JP2002203560A - Non-aqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-aqueous electrolyte secondary battery which is excellent in productivity and quality. SOLUTION: The non-aqueous electrolyte secondary battery is constituted of a positive electrode 1 which contains a manganese containing oxide, a nickel containing oxide, and a binder as a positive-electrode active material, a negative electrode 12 in which at least one or more kinds of materials of a lithium metal, a lithium alloy or the material, which can dope/de-dope lithium are possible, are contained as a negative-electrode active material, and a non- aqueous electrolyte, wherein the above binder is the mixed binder containing polyfluorobinylidene and hexafluoropropylene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to lithium (Li)
The present invention relates to a non-aqueous electrolyte secondary battery including a positive electrode including a manganese-containing oxide containing manganese and manganese (Mn) and a nickel-containing oxide containing lithium and nickel (Ni).

[0002]

2. Description of the Related Art In recent years, with the advance of electronic technology, many small portable electronic devices such as a camera-integrated VTR (video tape recorder), a mobile phone and a laptop computer have become widespread. Have been. Therefore, as a portable power supply used for them, a battery that is small and lightweight and has a high energy density,
In particular, the development of secondary batteries is underway. Above all, lithium ion secondary batteries using a non-aqueous electrolyte are greatly expected because they can obtain higher energy density than conventional lead batteries or nickel cadmium batteries using a liquid electrolyte using water as a solvent.

As the positive electrode material of this lithium ion secondary battery, lithium-cobalt composite oxide, lithium-manganese composite oxide, lithium-nickel composite oxide and the like have been put to practical use. Among these, the lithium-cobalt composite oxide has the best balance in various aspects such as battery capacity, cost, and thermal stability, and is currently widely used. In contrast, lithium-manganese composite oxides have drawbacks such as low battery capacity and slightly poor high-temperature storage characteristics, while lithium-nickel composite oxides have drawbacks such as slightly lower thermal stability. These are excellent in terms of raw material price and stable supply, and research is being conducted for future utilization. For example, recently, by mixing and using a lithium-manganese composite oxide and a lithium-nickel composite oxide, the disadvantages of both are complemented, and expansion and contraction of the positive electrode during charging and discharging are suppressed, and the charge-discharge cycle is reduced. A technique for improving characteristics has been proposed (see Japanese Patent Application Laid-Open No. 8-45498).

[0004]

In the above-mentioned non-aqueous electrolyte secondary battery, the positive electrode is usually prepared by mixing a positive electrode active material, a binder, and if necessary, a conductive material and the like. It is formed by preparing a mixture and applying the positive electrode mixture on a positive electrode current collector. As the binder, polyvinylidene fluoride (hereinafter referred to as PVdF) is usually used.

However, the positive electrode active material containing the above-described positive electrode material has a problem that it is easily gelled when preparing a positive electrode mixture by mixing PVdF as a binder.
Here, the gel of the positive electrode mixture loses its fluidity. As a result, it becomes impossible to apply the positive electrode mixture onto the positive electrode current collector, so that the positive electrode mixture must be re-prepared, resulting in reduced productivity, or when applying the positive electrode mixture onto the positive electrode current collector. In such a case, uneven coating occurs, and the quality of the positive electrode is degraded, which causes problems in productivity and quality.

Therefore, the present invention has been made in view of the above-mentioned conventional circumstances, and has as its object to provide a non-aqueous electrolyte secondary battery excellent in productivity and quality.

[0007]

In order to achieve the above object, a non-aqueous electrolyte secondary battery according to the present invention comprises lithium (Li), manganese (Mn), a metal element other than manganese, and boron (B). And at least one first element selected from the group consisting of oxygen (O) and a molar ratio of the first element to manganese (first element / manganese) of 0.01 / 1. A manganese-containing oxide in a range of 99 or more and 0.5 / 1.5 or less, at least one second element selected from the group consisting of lithium, nickel (Ni), metal elements other than nickel, and boron; A nickel-containing oxide containing oxygen and having a molar ratio of the second element to nickel (second element / nickel) in the range of 0.01 / 0.99 to 0.5 / 0.5. And containing An active material, a positive electrode comprising a binder, a lithium metal as a negative electrode material, a lithium alloy,
Alternatively, a negative electrode containing at least one or more materials capable of doping / dedoping lithium and a non-aqueous electrolyte are provided, and the binder is polyvinylidene fluoride (hereinafter referred to as PVdF).
Called. ) And hexafluoropropylene (hereinafter H
Called FP. ) Is contained.

[0008] The non-aqueous electrolyte secondary battery according to the present invention having the above-described structure is characterized in that the above-described P
A mixed binder of VdF and HFP is used. When the above-mentioned positive electrode active material is used, PV is used as a binder of the positive electrode mixture.
If dF is used, the positive electrode mixture gels, which causes a problem with respect to the productivity and quality of the positive electrode, that is, the productivity and quality of the nonaqueous electrolyte secondary battery.

However, by using a mixed binder of PVdF and HFP as the binder, gelation of the positive electrode mixture is prevented. Thereby, even when a positive electrode active material containing a manganese-containing oxide and a nickel-containing oxide is used as the positive electrode active material, the positive electrode mixture maintains good fluidity. As a result, problems relating to productivity and quality due to gelling of the positive electrode mixture are prevented, and a positive electrode excellent in productivity and quality is realized. By using this positive electrode, a non-aqueous electrolyte secondary battery having excellent productivity and quality can be realized.

[0010] In order to achieve the above-mentioned object, a non-aqueous electrolyte secondary battery according to the present invention comprises a lithium (Li), manganese (Mn), metal element other than manganese, and boron (B). It contains at least one selected first element and oxygen (O) and has a molar ratio of the first element to manganese (first element / manganese) of:
A manganese-containing oxide in the range of 0.01 / 1.99 or more and 0.5 / 1.5 or less, lithium and nickel (N
i) and at least one second element selected from the group consisting of boron and a metal element other than nickel and oxygen, and the molar ratio of the second element to nickel (second element / nickel) A positive electrode active material containing a nickel-containing oxide in the range of 0.01 / 0.99 or more and 0.5 / 0.5 or less, a positive electrode containing a binder, and lithium as a negative electrode material A negative electrode containing at least one of a metal, a lithium alloy, and a material capable of doping and undoping lithium, and a non-aqueous electrolyte, wherein the binder is polyvinylidene fluoride and a styrene-butadiene-based latex (hereinafter, referred to as a latex) , SBR).

The non-aqueous electrolyte secondary battery according to the present invention having the above-described structure is characterized in that the above-described P
A mixed binder of VdF and SBR is used. When the above-mentioned positive electrode active material is used, PV is used as a binder of the positive electrode mixture.
If dF is used, the positive electrode mixture gels, which causes a problem with respect to the productivity and quality of the positive electrode, that is, the productivity and quality of the nonaqueous electrolyte secondary battery.

