JP4575212B2 - Non-aqueous electrolyte air battery - Google Patents

Description

The present invention particularly relates to a non-aqueous electrolyte air battery using oxygen as a positive electrode active material and a non-aqueous electrolyte as an electrolyte.

In recent years, miniaturization of mobile devices has been progressing rapidly, and power supply for mobile devices is also required to have a high energy density. Furthermore, the digitization of portable devices is progressing, and a pulse-shaped large current discharge capability has begun to be required. An air battery using oxygen in the air as a positive electrode active material has a higher capacity than other sealed batteries and is promising as a next-generation power source. In particular, a non-aqueous electrolyte air battery using lithium as a negative electrode active material (air lithium battery) is a battery capable of realizing an energy density higher than that of an air zinc battery that has already been put into practical use. For example, US Pat. No. 5,510,209 ( Patent Literature 1) discloses an air lithium battery in which manganese dioxide is supported as a catalyst on a positive electrode.
US Pat. No. 5,510,209

  As described above, the conventional air lithium battery has a problem that the battery life is shortened when a large current is discharged. As described above, air lithium uses oxygen in the air at the time of discharge, but moisture in the air is taken into the battery simultaneously with oxygen and hydrolyzes lithium as the negative electrode active material. When the flowing current is small, the required amount of oxygen is small, so the amount of moisture that enters the battery is also small, and the life is prolonged. However, in order to cope with large current discharge, it is necessary to take in a large amount of oxygen inside the battery, and at the time of discharge, a large amount of moisture penetrates into the battery and quickly hydrolyzes the negative electrode, shortening the battery life. Resulting in. When using a battery with a large current at all times, the service life will not be a major problem because the usage time will be short. When performing pulse-shaped high-current discharge, a large flow path of air from the outside of the battery to the positive electrode is necessary to secure the amount of oxygen necessary for high-current discharge, and steady-state low-current discharge is not possible. During the process, moisture in the atmosphere enters into the battery due to convection, and the battery life is shortened. In order to solve this problem, studies have been made on an oxygen selective permeable membrane through which oxygen is blocked and moisture is blocked. However, since the oxygen permeation rate is not sufficient, it cannot sufficiently cope with a large current discharge.

A nonaqueous electrolyte air battery according to claim 1 of the present invention includes a positive electrode, a negative electrode, a nonaqueous electrolyte formed between the positive electrode and the negative electrode, and a case including an air hole for supplying oxygen to the positive electrode. The positive electrode is composed of two layers having different compositions, and a layer having at least oxygen reducing ability is disposed on the air hole side, and a layer having at least lithium ion storage ability is disposed on the negative electrode side. The layer having the ability to occlude lithium ions comprises an active material having an ability to occlude lithium ions at 2.0 V to 2.9 V (vs. Li), a conductive agent, and a binder. And That is, the structure of the present invention employs a structure in which an air battery and a normal lithium ion secondary battery are bonded back to back in one battery case. As a result, even if the amount of air supplied to the air battery is reduced by reducing the amount of air taken in and reducing the ingress of moisture in the air, the normal lithium ion secondary battery is another battery. Since power can be supplied by batteries, it can flexibly cope with sudden load fluctuations.

  The nonaqueous electrolyte air battery according to claim 2 is characterized in that, in claim 1, the active material having the ability to occlude lithium ions has a reversible ability to occlude and release lithium ions.

Nonaqueous electrolyte air battery according to claim 3, in claim 2, the active material having ability to occlusion of the lithium ions, manganese oxide, vanadium pentoxide (V ₂ O _5), copper oxide, V _{2 O 5 / TeO 2, V 2} O 5 / P 2 O 5, V 2 O 5 / B 2 O 3, CuV 2 O 6, Cu 2 V 2 O 7, T iS 2, LiFeO 2, chromium oxide, tri- molybdenum oxide (MoO _3), titanium dioxide (TiO _2), a good Ri transition metal oxide selected.

Nonaqueous electrolyte air battery according to claim 4 resides in that in Claim 1, active material having the ability to absorb the lithium ions, characterized in that it is contained 70% by weight or more.

