JP3081981B2 - Non-aqueous electrolyte secondary battery and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte secondary battery using a material capable of inserting and extracting lithium as a negative electrode active material and a positive electrode active material and using a lithium ion conductive non-aqueous electrolyte. The present invention relates to a novel secondary battery having high voltage, high energy density, excellent charge / discharge characteristics, and long cycle life.

[0002]

2. Description of the Related Art A non-aqueous electrolyte battery using lithium as a negative electrode active material has advantages such as high voltage, high energy density, small self-discharge, and excellent long-term reliability. It is already widely used as a power source for cameras and the like. However, with the recent remarkable development of portable electronic devices and communication devices,
A wide variety of devices that require a large current output from batteries as power sources have emerged. From the viewpoint of economy and reduction in size and weight of devices, rechargeable and high-energy density secondary batteries are strongly demanded. Have been. For this reason, research and development for promoting the conversion of the non-aqueous electrolyte battery having a high energy density into a secondary battery has been actively carried out, and some of them have been put to practical use. However, energy density, charge / discharge cycle life, reliability, etc. Not enough.

Conventionally, as a positive electrode active material constituting a positive electrode of this type of secondary battery, the following three types are used depending on the form of charge / discharge reaction.
Species types have been found. The first type is a metal chalcogenide such as TiS ₂ , MoS ₂ , NbSe ₃ , MnO ₂ , MoO ₃ , V ₂ O ₅ , Li _x CoO ₂ , L
_{i X NiO 2, Li x Mn} 2 O 4 or the like as a so metal oxides, only crystals of the interlayer and the grating position or the interstitial gap lithium-ion (cation) of intercalation and deintercalation reactions and the like Type that comes in and out. Second
The type is a type in which mainly anions alone are stably introduced and removed by doping and undoping reactions, such as conductive polymers such as polyaniline, polypyrrole, and polyparaphenylene. The third type is a type (intercalation, deintercalation or doping, undoping, etc.) in which both lithium cations and anions can enter and exit, such as graphite intercalation compounds and conductive polymers such as polyacene. .

On the other hand, as the negative electrode active material constituting the negative electrode of this type of battery, when metallic lithium is used alone, the electrode potential is the lowest, so that a positive electrode using the above-described positive electrode active material is used. The output voltage of the combined battery is the highest, and the energy density is high, which is preferable.However, dendrites and passive compounds are generated on the negative electrode due to charge and discharge, and there is a problem that deterioration due to charge and discharge is large and cycle life is short. . In order to solve this problem, (1) lithium and Al, Zn, Sn, Pb, Bi, Cd
(2) WO ₂ , MoO ₂ , Fe
Inorganic compounds such as ₂ O ₃ , TiS ₂ , graphite, intercalation compounds or insertion compounds in which lithium ions are occluded in the crystal structure of a carbonaceous material obtained by calcining an organic substance, and (3) doping lithium ions It has been proposed to use a material capable of inserting and extracting lithium ions, such as conductive polymers such as polyacene and polyacetylene.

[0005]

However, in general, a negative electrode using a material capable of inserting and extracting lithium ions other than lithium metal as described above and a positive electrode active material as described above are used as the negative electrode active material. When a battery is configured by combining the positive electrode and the positive electrode, the operating voltage of the battery is higher than that of the negative electrode active material because the electrode potential of these negative electrode active materials is more noble than the electrode potential of metallic lithium. There is the disadvantage that it is much lower. For example, lithium and A
l, Zn, Pb, Sn, Bi, 0.2~0.8V in the case of using an alloy of Cd, etc., carbon - 0 to 1 V in a lithium intercalation compound, a lithium ion insertion compound such as MoO ₂ and WO ₂ 0 The operating voltage is reduced by 0.5 to 1.5 V.

In addition, since elements other than lithium also serve as negative electrode components, the capacity and energy density per volume and weight are significantly reduced. Further, when the alloy of lithium and another metal of the above (1) is used, the efficiency of use of lithium during charge and discharge is low, and cracks occur in the electrodes due to repetition of charge and discharge, causing cracks and the like. Therefore, there is a problem that the cycle life is short, and in the case of the lithium intercalation compound or the insertion compound of (2), deterioration such as collapse of a crystal structure or generation of an irreversible substance due to overcharging / discharging occurs, and a high electrode potential ( There is a drawback that the output potential of a battery using this is low because there are many precious materials, and in the case of the conductive polymer of (3), the charge / discharge capacity, particularly the charge / discharge capacity per volume is small. There's a problem.