However, by using a mixed binder of PVdF and SBR as the binder, the positive electrode mixture is prevented from gelling. Thereby, even when a positive electrode active material containing a manganese-containing oxide and a nickel-containing oxide is used as the positive electrode active material, the positive electrode mixture maintains good fluidity. As a result, problems relating to productivity and quality due to gelling of the positive electrode mixture are prevented, and a positive electrode excellent in productivity and quality is realized. By using this positive electrode, a non-aqueous electrolyte secondary battery having excellent productivity and quality can be realized.

Further, in order to achieve the above-mentioned object, a non-aqueous electrolyte secondary battery according to the present invention comprises a lithium (Li), manganese (Mn), metal element other than manganese, and boron (B). It contains at least one selected first element and oxygen (O) and has a molar ratio of the first element to manganese (first element / manganese) of:
A manganese-containing oxide in the range of 0.01 / 1.99 or more and 0.5 / 1.5 or less, lithium and nickel (N
i) and at least one second element selected from the group consisting of boron and a metal element other than nickel and oxygen, and the molar ratio of the second element to nickel (second element / nickel) A positive electrode active material containing a nickel-containing oxide in the range of 0.01 / 0.99 or more and 0.5 / 0.5 or less, a positive electrode containing a binder, and lithium as a negative electrode material A negative electrode containing at least one of a metal, a lithium alloy, and a material capable of doping and undoping lithium; and a non-aqueous electrolyte, wherein the binder is a copolymer of polyvinylidene fluoride and hexafluoropropylene. It is characterized by being united.

The non-aqueous electrolyte secondary battery according to the present invention having the above-described structure is characterized in that the above-described P
A copolymer of VdF and HFP is used. When the above-described positive electrode active material is used, PVd is used as a binder of the positive electrode mixture.
When F is used, the positive electrode mixture gels, and a problem arises with respect to the productivity and quality of the positive electrode, that is, the productivity and quality of the nonaqueous electrolyte secondary battery.

However, by using a copolymer of PVdF and HFP as the binder, the positive electrode mixture is prevented from gelling. Thereby, even when a positive electrode active material containing a manganese-containing oxide and a nickel-containing oxide is used as the positive electrode active material, the positive electrode mixture maintains good fluidity. As a result, problems related to productivity and quality caused by gelation of the positive electrode mixture are prevented,
A positive electrode excellent in productivity and quality is realized. By using this positive electrode, a non-aqueous electrolyte secondary battery having excellent productivity and quality can be realized.

[0016]

Embodiments of the present invention will be described below in detail with reference to the drawings.

FIG. 1 shows a cross-sectional structure of a nonaqueous electrolyte secondary battery according to one embodiment of the present invention. This non-aqueous electrolyte secondary battery is a so-called cylindrical type, and has a band-shaped positive electrode 11 and a negative electrode 12 inside a substantially hollow cylindrical battery can 1.
Electrode body 10 wound with a separator 13
have. The battery can 1 is made of, for example, iron (Fe) plated with nickel, and has one end closed and the other end open. Inside the battery can 1,
A pair of insulating plates 2 and 3 are arranged perpendicular to the winding peripheral surface so as to sandwich the winding electrode body 10.

At the open end of the battery can 1, a battery cover 4, a safety valve mechanism 5 provided inside the battery cover 4, and a PTC (Positive Temperature Coefficient; PTC)
Element 6 is attached by caulking via a gasket 7, and the inside of the battery can 1 is sealed. The battery lid 4 is made of, for example, the same material as the battery can 1. The safety valve mechanism 5 includes a thermal resistance element 6
When the internal pressure of the battery becomes higher than a certain level due to an internal short circuit or external heating, the disk plate 5a is inverted and the battery lid 4 and the wound electrode body are electrically connected to each other. The electrical connection with 10 is cut off. The heat sensitive resistance element 6 limits the current by increasing the resistance value when the temperature rises, and prevents abnormal heat generation due to a large current, and is made of, for example, barium titanate-based semiconductor ceramics. The gasket 7 is made of, for example, an insulating material, and its surface is coated with asphalt.

The wound electrode body 10 includes, for example, the center pin 1
It is wound around 4. A positive electrode lead 15 made of aluminum (Al) or the like is connected to the positive electrode 11 of the wound electrode body 10, and a negative electrode lead 16 made of nickel or the like is connected to the negative electrode 12. The positive electrode lead 15 is welded to the safety valve mechanism 5 so that the battery cover 4
The negative electrode lead 16 is electrically connected to the battery can 1 by welding.

The positive electrode 11 includes, for example, a positive electrode mixture layer and a positive electrode current collector layer, and has a structure in which a positive electrode mixture layer is provided on both surfaces or one surface of the positive electrode current collector layer. . The positive electrode current collector layer is made of, for example, a metal foil such as an aluminum foil, a nickel foil, or a stainless steel foil. The positive electrode mixture layer includes a positive electrode active material containing a manganese-containing oxide and a nickel-containing oxide described below, a binder, and, if necessary, a conductive material such as graphite.

The manganese-containing oxide contains lithium, manganese, at least one first element selected from the group consisting of metal elements other than manganese and boron, and oxygen. The manganese-containing oxide has, for example, a cubic (spinel) structure or a tetragonal structure, and the first element is present at a part of the site of the manganese atom by being replaced with the manganese atom. Formula manganese-containing oxide, expressed the first element in _{Ma Li x Mn 2-y Ma} y
Represented by the O _4. Here, the value of x is in the range of 0.9 ≦ x ≦ 2, and the value of y is in the range of 0.01 ≦ y ≦ 0.5. That is, the composition ratio of the first element to manganese, Ma / Mn, is not less than 0.01 / 1.99 and not more than 0.1 in terms of molar ratio.
The range is 5 / 1.5 or less.

Nickel-containing oxides include lithium and nickel.
Group consisting of Kel, metal elements other than nickel, and boron
At least one second element selected from the group consisting of
Contains. This nickel-containing oxide has, for example, a layered structure.
And the second element is a nickel atom site
Is present by being replaced with a nickel atom. Ni
The chemical formula of the Kel-containing oxide represents the second element by Mb
And typically LiNi _1-zMb_zO₂Indicated by
The composition ratio of lithium and oxygen is Li: O = 1: 2.
The value of z may be within the range of 0.01 ≦ z ≦ 0.5
It is. That is, the composition of the second element with respect to nickel
The ratio Mb / Ni is 0.01 / 0.99 or more in a molar ratio of 0.1 to 0.9.
It is within the range of 5 / 0.5 or less.