The nonaqueous electrolyte air battery according to claim 5 is characterized in that, in claim 1, the layer having oxygen reducing ability comprises at least a carbonaceous material having a specific surface area of 600 m ² / g or more and a binder.

  The non-aqueous electrolyte air battery provided by the present invention operates as an air lithium battery using oxygen in the air when the layer having oxygen reducing ability in the positive electrode functions during low current discharge, while the positive electrode during high current discharge. The layer having the lithium ion occlusion ability functions to drive as a lithium battery without using oxygen in the air. Thereby, it is not necessary to consume a large amount of oxygen even during a large current discharge, and moisture in the air can be prevented from entering the battery simultaneously with oxygen. That is, it is possible to realize a non-aqueous electrolyte air battery that has a high capacity and can cope with pulsed large current discharge.

  Furthermore, in the nonaqueous electrolyte air battery according to the present invention, the active material contained in the layer having oxygen reducing ability in the positive electrode preferably has a reversible ability to occlude and release lithium ions. The non-aqueous electrolyte air battery according to the present invention operates as an air battery at the time of low current discharge because lithium ions are occluded in the active material contained in the layer having oxygen reducing ability in the positive electrode at the time of large current discharge. In this case, the voltage rises and the active material discharged during the large current discharge can be charged again.

  As described above in detail, according to the present invention, a water electrolyte air battery having a high capacity and excellent pulse discharge characteristics can be provided.

  Hereinafter, the positive electrode, non-aqueous electrolyte, negative electrode, and storage case according to the present invention will be described.

1) Positive Electrode The positive electrode includes a positive electrode current collector and a positive electrode layer supported on the positive electrode current collector. The positive electrode layer is composed of two layers each having a different composition, and a layer having at least oxygen reducing ability is disposed on the air hole side, and a layer having at least lithium ion storage ability is disposed on the negative electrode side.

As the layer having oxygen reducing ability, a carbonaceous material having a specific surface area of 600 m ² / g or more and a binder can be used. The carbonaceous material and the binder are mixed, and this mixture is formed into a film. It can be formed by rolling into a film and drying. Alternatively, for example, a carbonaceous material and a binder can be mixed in a solvent, applied to a current collector, dried and rolled, and formed. In addition, it is preferable to support a particulate catalyst on the surface of the carbonaceous material, thereby increasing the efficiency of the oxygen reduction reaction.

  Examples of the carbonaceous material include ketjen black, acetylene black, carbon black, furnace black, activated carbon, activated carbon fiber, and charcoal. For activated carbons having low conductivity, it is preferable to add a highly conductive carbonaceous material such as acetylene black to the activated carbon to increase the conductivity of the positive electrode layer.

Examples of the catalyst include cobalt phthalocyanine, cobalt porphyrin, cerium oxide (CeO ₂ ), aluminum (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), silver oxide (AgO), lithium tungstate (Li ₂ WO ₄ ), and molybdenum. Lithium oxide (Li ₂ MoO ₄ ), lithium manganese cobaltate (LiMn _x Co _y O ₄ ), lanthanum calcium cobalt composite oxide (La _x Ca _y CoO _3-z ), lanthanum strontium cobalt oxide (La _x Sr _y CoO) _3-z ), sodium lanthanum manganate (Na _x La _y MnO ₃ ), potassium lanthanum manganate (K _x La _y MnO _3-z ), rubidium lanthanum manganate (Rb _x La _y MnO _3-z ), copper manganese Complex oxide (Cu _x Mn _y O ₄ ) And manganese oxide (MnO _x ).

  Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-butadiene rubber (EPBR), and styrene-butadiene rubber (SBR).