Therefore, in order to obtain a secondary battery having a high voltage, a high energy density, excellent charge / discharge characteristics and a long cycle life, the electrode potential with respect to lithium is low (low) and lithium during charge / discharge is required. It is necessary to use a negative electrode active material which is free from deterioration such as collapse of a crystal structure and generation of an irreversible substance due to occlusion and release of ions, and has a large amount capable of reversibly storing and releasing lithium ions, that is, an effective charge / discharge capacity.

On the other hand, the above-mentioned positive electrode active material of the first type generally has a large energy density, but has a drawback that when overcharged or overdischarged, deterioration due to crystal collapse or generation of irreversible material is large. . On the other hand, the second and third types have a disadvantage that the capacity and the energy density are small.

For this reason, in order to obtain a secondary battery having excellent overcharge characteristics and overdischarge characteristics and a high capacity and a high energy density, there is no collapse of crystals or generation of irreversible substances due to overcharge and overdischarge, and It is necessary to use a positive electrode active material having a large amount capable of reversibly storing and releasing lithium ions.

[0010]

Means for Solving the Problems The present invention for solving such problems described above, as an active material for positive electrode of this type of battery, the (1) formula _{Li x1 M y B z O 2} ( 1) (where M is a transition metal, and x1, y, and z are each 0 <x1 ≦ 1.15, 0.85 ≦ y + z ≦ 1.3, 0 ≦
z) Lithium transition metal composite oxide or lithium boron transition metal composite oxide having a layered structure represented by the formula (2), and Li _x2 MnO (2) of the above formula (2) (where 0 ≦ x2 ) Is proposed to use a composite oxide of manganese Mn and lithium Li.

The lithium transition metal composite oxide or lithium boron transition metal composite oxide used as the positive electrode active material of the battery of the present invention can be synthesized as follows. That is, each of lithium Li, transition metal M, and boron B alone or each oxide, hydroxide or carbonate,
A salt such as a nitrate is mixed at a predetermined ratio, and the mixture is heated to a temperature of 600 ° C. or more in air or an atmosphere containing oxygen, preferably 70 ° C.
It is obtained by heating and baking at a temperature of 0 to 900 ° C. Oxides thereof as sources of Li, M, B, etc.,
Alternatively, in the case of using a compound having oxygen, heat synthesis can be performed in an inert atmosphere. The heating time of 4 to 50 hours is usually sufficient, but it is effective to repeat the firing, cooling, and pulverizing and mixing processes several times in order to promote the synthesis reaction and improve the uniformity.

In the formula (1), the Li amount x1 is a stoichiometric composition x1 = 1 as a standard in the above heat synthesis, but ± 1.
A non-stoichiometric composition of about 5% is also possible, and 0 <x1 ≦ 1.15 can be achieved by electrochemical intercalation, deintercalation, or the like. As the transition metal M, Co, Ni, Fe, Mn, Cr, V and the like are preferable.
In particular, Co and Ni are preferable because of their excellent charge / discharge characteristics. As the boron amount z and the transition metal M amount y, 0 ≦ z and 0.
When 85 ≦ y + z ≦ 1.3, the effects on reduction of polarization (internal resistance) during charge and discharge, improvement of cycle characteristics, and the like are remarkable, which is preferable. On the other hand, the charge / discharge capacity in each cycle decreases when the boron amount z is too large, and becomes maximum when 0 <z ≦ 0.5. Therefore, this range is particularly preferable.

Preferred methods for producing the composite oxide of manganese and lithium used as the active material of the negative electrode of the battery of the present invention include, but are not limited to, the following two methods. In the first method, each of the above-described manganese and lithium alone or a compound having oxygen thereof is mixed at a predetermined molar ratio, and heated in an inert atmosphere or in a vacuum or in an atmosphere in which the amount of oxygen is controlled. It is a method of combining. The respective compounds of manganese and lithium as starting materials include oxides, hydroxides, salts such as carbonates and nitrates or organic compounds, etc. Any compound that produces The heating temperature varies depending on the starting material and the heating atmosphere, but synthesis is possible at 400 ° C or higher, preferably 600 ° C or higher, more preferably 70 ° C or higher.
A temperature of 0 ° C. or higher is preferred.

