is a characteristic view which shows the relationship between the sum total of the thickness of a positive mix layer and a negative mix layer, and initial stage capacity | capacitance. It is a characteristic view which shows the relationship between the ratio of the thickness with respect to the negative mix layer of a positive mix layer, and the capacity | capacitance maintenance factor on low temperature conditions. It is a characteristic view which shows the relationship between the ratio of the thickness with respect to the negative mix layer of a positive mix layer, and the capacity | capacitance maintenance factor in high temperature heavy load.

  Embodiments of a nonaqueous electrolyte secondary battery according to the present invention will be described below with reference to the drawings.

  As shown in FIG. 1, the nonaqueous electrolyte secondary battery 1 includes a battery element 5 in which a positive electrode material 2 and a negative electrode material 3 each having a band shape are stacked via a separator 4 and wound in a spiral shape. This is a so-called cylindrical battery that is sealed in a cylindrical battery can 6 together with a non-aqueous electrolyte.

  The positive electrode material 2 is made of a positive electrode active material capable of electrically releasing lithium and reversibly occluding on both surfaces of a positive electrode current collector 7 made of a metal foil such as an aluminum foil. The positive electrode mixture layer 8 to be contained is formed. Further, a positive electrode lead 9 is attached to the positive electrode material 2 in the vicinity of one end in the longitudinal direction.

As the positive electrode active material contained in the positive electrode mixture layer 8, the general formula _{Li x Mn 2-y M '} y O 4 ( provided that the value of x is 0.9 ≦ x, y values 0.01 ≦ y ≦ 0.5, M ′ is one of Fe, Co, Ni, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, Ge Or a lithium-manganese composite oxide represented by the general formula LiNi _1-z M ″ _z O ₂ (where z is in the range of 0.01 ≦ z ≦ 0.5, and M ″ Li, nickel represented by Fe, Co, Mn, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, Ge) Mixed materials with complex oxides are used. The lithium-manganese composite oxide has, for example, a spinel structure, and M ′ is present in place of a manganese atom at a part of the site of the manganese atom. The lithium / nickel composite oxide has a layered structure, for example, and M ″ is substituted with a part of the site of nickel atoms. These lithium-manganese composite oxides and lithium-nickel composite oxides are considered to have stable crystal structures by replacing part of manganese or nickel with other elements as described above. Can be improved.

  The composition ratio between manganese and element M ′ in the lithium / manganese composite oxide and the composition ratio between nickel and element M ″ in the lithium / nickel composite oxide, that is, the values of x, y, and z described above. The reason is that if the replacement amount is smaller than this, a sufficient effect cannot be obtained, and if the replacement amount is larger than this, the high load discharge capacity after high-temperature storage is lowered. In addition, the elements substituted for manganese atoms and nickel atoms are described above because the lithium-manganese composite oxide or lithium-nickel composite oxide material in which these elements are substituted with a part of manganese or nickel This is because it can be obtained relatively easily and is chemically stable.

  As described above, a mixed material of a lithium / manganese composite oxide and a lithium / nickel composite oxide is used for the positive electrode active material, but these have a mass ratio of 10 wt% to 80 wt% with respect to the lithium / manganese composite oxide. The lithium / nickel composite oxide is mixed at 90 wt% to 20 wt%. Lithium-manganese composite oxide has the characteristic of shrinking during charging, and can reduce volume changes that occur during charging and discharging. The reason why the lithium / manganese composite oxide and the lithium / nickel composite oxide are mixed within the above-described range is that when the lithium / manganese composite oxide is less than 20 wt. This is because the battery capacity is reduced when it exceeds 80 wt%.

  These lithium / manganese composite oxide and lithium / nickel composite oxide are prepared, for example, as a lithium compound, a manganese compound or a nickel compound, and a compound containing element M ′ or a compound containing element M ″. After mixing at a ratio, it can be obtained by heating and baking at a temperature of 600 ° C. to 1000 ° C. in an oxygen-existing atmosphere. At that time, carbon salt, hydroxide, oxide, nitrate, organic acid salt, or the like is used as a raw material compound.

  In addition to the positive electrode active material described above, the positive electrode mixture layer 8 further contains a conductive material such as graphite and a binder such as polyvinylidene fluoride as necessary.

  In the negative electrode material 3, a negative electrode mixture layer 11 containing a negative electrode active material is formed on both surfaces of a negative electrode current collector 10 made of a metal foil such as a copper foil, a nickel foil, or a stainless steel foil. A negative electrode lead 12 is attached to the negative electrode material 3 in the vicinity of one end in the longitudinal direction.

  The negative electrode active material contained in the negative electrode mixture layer 11 is any one of lithium metal, lithium alloy, or a material capable of inserting and extracting lithium at a potential of 2 V or less with reference to the lithium metal potential. A kind or a mixed material in which two or more of these are mixed is used.