  On the other hand, the layer having the ability to occlude lithium ions is composed of an active material having the ability to occlude lithium ions at 2.0 V to 2.9 V (vs. Li), a conductive agent, and a binder. It can be formed by mixing an active material, a conductive agent, and a binder, rolling the mixture into a film, forming a film, and drying. Alternatively, it can be formed by mixing an active material, a conductive agent and a binder in a solvent, applying the mixture to a current collector, drying and rolling. The active material having the ability to occlude lithium ions is desirably contained in an amount of 70% by weight or more in the layer having the ability to occlude lithium ions. The active material desirably has a reversible ability to occlude and release lithium ions.

Examples of the positive electrode active material include manganese oxide (MnO ₂ ), vanadium pentoxide (V ₂ O ₅ ), copper oxide (CuO), V ₂ O ₅ / TeO ₂ , and V ₂ O ₅ / P ₂ O _5. , V ₂ O ₅ / B ₂ O ₃ , CuV ₂ O ₆ , Cu ₂ V ₂ O ₇ , Cr ₂ O ₅ , Cr ₃ O ₈ , TiS ₂ , LiFeO ₂ , chromium oxide (Cr ₃ O ₈ , CrO ₂ ), Molybdenum trioxide (MoO ₃ ), titanium dioxide (TiO ₂ ), and other metal oxides can be used.

  Examples of the carbonaceous material include carbonaceous materials such as natural graphite, artificial graphite, ketjen black, and acetylene black.

Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-butadiene rubber (EPBR), and styrene-butadiene rubber (SBR).

  In addition, the layer which has the oxygen reducing ability mentioned above and the layer which has lithium ion occlusion ability may mix each composition in a junction part.

As the current collector, it is preferable to use a porous conductive substrate (mesh, punched metal, expanded metal, etc.) in order to allow oxygen to diffuse quickly. Examples of the material of the conductive substrate include stainless steel, nickel, aluminum, iron, and titanium. The current collector may be coated with an oxidation-resistant metal or alloy on the surface in order to suppress oxidation.

2) Non-aqueous electrolyte As the non-aqueous electrolyte, various non-aqueous electrolytes that have been conventionally used as electrolytes for lithium ion secondary batteries can be used. For example, an organic solvent-based non-aqueous electrolyte solution in which a supporting electrolyte is dissolved in an organic solvent, a room-temperature molten salt-based non-aqueous electrolyte solution in which a supporting electrolyte is dissolved in a room temperature molten salt, or a polymer material and an organic solvent / room temperature molten salt A gel electrolyte solution made of a nonaqueous electrolyte solution can be used.

  Examples of the organic solvent used in the organic solvent-based non-aqueous electrolyte include propylene carbonate (PC), ethylene carbonate (EC), vinylene carbonate (VC), dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, and isopropio. Carbonates such as methyl carbonate can be used. These solvents can be used alone or in the form of a mixture of two or more. When used as a mixture, in addition to the carbonate ester, esters such as ethyl propionate, methyl propionate, γ-butyrolactone (γ-BL), ethyl acetate, methyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, ethylene A solvent selected from the group consisting of ethers such as glycodidiethyl ether and various solvents in which a substituent is introduced into the compound can be used. Preferred compositions of the mixed solvent include EC and PC, EC and PC and VC, EC and VC, EC and DEC, EC and DEC and VC, EC and PC and DEC, EC and PC and DEC and VC, EC and γ -BL, VC and γ-BL, EC and γ-BL and VC, EC and γ-BL and DEC, EC and γ-BL and DEC and VC, EC and PC and γ-BL, EC and PC and γ-BL And VC, EC, PC, γ-BL and DEC, EC, PC, γ-BL, DEC and VC. Each mixed solvent preferably contains PC. The volume ratio of PC is more preferably in the range of 10 to 80%. Moreover, it is preferable to make the volume ratio of EC into the range of 10 to 80%. More preferably, the volume ratio of PC and EC is in the range of 25 to 65%.