The composite oxide of manganese and lithium thus obtained can be used as an active material for a negative electrode as it is or after being subjected to processing such as pulverization and sizing as required. In the same manner as in the second method described below, lithium ions are further stored in the composite oxide by an electrochemical reaction between the lithium-containing manganese composite oxide and metallic lithium or a lithium-containing substance. Alternatively, conversely, a compound having a lithium content increased or decreased by releasing lithium ions from the composite oxide may be used as the active material.

The second method is a method of obtaining a composite oxide of manganese and lithium by absorbing lithium ions in MnO by an electrochemical reaction between manganese monoxide MnO and lithium or a substance containing lithium. . Examples of the substance containing lithium for use in this electrochemical reaction include, for example, substances capable of inserting and extracting lithium ions such as those used for the positive electrode active material or the negative electrode active material mentioned in the section of the prior art. Can be used.

Such occlusion of lithium ions by electrochemical reaction to MnO can be performed in the battery after the battery is assembled or in or outside the battery during the battery manufacturing process. Specifically, it can be performed as follows. That is, (1) MnO or a mixture obtained by mixing them with a conductive agent and a binder into a predetermined shape is used as one electrode (working electrode), and lithium metal or a substance containing lithium is used as the other electrode. An electrochemical cell is constructed by contacting a lithium ion conductive non-aqueous electrolyte as an electrode (counter electrode) with both electrodes facing each other, and conducting or discharging an appropriate current in the direction in which the working electrode undergoes a cathodic reaction. Method to occlude lithium ions into MnO. A non-aqueous electrolyte secondary battery is formed by using the obtained working electrode as a negative electrode as it is or as an active material constituting the negative electrode.

(2) MnO or a mixture thereof with a conductive agent and a binder is formed into a predetermined shape, and lithium or an alloy of lithium is pressed or contacted and laminated to form a negative electrode. Incorporate into a water electrolyte secondary battery. A method in which the laminated electrode contacts the electrolyte in the battery to form a kind of local battery, self-discharges, and electrochemically occludes lithium in MnO.

[0018] (3) of MnO constitutes a negative electrode as an active material of the negative electrode, a nonaqueous using a positive electrode active material Li _x1 M _y B _z O ₂ of the lithium ion containing lithium in the positive electrode capable of absorbing and releasing the invention Construct an electrolyte secondary battery. A method in which lithium ions are inserted into MnO by charging or discharging when used as a battery.

The composite oxide Li _x2 MnO of manganese and lithium thus obtained is used as the active material of the negative electrode. In the formula (2), the composition ratio of manganese Mn and oxygen O is 1: 1 as described above as a standard, but a non-stoichiometric compound often occurs due to the deficiency of manganese Mn or oxygen O during synthesis. The extent of the defect extends to ± 25%. Such nonstoichiometric compositions are also included in the present invention. The content x2 of lithium may be within a range in which the composite oxide is stably present, and is particularly preferably in a range of 0 ≦ x2 ≦ 2.

On the other hand, as the electrolyte, γ-butyrolactone, propylene carbonate, ethylene carbonate,
LiClO ₄ , LiPF ₆ , LiB as a supporting electrolyte in a single or mixed organic solvent such as butylene carbonate, dimethyl carbonate, diethyl carbonate, methylformate, 1,2-dimethoxyethane, tetrahydrofuran, dioxolan, dimethylformamide, etc.
An organic electrolytic solution in which a lithium ion dissociable salt such as F ₄ or LiCF ₃ SO ₃ is dissolved; a polymer solid electrolyte in which the lithium salt is dissolved in a polymer such as polyethylene oxide or a crosslinked polyphosphazene; or Li ₃ N , LiI, etc., as long as it is a lithium ion conductive non-aqueous electrolyte such as an inorganic solid electrolyte.

[0021]

According to the present invention, the above-mentioned L capable of inserting and extracting lithium is used.
The ix ₂ MnO negative electrode active material, using Li _x 1M _y BzO ₂ in the positive electrode active material, by using a lithium ion conductive non-aqueous electrolyte, a high voltage, excellent and charge-discharge characteristics at high energy density, cycle A new secondary battery having a long life can be provided.

The negative electrode according to the present invention using the composite oxide Lix ₂ MnO of manganese and lithium as an active material has a large charge / discharge capacity in a base region where the electrode potential with respect to metallic lithium is 0 to 1.5 V, and has an excessively high charge / discharge capacity. Deterioration due to charge overdischarge is small,
Has excellent cycle characteristics. Although the reason why such excellent charge / discharge characteristics are obtained is not necessarily clear, the composite oxide Li _x2 MnO of manganese and lithium, which is the negative electrode active material of the present invention, has a high mobility of lithium ions in this structure. It is presumed that lithium ions are easily absorbed and released because there are so many sites capable of occluding lithium ions.