Examples of the material capable of inserting and extracting lithium include lithium metal and lithium alloy compounds. The lithium alloy compound here, for example, those represented by the chemical formula D _s E _t Li _u. In this chemical formula, D represents at least one of a metal element and a semiconductor element capable of forming an alloy or compound with lithium, and E represents at least one of a metal element and a semiconductor element other than lithium and D. The values of s, t, and u are 0 <s, 0 ≦ t, and 0 ≦ u, respectively. Here, the metal element or semiconductor element capable of forming an alloy or compound with lithium is preferably a group 4B metal element or semiconductor element, particularly preferably Si or Sn, and most preferably Si. Examples of metal elements or semiconductor elements capable of forming an alloy or compound with lithium include Mg, B, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi, Cd, Ag, Zn, Hf, Zr, and Y. And alloys thereof such as Li-Al, Li-Al-M (M is one or more of 2A, 3B, 4B transition metal elements), AlSb, CuMgSb, and the like. Furthermore, in the present invention, elements such as B, Si, As, and the like, which are semiconductor elements, are included in the metal element.

These alloys or compounds are also preferable. For example, M _x Si (M is one or more metal elements excluding Si and x is 0 <x) or M _x Sn (M is one excluding Sn). These are the above metal elements, and x is 0 <x.). Specifically, SiB ₄ , SiB ₆ , Mg ₂ Si, Mg ₂ Sn, Ni ₂ Si, TiSi ₂ , MoSi ₂ , CoSi ₂ , NiSi ₂ , CaSi ₂ , CrSi ₂ , Cu ₅ Si, FeSi ₂ , MnSi ₂ , _{NbSi 2, TaSi 2, VSi 2} , WSi 2 or ZnSi _2, and the like.

Furthermore, as a material capable of inserting and extracting lithium, the elements or compounds that can be alloyed or compounded with lithium as described above can also be used. That is, one or more types of 4B group elements may be contained in this material, and metal elements other than the 4B group containing lithium may be contained. Examples of such a material include SiC, Si ₃ N ₄ , Si ₂ N ₂ O, Ge ₂ N ₂ O, SiO _x (0 <x ≦ 2), SnO _x (0 <x ≦ 2), LiSiO, LiSnO, and the like. Can be illustrated.

  In addition to the materials described above, examples of the material capable of inserting and extracting lithium include carbon materials, metal oxides, and polymer materials. Examples of the carbon material include non-graphitizable carbon, artificial graphite, coke, graphite, glassy carbon, a fired organic polymer compound, carbon fiber, activated carbon, or carbon black. Among these, coke includes pitch coke, needle coke, petroleum coke, and the like. Organic polymer compound fired bodies are obtained by firing a polymer material such as a phenol resin or a furan resin at an appropriate temperature. The one that has become. In addition, examples of the metal oxide include iron oxide, ruthenium oxide, molybdenum oxide, and tin oxide, and examples of the polymer material include polyacetylene and polypyrrole.

  In addition to the negative electrode active material described above, the negative electrode mixture layer 11 further contains a binder such as polyvinylidene fluoride as necessary.

  The positive electrode material 2 and the negative electrode material 3 described above constitute a battery element 5 of a so-called jelly roll type, which is produced by being laminated and wound via a separator 4. In order to stably produce the jelly roll type battery element without any problems in the process, the total thickness of each of the positive electrode mixture layer 8 and the negative electrode mixture layer 11, specifically, formed on both surfaces of the current collector. It is preferable that the total thickness of the mixture layer be in the range of 80 μm to 250 μm. That is, when the total thickness of the mixture layer is less than 80 μm, the thickness of the single-sided coating portion is less than 40 μm, but the currently used electrode material has a maximum particle size of about 40 μm in terms of particle size distribution. This is because a problem such as faint coating occurs in a portion where large particles exist. In addition, if the total thickness of the mixture layer exceeds 250 μm, there is a problem that the active material is peeled off from the current collector or cracks are generated.

  And the positive electrode material 2 and the negative electrode material 3 are the total thickness B of the negative mix layer 11 of the total thickness A of the positive mix layer 8 in the range of the total thickness of the positive mix layer 8 and the negative mix layer 11 mentioned above. The ratio A / B is 0.320 to 3.125, and the ratio A / B is 0.4 to 2.5 within this range, and the total thickness A of the positive electrode mixture layer 8 and the negative electrode mixture layer When the total sum (A + B) of the total thickness B of 11 is 230 μm to 450 μm, the low temperature load characteristics, the high temperature heavy load cycle characteristics, and the initial capacity of the nonaqueous electrolyte secondary battery 1 are improved. This is because when the sum (A + B) of the total thickness A of the positive electrode mixture layer 8 and the total thickness B of the negative electrode mixture layer 11 exceeds 450 μm, the low temperature load characteristics are reduced as the ion diffusibility decreases due to the increase of the mixture layer. This is because when the thickness is less than 230 μm, the relative active material filling amount decreases, and the capacity decreases to the same level or lower than that of a battery that is currently in practical use. When the ratio A / B of the total thickness A of the positive electrode mixture layer 8 to the total thickness B of the negative electrode mixture layer 11 is less than 0.4 or exceeds 2.5, the positive electrode mixture layer 8 and the negative electrode mixture The difference in thickness with the agent layer 11 increases, and the difference in curvature increases when wound. When the ratio A / B is less than 0.4, the ratio A / B When the value exceeds 2.5, a large load is applied to the positive electrode material 2. For this reason, it is because the mixture layer peels from the current collector by repeating the charge / discharge cycle of the high temperature heavy load, and the cycle characteristics of the high temperature heavy load are deteriorated.