These manganese-containing oxides and nickel-containing oxides are considered to stabilize the crystal structure by substituting a part of manganese or nickel with the other elements described above. In the next battery,
High temperature storage characteristics can be improved. The composition ratio Ma / Mn of the first element with respect to manganese is set to a molar ratio of 0.01 / 1.99 or more and 0.5 / 1.5 or less, and the composition ratio Mb / Ni of the second element with respect to nickel is set at a molar ratio. When the amount is 0.01 / 0.99 or more and 0.5 / 0.5 or less, a sufficient effect cannot be obtained if the amount of substitution is smaller than this, and if the amount of substitution is larger than this, after high temperature storage. This is because the high-load discharge capacity of the above is reduced.

As the first element, specifically, iron (F
e), cobalt (Co), nickel (Ni), copper (C
u), zinc (Zn), aluminum (Al), tin (S
n), chromium (Cr), vanadium (V), titanium (T
i), magnesium (Mg), calcium (Ca), strontium (Sr), boron (B), gallium (G
a), at least one selected from the group consisting of indium (In), silicon (Si), and germanium (Ge)
Species are preferred, and as the second element, specifically, iron,
Cobalt, manganese, copper, zinc, aluminum, tin,
Boron, gallium, chromium, vanadium, titanium, magnesium, calcium, strontium, indium,
At least one selected from the group consisting of silicon and germanium is preferred. This is because a manganese-containing oxide or a nickel-containing oxide containing these as the first element or the second element can be obtained relatively easily and is chemically stable.

The mixing ratio of the manganese-containing oxide and the nickel-containing oxide in the positive electrode 11 is, by mass ratio, 10 to 80 of the manganese-containing oxide and 90 to 90 of the nickel-containing oxide.
It is preferably 20. Since the manganese-containing oxide is significantly deteriorated in the electrolyte described later in a high-temperature atmosphere, if the content of the manganese-containing oxide is larger than this, the internal resistance increases after high-temperature storage, and the capacity decreases. It is because. Further, since the nickel-containing oxide has a low discharge potential, if the content of the nickel-containing oxide is larger than this, the high-load discharge capacity at a high-potential cutoff after high-temperature storage becomes low. .

The average particle size of the manganese-containing oxide and the nickel-containing oxide is preferably 30 μm or less. If the average particle diameter is larger than this, expansion and contraction of the positive electrode 11 due to charge and discharge cannot be sufficiently suppressed, and sufficient charge and discharge cycle characteristics cannot be obtained at room temperature.

As the manganese-containing oxide and the nickel-containing oxide, for example, a compound containing a lithium compound, a manganese compound and a first element, or a compound containing a lithium compound, a nickel compound and a second element are prepared. After mixing them at a desired ratio, they can be obtained by heating and firing at a temperature of 600 ° C. to 1000 ° C. in an atmosphere containing oxygen. At that time, as a compound of a raw material, a carbonate, a hydroxide, an oxide, a nitrate, an organic acid salt or the like is used.

In this non-aqueous electrolyte secondary battery, polyvinylidene fluoride (hereinafter referred to as PVdF) is used as a binder.
Called. ) And hexafluoropropylene (hereinafter H
Called FP. ) And / or a styrene-butadiene-based latex (hereinafter referred to as SBR). That is, in this nonaqueous electrolyte secondary battery, the positive electrode mixture layer includes the positive electrode active material containing the manganese-containing oxide and the nickel-containing oxide described above, PVdF and HF.
It is configured to contain a mixed binder with P and / or SBR.

The positive electrode active material containing manganese-containing oxide and nickel-containing oxide described above is used as a binder as PVA.
When dF is used, there is a problem that the positive electrode mixture is easily gelled when a positive electrode mixture is prepared by mixing the positive electrode active material and the binder. Here, since the positive electrode mixture loses its fluidity when gelled, it becomes impossible to apply the positive electrode mixture on the positive electrode current collector layer, and the positive electrode mixture must be re-prepared, thereby lowering productivity. Alternatively, when the positive electrode mixture is applied on the positive electrode current collector layer, uneven coating may occur, and the quality of the positive electrode may be degraded, thereby causing a problem in productivity and quality.

Therefore, in the present invention, when a positive electrode mixture is prepared by mixing a positive electrode active material and a binder, a mixed binder of PVdF and HFP and / or SBR is used as the binder. . By using a mixed binder of PVdF and HFP and / or SBR as the binder, it is possible to prevent the positive electrode mixture from gelling. This allows
Even when a positive electrode active material containing a manganese-containing oxide and a nickel-containing oxide is used as the positive electrode active material, the positive electrode mixture can maintain good fluidity. As a result, it is impossible to apply the positive electrode mixture on the positive electrode current collector layer, so that the positive electrode mixture has to be re-prepared, and the productivity is reduced, or the positive electrode mixture is applied on the positive electrode current collector layer. In this case, it is possible to prevent problems such as uneven coating and deterioration of the quality of the positive electrode, thereby realizing a positive electrode excellent in productivity and quality. By using this positive electrode, a non-aqueous electrolyte secondary battery having excellent productivity and quality can be realized.

Here, the mixing ratio of PVdF and HFP when preparing the above-mentioned mixed binder is PVdF9 by mass ratio.
It is preferable that HFP is 5 to 50% with respect to 5 to 50%. If the mixing ratio of HFP is too large in the mixed binder described above, the positive electrode active material is separated from the positive electrode current collector due to swelling of the nonaqueous electrolyte solution described below, and the cycle characteristics of the nonaqueous electrolyte secondary battery are reduced. This may affect load characteristics.

When preparing the above-mentioned mixed binder, the mixing ratio of PVdF and SBR is expressed by mass ratio of PVdF95.
It is preferable that SBR is 5 to 50% with respect to ５０50%. If the mixing ratio of SBR is too large in the above-mentioned mixed binder, the discharge capacity of the non-aqueous electrolyte secondary battery is reduced.

Therefore, in the mixed binder, PVd
By setting the mixing ratio of F to HFP or SBR within the above range, the above-described effects can be surely obtained.

As a mixed binder, PVdF is mixed with HFP.
And SBR may be mixed to prepare a mixed binder. In such a case, the same effect as above can be obtained.

Further, the same effect as described above can be obtained by using a polymer obtained by copolymerizing PVdF and HFP as a binder. Also in this case, PVdF and H
The mixing ratio with FP is preferably such that the mass ratio of PVdF is 95 to 50% and HFP is 5 to 50%. PVdF
By setting the ratio of HFP to HFP in such a range,
The above-described effects can be reliably obtained.

The negative electrode 12 is, for example, similar to the positive electrode 11,
The negative electrode current collector layer has a structure in which negative electrode mixture layers are respectively provided on both surfaces or one surface. The negative electrode current collector layer is made of, for example, a metal foil such as a copper foil, a nickel foil, and a stainless steel foil. The negative electrode mixture layer is, for example, lithium metal or, for example, 2
It is capable of absorbing and desorbing lithium at a potential of V or less, that is, it comprises one or more of the negative electrode materials capable of doping and undoping. Contains a binder such as vinylidene.

Examples of the negative electrode material capable of doping / dedoping 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 a 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 s> 0, t ≧ 0, and u ≧ 0, respectively.