Specific examples of the supporting electrolyte include LiPF ₆ , Li [PF ₃ (C ₂ F ₅ ) ₃ ], Li [PF ₃ (CF ₃ ) ₃ ], LiBF ₄ , Li [BF ₂ (CF ₃ ) ₂ ]. _{, Li [BF 2 (C 2} F 5) 2], Li [BF 3 (CF 3)], Li [BF 3 (C 2 F 5)], Li [B (COOCOO) 2] (LiBOB), LiCF 3 SO ₃ (LiTf), LiC ₄ F ₉ SO ₃ (LiNf), Li [(CF ₃ SO ₂ ) ₂ N] (LiTFSI), Li [(C ₂ F ₅ SO ₂ ) ₂ N] (LiBETI), Li [ (CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) N], Li [(CN) ₂ N] (LiDCA), Li [(CF ₃ SO ₂ ) ₃ C], Li [(CN) ₃ C], etc. Can be used. The concentration of the supporting electrolyte is preferably 0.1 to 4 mol / L. A more desirable concentration is 0.5 to 2 mol / L.

  Examples of the room temperature molten salt used in the room temperature molten salt nonaqueous electrolyte include those composed of cations such as imidazolium ions and ammonium ions and various anions.

Specific examples of the cation include N, N, N-trimethylbutylammonium ion, N-ethyl-N, N-dimethylpropylammonium ion, N-ethyl-N, N-dimethylbutylammonium ion, and N, N-dimethyl. -N-propylbutylammonium ion, N- (2-methoxyethyl) -N, N-dimethylethylammonium ion, 1-ethyl-3-methylimidazolium ion, 1-methyl-3-propylimidazolium ion, 1- Butyl-3-methylimidazolium ion, 1-ethyl-2,3-dimethylimidazolium ion, 1-ethyl-3,4-dimethylimidazolium ion, 1-ethyl-2,3,4-trimethylimidazolium ion, 1-ethyl-2,3,5-trimethylimidazolium ion, N-methyl Ru-N-propylpyrrolidinium ion, N-butyl-N-methylpyrrolidinium ion, N-sec-butyl-N-methylpyrrolidinium ion, N- (2-methoxyethyl) -N-methylpyrrolidinium ion, N -(2-ethoxyethyl) -N-methylpyrrolidinium ion, N-methyl-N-propylpiperidinium ion, N-butyl-N-methylpiperidinium ion, N-sec-butyl-N-methylpiperidinium ion, Examples thereof include N- (2-methoxyethyl) -N-methylpiperidinium ion and N- (2-ethoxyethyl) -N-methylpiperidinium ion. Among them, N, N, N-trimethylbutylammonium ion, N-ethyl-N, N-dimethylpropylammonium ion, N-ethyl-N, N-dimethylbutylammonium ion, N- (2-methoxyethyl) -N, N-dimethylethylammonium ion, 1-ethyl-3-methylimidazolium ion, 1-ethyl-2,3-dimethylimidazolium ion, N-methyl-N-propylpyrrolidinium ion, N-butyl-N-methylpyrrole Dinium ion, N-methyl-N-propylpiperidinium ion, N-butyl-N-methylpiperidinium ion and the like are preferable.

Specific examples of the anion include PF ₆ ⁻ , [PF ₃ (C ₂ F ₅ ) ₃ ] ⁻ , [PF ₃ (CF ₃ ) ₃ ] ⁻ , BF ₄ ⁻ , and [BF ₂ (CF ₃ ) ₂ ] ^−. , [BF ₂ (C ₂ F ₅ ) ₂ ] ⁻ , [BF ₃ (CF ₃ )] ⁻ , [BF ₃ (C ₂ F ₅ )] ⁻ , [B (COOCOO) ₂ ⁻ ] (BOB ⁻ ), CF ₃ SO ₃ ⁻ (Tf ⁻ ), C ₄ F ₉ SO ₃ ⁻ (Nf ⁻ ), [(CF ₃ SO ₂ ) ₂ N] ⁻ (TFSI ⁻ ), [(C ₂ F ₅ SO ₂ ) ₂ N] ⁻ (BETI ⁻ ), [(CF ₃ SO ₂ ) (C ₄ F ₉ SO ₂ ) N] ⁻ , [(CN) ₂ N] ⁻ (DCA ⁻ ), [(CF ₃ SO ₂ ) ₃ C] ⁻ , [ (CN) ₃ C] ^- or the like can be used.

