JP3515492B2 - Non-aqueous electrolyte battery - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte battery using oxygen as a positive electrode active material, and more particularly to a non-aqueous electrolyte battery using oxygen as a positive electrode active material.

[0002]

2. Description of the Related Art In recent years, the market for portable information devices such as mobile phones and electronic mail terminals has been expanding rapidly, and as these devices have become smaller and lighter, power sources have become smaller and lighter. I've been asked for. Currently, a lithium ion secondary battery having a high energy density is mainly used in these portable devices, but further higher capacity is required. A non-aqueous electrolyte battery using oxygen in the air as a positive electrode active material can be expected to have a higher capacity because one of the battery active materials is oxygen in the air and it is not necessary to incorporate it in the battery. For example, J. Electroche
m. Soc. , Vol. 143, No. 1, p. 1 discloses an air lithium secondary battery having a structure described below. This air lithium secondary battery comprises an acetylene black layer carrying cobalt phthalocyanine as a catalyst and a polymer electrolyte film composed of polyacrylonitrile, ethylene carbonate, propylene carbonate and LiPF ₆ pressed onto a nickel mesh or an aluminum mesh. A positive electrode, a negative electrode made of a lithium foil, a polymer electrolyte layer interposed between the positive electrode and the negative electrode, and an oxygen permeable film laminated on the positive electrode, and the four-layer laminate is formed into a film shape. It was done. In addition, as a matter of course, the terminals are taken out of the exterior film from the positive electrode and the negative electrode. A large number of small holes are provided on the surface of the exterior film on the positive electrode side so that air is introduced into the positive electrode through the oxygen permeable film. Further, US Pat. No. 5,510,209 discloses the discharge characteristics of an air lithium secondary battery having the same structure as above and using graphite or acetylene black as a positive electrode carbon material.

However, the positive electrode capacity of the air lithium secondary battery disclosed herein is at most 1400 to 16
Since it is 00 mAh / g, the capacity of the entire battery is regulated, and it is hard to say that the high capacity originally possessed by the non-aqueous electrolyte battery is utilized. Further, although the conditions other than the positive electrode material are almost the same, the battery capacity is greatly different when the carbon material is different. However, no knowledge has been obtained as to what characteristic of the carbon material determines the capacity of the positive electrode, and therefore there is no guideline for increasing the capacity.

[0004]

As described above, the conventional non-aqueous electrolyte battery has not achieved a sufficiently high capacity.

The present invention has been made in view of such circumstances, and an object thereof is to provide a high-capacity air lithium battery.

[0006]

The non-aqueous electrolyte battery of the present invention has a pore volume of 1.0 m occupied by pores having a diameter of 1 nm or more.
A positive electrode mainly containing 1 / g or more of carbonaceous material, a negative electrode including a negative electrode active material that occludes and releases metal ions, a non-aqueous electrolyte layer sandwiched between the positive electrode and the negative electrode, and the carbonaceous material
Air holes for taking in oxygen are formed in the positive electrode, the negative electrode, and
And a storage case for storing the non-aqueous electrolyte layer .

The metal ions can be lithium ions.

The negative electrode active material can be used as a secondary battery by using a material capable of absorbing and releasing the metal ions.

The non-aqueous electrolyte battery of the present invention has a diameter of 1
a positive electrode in which a carbonaceous material having a pore volume of 1.0 nm / g or more occupied by pores of nm or more is supported on a current collector surface, and a negative electrode including a negative electrode active material having an ability to insert and extract lithium ions, A separator containing a non-aqueous electrolyte and sandwiched between the positive electrode and the negative electrode, and a storage case in which air holes for taking oxygen into the carbonaceous material are formed and which stores the positive electrode, the negative electrode, and the electrolyte. .

It is well known that there are many kinds of carbonaceous materials, and the classification and nomenclature thereof are various depending on the manufacturing method, structure and characteristics. As a result of repeated studies on what kind of carbon material is suitable for the positive electrode of an air lithium battery, it has been found that the size and volume of the pores of the carbon material are important factors. That is, it was found that a carbon material having a pore volume of 1.0 ml / g or more in a region having a pore diameter of 1 nm or more gives a high capacity positive electrode. Up to now, there have been examples focusing on the specific surface area of carbon materials, but there is no finding focusing on the relationship between the pore size or pore volume and the positive electrode capacity, and this relationship has not been clarified at all until now. Is. The non-aqueous electrolyte layer referred to here may be in any form of a solution system represented by an organic solvent system containing a lithium salt and a solid membrane system represented by a polymer solid electrolyte system also containing a lithium salt. Absent.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION As an example of the non-aqueous electrolyte battery of the present invention, a cross-sectional view of an air lithium battery is shown in FIG.
The present invention will be described in detail with reference to the drawings.