Here, as a metal element or a semiconductor element capable of forming an alloy or a compound with lithium, 4B
Group metal elements or semiconductor elements are preferred, particularly preferably silicon or tin, and most preferably silicon. Examples of metals or semiconductors that can form alloys or compounds with lithium include Mg, B, Al, and G.
a, In, Si, Ge, Sn, Pb, Sb, Bi, C
d, Ag, Zn, Hf, Zr, Y and their alloy compounds, for example, Li-Al, Li-Al-M (wherein,
M is composed of one or more of 2A, 3B and 4B transition metal elements. ) AlSb, CuMgSb and the like. In addition, these alloys or compounds are also preferable. For example, M _x Si (where M is one or more metal elements excluding Si and x is 0 <x) or M _x Sn (where
M is one or more metal elements except Sn, and x is 0 <
x. ). Specifically, SiB ₄ , S
iB ₆ , Mg ₂ Si, Mg ₂ Sn, Ni ₂ Si, TiS
i ₂ , MoSi ₂ , CoSi ₂ , NiSi ₂ , CaSi
_{2, CrSi 2, Cu 5 Si} , FeSi 2, MnS
_{i 2, NbSi 2, TaSi 2} , VSi 2, such as WSi ₂ or ZnSi ₂ and the like.

Further, as the anode material, the above-mentioned elements or compounds which can be alloyed or compounded with lithium can also be used. That is, in this material,
One or more kinds of group 4B elements may be contained, and metal elements other than group 4B containing lithium may be contained.
Such materials include SiC, Si ₃ N ₄ , Si ₂
N ₂ O, Ge ₂ N ₂ O, SiO _x (where x is 0 <x ≦
2. ), SnO _x (where x is 0 <x ≦ 2), LiSiO, LiSnO and the like.

Further, as the negative electrode material, the above-mentioned elements or compounds which can be alloyed or compounded with lithium can also be used. That is, in this material,
One or more kinds of group 4B elements may be contained, and metal elements other than group 4B containing lithium may be contained.
Such materials include SiC, Si3N4, Si2
N2O, Ge2N2O, SiOx (where x is 0 <x ≦
2. ), SnOx (where x is 0 <x ≦ 2), LiSiO, LiSnO, and the like.

Examples of the negative electrode material capable of doping and undoping lithium include a carbon material, a metal oxide, and a polymer material. As a carbon material, for example,
Examples include non-graphitizable carbon, artificial graphite, cokes, graphites, glassy carbons, fired organic polymer compounds, carbon fibers, activated carbon, and carbon blacks. Among them, cokes include pitch coke, needle coke, petroleum coke, etc. An organic polymer compound fired body is obtained by firing a polymer material such as phenol resin or furan resin at an appropriate temperature to carbonize. Means what you do. 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.

The separator 13 is made of, 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 nonwoven fabric. It may have a structure in which porous films are stacked.

The separator 13 is impregnated with a non-aqueous electrolyte which is a liquid non-aqueous electrolyte. The non-aqueous electrolyte is a non-aqueous solvent in which, for example, a lithium salt is dissolved as an electrolyte salt. Examples of the non-aqueous solvent include propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, γ-butyllactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3 -Dioxolan, 4-methyl-1,3-dioxolan, diethyl ether, sulfolane, methylsulfolane, acetonitrile, propionitrile, anisole, acetate, butyrate or propionate, and the like.
Seeds or a mixture of two or more kinds is used.

As the lithium salt, for example, LiCl
O ₄ , LiAsF ₆ , LiPF ₆ , LiBF ₄ , LiB
(C ₆ H ₅ ), LiCH ₃ SO ₃ , LiCF ₃ SO ₃ ,
There are LiCl, LiBr, and the like, and one or more of these are used in combination.

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

In this non-aqueous electrolyte secondary battery, when charged, for example, lithium ions are separated from the positive electrode 11 and occluded in the negative electrode 12 through the electrolyte impregnated in the separator 13. When the discharge is performed, for example, lithium ions are released from the negative electrode 12 and occluded in the positive electrode 11 via the electrolyte impregnated in the separator 13. Here, since the positive electrode 11 contains the manganese-containing oxide containing the first element and the nickel-containing oxide containing the second element, the battery capacity does not decrease even after storage at a high temperature, and the high capacity is maintained. And a large discharge energy can be obtained even when a high-load discharge is performed under a high potential cutoff condition of, for example, 3.3 V. This non-aqueous electrolyte secondary battery can be manufactured, for example, as follows.

First, for example, a manganese-containing oxide, a nickel-containing oxide, and, if necessary, a conductive agent and a binder are mixed to prepare a positive electrode mixture. -Disperse in a solvent such as pyrrolidone to obtain a paste-like positive electrode mixture slurry. The positive electrode mixture slurry is applied to the positive electrode current collector layer, the solvent is dried, and then compression molded by a roller press or the like to form a positive electrode mixture layer, and the positive electrode 11 is manufactured.

Next, for example, a negative electrode mixture is prepared by mixing a negative electrode material and a binder as necessary, and this negative electrode mixture is dispersed in a solvent such as N-methyl-2-pyrrolidone to form a paste. Negative electrode mixture slurry. The negative electrode mixture slurry is applied to the negative electrode current collector layer, the solvent is dried, and then compression-molded by a roller press or the like to form a negative electrode mixture layer, and the negative electrode 12 is manufactured.

Subsequently, the positive electrode lead 15 is attached to the positive electrode current collector layer by welding or the like, and the negative electrode lead 16 is attached to the negative electrode current collector layer by welding or the like. Thereafter, the positive electrode 11 and the negative electrode 12 are wound via the separator 13,
The distal end of the positive electrode lead 15 was welded to the safety valve mechanism 5 and the distal end of the negative electrode lead 16 was welded to the battery can 1.
The wound positive electrode 11 and negative electrode 12 are sandwiched between a pair of insulating plates 2 and 3 and housed inside the battery can 1. Positive electrode 11 and negative electrode 12
Is stored in the battery can 1 and then a non-aqueous electrolyte is injected into the battery can 1 and impregnated in the separator 13.

Thereafter, the battery cover 4 is attached to the open end of the battery can 1.
The safety valve mechanism 5 and the thermal resistance element 6 are fixed by caulking via the gasket 7. Thus, the non-aqueous electrolyte secondary battery shown in FIG. 1 is formed.

The present invention has been described with reference to the embodiment and the examples. However, the present invention is not limited to the above description, and can be appropriately changed without departing from the gist of the present invention.

Therefore, in the above description, an example of a cylindrical non-aqueous electrolyte secondary battery having a wound structure has been specifically described. However, the present invention is not limited to this. The present invention can also be applied to a secondary battery. Also, the shape of the battery is not limited to a cylindrical shape, and non-cylindrical non-cylindrical batteries having various shapes such as a coin type, a button type, a square type, or a type in which an electrode element is sealed inside a laminated film other than the cylindrical type. The same can be applied to a water electrolyte secondary battery.