In particular, BF ₄ ⁻ , [BF ₃ (CF ₃ )] ⁻ , [BF ₃ (C ₂ F ₅ )] ⁻ , BOB ⁻ , TFSI ⁻ and BETI ⁻ are preferable. This is because when these anions are used, the viscosity of the molten salt is low, the heat resistance is high, and the oxidation resistance is electrochemically high.

  As the supporting electrolyte, the same supporting electrolyte as that used in the organic solvent-based non-aqueous electrolyte described above can be used. The anion constituting the supporting electrolyte may be the same as or different from the anion constituting the room temperature molten salt. The concentration of the supporting electrolyte is preferably 0.1 to 4 mol / L. A more desirable concentration is 0.5 to 2 mol / L.

As the gel electrolyte, a mixture of the above-mentioned organic solvent-based non-aqueous electrolyte solution or room temperature molten salt-based non-aqueous electrolyte and a polymer material can be used. Examples of the polymer material include polyethylene oxide (PEO), polyacrylonitrile (PAN), PVdF, polymethacrylic acid, polymethacrylic acid ester, polyacrylic acid, polyacrylic acid ester, and the like.

3) Negative electrode The negative electrode includes a negative electrode current collector and a negative electrode layer carried on the negative electrode current collector. The negative electrode layer may be composed of a negative electrode active material and a binder. The negative electrode active material only needs to have at least lithium ion releasing ability, and as the negative electrode active material, various negative electrode active materials conventionally used as negative electrode materials for lithium primary batteries and lithium ion secondary batteries can be used. .

  As the negative electrode active material, it is desirable to use at least one material selected from the group consisting of metal oxide, metal sulfide, metal nitride, lithium metal, lithium alloy, lithium composite oxide, and carbonaceous material, for example. .

  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, and lithium manganese nitride.

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

As the carbonaceous material, a carbonaceous material in which lithium ions are occluded can be used, for example, graphite materials such as graphite, coke, carbon fiber, and spherical carbon or carbonaceous materials, thermosetting resins, isotropic pitches, Examples include mesophase pitch, mesophase pitch-based carbon fiber, mesophase microspheres and the like obtained by heat-treating a graphite material or carbonaceous material obtained by heat treatment at 500 to 3000 ° C.

  As the negative electrode current collector, for example, a porous conductive substrate or a nonporous conductive substrate can be used. These conductive substrates can be formed from, for example, copper, aluminum, stainless steel, or nickel. As a conductive substrate having a porous structure, a mesh, punched metal, expanded metal or the like is used, or a metal foil having a negative electrode active material-containing layer supported thereon and then having a hole formed in the metal foil. It can be used as a conductive substrate having a porous structure.

  Examples of the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), ethylene-propylene-butadiene rubber (EPBR), styrene-butadiene rubber (SBR), carboxymethylcellulose (CMC), and the like. Can do.

4) Container (storage case)
This container can be formed from, for example, a metal plate, a sheet having a resin layer, or the like.

  The metal plate can be made of, for example, iron, stainless steel, or aluminum.

  The sheet is preferably composed of a metal layer and a resin layer covering the metal layer. The metal layer is preferably formed from an aluminum foil. Meanwhile, the resin layer can be formed from a thermoplastic resin such as polyethylene, polypropylene, or polyester. The resin layer can be a single layer or a multilayer structure.

  An example of the nonaqueous electrolyte battery according to the present invention is shown in FIG. For example, an electrode group 2 is accommodated in a storage case 1 formed of a laminated film or thin plate.

  The electrode group 2 includes a positive electrode having a structure in which a positive electrode layer is supported on a positive electrode current collector made of, for example, a porous conductive substrate, and a structure in which a negative electrode active material layer is supported on a negative electrode current collector made of, for example, a conductive substrate And a separator interposed between the positive electrode and the negative electrode. In addition, the nonaqueous electrolyte nonaqueous electrolyte solution which has a normal temperature molten salt as a main component is hold | maintained at the positive electrode, the separator, and the negative electrode.