  Therefore, for the reasons described above, the ratio A / B of the total thickness A of the positive electrode mixture layer 8 to the total thickness B of the negative electrode mixture layer 11 is 0.4 to 2.5, and the total thickness of the positive electrode mixture layer 8 is The positive electrode mixture layer 8 and the negative electrode mixture layer 11 are formed in a thickness range of 80 μm to 250 μm, respectively, so that the total sum (A + B) of the total thickness B of A and the negative electrode mixture layer 11 is 230 μm to 450 μm. .

  The separator 4 separates the positive electrode active material layer 8 of the positive electrode material 2 from the negative electrode active material layer 11 of the negative electrode material 3, and is a known separator that is normally used as a separator for this type of nonaqueous electrolyte battery. For example, a porous film made of a polyolefin-based material such as polypropylene or polyethylene, or a porous film made of an inorganic material such as a ceramic non-woven fabric is used. Moreover, the separator 4 needs to be as thin as possible from the relationship between lithium ion conductivity and energy density. Specifically, the thickness of the separator is suitably 50 μm or less, for example.

  As will be described later, the separator 4 is impregnated with a non-aqueous electrolyte that is injected into the battery can 6.

  As the non-aqueous electrolyte, a solution in which an electrolyte is dissolved in an aprotic non-aqueous solvent is used. Examples of the non-aqueous solvent include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, γ-butyl lactone, sulfolane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 2-methyltetrahydrofuran, 4-methyl- 1,3-dioxolane, methyl propionate, methyl butyrate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate and the like can be used. In particular, from the viewpoint of voltage stability, it is preferable to use cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate, and vinylene carbonate, and chain carbonates such as dimethyl carbonate, diethyl carbonate, and dipropyl carbonate. Moreover, such a non-aqueous solvent may be used individually by 1 type, and may be used in mixture of 2 or more types.

As the electrolytes dissolved in the non-aqueous solvent, for _{example, LiPF 6, LiClO 4, LiAsF} 6, LiBF 4, LiCF 3 SO 3, LiN (CF 3 SO 2) 2 and lithium salt one or two The above can be mixed and used. Among these lithium salts, it is particularly preferable to use LiPF ₆ or LiBF ₄ .

  As shown in FIG. 1, the battery element 5 is formed by laminating the above-described positive electrode material 2 and negative electrode material 3 with a separator 4 interposed therebetween, and is wound around, for example, a center pin 13.

  At this time, in the nonaqueous electrolyte secondary battery 1, the portion of the battery element 5 where the positive electrode material 2 and the negative electrode material 3 face each other, specifically, the negative electrode material located on the outermost periphery of the battery element 5 facing the battery can 6. 3 and the capacity ratio (positive electrode / negative electrode) of the positive electrode material 2 to the negative electrode material 3 excluding a portion where the negative electrode material 3 faces the innermost periphery of the battery element 5 and face each other. The battery element 5 is produced so as to be 03. The non-aqueous electrolyte secondary battery 1 has improved cycle characteristics and storage characteristics by setting the capacity ratio of the positive electrode material 2 to the negative electrode material 3 in the above-described range. In the nonaqueous electrolyte secondary battery 1, it is most preferable that the battery element 5 is manufactured so that the positive electrode material 2 and the negative electrode material 3 have the same capacity, that is, the capacity ratio is 1.0. Even with the capacity ratio in the above range, cycle characteristics and storage characteristics equivalent to those when the capacity ratio is 1.0 can be obtained.

  The battery can 6 has a bottomed cylindrical shape with one end open and the other end closed, and has an inner surface plated with nickel. At the open end of the battery can 6, a lid body 14, a safety valve mechanism 15 provided inside the lid body, and a thermal resistance element (Positive Temperature Coefficient: PTC element) 16 are interposed via a gasket 17. The battery can 6 is hermetically sealed. The lid 14 is made of the same material as the battery can 6. The safety valve mechanism 15 is electrically connected to the lid body 14 via the PTC element 16, and when the internal pressure of the battery exceeds a certain level due to an internal short circuit or external heating, the disk plate is inverted and the lid The electrical connection between the body 14 and the battery element 5 is cut off. When the temperature rises, the PTC element 16 limits the current by increasing the resistance value and prevents abnormal heat generation due to a large current, and is made of, for example, barium titanate semiconductor ceramics. The gasket 17 is made of, for example, an insulating material, and asphalt is applied to the surface. A pair of insulating plates 18 a and 18 b are disposed inside the battery can 6 so as to sandwich the battery element 5.

  The non-aqueous electrolyte secondary battery 1 described above is manufactured as follows.

  First, a positive electrode mixture was prepared by adding a mixed material of a lithium / manganese composite oxide and a lithium / nickel composite oxide as a positive electrode active material, and if necessary, a conductive material and a binder. The agent is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a paste-like positive electrode mixture slurry. And after apply | coating this positive electrode mixture slurry on both surfaces of the positive electrode electrical power collector 7, and drying it, the positive mix layer 8 is compression-molded with a roller press etc., and the positive electrode material 2 is produced.

  Next, a negative electrode active material, and if necessary, a negative electrode mixture is prepared by adding a binder, and the negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to obtain a paste-like negative electrode mixture. A slurry is obtained. And after apply | coating this negative mix slurry on both surfaces of the negative electrode collector 10 and making it dry, the negative mix layer 11 is compression-molded with a roller press etc., and the negative electrode material 3 is produced.