In FIG. 1, an electrode group 2 is housed in a housing case 1 such as a laminated film.

The electrode group 2 includes a positive electrode 5 having a structure in which a carbonaceous material layer 4 is supported on a positive electrode current collector 3 made of, for example, a porous conductive substrate, and a negative electrode current collector 6 made of, for example, a porous conductive substrate. A negative electrode 8 having a structure in which a negative electrode active material layer 7 is carried, and a non-aqueous electrolyte layer 9 interposed between the positive electrode 5 and the negative electrode 8.
Composed of and. In this figure, the non-aqueous electrolyte layer 9 has a structure including a separator.

One ends of a positive electrode terminal 11 and a negative electrode terminal 12 are connected to the positive electrode current collector 3 and the negative electrode current collector 6, respectively, and the other ends of the positive electrode terminal 11 and the negative electrode terminal 12 are
Each is extended to the outside of the storage case 1.

Further, an air hole 13 is formed on the side surface of the positive electrode of the storage case 1 formed on the positive electrode.
The air (oxygen in the air) supplied from the air diffusion layer 10
To reach a carbonaceous material.

Further, a seal tape 14 for closing the air holes 13 is removably arranged on the outer surface of the storage case 1. When the battery is used, the seal tape 14 is removed to allow air to the carbonaceous material layer 4. It can be supplied.

[0017] For example, shows a cell reaction when using metallic lithium as the negative electrode active material below. Discharge reaction (when using battery) Negative electrode: 2Li → 2Li ⁺ + 2e ⁻ (1) Positive electrode: 2Li ⁺ + 2e ⁻ + O ₂ → Li ₂ O ₂ (2) or 2Li ⁺ + 2e ⁻ + 1 / 2O ₂ → Li ₂ O (3 ) Charging reaction (during battery charging) Negative electrode: 2Li ⁺ + 2e ⁻ → 2Li (4) Positive electrode: Li ₂ O ₂ → 2Li ⁺ + 2e ⁻ + O ₂ (5) or Li ₂ O → 2Li ⁺ + 2e ⁻ + 1 / 2O ₂ ( 6) When a carbonaceous material that absorbs and releases lithium ions is used for the negative electrode, the reaction at the negative electrode is shown as follows. Discharge reaction (when using battery) Negative electrode: C ₆ Li → C ₆ + Li ⁺ + e ⁻ (7) Charge reaction (when charging battery) Negative electrode: C ₆ + Li ⁺ + e ⁻ → C ₆ Li (8) When discharging, the formula (1) ), (2), (3), and (7), electrons and lithium ions are emitted from the negative electrode, while the positive electrode takes in electrons and at the same time oxygen taken from outside the battery reacts with lithium ions to produce lithium. Oxides are formed.

When charging, equations (4), (5),
As shown in (6) and (8), in the negative electrode, lithium ions are taken in together with the electrons, while in the positive electrode, lithium ions and oxygen are released together with the electrons.

Next, the positive electrode 5, the negative electrode 8 and the non-aqueous electrolyte layer 9 will be described in detail.

1) Positive Electrode The positive electrode 5 is composed of the positive electrode current collector 3 and the carbonaceous material layer 4 formed in contact with the positive electrode current collector 3.

The current collector 3 is for reducing the loss of electrons while moving from the carbonaceous material layer 4 to the positive electrode terminal 11, and is made of a conductive material such as stainless steel, nickel, aluminum, iron, titanium, or the like. Composed of materials. In addition,
In order to suppress the oxidation of the current collector 3, the surfaces of these materials may be coated with an oxidation resistant metal or alloy.

The current collector 3 is preferably made of a porous material in order to diffuse oxygen rapidly.
For example, mesh, punched metal, expanded metal, or the like can be used.

The carbonaceous material layer 4 can be formed, for example, by mixing a carbonaceous material and a binder, rolling this mixture into a film to form a film, and drying.

Alternatively, for example, it can be formed by mixing a carbonaceous material and a binder in a solvent, applying this to the current collector 3, drying and rolling.