In the above description, the case where a non-aqueous electrolyte obtained by dissolving an electrolyte salt in a non-aqueous solvent is used as an example of the non-aqueous electrolyte has been described, but the present invention is not limited to this. Rather, as a non-aqueous electrolyte, a gel electrolyte composed of an electrolyte salt, a swelling solvent, and a matrix polymer, a solid polymer electrolyte composed of a composite of an ion conductive polymer and an electrolyte salt, an ion conductive inorganic ceramic, glass Also, the present invention can be applied to a case where a non-aqueous electrolyte material or the like obtained by mixing an inorganic solid electrolyte mainly containing ionic crystals or the like and a non-aqueous electrolyte is used.

For example, when a gel electrolyte is used as the non-aqueous electrolyte, the composition of the gel electrolyte and the structure of the matrix polymer constituting the gel electrolyte are not limited as long as the ionic conductivity of the gel electrolyte is 1 mS / cm or more. No problem.

Specific examples of the matrix polymer include polyacrylonitrile, polyvinylidene fluoride, a copolymer of polyvinylidene fluoride and polyhexafluoropropylene, polytetrafluoroethylene, polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, and polypropylene. Sphazen, polysiloxane, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethacrylic acid, styrene-butadiene rubber, nitrile-butadiene rubber, polystyrene, polycarbonate, and the like can be used. In particular, in consideration of electrochemical stability, it is preferable to use polyacrylonitrile, polyvinylidene fluoride, polyhexafluoropropylene, polyethylene oxide, or the like.

Further, the weight of the matrix polymer required for producing the gel electrolyte is difficult to specify unequivocally because it depends on the compatibility between the matrix polymer and the non-aqueous electrolyte. 5% by weight to 50% of electrolyte
It is preferable to set the weight%.

[0057]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on specific experimental results.

<Sample 3> In the example, the cylindrical nonaqueous electrolyte secondary battery shown in FIG. 1 was manufactured.

First, lithium carbonate (Li ₂ CO ₃ ), manganese dioxide (MnO ₂ ) and nichrome trioxide (Cr
O ₃ ) and 5 in air at a temperature of 850 ° C.
Lithium, manganese and first element (Ma)
Containing chromium as a manganese-containing oxide LiMn
_1.9 Cr _0.1 O ₄ was produced.

Next, the obtained manganese-containing oxide was pulverized to have an average particle size of 20 μm. The measurement of the average particle size was performed by a laser diffraction method. In addition, lithium hydroxide (LiO
H), nickel monoxide (NiO) and cobalt monoxide (C
oO) in air at a temperature of 750.degree.
Lithium, nickel and second element (Mb)
-Containing oxide LiNi containing cobalt as the material
_0.8 Co _0.2 O ₂ was produced.

Next, the obtained nickel-containing oxide was pulverized to an average particle size of 10 μm. The measurement of the average particle size was similarly performed by the laser diffraction method.

Next, a mixed binder of HFP and PVdF was prepared as a binder. Here, the mixing ratio of HFP and PVdF was HFP: PVdF = 5: 95 by mass ratio.

Subsequently, the obtained manganese-containing oxide and nickel-containing oxide were mixed at a weight ratio of 2: 8, and then 91 parts by weight of the mixed powder and 6 parts by weight of graphite as a conductive agent and 3 parts by weight of the mixed binder prepared above was mixed to prepare a positive electrode mixture. Here, the mixing ratio between the manganese-containing oxide and the nickel-containing oxide is
In the mixing ratio of the binder specified in the present invention according to the present invention, the mixing ratio was set so that the positive electrode mixture was most likely to gel. After preparing the positive electrode mixture, this positive electrode mixture was mixed with N-
Dispersed in methylpyrrolidone to form a positive electrode mixture slurry, uniformly coated on both sides of a positive electrode current collector layer composed of a 20 μm-thick strip-shaped aluminum foil, dried, compression molded to form a positive electrode mixture layer, The positive electrode 11 was produced. Thereafter, a positive electrode lead 15 made of aluminum was attached to one end of the positive electrode current collector layer.

Next, 30 parts by weight of coal tar pitch as a binder was added to 100 parts by weight of coal-based coke as a filler, mixed at about 100 ° C., and then compression-molded by a press machine, and then pressed at a temperature of 1000 ° C. or less. A carbon molded body was produced by heat treatment. Subsequently, the carbon molded body is impregnated with a coal tar pitch melted at a temperature of 200 ° C. or less, and a heat treatment is performed at a temperature of 1000 ° C. or less. Heat treatment was performed to produce a graphitized molded body. Thereafter, the graphitized molded product was pulverized and classified to obtain a powder.

Structural analysis of the obtained graphitized powder by X-ray diffraction revealed that the (002) plane spacing was 0.337 nm and the (002) plane C-axis crystallite thickness was 50. It was 0 nm. The true density determined by the pycnometer method is 2.23 g / cm ³ , the bulk density is 0.83 g / cm ³ , and the average shape parameter is 10
Met. In addition, BET (Brunauer, Emmett, Telle
The specific surface area determined by the r) method is 4.4 m ² / g,
The particle size distribution obtained by the laser diffraction method is as follows.
1.2 μm, cumulative 10% particle size is 12.3 μm, cumulative 50
% Particle size is 29.5 μm, cumulative 90% particle size is 53.7 μm
Met. In addition, the breaking strength of the graphitized particles determined using a Shimadzu micro compression tester (manufactured by Shimadzu Corporation) was 7.0 × 10 ⁷ Pa on average.

After obtaining the graphitized powder, the mixed powder 90
By weight, a negative electrode mixture was prepared by mixing 10 parts by weight of polyvinylidene fluoride as a binder and then dispersed in N-methylpyrrolidone as a solvent to obtain a negative electrode mixture slurry. After preparing the negative electrode mixture slurry, this negative electrode mixture slurry is uniformly applied to both surfaces of a negative electrode current collector layer made of a 10-μm-thick strip-shaped copper foil, dried, compression-molded to form a negative electrode mixture layer. The negative electrode 12 was formed. Thereafter, a copper negative electrode lead 16 was attached to one end of the negative electrode current collector layer.

After producing the positive electrode 11 and the negative electrode 12, respectively, a separator 13 made of a microporous polypropylene film having a thickness of 25 μm is prepared, and the negative electrode 12, the separator 13, the positive electrode 11, and the separator 13 are laminated in this order to have a diameter of 4. A number of spirals were wound around a 0 mm core, and the outermost periphery was fixed with an adhesive tape to produce a wound electrode body 10.