  At this time, the positive electrode mixture layer 8 of the positive electrode material 2 and the negative electrode mixture layer 11 of the negative electrode material 3 have a ratio A / B of the total thickness A of the positive electrode mixture layer 8 to the total thickness B of the negative electrode mixture layer 11. The total thickness A of the positive electrode mixture layer 8 and the total thickness B of the negative electrode mixture layer 11 (A + B) are 0.4 to 2.5, and the thicknesses are 80 μm to 250 μm, respectively. Formed in range.

  Subsequently, the positive electrode lead 9 is attached to the positive electrode material 2 and the negative electrode lead 12 is attached to the negative electrode material 3 by a method such as welding, and the battery element 5 is manufactured by stacking and winding the separator 4 therebetween.

  At this time, the battery element 5 is manufactured so that the capacity ratio of the positive electrode material 2 and the negative electrode material 3 facing each other with the separator 4 interposed therebetween is in the range of 0.8 to 1.03.

And while the front-end | tip part of the positive electrode lead 9 is welded to the safety valve mechanism 15, the front-end | tip part of the negative electrode lead 12 is welded to the battery can 6, and the battery element 5 is pinched | interposed into a pair of insulating plates 18a and 18b inside the battery can 6. Store. After the battery element 5 is housed in the battery can 6 in this way, a non-aqueous electrolyte is injected into the battery can 6 and impregnated in the separator 4.
Then, the non-aqueous electrolyte secondary battery 1 is manufactured by caulking the lid 14, the safety valve mechanism 15, and the PTC element 16 with a gasket 17, fixing, and closing the open end of the battery can 6.

  The non-aqueous electrolyte secondary battery 1 described above operates as follows.

  In this non-aqueous electrolyte secondary battery 1, lithium ions are desorbed from the positive electrode material 2 and charged in the negative electrode material 3 through the electrolytic solution impregnated in the separator 4 for charging. At the time of discharge, lithium ions are desorbed from the negative electrode material 3 and inserted into the positive electrode material 2 through the electrolytic solution impregnated in the separator 4. Charging / discharging is repeated by repeating such a reaction in which lithium ions from the positive electrode material 2 enter and exit the negative electrode active material in the negative electrode mixture layer 11.

  In the nonaqueous electrolyte secondary battery 1, it is only necessary to satisfy any of the above-described ratio and sum of the thicknesses of the mixture layers or the capacity ratio of the opposing electrode material. At this time, by setting the ratio of the thicknesses of the positive electrode mixture layer 8 and the negative electrode mixture layer 11 and the total thickness of the positive electrode mixture layer 8 and the negative electrode mixture layer 11 within the above-described ranges, The capacity, low temperature load characteristics, and cycle characteristics under high temperature heavy load are improved, and the ratio of the capacity of the positive electrode material 2 to the capacity of the negative electrode material 3 is within the above-described range, thereby improving the cycle characteristics and storage characteristics.

  Further, in the above-described embodiment, the nonaqueous electrolyte secondary battery 1 using the nonaqueous electrolytic solution has been described as an example. However, the present invention is not limited to this, and the conductive polymer compound is not limited thereto. The present invention can also be applied to a solid electrolyte battery using a polymer solid electrolyte containing a single substance or a mixture, and a gel electrolyte battery using a gel solid electrolyte containing a swelling solvent.

  Specific examples of the conductive polymer compound contained in the polymer solid electrolyte or gel electrolyte include silicon, acrylic, acrylonitrile, polyphosphazene-modified polymer, polyethylene oxide, polypropylene oxide, fluorine-based polymer, or these compounds. And composite polymers, cross-linked polymers, modified polymers, and the like. Examples of the fluorine polymer include poly (vinylidene fluoride), poly (vinylidene fluoride-co-hexafluoropropylene), poly (vinylidene fluoride-co-tetrafluoroethylene), poly (vinylidene fluoride-co-trifluoroethylene). ) And the like.

  Further, the present invention is not particularly limited with respect to the cylindrical battery, the square shape, the coin shape, the button shape, and the like, and has various sizes such as a thin shape and a large size. Can do. Furthermore, in the above-described embodiment, the iron battery can 6 is used as the exterior material, but the present invention is not limited to this, and a flexible film-shaped exterior material such as an aluminum laminate material may be used.

  Hereinafter, the present invention will be described based on specific experimental results.

  First, in conducting the experiment, test batteries of Examples and Comparative Examples were produced as follows.

Example 1
First, the positive electrode material was produced as follows.

First, 91 parts by weight of the positive electrode active material, 6 parts by weight of graphite as a conductive material, and 3 parts by weight of polyvinylidene fluoride (PVdF) as a binder were mixed to prepare a positive electrode mixture. At this time, the positive electrode active material was mixed with lithium hydroxide (LiOH), nickel monoxide (NiO), and cobalt monoxide (CoO) and baked in air at 750 ° C. for 5 hours to obtain LiNi0.8CoO. 2O2 (hereinafter referred to as the positive electrode 1) is mixed with 50 wt%, lithium carbonate (Li ₂ CO ₃ ), manganese dioxide (MnO ₂ ), and dichromium trioxide (Cr ₂ O ₃ ) in air at 850 ° C. A mixed material in which LiMn _1.9 Cr _0.1 O ₄ (hereinafter referred to as positive electrode 2) obtained by firing for 5 hours was mixed at a ratio of 50 wt% was used.