The carbonaceous material preferably comprises a carbonaceous material having a pore size of 1 nm or more and a pore volume of 1.0 ml / g or more in the carbonaceous material. Air lithium battery
Li ₂ O was introduced into the pores of the positive electrode carbon material as the discharge reaction proceeded.
And lithium oxide such as Li ₂ O ₂ accumulates. So-called micropores having a pore diameter of 1 nm or less in the carbon material are quickly blocked by the accumulation of this oxide and inhibit the discharge reaction, so that the contribution to the capacity is very small. Therefore,
A carbon material having a large number of pores in the region of mesopores having a pore diameter of 1 nm or more gives a high capacity as a positive electrode of a non-aqueous electrolyte battery, and in order to give a high capacity exceeding 1600 mAh / g per unit weight, a mesopore is required. 1.0 ml / in the pore area
It is necessary to have a pore volume of g or more.

However, the pore volume is 4.0 ml / g
If it exceeds, the bulk density of the carbon material becomes extremely large,
The capacity per unit volume decreases. Therefore, it is more preferable to have a pore volume of 1.0 ml / g or more and 4.0 ml / g or less in the mesopore region of 1 nm or more.

Further, as the carbonaceous material, a material to which a catalyst is added in order to efficiently carry out the reduction reaction of oxygen can be used. As such a catalyst, for example, a catalyst having a function of lowering the oxygen generation overvoltage such as cobalt phthalocyanine can be used.

While maintaining the shape of the carbonaceous material in layers,
Examples of the binder for attaching to the current collector include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SB).
R) or the like can be used.

The mixing ratio of the carbonaceous material and the binder is 70 to 98% by weight of the carbonaceous material and 2 to 30% by weight of the binder.
It is preferably in the range of.

2) Negative Electrode The negative electrode 8 shown in FIG. 1 has the negative electrode active material layer 7 on the negative electrode current collector 6.
Is formed.

The negative electrode current collector 6 is not limited to a conductive substrate having a porous structure like the positive electrode current collector 3, and a non-porous conductive substrate can also be used. These conductive substrates can be made of, for example, copper, stainless steel, or nickel. However, when a layer having high conductivity is formed as the negative electrode active material layer, it is not particularly necessary to provide it.

A negative electrode active material layer 7 formed on the surface of the current collector 6
For example, a layer composed of a negative electrode active material and a binder may be formed. For example, the negative electrode active material and the binder are kneaded in the presence of a solvent, the resulting suspension is applied to a current collector, dried, and then pressed once at a desired pressure or in multiple stages of 2 to 5 times. It can be manufactured by pressing.

As the negative electrode active material, for example, a material which absorbs and releases lithium ions can be used. Examples of the material that absorbs and releases lithium ions include metal oxides, metal sulfides, metal nitrides or lithium metal,
All materials conventionally used for lithium ion batteries or lithium batteries such as lithium alloys, lithium composite oxides, and carbonaceous materials can be used.

Examples of the carbonaceous material capable of inserting and extracting lithium ions include graphite materials such as graphite, coke, carbon fiber, and spherical carbon or carbonaceous materials, thermosetting resins, isotropic pitch, mesophase pitch, mesophase pitch. 500 for carbon-based carbon fibers, mesophase spheres, etc.
A graphitic material or a carbonaceous material obtained by performing a heat treatment at 3000 ° C. can be mentioned.

Examples of the metal oxide include tin oxide, silicon oxide, lithium titanium oxide, niobium oxide, and tungsten oxide.

Examples of the metal sulfide include tin sulfide and titanium sulfide.

Examples of the metal nitride include lithium cobalt nitride, lithium iron nitride, lithium manganese nitride and the like.

Examples of the lithium alloy include lithium aluminum alloy, lithium tin alloy, lithium lead alloy, lithium silicon alloy and the like.

Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR),
Carboxymethyl cellulose (CMC) or the like can be used. The blending ratio of the carbonaceous material and the binder is 80 to 98% by weight of the carbonaceous material and 2 to 20% by weight of the binder.
It is preferably in the range of. Particularly, the carbonaceous material is preferably in the range of 5 to ²⁰ g / m ² in the state where the negative electrode is manufactured.

When a metal material such as lithium ion or a lithium alloy is used as the negative electrode active material, these metal materials can be processed into a sheet shape by themselves, so that a binder is not used. A negative electrode active material layer can be formed. In addition, since the negative electrode active material layer formed of these metal materials has excellent conductivity, the negative electrode active material sheet can be directly connected to the negative electrode terminal without separately providing a current collector.

When the air lithium battery is used as the primary battery, it is sufficient that the negative electrode active material has only the ability to release lithium ions.