After the wound electrode body 10 is manufactured, the wound electrode body 10 is sandwiched between a pair of insulating plates 2 and 3, the negative electrode lead 16 is welded to the battery can 1, and the positive electrode lead 15 is welded to the safety valve mechanism 5. Then, the wound electrode body 10 was housed inside the nickel-plated iron battery can 1. In addition, in the battery can 1,
Outer diameter 18.0mm, inner diameter 17.38mm, can thickness 0.3
1 mm and a height of 65 mm were used. Wound electrode body 10
Was stored in the battery can 1, and then a non-aqueous electrolyte was injected into the battery can 1. As the non-aqueous electrolyte, one obtained by dissolving LiPF ₆ as an electrolyte salt at a ratio of 1.0 mol / l in a solvent obtained by mixing propylene carbonate and 1,2-dimethoxyethane in equal volumes was used. Thereafter, the battery lid 4 was caulked to the battery can 1 via a gasket 7 coated with asphalt on the surface, thereby producing the cylindrical nonaqueous electrolyte secondary battery shown in FIG.

<Sample 1> A cylindrical non-aqueous electrolyte secondary battery was prepared in the same manner as in Sample 3, except that only PVdF was used as the binder.

<Sample 2> In preparing the mixed binder, the mixing ratio of HFP and PVdF was changed to HFP:
A cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that PVdF was set to 3:97.

<Sample 4> In preparing the mixed binder, the mixing ratio of HFP and PVdF was changed to HFP:
A cylindrical nonaqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that PVdF was set to 50:50.

<Sample 5> In preparing the mixed binder, the mixing ratio of HFP and PVdF was changed to HFP:
A cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that PVdF was set to 60:40.

<Sample 6> A cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that only HFP was used as the binder.

With respect to the non-aqueous electrolyte secondary batteries of Samples 1 to 6 manufactured as described above, the discharge capacity as a battery characteristic was examined by the following method.

After setting the discharge capacity charging voltage to 4.2 V and performing constant current-constant voltage charging at 400 mA for 8 hours, the final voltage was set at 200 mA.
The discharge capacity was measured by discharging to 5V.

Table 1 shows the results. In Table 1, the binder prepared as described above and contained in the positive electrode mixture is generally referred to as binder 1.

Further, the properties of the positive electrode mixture and the state of peeling of the positive electrode mixture layer from the positive electrode current collector at the time of producing each nonaqueous electrolyte secondary battery were visually evaluated. The results are shown in Table 1. In Table 1, in the column of “coating film characteristics”, ◎ indicates that the area density can be applied within ± 5% from the design, and ○ indicates that the area density can be applied within the range of ± 5 to 10% from the design. , △ means that the area density is 10
% Or more, which means that a hole may be formed in the coating film. In Table 1, in the column of “peeling”, “○” indicates that the peeling strength is 1 kgf / mm or more, and “△” indicates that the peeling strength is 0.1 kgf / mm to 1 kg.
x means that the peel strength is 0.1 kgf
/ Mm.

[0078]

[Table 1]

From Table 1, it can be seen that as binder 1 of the positive electrode mixture, H
It can be seen that the desired discharge capacity can be obtained in the nonaqueous electrolyte secondary batteries of Samples 2 to 5 using the mixed binder prepared by mixing FP and PVdF. In addition, it can be seen that the peel strength of the positive electrode mixture layer and the coating film characteristics have been achieved to practical standards.

In particular, when the mixing ratio of HFP and PVdF is 5:
In the nonaqueous electrolyte secondary batteries of Sample 3 and Sample 4, which have a ratio of 95 and 50:50, good discharge capacity is obtained. The properties of the positive electrode mixture were also good, and no peeling of the positive electrode active material layer from the positive electrode current collector was observed.

On the other hand, as a binder for the positive electrode mixture,
In the non-aqueous electrolyte secondary battery of Sample 1 using only PVdF, a favorable value was obtained for the discharge capacity, and peeling of the positive electrode active material layer from the positive electrode current collector was not observed. However, when preparing the positive electrode mixture, the positive electrode mixture gelled, and the properties of the positive electrode mixture could not be said to be good.

As a binder for the positive electrode mixture, PVdF
In the non-aqueous electrolyte secondary battery of Sample 6 using only the above, a good value was obtained for the discharge capacity, and the properties of the positive electrode mixture were also good. However, peeling of the positive electrode active material layer from the positive electrode current collector layer was observed.

Accordingly, by using a mixed binder prepared by mixing HFP and PVdF as the binder for the positive electrode mixture, the properties of the positive electrode mixture are good, and the positive electrode active material No separation from the positive electrode current collector layer
It can be said that a nonaqueous electrolyte secondary battery having a good discharge capacity can be configured.

In particular, when the mixing ratio of HFP and PVdF is 5:
95-50: 50, that is, the mixing ratio of HFP is 5
By setting the content in the range of wt% to 50 wt%, the properties of the positive electrode mixture are the best, and the nonaqueous electrolyte secondary material having a very good discharge capacity without peeling off the positive electrode active material layer from the positive electrode current collector layer. It can be said that a battery can be configured.

<Sample 7> When preparing a mixed binder, SBR and PVdF were mixed to prepare a mixed binder, and the mixing ratio of SBR and PVdF was determined by the mass ratio of SBR:
A cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that PVdF was set to 3:97.

<Sample 8> When preparing the mixed binder, SBR and PVdF were mixed to prepare a mixed binder, and the mixing ratio of SBR and PVdF was determined by the mass ratio of SBR:
A cylindrical nonaqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that PVdF was set to 10:90.

<Sample 9> When preparing a mixed binder, SBR and PVdF were mixed to prepare a mixed binder, and the mixing ratio of SBR and PVdF was determined by the mass ratio of SBR:
A cylindrical nonaqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that PVdF was set to 50:50.

<Sample 10> In preparing the mixed binder, SBR and PVdF were mixed to prepare a mixed binder, and the mixing ratio of SBR and PVdF was determined by the mass ratio of SBR:
A cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that PVdF was set to 60:40.

<Sample 11> A cylindrical non-aqueous electrolyte secondary battery was manufactured in the same manner as in Sample 3, except that only SBR was used as the binder.

With respect to the non-aqueous electrolyte secondary batteries of Samples 7 to 11 manufactured as described above, the discharge capacity as a battery characteristic was examined in the same manner as described above. The results are shown in Table 1. In Table 1, SBR and PV
The mixed binder prepared by mixing with dF is generally referred to as Binder 2. In addition, the meaning of the symbol in Table 1 shall conform to the above.

From Table 1, it can be seen that as binder 2 of the positive electrode mixture, S
It can be seen that in the nonaqueous electrolyte secondary batteries of Samples 7 to 10 using the mixed binder prepared by mixing BR and PVdF, a desired discharge capacity was obtained. In addition, it can be seen that the peel strength of the positive electrode mixture layer and the coating film characteristics have been achieved to practical standards.