  Then, the positive electrode mixture is dispersed in N-methyl-2-pyrrolidone to obtain a paste-like positive electrode mixture slurry, and this positive electrode mixture slurry is uniformly applied to both surfaces of a strip-shaped aluminum foil serving as a positive electrode current collector. And dried to form a positive electrode mixture layer. Then, the positive electrode material was produced by performing press processing with a roll press. At this time, the positive electrode mixture slurry was applied and pressed so that the total thickness A of the positive electrode mixture layers formed on both surfaces of the positive electrode current collector was 80 μm.

  Next, a negative electrode material was produced as follows.

First, 90 parts by weight of the negative electrode active material and 10 parts by weight of PVdF as a binder were mixed to prepare a negative electrode mixture. At this time, a mixed material in which 45 parts by weight of Mg ₂ Si powder and artificial graphite were mixed was used as the negative electrode active material.

  Then, the negative electrode mixture is dispersed in N-methyl-2-pyrrolidone to form a slurry, and this slurry is uniformly applied to both sides of the strip-shaped copper foil that becomes the negative electrode current collector and dried to form a negative electrode mixture layer. Formed. Then, the negative electrode material was produced by performing press processing with a roll press machine. At this time, the negative electrode mixture slurry was applied and pressed so that the total thickness B of the negative electrode mixture layer formed on both surfaces of the negative electrode current collector was 150 μm.

  The positive electrode material obtained as described above and the negative electrode material were brought into close contact with each other through a separator made of a microporous polypropylene film, and a battery element was produced by winding a number of times in a spiral shape.

  Next, an insulating plate was inserted into the bottom of an iron battery can with nickel plating on the inside, and the battery element was housed. In order to collect the negative electrode, one end of a nickel negative electrode lead was pressed against the negative electrode, and the other end was welded to the battery can. Further, in order to collect the positive electrode, one end of an aluminum positive electrode lead was attached to the positive electrode, and the other end was electrically connected to the lid through a thin plate for current interruption.

And the non-aqueous electrolyte solution was inject | poured in this battery can, and the separator mentioned above was impregnated. This non-aqueous electrolyte was prepared by dissolving LiPF ₆ as an electrolyte at a concentration of 1.0 mol / l in a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate.

  Finally, the lid was fixed by caulking the battery can through a gasket coated with asphalt to produce a cylindrical test battery.

Example 2
The positive electrode material layer and the negative electrode material layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 80 μm and the total thickness B of the negative electrode material mixture layer was 200 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

Example 3
The positive electrode material layer and the negative electrode material mixture layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 150 μm and the total thickness B of the negative electrode material mixture layer was 80 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

Example 4
The positive electrode material layer and the negative electrode material layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 150 μm and the total thickness B of the negative electrode material mixture layer was 150 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

Example 5
The positive electrode material layer and the negative electrode material layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 150 μm and the total thickness B of the negative electrode material mixture layer was 250 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

Example 6
The positive electrode material layer and the negative electrode material layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 250 μm and the total thickness B of the negative electrode material mixture layer was 100 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

Example 7
The positive electrode material layer and the negative electrode material mixture layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 250 μm and the total thickness B of the negative electrode material mixture layer was 150 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

Example 8
The positive electrode material layer and the negative electrode material mixture layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 250 μm and the total thickness B of the negative electrode material mixture layer was 200 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

Comparative Example 1
The positive electrode material layer and the negative electrode material layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 80 μm and the total thickness B of the negative electrode material mixture layer was 80 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

Comparative Example 2
The positive electrode material layer and the negative electrode material layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 80 μm and the total thickness B of the negative electrode material mixture layer was 250 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

Comparative Example 3
The positive electrode material layer and the negative electrode material layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 250 μm and the total thickness B of the negative electrode material mixture layer was 80 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

Comparative Example 4
The positive electrode material layer and the negative electrode material layer were applied and formed so that the total thickness A of the positive electrode material mixture layer was 250 μm and the total thickness B of the negative electrode material mixture layer was 250 μm. A cylindrical test battery was prepared in the same manner as in Example 1.

  The initial capacities of the test batteries of Examples 1 to 8 and Comparative Examples 1 to 4 produced as described above were measured, and the low temperature load characteristics and the high temperature heavy load cycle characteristics were evaluated. The initial capacity was measured by charging with a constant voltage and constant current (0.2 C) with an upper limit voltage of 4.2 V, and then discharging with a constant current up to a discharge end voltage of 3.0 V. In addition, the evaluation of the low-temperature load characteristics was performed by charging each test battery with a constant voltage and constant current (0.2 C) with an upper limit voltage of 4.2 V under a temperature condition of −20 ° C., and then reaching a discharge end voltage of 3.0 V. The constant current discharge was performed. Thereafter, the same test battery was subjected to constant current charging under the condition of current 2C, and constant current discharge up to a discharge end voltage of 3.0 V was performed. And the ratio of the capacity | capacitance when charging / discharging was performed on the conditions of the electric current 2C with respect to the capacity | capacitance when charging / discharging on the conditions of electric current 0.2C was computed, and the low-temperature storage characteristic was evaluated. Furthermore, the cycle characteristics under high temperature and heavy load are as follows. Each test battery is charged with a constant voltage and constant current (1 C) with an upper limit voltage of 4.2 V under a temperature condition of 50 ° C. A constant current discharge was performed. This charge / discharge cycle was performed 100 times, and the ratio (capacity maintenance ratio) of the battery capacity at the 100th cycle to the battery capacity at the second cycle was determined and evaluated. The results are shown in Table 1, FIG. 2, FIG. 3 and FIG.