On the other hand, Li _x1 used as a positive electrode active material
M _y B _z O ₂ is about 4V is the electrode potential relative to lithium metal
Or higher, and 0 <x ≦ 1.1
Reversible charge / discharge by intercalation and deintercalation of Li ions is possible between 5, and deterioration due to overcharge and overdischarge is small, and excellent cycle characteristics are obtained. In particular, when the content z of boron B is 0.05 ≦ z <
At 0.5, the polarization is small and the cycle characteristics are excellent. Although the reason why such excellent charge / discharge characteristics are obtained is not necessarily clear, the cathode active material Li _x1 M of the present invention is not clearly _{understood.
y} B _z O ₂ is a layered oxide Li _x1 M containing no B
B by such a part of the M atoms in _{y 'O 2} is replaced by B atoms
It is presumed that this is because the crystal structure and the electronic structure are changed, so that the Li ion conductivity is increased and the insertion and extraction of lithium ions are facilitated.

Therefore, a battery using the negative electrode active material and the positive electrode active material has an extremely large amount of reversible insertion and extraction of lithium ions, that is, a remarkably large charge / discharge capacity, and a small charge / discharge polarization. , And further exhibit almost no degradation such as decomposition or crystal collapse due to overcharge and overdischarge, and exhibit excellent characteristics with extremely stable and long cycle life.

Hereinafter, the present invention will be described in more detail by way of examples.

[0026]

【Example】

(Embodiment 1) FIG. 1 is a sectional view of a coin-type battery showing an example of a non-aqueous electrolyte secondary battery according to the present invention. In the figure, reference numeral 1 denotes a negative electrode case also serving as a negative electrode terminal, which is formed by drawing a stainless steel plate having one outer surface Ni-plated. Reference numeral 3 denotes a negative electrode formed by using a negative electrode active material according to the present invention, which will be described later. The negative electrode case 1 includes a negative electrode current collector 2 made of a conductive adhesive containing carbon as a conductive filler.
Adhered to. Reference numeral 7 denotes a stainless steel positive electrode case in which one outer surface is Ni-plated, and also serves as a positive electrode terminal. Reference numeral 5 denotes a positive electrode formed by using a positive electrode active material according to the present invention, which will be described later, and is bonded to a positive electrode case 7 by a positive electrode current collector 6 made of a conductive adhesive using carbon as a conductive filler. Reference numeral 4 denotes a separator made of a porous film of polypropylene, which is impregnated with an electrolytic solution. Reference numeral 8 denotes a gasket mainly composed of polypropylene, which is interposed between the negative electrode case 1 and the positive electrode case 7 to maintain the electrical insulation between the negative electrode and the positive electrode, and at the same time, the opening edge of the positive electrode case is bent inward and caulked. The battery contents are hermetically sealed. The electrolyte is propylene carbonate
Lithium perchlorate LiC in a mixed solvent of 1: 1, 2: 2 volume ratio of ethylene carbonate and 1,2-dimethoxyethane
A solution obtained by dissolving lO ₄ at 1 mol / l was used. The size of the battery was 20 mm in outer diameter and 1.6 mm in thickness.

The negative electrode 3 was manufactured as follows. A commercially available manganese monoxide MnO having a purity of 99.9% was pulverized and sized using an automatic mortar to a particle size of 53 μm or less as a negative electrode active material according to the present invention. Graphite was used as a conductive agent and crosslinked as a binder. 65: 2 weight ratio acrylic resin
The mixture was mixed at a ratio of 0:15 to form a negative electrode mixture. Then, the negative electrode mixture was mixed at ² ton / cm ² with a diameter of 15 mm and a thickness of 0.2.
After pressure molding into a 3 mm pellet, the product was dried by heating under reduced pressure at 200 ° C. for 10 hours to obtain a negative electrode.

The positive electrode 5 was manufactured as follows. Lithium hydroxide LiOH.H ₂ O and cobalt carbonate CoCO ₃ are weighed so that the molar ratio of Li: Co becomes 1: 1 and sufficiently mixed using a mortar, and the mixture is heated to 850 ° C. in the atmosphere. For 12 hours, cooled and then crushed and sized to a particle size of 53 μm or less. This firing and pulverizing and sizing were repeated twice to synthesize the positive electrode active material LiCoO _{2 according} to the present invention.