In particular, when the mixing ratio of SBR and PVdF is 1
In the nonaqueous electrolyte secondary batteries of Samples 8 and 9 at 0:90 and 50:50, good discharge capacity was obtained, and the properties of the positive electrode mixture were also good. Further, no peeling of the positive electrode active material layer from the positive electrode current collector layer was observed.

On the other hand, as a binder for the positive electrode mixture,
In the nonaqueous electrolyte secondary battery of Sample 11 using only SBR, the properties of the positive electrode mixture were good, and no separation was observed from the positive electrode current collector layer of the positive electrode active material layer. However, a sufficient discharge capacity was not obtained.

Therefore, from the above, by using a mixed binder prepared by mixing SBR and PVdF as a binder for the positive electrode mixture, the properties of the positive electrode mixture are good and the positive electrode active material No separation from the positive electrode current collector layer
It can be said that a nonaqueous electrolyte secondary battery having a good discharge capacity can be configured.

In particular, when the mixing ratio of SBR and PVdF is 5:
95-50: 50, that is, the mixing ratio of HFP is 5
By setting the content in the range of wt% to 50 wt%, the properties of the positive electrode mixture are the best, and the nonaqueous electrolyte secondary material having a very good discharge capacity without peeling off the positive electrode active material layer from the positive electrode current collector layer. It can be said that a battery can be configured.

<Sample 12> HFP and PVdF are
A cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that a copolymer obtained by polymerizing HFP: PVdF at a mass ratio of 3:97 was used as a binder for the positive electrode mixture.

<Sample 13> HFP and PVdF are
A cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that a copolymer obtained by polymerizing HFP: PVdF = 5: 95 by mass ratio was used as a binder for the positive electrode mixture.

<Sample 14> HFP and PVdF are
A cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that a copolymer obtained by polymerizing HFP: PVdF = 50: 50 by mass ratio was used as a binder for the positive electrode mixture.

<Sample 15> HFP and PVdF are
A cylindrical non-aqueous electrolyte secondary battery was produced in the same manner as in Sample 3, except that a copolymer obtained by polymerization at a mass ratio of HFP: PVdF = 60: 40 was used as a binder for a positive electrode mixture.

Samples 12-
For the non-aqueous electrolyte secondary battery of Sample 15, the discharge capacity was examined as the battery characteristics in the same manner as described above.

Table 1 shows the results. In Table 1, a copolymer of HFP and PVdF is generally referred to as a binder 3. In addition, the meaning of the symbol in Table 1 shall conform to the above.

As shown in Table 1, as binder 3 of the positive electrode mixture, H
Sample 1 using a copolymer of FP and PVdF
It can be seen that in the non-aqueous electrolyte secondary batteries of Samples 2 to 15, a desired discharge capacity can be obtained. In addition, it can be seen that the peel strength and coating film characteristics of the positive electrode mixture layer are achieved to practical standards.

In particular, in the nonaqueous electrolyte secondary batteries of Samples 13 and 14 using copolymers obtained by polymerizing HFP and PVdF at a weight ratio of 5:95 and 50:50, a good discharge capacity was obtained. The properties of the positive electrode mixture were also good. Further, no peeling of the positive electrode active material layer from the positive electrode current collector layer was observed.

Therefore, based on these facts, HFP and PVdF were used as binders for the positive electrode mixture in a weight ratio of 5: 5.
By using a copolymer polymerized at a ratio of 95 to 50:50, the properties of the positive electrode mixture are very good, the positive electrode active material layer does not peel off from the positive electrode current collector, and the discharge capacity is very good. It can be said that a non-aqueous electrolyte secondary battery having

[0105]

The non-aqueous electrolyte secondary battery according to the present invention has at least one first element selected from the group consisting of lithium (Li), manganese (Mn), a metal element other than manganese, and boron (B). And a molar ratio of the first element to manganese (first element / oxygen (O)).
Manganese) is 0.01 / 1.99 or more and 0.5 / 1.5
A manganese-containing oxide in the following range, at least one second element selected from the group consisting of lithium, nickel (Ni), a metal element other than nickel, and boron, and oxygen, and The molar ratio of the second element (second element / nickel) is 0.01 / 0.
A positive electrode active material containing a nickel-containing oxide in the range of 99 or more and 0.5 / 0.5 or less, a positive electrode containing a binder, and lithium metal, a lithium alloy, or A negative electrode containing at least one or more materials capable of doping and undoping lithium is provided, and a non-aqueous electrolyte is used, wherein a binder is polyvinylidene fluoride (hereinafter referred to as P
VdF. ) And hexafluoropropylene (hereinafter referred to as HFP).

In the non-aqueous electrolyte secondary battery according to the present invention having the above-described structure, since the mixed binder of PVdF and HFP is used as the binder, the positive electrode mixture is prevented from gelling. Can be. Thereby, even when a positive electrode active material containing a manganese-containing oxide and a nickel-containing oxide is used as the positive electrode active material, the positive electrode mixture can maintain good fluidity. As a result, it is possible to prevent problems relating to productivity and quality due to gelation of the positive electrode mixture, and to realize a positive electrode and a nonaqueous electrolyte secondary battery excellent in productivity and quality.

The non-aqueous electrolyte secondary battery according to the present invention has at least one first element selected from the group consisting of lithium (Li), manganese (Mn), a metal element other than manganese, and boron (B). And a molar ratio of the first element to manganese (first element / manganese) is not less than 0.01 / 1.99 and not more than 0.5 /
A manganese-containing oxide in a range of 1.5 or less, and at least one second element selected from the group consisting of lithium, nickel (Ni), a metal element other than nickel, and boron; and oxygen. And the molar ratio of the second element to nickel (second element / nickel) is 0.01
A positive electrode active material containing a nickel-containing oxide in the range of /0.99 or more and 0.5 / 0.5 or less, a positive electrode containing a binder, and lithium metal or lithium as a negative electrode material An alloy or a negative electrode containing at least one kind of material capable of doping / dedoping lithium and a non-aqueous electrolyte, wherein a binder is polyvinylidene fluoride and a styrene-butadiene-based latex (hereinafter, referred to as SBR) ) Is contained.

In the non-aqueous electrolyte secondary battery according to the present invention having the above-described structure, since a mixed binder of PVdF and SBR is used as the binder, it is possible to prevent the positive electrode mixture from gelling. Can be. Thereby, even when a positive electrode active material containing a manganese-containing oxide and a nickel-containing oxide is used as the positive electrode active material, the positive electrode mixture can maintain good fluidity. As a result, it is possible to prevent problems relating to productivity and quality due to gelation of the positive electrode mixture, and to realize a positive electrode and a nonaqueous electrolyte secondary battery excellent in productivity and quality.