  As shown in Table 1, FIG. 2, FIG. 3 and FIG. 4, the sum (A + B) of the total thickness A of the positive electrode mixture layer and the total thickness B of the negative electrode mixture layer is in the range of 230 μm to 450 μm, and the positive electrode Example 1 in which a positive electrode mixture layer and a negative electrode mixture layer were formed in a ratio A / B of the total thickness A of the mixture layer to the total thickness B of the negative electrode mixture layer in the range of 0.4 to 2.5. The battery of Example 8 has good results in all of the low temperature load characteristics, the high temperature heavy load cycle characteristics, and the initial capacity.

  In contrast, the battery of Comparative Example 1 in which the sum (A + B) of the total thickness A of the positive electrode mixture layer and the total thickness B of the negative electrode mixture layer is 160 μm is shown in Table 1 and FIG. The initial capacity is significantly lower than that of the battery of the example. This is presumably because the relative filling amount of the active material is reduced because the positive electrode mixture layer and the negative electrode mixture layer are both too thin.

  In addition, as shown in Table 1 and FIG. 3, the battery of Comparative Example 4 in which the sum (A + B) of the total thickness A of the positive electrode mixture layer and the total thickness B of the negative electrode mixture layer is 500 μm is included in each example. The low-temperature load characteristic is remarkably lowered as compared with the battery. This is presumably because the ion diffusibility was lowered because the positive electrode mixture layer and the negative electrode mixture layer were too thick.

  Further, the batteries of Comparative Example 2 and Comparative Example 3 in which the ratio A / B of the total thickness A of the positive electrode mixture layer to the total thickness B of the negative electrode mixture layer were 0.32 and 3.13, respectively, are shown in Table 1 and As shown in FIG. 4, the cycle characteristics at high temperature and heavy load are remarkably deteriorated as compared with the batteries of the respective examples. This is because the difference in thickness between the positive electrode mixture layer and the negative electrode mixture layer becomes too large, and the difference in curvature between the positive electrode material and the negative electrode material increases when wound when producing a battery element, In Comparative Example 2 in which the ratio A / B is less than 0.32 and 0.4, a large load is applied to the negative electrode material, and in Comparative Example 3 in which the ratio A / B exceeds 3.13 and 2.5, a large load is applied to the positive electrode material. It is considered that the mixture layer was peeled from the current collector by repeating the heavy load charge / discharge cycle.

  From this result, when forming the positive electrode mixture layer and the negative electrode mixture layer in the range of 80 μm to 250 μm defined by the problems in the conventional process, the total thickness A of the positive electrode mixture layer and the total of the negative electrode mixture layer are The sum (A + B) of the thickness B is in the range of 230 μm to 450 μm, and the ratio A / B of the total thickness A of the positive electrode mixture layer to the total thickness B of the negative electrode mixture layer is in the range of 0.4 to 2.5. It can be seen that the formation of the positive electrode mixture layer and the negative electrode mixture layer improves the low temperature load characteristics, the cycle characteristics under high temperature heavy loads, and the initial capacity.

  Next, test batteries of Examples 9 to 16 and Comparative Examples 5 to 8 were produced as follows.

Example 9
First, the positive electrode material was produced as follows.

First, 91 parts by weight of the positive electrode active material, 6 parts by weight of graphite as a conductive material, and 3 parts by weight of polyvinylidene fluoride (PVdF) as a binder were mixed to prepare a positive electrode mixture. At this time, LiNi _0.8 Co _0.2 obtained by mixing lithium hydroxide (LiOH), nickel monoxide (NiO), and cobalt monoxide (CoO) as the positive electrode active material and firing in air at 750 ° C. for 5 hours. 70 wt% of O ₂ (hereinafter referred to as positive electrode 1), lithium carbonate (Li ₂ CO ₃ ), manganese dioxide (MnO ₂ ), and dichromium trioxide (Cr ₂ O ₃ ) were mixed and 850 ° C. in the air. A mixed material in which LiMn _1.9 Cr _0.1 O ₄ (hereinafter referred to as positive electrode 2) obtained by firing for 5 hours at a ratio of 30 wt% was used.

  Then, the positive electrode mixture is dispersed in N-methyl-2-pyrrolidone to obtain a paste-like positive electrode mixture slurry, and this positive electrode mixture slurry is uniformly applied to both surfaces of the aluminum foil serving as the positive electrode current collector and dried. To form a positive electrode mixture layer. Then, the positive electrode material was produced by performing press processing with a roll press.

  Next, a negative electrode material was produced as follows.

  First, 90 parts by weight of artificial graphite as a negative electrode active material and 10 parts by weight of PVdF as a binder were mixed to prepare a negative electrode mixture. Then, the negative electrode mixture was dispersed in N-methyl-2-pyrrolidone to form a slurry, and this slurry was uniformly applied to both sides of the copper foil serving as the negative electrode current collector and dried to form a negative electrode mixture layer. . Then, the negative electrode material was produced by performing press processing with a roll press machine.