This product is used as a positive electrode active material, graphite is mixed as a conductive agent, and a fluorine resin or the like is mixed as a binder in a weight ratio of 80: 15: 5 to form a positive electrode mixture.
Next, this positive electrode mixture was applied at ² ton / cm ² and a diameter of 16.2 m.
m after being pressed into 0.67 mm thick pellets
What was dried by heating under reduced pressure at 0 ° C. for 10 hours was used as a positive electrode.

The thus prepared battery (battery A) was aged at room temperature for one week, and then subjected to a charge / discharge test described later. The battery A was charged at a constant current of 1 mA at a charge end voltage of 4.4 V and a discharge end voltage of 2.0 V.
FIG. 2 shows the charge / discharge characteristics of the first and second cycles when the charge / discharge cycle was performed under the conditions described above, and FIG. 3 shows the cycle characteristics. The charge / discharge cycle was started from charging.

In the battery A, lithium ions are released from the positive electrode active material into the electrolyte by charging, and the lithium ions move in the electrolyte and react with the negative electrode active material in an electrode.
Li _x2 MnO lithium-manganese composite oxide electrochemically lithium ions in the active material containing lithium is occluded
Is generated. Next, at the time of discharging, lithium ions are released from the lithium manganese composite oxide of the negative electrode into the electrolyte, move in the electrolyte and are occluded by the positive electrode active material, so that charging and discharging can be stably repeated. Here, the negative electrode active material is a composite oxide L containing lithium by the first charge.
After the generation of i _x2 MnO, in the subsequent discharge-charge cycle, a lithium-containing composite oxide Li _{x2 ′} MnO is formed except at the time of complete discharge.

As is clear from FIGS. 2 and 3, the battery A according to the present invention has a remarkably large charge / discharge capacity.
Further, the decrease in the discharge capacity (charge / discharge efficiency) relative to the charge capacity is extremely small except in the first cycle, and the decrease in the discharge capacity (cycle deterioration) due to repeated charge / discharge is also small.
Furthermore, it can be seen that the difference in operating voltage between charging and discharging is extremely small over the entire charging and discharging region, the polarization (internal resistance) of the battery is extremely small, and large-current charging and discharging is easy.

The reason why the decrease in the discharge capacity in the first cycle (initial loss) with respect to the charge capacity in the first cycle is slightly large is that lithium ions are electrochemically added to the negative electrode active material in the first cycle charge. At the time of occlusion, the main cause is a side reaction that occurs between Li and graphite or a binder added as a conductive agent to the negative electrode mixture, and is occluded by MnO of the negative electrode active material, during discharge. L remaining without being released
It is considered that i exists.

Example 2 In FIG. 1, the negative electrode 3 was manufactured as follows. The same negative electrode active material and negative electrode mixture as in Example 1 were pressed at ² ton / cm ² into a pellet having a diameter of 15 mm and a thickness of 0.33 mm, and then dried by heating under reduced pressure at 200 ° C. for 10 hours. A lithium-negative electrode composite pellet-laminated electrode obtained by punching out a lithium foil having a predetermined thickness to a diameter of 14 mm on the top thereof was used as a negative electrode.

The positive electrode 5 was manufactured as follows. Lithium hydroxide LiOH.H ₂ O, cobalt carbonate CoCO _3, and boron oxide B ₂ O ₃ were prepared at a molar ratio of Li: Co: B of 1: 0.
The mixture was weighed so as to be 9: 0.1, sufficiently mixed using a mortar, and heated and fired in the air at a temperature of 850 ° C. for 12 hours. After cooling, the mixture was pulverized and sized to a particle size of 53 μm or less.
This firing and pulverization and sizing were repeated twice to synthesize the positive electrode active material LiCo _0.9 B _0.1 O _{2 according} to the present invention.

This product is used as a positive electrode active material, and graphite is mixed as a conductive agent with fluorine resin and the like as a binder in a weight ratio of 80: 15: 5 to form a positive electrode mixture.
Next, this positive electrode mixture was applied at ² ton / cm ² and a diameter of 16.2 m.
m after being pressed into a 0.47 mm thick pellet.
What was dried by heating under reduced pressure at 0 ° C. for 10 hours was used as a positive electrode.