3) Non-Aqueous Electrolyte Layer For the non-aqueous electrolyte layer, as described above, two types of shapes can be adopted: a liquid system and a solid electrolyte system.

First, in the case of a liquid system, a liquid electrolyte prepared by dissolving a lithium salt in a non-aqueous solvent can be used for the non-aqueous electrolyte layer. As the non-aqueous solvent, a non-aqueous solvent known as a solvent for lithium secondary batteries can be used. For example, propylene carbonate (PC), ethylene carbonate (EC), or a mixed solvent of both of them (referred to as a first solvent) and one or more non-solvents having a lower viscosity than PC or EC and a donor number of 18 or less. It is preferable to use a non-aqueous solvent mainly composed of a mixed solvent with an aqueous solvent (hereinafter referred to as a second solvent).

As the second solvent, a chain carbonate containing a carbonic acid ester bond or an ester bond in the molecule is preferable, and among them, dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC), methylpropyl carbonate ( MP
C), isopropiomethyl carbonate, ethyl propionate, methyl propionate, γ-butyrolactone (γ
-BL), ethyl acetate, methyl acetate and the like.
These second solvents can be used alone or in the form of a mixture of two or more kinds. In particular, the second type solvent has a boiling point of 9
It is preferably 0 ° C. or higher.

The blending amount of the EC or PC in the mixed solvent is preferably 10 to 80% by volume.
A more preferable amount of EC or PC is 20 by volume.
~ 75%.

Specific examples of the mixed solvent are EC and P.
C, EC and DEC, EC and PC and DEC, EC and γ-B
L, EC and γ-BL and DEC, EC and PC and γ-BL,
A mixed solvent of EC, PC, γ-BL and DEC, in which the volume ratio of EC is 10 to 80%, is preferable. A more preferable EC volume ratio is in the range of 25 to 65%.

Examples of the electrolyte contained in the non-aqueous electrolyte include
For example, lithium perchlorate (LiClO _Four), Phosphorus hexafluoride
Lithium acid (LiPF₆), Lithium tetrafluoroborate (L
iBF _Four), Lithium trifluoromethanesulfonate
(LiCF₃SO₃), Bistrifluoromethanesulfoni
Lithium amide [LiN (CF₃SO₂)₂], Etc.
Examples include but are not limited to thium salts (electrolytes).
Not something.

The amount of the electrolyte dissolved in the non-aqueous solvent is
It is preferably 0.5 to 2.5 mol / l.

When a liquid non-aqueous electrolyte layer is used, as described above, the non-aqueous electrolyte layer is formed by impregnating and holding this non-aqueous electrolyte in the separator.

As the separator, for example, a porous film containing polyethylene, polypropylene, or PVdF, a synthetic resin non-woven fabric, a glass fiber non-woven fabric, or the like can be used.

The separator preferably has a porosity in the range of 30 to 90%. This is due to the following reasons. When the porosity is less than 30%, it may be difficult to obtain high electrolyte retention in the separator. On the other hand, if the porosity exceeds 90%, sufficient separator strength may not be obtained. A more preferable range of porosity is 35 to 60%.

When using a solid electrolyte-based non-aqueous electrolyte layer
Is a film containing a polymer material in which a lithium salt is dissolved.
It can be used as a polymer solid electrolyte. Polymer material
Examples of the material include polyethylene oxide (PE
O), polyvinylidene fluoride (PVdF), poly
Acrylonitrile (PAN) etc. can be mentioned.
The same lithium salt as described above, for example, lithium perchlorate
System, lithium hexafluorophosphate, lithium tetrafluoroborate,
Lifluoromethanesulfonate lithium (LiCF ₃S
O₃), Bistrifluoromethylsulfonylimidolithi
Um [LiN (CF₃SO₂)₂] And so on
It In addition, the solid electrolyte layer has improved ionic conductivity.
Therefore, it is preferable to add an organic solvent. Such existence
As the organic solvent, for example, ethylene carbonate (E
C), propylene carbonate (PC), γ-butyrola
Ketone (γ-BL), fluorine-containing carbonates, chains
Specific examples thereof include carbonates. The organic solution
As the medium, these may be used alone, but two or more types may be combined.
You may use it together.

Although the air lithium secondary battery has been described above as an example of the non-aqueous electrolyte battery of the present invention, it is possible to occlude and release metal ions such as sodium, aluminum, magnesium and cesium as the negative electrode active material. It can also be used as another air metal secondary battery using the material.

When producing another air metal secondary battery, sodium, aluminum,
A metal salt such as magnesium or cesium may be used.