  The positive electrode material obtained as described above and the negative electrode material were laminated via a separator made of a microporous polypropylene film to produce a battery element.

Next, the battery element was housed inside a positive electrode can having an iron shallow plate shape with nickel plating inside, and a non-aqueous electrolyte was injected into the positive electrode can to impregnate the separator described above. This non-aqueous electrolyte was prepared by dissolving LiPF ₆ as an electrolyte at a concentration of 1.0 mol / l in a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate. Finally, the positive electrode can was caulked and the negative electrode cup was fixed through a gasket coated with asphalt, thereby sealing the positive electrode can and producing a coin-type test battery.

  And when the charge capacity of the positive electrode material and the negative electrode material was measured, both were 11.2 mAh. In addition, the capacity | capacitance of a positive electrode material is charged and measured by the constant voltage constant current (0.2C) of upper limit voltage 4.2V, and the charge capacity of a negative electrode material is the constant voltage constant current (0.05C) of upper limit voltage 5mV. Measured by charging with

Example 10
A test battery was produced in the same manner as in Example 1 except that the mass ratio of the mixed material used as the positive electrode active material was 90 wt% for the positive electrode 1 and 10 wt% for the positive electrode 2. And when the charge capacity of the positive electrode material and the negative electrode material was measured, both were 11.7 mAh.

Example 11
A test battery was produced in the same manner as in Example 1 except that the mass ratio of the mixed material used as the positive electrode active material was 20 wt% for the positive electrode 1 and 80 wt% for the positive electrode 2. And when the charge capacity of the positive electrode material and the negative electrode material was measured, both were 11.6 mAh.

Example 12
A test battery was produced in the same manner as in Example 1 except that the mass ratio of the mixed material used as the positive electrode active material was 70 wt% for the positive electrode 1 and 30 wt% for the positive electrode 2. And when the charge capacity of the positive electrode material and the negative electrode material was measured, the positive electrode material was 11.5 mAh and the negative electrode material was 14.3 mAh.

Example 13
A test battery was produced in the same manner as in Example 1 except that the mass ratio of the mixed material used as the positive electrode active material was 70 wt% for the positive electrode 1 and 30 wt% for the positive electrode 2. And when the charge capacity of the positive electrode material and the negative electrode material was measured, the positive electrode material was 11.6 mAh and the negative electrode material was 11.2 mAh.

Example 14
The mixed material used as the positive electrode active material has a mass ratio of 70 wt% for the positive electrode 1, 30 wt% for the positive electrode 2, and a mixed material in which 55 parts by weight of Mg ₂ Si powder and 35 parts by weight of artificial graphite are mixed in the negative electrode active material. A test battery was produced in the same manner as in Example 1 except that it was used. And when the charge capacity of the positive electrode material and the negative electrode material was measured, both were 14.0 mAh.

Example 15
The mixed material used as the positive electrode active material has a mass ratio of 70 wt% for the positive electrode 1, 30 wt% for the positive electrode 2, and a mixed material in which 55 parts by weight of Mg ₂ Si powder and 35 parts by weight of artificial graphite are mixed in the negative electrode active material. A test battery was produced in the same manner as in Example 1 except that it was used. And when the charge capacity of the positive electrode material and the negative electrode material was measured, the positive electrode material was 14.0 mAh and the negative electrode material was 13.6 mAh.

Comparative Example 5
A test battery was produced in the same manner as in Example 1 except that only the positive electrode 1 was used as the positive electrode active material. And when the charge capacity of the positive electrode material and the negative electrode material was measured, both were 11.5 mAh.

Comparative Example 6
A test battery was prepared in the same manner as in Example 1 except that only the positive electrode 2 was used as the positive electrode active material. And when the charge capacity of the positive electrode material and the negative electrode material was measured, both were 11.7 mAh.

Comparative Example 7
A test battery was produced in the same manner as in Example 1 except that the mass ratio of the mixed material used as the positive electrode active material was 70 wt% for the positive electrode 1 and 30 wt% for the positive electrode 2. And when the charge capacity of the positive electrode material and the negative electrode material was measured, the positive electrode material was 11.6 mAh and the negative electrode material was 15.3 mAh.

Comparative Example 8
A test battery was produced in the same manner as in Example 1 except that the mass ratio of the mixed material used as the positive electrode active material was 70 wt% for the positive electrode 1 and 30 wt% for the positive electrode 2. And when the charge capacity of the positive electrode material and the negative electrode material was measured, the positive electrode material was 11.5 mAh and the negative electrode material was 11.0 mAh.

Comparative Example 9
The mixed material used as the positive electrode active material has a mass ratio of 70 wt% for the positive electrode 1, 30 wt% for the positive electrode 2, and a mixed material in which 55 parts by weight of Mg ₂ Si powder and 35 parts by weight of artificial graphite are mixed in the negative electrode active material. A test battery was produced in the same manner as in Example 1 except that it was used. And when the charge capacity of the positive electrode material and the negative electrode material was measured, the positive electrode material was 14.0 mAh and the negative electrode material was 13.4 mAh.

  The cycle characteristics and storage characteristics of each test battery of Examples 9 to 15 and Comparative Examples 5 to 9 produced as described above were evaluated. The results are shown in Table 2.