  One end of each of the positive electrode terminal 3 and the negative electrode terminal 4 is connected to the positive electrode current collector and the negative electrode current collector, and the other end of each of the positive electrode terminal 3 and the negative electrode terminal 4 extends to the outside of the storage case 1. Yes.

    Hereinafter, embodiments of the present invention will be described in more detail with reference to the drawings.

Example 1
The batteries of the following examples naturally realize the battery of FIG. 1 described above, and here, the description will focus on the detailed description that could not be introduced in the description of FIG.

80 wt% of ketjen black (specific surface area 1200 m ² / g), 10 wt% of cobalt phthalocyanine, and 10 wt% of PTFE were mixed as raw materials for the layer having oxygen reducing ability, and charged into a 30 mm square mold. Further, 80% by weight of manganese dioxide, 10% by weight of acetylene black, and 10% of PTFE were mixed as raw materials for the layer having lithium ion storage ability, and charged into the 30 mm squares described above. The mixture was pressed and cut to obtain a sheet-like positive electrode layer having a thickness of 200 μm and comprising two layers having different compositions. A stainless steel mesh, which is a positive electrode current collector, was pressure-bonded to the surface of the obtained positive electrode layer having a lithium ion occlusion ability to produce a positive electrode. Furthermore, one end of the positive electrode terminal was connected to a portion of the obtained positive electrode where the positive electrode current collector was exposed.

  Next, one end of a negative electrode terminal was connected, and a negative electrode obtained by pressing a metal lithium foil onto a nickel mesh, a separator made of a glass filter, a polypropylene nonwoven fabric, and an air diffusion layer made of a PTFE porous membrane were prepared.

LiClO ₄ was dissolved in an EC / PC mixed solvent at a rate of 1M to obtain a nonaqueous electrolyte. After impregnating the separator with the nonaqueous electrolyte, a negative electrode, a separator, a positive electrode, and an air diffusion layer were sequentially laminated. This laminate was stored in a laminate film for a storage container. The laminated film was provided with air holes, and the air holes were stored so as to be disposed on the air diffusion layer. Further, a sealing tape was applied to the air hole to close it. Moreover, the other end of the positive electrode terminal and the negative electrode terminal was extended from the opening part of the laminate film.

  The discharge capacity in the atmosphere of this nonaqueous electrolyte air battery was measured under the following conditions.

  After removing the sealing tape from the non-aqueous electrolyte air battery, discharge was performed at a discharge current of 0.01 mA at a temperature of 20 ° C., and pulse discharge of 0.1 mA for 0.1 second was performed every 10 seconds, and the voltage was 2.0 V. When the discharge capacity time was measured, the discharge time was 150 hours.

(Example 2)
80% by weight of ketjen black, 10% by weight of La _0.6 Ca _0.4 CoO _{3 and} 10% by weight of PTFE are used as raw materials for the layer having oxygen reducing ability, and vanadium pentoxide 80 is used as the raw material for the layer having lithium ion storage ability. Example 1 except that a normal temperature molten salt-based nonaqueous electrolyte in which LiTFSI was dissolved in EMITFSI at a rate of 1 M / L was used as a nonaqueous electrolyte, using 10% by weight, 10% by weight of acetylene black, and 10% by weight of PTFE. A non-aqueous electrolyte air battery was produced in the same manner. When the obtained battery was subjected to a discharge test under the same conditions as in Example 1, the discharge time was 120 hours.

(Example 3)
A layer having lithium ion occlusion ability by using 80% by weight of acetylene black (specific surface area 650 m ² / g), 10% by weight of Rb _0.2 La _0.8 MnO _{3 and} 10% by weight of PTFE as a raw material for the layer having oxygen reducing ability. 80% by weight of LiFeO ₂ , 10% by weight of acetylene black and 10% by weight of PTFE were used as raw materials, and a room temperature molten salt nonaqueous electrolyte in which LiBOB was dissolved in EMIBF ₄ at a rate of 1 M / L was used as a nonaqueous electrolyte. Except for the above, a nonaqueous electrolyte air battery was produced in the same manner as in Example 1. When the obtained battery was subjected to a discharge test under the same conditions as in Example 1, the discharge time was 110 hours.