[0055]

EXAMPLES The present invention will be described in detail below based on examples.

Example 1 The pore volume and pore size distribution of Ketjen Black EC600JD (manufactured by Ketjen Black International), which is a carbonaceous material, were determined from the analysis of adsorption isotherms by the nitrogen gas adsorption method. The analysis is based on the DH method (Do
by llmore & Heal Method)
For the micropores, the t-plot method was used.

As a result, the volume of pores having an average diameter of 1 nm or more was 2.15 ml / g. Also, the pores are 1-2
It was widely distributed in the range of 0 nm. As a result of analysis by t-plot, it was found that this material had almost no micropores of 1 nm or less, and the specific surface area by the BET method was 1350 m ² / g.

This carbonaceous material and binder (made by DuPont: product name Teflon) The granules were mixed in a weight ratio of 9: 1, and this mixture was molded into a sheet. The film thickness is 18
It was 0 μm. This carbonaceous material layer was pressure-bonded to a titanium mesh serving as a current collector to produce a positive electrode. The size of the electrode is 2 cm × 2 cm.

Further, a positive electrode terminal was joined to the positive electrode current collector.

On the other hand, lithium metal was used as the negative electrode active material, and the negative electrode was prepared by pressure bonding to a nickel mesh as a current collector. The size of the electrode is also 2 cm × 2 cm. Further, a negative electrode terminal was connected to the current collector of this negative electrode.

In a solvent system prepared by mixing 50% by volume of ethylene carbonate and 50% by volume of propylene carbonate, 1.
A non-aqueous electrolyte was prepared by dissolving lithium perchlorate, which is an electrolyte, at a rate of 5 mol / l.

The positive electrode and the negative electrode were laminated in a sandwich form with a glass filter separator interposed therebetween, and a polypropylene nonwoven fabric was laminated on the outer side of the positive electrode as an air diffusion layer, and the obtained four-layer laminate was provided with air holes on the positive electrode side. It was stored in an opened bag-shaped laminate film. A sealing tape was attached to the air holes of the laminate film in advance. Further, the positive electrode terminal and the negative electrode terminal were extended to the outside from the opening of the unsealed portion of the bag-shaped laminate film.

From this opening, the non-aqueous electrolyte was 550 μm.
After being injected into the 1-separator, the opening of the laminate film was heat-sealed and sealed. In this way, a non-aqueous electrolyte battery having a structure as shown in FIG. 1 was produced.

The seal tape of this battery was peeled off, and a charge / discharge test was conducted in the atmosphere at a discharge current density of 0.1 mA / cm ² . The discharge capacity of the positive electrode in the third cycle is 2450 mAh.
/ G.

Example 2 Tetralithium naphthalene-1,4,5,8-tetracarboxylate was heated at 800 ° C. for 12 hours in an argon gas atmosphere. The product was pulverized, washed with hydrochloric acid and water, and dried under vacuum at 200 ° C. for 8 hours to produce a carbonaceous material.

The volume of pores of the carbonaceous material in the range of 1 to 20 nm, the volume of micropores having a pore diameter of 1 nm or less, and the specific surface area were examined in the same manner as in Example 1. Each of them was 1.16 ml / g. , 0.095 ml / g, 1200
m was ² / g. A positive electrode was prepared in the same manner as in Example 1 except that a mixture of 95% by weight of this carbonaceous material and 5% by weight of a binder was used.

A non-aqueous electrolyte battery was produced in the same manner as in Example 1 except that this positive electrode was used.

A charge / discharge test of the obtained non-aqueous electrolyte battery was conducted in the same manner as in Example 1. As a result, the discharge capacity of the positive electrode at the third cycle was 1870 mAh / g.

Comparative Example 1 Instead of Ketjen Black EC600JD (made by Ketjen Black International) as a carbonaceous material,
A non-aqueous electrolyte battery having the structure shown in FIG. 1 was produced in the same manner as in Example 1 except that Ketjen Black EC (also manufactured by Ketjen Black International) was used.

The carbonaceous material has a pore volume in the range of 1 to 20 nm, a micropore volume of 1 nm or less, and a BET.
When the specific surface area was measured in the same manner as in Example 1, it was 0.692 ml / g, 0.351 ml / g, and 735 m, respectively.
It was ² / g.

A charge / discharge test of this non-aqueous electrolyte battery was carried out in the same manner as in Example 1. The discharge capacity of the positive electrode at the third cycle was 670 mAh / g, which was clearly smaller than that in Example. There wasn't.