Except for this, a battery B similar to the battery A of Example 1 was prepared. The battery thus manufactured was aged at room temperature for one week, and then subjected to a charge / discharge test described later. Due to this aging, the lithium-negative electrode mixture pellet electrode of the negative electrode came into contact with the non-aqueous electrolyte in the battery, and substantially all of the lithium foil was electrochemically occluded in the negative electrode mixture.

The battery B thus obtained is also
3. End voltage of charging at a constant current of 1 mA as in Example 1.
A charge / discharge cycle test was performed under the conditions of 4 V and a discharge end voltage of 2.0 V. FIG. 4 shows the charge / discharge characteristics of the first and second cycles, and FIG. 5 shows the cycle characteristics.

As is clear from the figure, the battery B of this embodiment is
It can be seen that the battery A has better charge / discharge characteristics than the battery A of Example 1. In particular, there is almost no decrease (initial loss) in the discharge capacity in the first cycle relative to the charge capacity in the first cycle,
It can be seen that it is significantly improved as compared with the battery A of Example 1. In this method, lithium corresponding to a side reaction with a conductive agent or a binder during charge / discharge or a residual amount in MnO is previously laminated on a negative electrode mixture to assemble a battery and make the electrolyte come into contact with the electrolyte in the battery. As a result, the lithium was spontaneously reacted with the negative electrode mixture after the battery was assembled to cause occlusion, so that no lithium loss occurred in the negative electrode during charging and discharging.

It can also be seen that the use of a composite oxide containing boron as the positive electrode active material significantly reduces cycle deterioration.

[0041]

As has been described above in detail, the present invention uses a lithium-boron transition metal composite oxide Li _x1 M _y B _z O ₂ as the active material of the positive electrode of the nonaqueous electrolyte secondary battery, the active material of the negative electrode The lithium manganese composite oxide Li _x2 MnO is used as the amount, and the amount capable of reversibly inserting and extracting lithium ions by charge and discharge, that is, the charge and discharge capacity is remarkably large, and the polarization of charge and discharge is small, so that at a large current, It is capable of charging and discharging, has little degradation such as decomposition and crystal collapse due to overcharging and overdischarging, and has a very high stability and a long cycle life. Has an effect.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of the structure of a battery implemented in the present invention.

FIG. 2 is an explanatory diagram showing charge and discharge characteristics of a battery according to the present invention in a first cycle and a second cycle.

FIG. 3 is an explanatory diagram showing cycle characteristics of a battery according to the present invention.

FIG. 4 is an explanatory diagram showing charge / discharge characteristics of a battery according to the present invention in a first cycle and a second cycle.

FIG. 5 is an explanatory diagram showing cycle characteristics of a battery according to the present invention.

[Description of Signs] 1 Negative electrode case 2 Negative electrode current collector 3 Negative electrode 4 Separator 5 Positive electrode 6 Positive electrode current collector 7 Positive electrode case 8 Gasket

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Fumiharu Iwasaki 6-31-1 Kameido, Koto-ku, Tokyo Inside Seiko Electronic Industries Co., Ltd. (72) Inventor Akifumi Sakata 6-31-1, Kameido, Koto-ku, Tokyo No. Seiko Electronics Co., Ltd. (72) Inventor Seiji Yahagi 6-31-1, Kameido, Koto-ku, Tokyo Seiko Electronics Co., Ltd. (56) References JP-A-4-324258 (JP, A) JP-A-4-237970 (JP, A) JP-A-6-60867 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01M 4/02-4/04 H01M 4/58 H01M 10/40

Claims (2)

(57) [Claims] 1. A negative electrode, a positive electrode and a lithium ion conductive non-conductive material.
A non-aqueous electrolyte secondary battery comprising at least a water electrolyte.
There are, in general formula _{Li x1 M y B z O 2} ( where, M is one or more transition metal
X1, y and z are each 0 <X1 ≦ 1.15,
0.85 ≦ y + z ≦ 1.3, 0 <z)
And a positive electrode using a composite oxide of the following formula as an active material: manganese monoxide MnO or a general formula Li _x2 MnO (provided that
0 <X2) complex of manganese Mn and lithium Li
And a negative electrode using a composite oxide as an active material.
Non-aqueous electrolyte secondary battery. 2. In a battery after battery assembly or in a battery manufacturing process
Manganese monoxide inside or outside the battery
MnO and lithium or a substance containing lithium
Reacts with the manganese monoxide MnO by electrochemical reaction of
To form a composite oxide of manganese and lithium
2. The non-aqueous electrolyte secondary battery according to claim 1, wherein
Pond manufacturing method.