Further, the non-aqueous electrolyte secondary battery according to the present invention has at least one first element selected from the group consisting of lithium (Li), manganese (Mn), a metal element other than manganese, and boron (B). And a molar ratio of the first element to manganese (first element / manganese) is not less than 0.01 / 1.99 and not more than 0.5 /
A manganese-containing oxide in a range of 1.5 or less, and at least one second element selected from the group consisting of lithium, nickel (Ni), metal elements other than nickel, and boron, and oxygen. And the molar ratio of the second element to nickel (second element / nickel) is 0.01
A positive electrode active material containing a nickel-containing oxide in the range of /0.99 or more and 0.5 / 0.5 or less, a positive electrode containing a binder, and lithium metal or lithium as a negative electrode material An alloy, or a negative electrode containing at least one or more materials capable of doping / dedoping lithium and a non-aqueous electrolyte, wherein the binder is a copolymer of polyvinylidene fluoride and hexafluoropropylene. It is characterized by the following.

In the non-aqueous electrolyte secondary battery according to the present invention having the above-described structure, a copolymer of PVdF and HFP is used as a binder, so that the positive electrode mixture can be prevented from gelling. it can. Thereby, even when a positive electrode active material containing a manganese-containing oxide and a nickel-containing oxide is used as the positive electrode active material, the positive electrode mixture can maintain good fluidity. As a result, it is possible to prevent problems relating to productivity and quality due to gelation of the positive electrode mixture, and to realize a positive electrode and a nonaqueous electrolyte secondary battery excellent in productivity and quality.

Therefore, according to the present invention, it is possible to provide a non-aqueous electrolyte secondary battery excellent in productivity and quality.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing a configuration example of a nonaqueous electrolyte secondary battery to which the present invention is applied.

[Explanation of symbols]

1 battery can, 2, 3 insulating plate, 4 battery lid, 5 safety valve mechanism, 6 thermal resistance element, 7 gasket, 10 wound electrode body, 11 positive electrode, 12 negative electrode, 13 separator,
14 Center pin, 15 Positive lead, 16 Negative lead

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5H029 AJ14 AK03 AK19 AL07 AL12 AM03 AM04 AM05 AM07 BJ02 BJ14 DJ08 EJ12 EJ14 HJ01 HJ02 5H050 AA19 BA17 CA08 CA09 CA29 CB08 DA11 EA23 EA24 FA05 HA01 HA02

Claims (9)

[Claims] At least one first element selected from the group consisting of lithium (Li), manganese (Mn), a metal element other than manganese, and boron (B), and oxygen (O). The molar ratio of the first element to the manganese (first element / manganese) is 0.01 /
A manganese-containing oxide in the range of 1.99 to 0.5 / 1.5, and at least one second element selected from the group consisting of lithium, nickel (Ni), metal elements other than nickel, and boron; And a molar ratio of the second element to the nickel (second element).
Element / nickel) is 0.01 / 0.99 or more and 0.5 /
A positive electrode containing a nickel-containing oxide in a range of 0.5 or less, a positive electrode containing a binder, and lithium metal, a lithium alloy, or lithium as a negative electrode material. At least one of the possible materials
A non-aqueous electrolyte secondary battery, comprising: a negative electrode containing at least one kind; and a non-aqueous electrolyte, wherein the binder is a mixed binder containing polyvinylidene fluoride and hexafluoropropylene. . 2. The binder according to claim 1, wherein a mixing ratio of the polyvinylidene fluoride and hexafluoropropylene is a mass ratio,
2. The nonaqueous electrolyte secondary battery according to claim 1, wherein the binder is a mixture of the polyvinylidene fluoride 95 to 50 and the hexafluoropropylene 5 to 50. 5. 3. The mixing ratio of the manganese-containing oxide and the nickel-containing oxide in the positive electrode is expressed by mass ratio,
The non-aqueous electrolyte secondary battery according to claim 1, wherein the nickel-containing oxide is 90 to 20 with respect to the manganese-containing oxide 10 to 80. 4. It comprises oxygen (O) and at least one first element selected from the group consisting of lithium (Li), manganese (Mn), metal elements other than manganese, and boron (B). The molar ratio of the first element to the manganese (first element / manganese) is 0.01 /
A manganese-containing oxide in the range of 1.99 to 0.5 / 1.5, and at least one second element selected from the group consisting of lithium, nickel (Ni), metal elements other than nickel, and boron; And a molar ratio of the second element to the nickel (second element).
Element / nickel) is 0.01 / 0.99 or more and 0.5 /
A positive electrode containing a nickel-containing oxide in a range of 0.5 or less, a positive electrode containing a binder, and lithium metal, a lithium alloy, or lithium as a negative electrode material. At least one of the possible materials
A non-aqueous electrolyte comprising: a negative electrode containing at least one of a plurality of types; and a non-aqueous electrolyte, wherein the binder is a mixed binder containing polyvinylidene fluoride and a styrene-butadiene-based latex. Next battery. 5. The binder according to claim 1, wherein the mixing ratio of the polyvinylidene fluoride and the styrene-butadiene-based latex is:
The non-aqueous electrolyte secondary battery according to claim 4, wherein the binder is a mixed binder in which the styrene-butadiene latex (5 to 50) is mixed with the polyvinylidene fluoride (95 to 50) in mass ratio. 6. The mixing ratio of the manganese-containing oxide and the nickel-containing oxide in the positive electrode is expressed by mass ratio,
The non-aqueous electrolyte secondary battery according to claim 4, wherein the nickel-containing oxide is 90 to 20 with respect to the manganese-containing oxide 10 to 80. 7. It comprises oxygen (O) and at least one first element selected from the group consisting of lithium (Li), manganese (Mn), metal elements other than manganese, and boron (B). The molar ratio of the first element to the manganese (first element / manganese) is 0.01 /
A manganese-containing oxide in the range of 1.99 to 0.5 / 1.5, and at least one second element selected from the group consisting of lithium, nickel (Ni), metal elements other than nickel, and boron; And a molar ratio of the second element to the nickel (second element).
Element / nickel) is 0.01 / 0.99 or more and 0.5 /
A positive electrode containing a nickel-containing oxide in a range of 0.5 or less, a positive electrode containing a binder, and lithium metal, a lithium alloy, or lithium as a negative electrode material. At least one of the possible materials
A non-aqueous electrolyte secondary battery comprising: a negative electrode containing at least one of the following types; and a non-aqueous electrolyte, wherein the binder is a copolymer of polyvinylidene fluoride and hexafluoropropylene. 8. The copolymer is characterized in that the mixing ratio of the polyvinylidene fluoride and hexafluoropropylene is in a mass ratio of 95 to 50 of the polyvinylidene fluoride and 5 to 50 of the hexafluoropropylene. The non-aqueous electrolyte secondary battery according to claim 7, wherein 9. The mixing ratio of the manganese-containing oxide and the nickel-containing oxide in the positive electrode is by mass ratio, that is, the manganese-containing oxide is 10 to 80 and the nickel-containing oxide is 90 to 20. 7. The method according to claim 7, wherein
The non-aqueous electrolyte secondary battery according to the above.