Comparative Example 2 As a carbonaceous material, Ketjen Black EC600JD
(Made by Ketjen Black International) A non-aqueous electrolyte battery having the structure of FIG. 1 was produced in the same manner as in Example 1 except that commercially available palm shell activated carbon was used instead of.

The pore volume of this activated carbon in the range of 1 to 20 nm, the micropore volume of 1 nm or less, and the BET specific surface area were determined to be 0.216 ml / each.
g, 0.592 ml / g, 1286 m ² / g.

A charge / discharge test of this non-aqueous electrolyte battery was carried out in the same manner as in Example 1. As a result, the discharge capacity of the positive electrode at the third cycle was 511 mAh / g, which was also smaller than that in Example. .

Comparative Example 3 As a carbonaceous material, Ketjen Black EC600JD
(Made by Ketjen Black International) A non-aqueous electrolyte battery having the structure shown in FIG. 1 was produced in the same manner as in Example 1 except that commercially available activated carbon fiber was used instead of.

The pore volume of this activated carbon in the range of 1 to 20 nm, the micropore volume of 1 nm or less, and the BET specific surface area were determined to be 0.102 ml / each.
g, 0.361 ml / g, 779 m ² / g.

Further, when a charge / discharge test of this non-aqueous electrolyte battery was conducted in the same manner as in Example 1, the discharge capacity of the positive electrode at the third cycle was only 18.6 mAh / g. The above Examples and Comparative Examples are summarized in Table 1 below.

[Table 1]

[0078]

As described in detail above, by using the carbonaceous material according to the present invention as the positive electrode, a high capacity non-aqueous electrolyte battery can be obtained.

[Brief description of drawings]

FIG. 1 is a sectional view schematically showing the structure of a non-aqueous electrolyte battery according to the present invention.

[Explanation of symbols]

1. Exterior material 2. Electrode group 3. Positive electrode collector 4. Carbonaceous material layer 5. Positive electrode 6. Negative electrode current collector 7. Negative electrode active material layer 8. Negative electrode 9. Non-aqueous electrolyte layer 10. Air diffusion layer 11. Positive terminal 12. Negative terminal 13. Air hole 14. sealing tape

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takahisa Osaki, 1 Komukai Toshiba Town, Saiwai-ku, Kawasaki City, Kanagawa Prefecture, Toshiba Research & Development Center Co., Ltd. (72) Inventor Tetsuo Okuyama, Komukai Toshiba Town, Kawasaki City, Kanagawa Prefecture No. 1 in Toshiba Research & Development Center (56) Reference JP 62-154461 (JP, A) JP 9-161801 (JP, A) JP 10-208985 (JP, A) JP 58-157067 (JP, A) JP 58-48369 (JP, A) JP 56-45575 (JP, A) JP 59-173979 (JP, A) JP 8-321306 (JP, A) A) JP-A-9-293507 (JP, A) JP-A-2001-35493 (JP, A) JP-A-10-83836 (JP, A) JP-A-10-21919 (JP, A) JP-A-4- 39864 (JP, A) US Patent 3645795 (US, A) (58) Fields (Int.Cl. ⁷ , DB name) H01M 4/58 H01M 4/02 H01M 10/40

Claims (4)

(57) [Claims] 1. A positive electrode mainly composed of a carbonaceous material having a pore volume of 1.0 ml / g or more occupied by pores having a diameter of 1 nm or more, and a negative electrode comprising a negative electrode active material which occludes and releases metal ions, and electrolyte layer nonaqueous sandwiched positive electrode and the negative electrode, before
An air hole for taking in oxygen is formed in the carbonaceous material.
A storage case that stores the electrode, the negative electrode, and the non-aqueous electrolyte layer.
Nonaqueous electrolyte battery characterized by comprising a scan. 2. The non-aqueous electrolyte battery according to claim 1, wherein the metal ions are lithium ions. 3. The non-aqueous electrolyte battery according to claim 1, wherein the negative electrode active material has the ability to store and release the metal ions. 4. A positive electrode in which a carbonaceous material having a pore volume of 1.0 ml / g or more occupied by pores having a diameter of 1 nm or more is supported on the surface of a current collector, and a negative electrode active material having an ability to insert and extract lithium ions. A negative electrode having a positive electrode, a negative electrode sandwiched between the positive electrode and the negative electrode, and a storage case for storing the positive electrode, the negative electrode and the electrolyte, in which air holes for taking oxygen into the carbonaceous material are formed. A non-aqueous electrolyte battery characterized by the above.