(Comparative Example 1)
As a positive electrode, 80% by weight of ketjen black, 10% by weight of cobalt phthalocyanine, and 10% by weight of PTFE were mixed to form a sheet having a thickness of 200 μm. A nonaqueous electrolyte air battery was produced in the same manner as in Example 1 except that the positive electrode was produced using the sheet. When the obtained battery was subjected to a discharge test under the same conditions as in Example 1, the discharge time was 1 minute. The cause is considered to be that the voltage dropped below 2V during pulse discharge.

(Comparative Example 2)
As a positive electrode, 80% by weight of manganese dioxide, 10% by weight of acetylene black, and 10% of PTFE were mixed to form a sheet having a thickness of 200 μm. A nonaqueous electrolyte air battery was produced in the same manner as in Example 1 except that the positive electrode was produced using the sheet. When the obtained battery was subjected to a discharge test under the same conditions as in Example 1, the discharge time was 40 hours. The cause is considered to be a small capacity as an air battery.

  As mentioned above, although embodiment of this invention was described, this invention is not restricted to these, In the category of the summary of the invention as described in a claim, it can change variously. In addition, the present invention can be variously modified without departing from the scope of the invention in the implementation stage. Furthermore, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment.

Sectional drawing which shows an example of the nonaqueous electrolyte battery which concerns on this invention.

Explanation of symbols

1 ... Storage container,
2 ... Electrode group,
3 ... positive terminal,
4 ... Negative terminal

Claims (6)

In the nonaqueous electrolyte air battery comprising a positive electrode, a negative electrode, a nonaqueous electrolyte formed between the positive electrode and the negative electrode, and a case having an air hole for supplying oxygen to the positive electrode, the positive electrode has a composition. consists of two layers having different, a layer having at least oxygen reducing ability to the air hole side, said layer having at least a lithium ion storage capacity on the negative electrode side are arranged, a layer having the lithium ion storage capacity may be lithium-ion A non-aqueous electrolyte air battery comprising an active material having a capacity of occluding at 2.0 V to 2.9 V (vs. Li), a conductive agent, and a binder.   The non-aqueous electrolyte air battery according to claim 1, wherein the active material capable of occluding lithium ions has a reversible occluding / releasing ability of lithium ions. Active material having ability to occlusion of the lithium ions, manganese oxide, vanadium pentoxide (V ₂ O _5), copper _{oxide, V 2 O 5 / TeO 2} , V 2 O 5 / P 2 O 5, _{V 2 O 5 / B 2 O} 3, CuV 2 O 6, Cu 2 V 2 O 7, T iS 2, LiFeO 2, chromium oxide, a three molybdenum oxide _(MoO 3), titanium dioxide (TiO _2), yo Ri The nonaqueous electrolyte air battery according to claim 2, wherein the transition metal oxide is selected. Nonaqueous electrolyte air battery according to claim 1, characterized in that active material having the ability to absorb the lithium ions is contained 70% by weight or more in a layer having the lithium ion storage capacity. ^2. The nonaqueous electrolyte air battery according to claim 1, wherein the layer having oxygen reducing ability comprises at least a carbonaceous material having a specific surface area of 600 m ² / g or more and a binder. In the nonaqueous electrolyte air battery comprising a positive electrode, a negative electrode, a nonaqueous electrolyte formed between the positive electrode and the negative electrode, and a case having an air hole for supplying oxygen to the positive electrode, the positive electrode has a composition. The layer having at least oxygen reduction ability on the air hole side and the layer having at least lithium ion storage ability on the negative electrode side are arranged, and the layer having lithium ion storage ability is composed of lithium ions. A non-aqueous electrolyte air battery comprising an active material having a capacity of occluding at 2.0 V to 2.9 V (vs. Li), a conductive agent, and a binder.

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