  The cycle characteristics were evaluated by charging each test battery with a constant voltage and constant current (0.2 C) having an upper limit voltage of 4.2 V, and then performing a constant current discharge up to a discharge end voltage of 3.0 V. Then, this charge / discharge cycle was performed 100 times, and the ratio (capacity maintenance ratio) of the battery capacity at the 100th cycle to the battery capacity at the second cycle was determined and evaluated. In addition, the storage characteristics were evaluated by performing constant-current constant-voltage charging for each test battery in a constant temperature bath at 23 ° C. under conditions of an upper limit voltage of 4.2 V and a current of 0.2 C, and then performing a constant-current discharge of 0.2 C. An initial discharge capacity was set up to a final voltage of 3.2V. Thereafter, the battery was charged again under the same conditions and stored in an oven at 60 ° C. for 2 weeks. The maximum value of each cycle discharge capacity after storage was taken as the capacity after storage, and the ratio (capacity recovery rate) to the initial discharge capacity was determined and evaluated.

As shown in Table 2, the mass ratio of the mixed material as the positive electrode active material is positive electrode 1, that is, 90 wt% to 20 wt% of lithium / nickel composite oxide, and positive electrode 2, ie, 10 wt% to 80 wt% of lithium / manganese composite oxide. %, And each of the test batteries of Examples 9 to 15 in which the capacity ratio of the positive electrode material to the negative electrode material is in the range of 0.8 to 1.03 is the artificial active material for the negative electrode active material. When either graphite or a mixed material of artificial graphite and Mg ₂ Si is used, good results are obtained with respect to both cycle characteristics and storage characteristics.

  On the other hand, although the capacity ratio is the same as that of Example 9 to Example 11, the batteries of Comparative Examples 5 and 6 using only the positive electrode 1 or the positive electrode 2 as the positive electrode active material have reduced storage characteristics. Yes.

  In addition, although the mass ratio between the positive electrode 1 and the positive electrode 2 is the same as that of Example 9 and Examples 12 to 15, the battery of Comparative Example 7 having a low capacity ratio of 0.76 has reduced storage characteristics, and the capacity ratio The batteries of Comparative Example 8 and Comparative Example 9 having a high 1.05 have poor cycle characteristics.

  From these results, a mixed material in which 90% to 20% by weight of lithium / nickel composite oxide and 10% to 80% by weight of lithium / manganese composite oxide are used as the positive electrode active material, and the capacity of the positive electrode material relative to the negative electrode material It can be seen that when the ratio is in the range of 0.8 to 1.03, the cycle characteristics and the storage characteristics are improved.

DESCRIPTION OF SYMBOLS 1 Nonaqueous electrolyte secondary battery, 2 Positive electrode material, 3 Negative electrode material, 4 Separator, 5 Battery element, 6 Battery can, 7 Positive electrode collector, 8 Positive electrode mixture layer, 10 Negative electrode collector, 1
1 Negative electrode mixture layer

Claims (5)

As the positive electrode active material, the general formula Li _x Mn _2−y M ′ _y O ₄ (where x is in the range of 0.9 ≦ x, y is in the range of 0.01 ≦ y ≦ 0.5, and M ′ is Li, represented by Fe, Co, Ni, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, or Ge. Manganese composite oxide and general formula LiNi _1-z M ″ _z O ₂ (where z is in the range of 0.01 ≦ z ≦ 0.5, and M ″ is Fe, Co, Mn, Cu Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, and Ge. The lithium / manganese composite oxide is 10 wt% to 80 wt%, and the lithium / nickel composite oxide is 90 wt% to 20 wt%. A positive electrode comprising a mixed material mixed so as to have a positive electrode mixture layer coated and formed on at least one surface of the positive electrode current collector;
A negative electrode active material containing at least one of lithium metal, a lithium alloy, or a material capable of occluding and desorbing lithium as a negative electrode active material, and having a negative electrode mixture layer formed by coating on at least one surface of the negative electrode current collector A negative electrode,
With a non-aqueous electrolyte,
The total thickness A, which is the total thickness of the positive electrode mixture layer formed on at least one surface of the positive electrode current collector, and the thickness of the negative electrode mixture layer formed on at least one surface of the negative electrode current collector The total thickness B is in the range of 80 μm to 250 μm, the ratio A / B of the total thickness A to the total thickness B is in the range of 0.4 ≦ A / B ≦ 1.0, and A nonaqueous electrolyte secondary battery in which a sum A + B of the total thickness A and the total thickness B is in a range of 230 μm ≦ A + B ≦ 450 μm. The nonaqueous electrolyte secondary battery according to claim 1, wherein the positive electrode and the negative electrode are stacked with a separator interposed therebetween, and wound so that the negative electrode is positioned on the outermost periphery. The nonaqueous electrolyte secondary battery according to claim 1, wherein the positive electrode mixture layer and the negative electrode mixture layer are formed on both surfaces of the positive electrode current collector and the negative electrode current collector, respectively. 2. The nonaqueous electrolyte secondary battery according to claim 1, wherein the positive electrode and the negative electrode are arranged to face each other, and a capacity ratio of the opposite positive electrodes to the negative electrode is 0.8 to 1.03. . The nonaqueous electrolyte secondary battery according to claim 1, wherein the negative electrode mixture layer contains a lithium alloy and a carbon material as a negative electrode active material.

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