WO2010073332A1 - リチウム空気電池 - Google Patents
リチウム空気電池 Download PDFInfo
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- WO2010073332A1 WO2010073332A1 PCT/JP2008/073569 JP2008073569W WO2010073332A1 WO 2010073332 A1 WO2010073332 A1 WO 2010073332A1 JP 2008073569 W JP2008073569 W JP 2008073569W WO 2010073332 A1 WO2010073332 A1 WO 2010073332A1
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- positive electrode
- electrode layer
- lithium
- air battery
- battery
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
- H01M12/065—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode with plate-like electrodes or stacks of plate-like electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention has been made in view of the above-described circumstances, and its main object is to provide a lithium-air battery capable of selectively using batteries of different characteristics according to the current density at the time of discharge.
- the first positive electrode layer and the second positive electrode layer are stacked and arranged in the order of the second positive electrode layer and the first positive electrode layer from the side of the negative electrode layer. It is because it becomes easy to take in oxygen.
- the present invention by using the above-described positive electrode active material, it is possible to separate the operating voltage range as a lithium-air battery and the operating voltage range as a lithium ion battery. As a result, it is possible to obtain a lithium-air battery capable of selectively using batteries of different characteristics according to the current density at the time of discharge. Specifically, it can function as a high capacity lithium air battery at the time of small current discharge, and can function as a high output lithium ion battery at the time of large current discharge. That is, it is possible to obtain a dual battery in which the function of a high capacity battery (lithium air battery) and the function of a high power battery (lithium ion battery) are incorporated into one battery. Further, since the lithium-air battery of the present invention has two battery functions having different characteristics, it is not necessary to install the two batteries separately, and downsizing and weight reduction can be achieved.
- FIG. 1 is a schematic cross-sectional view showing an example of the lithium-air battery of the present invention.
- the lithium-air battery 10 shown in FIG. 1 includes a negative electrode case 1a, a negative electrode current collector 2 formed on the inner bottom surface of the negative electrode case 1a, a negative electrode lead 2a connected to the negative electrode current collector 2, and a negative electrode current collector
- a positive electrode layer 4 formed on the body 2 and containing a negative electrode active material, and a positive electrode layer 4 comprising at least a first positive electrode layer 4a having oxygen reducing ability and a second positive electrode layer 4b having at least Li ion absorbing ability;
- a positive electrode current collector 5 for collecting the layer 4 a positive electrode lead 5a connected to the positive electrode current collector 5, a separator 6 disposed between the negative electrode layer 3 and the positive electrode layer 4, a negative electrode layer 3 and a positive electrode
- FIG. 2 is an explanatory view for explaining the difference between the conventional lithium air battery and the lithium air battery of the present invention.
- the conventional lithium air battery (lithium air battery described in Patent Document 1) has an operating voltage range as a lithium air battery and an operating voltage as a lithium ion battery at the time of discharge.
- the lithium air battery of the present invention as shown in FIG. 2 (b), the operating voltage range as the lithium air battery and the operating voltage range as the lithium ion battery are separated at the time of discharge. Therefore, it becomes possible to use different batteries of different characteristics depending on the current density at the time of discharge.
- the operating voltage range of the lithium-air battery at the time of discharge is a voltage range in which a Li oxide is formed from Li ions and oxygen, and is usually in the range of 2.0 V to 2.9 V (vs. Li). Therefore, in the present invention, by using a positive electrode active material having an average voltage smaller than 2.0 V (vs. Li) or an average voltage larger than 2.9 V (vs. Li), I tried to separate.
- the value of the average voltage of the positive electrode active material can be determined as follows.
- the positive electrode layer in the present invention has a first positive electrode layer having at least an oxygen reducing ability, and a second positive electrode layer having at least an Li ion storing ability.
- the first positive electrode layer in the present invention is a layer having at least oxygen reducing ability, and is usually a layer that functions as a positive electrode layer of a lithium-air battery.
- the first positive electrode layer usually has a resolution of Li oxide that decomposes the Li oxide (LiO 2 , Li 2 O 2 ) generated by the discharge reaction. .
- the first positive electrode layer in the present invention may contain a catalyst that promotes the reaction. It is because an electrode reaction is performed more smoothly.
- the conductive material preferably carries a catalyst.
- the catalyst include manganese dioxide and cobalt phthalocyanine.
- the content of the catalyst in the first positive electrode layer is preferably, for example, in the range of 1% by weight to 90% by weight. If the content of the catalyst is too small, sufficient catalytic function may not be exhibited. If the content of the catalyst is too large, the content of the conductive material relatively decreases, the reaction site decreases, and the battery capacity The reason is that there may be a decrease in
- the thickness of the first positive electrode layer varies depending on the use of the lithium air battery and the like, but is preferably in the range of 2 ⁇ m to 500 ⁇ m, and more preferably in the range of 5 ⁇ m to 300 ⁇ m.
- the average voltage of the positive electrode active material is in a range smaller than 2.0 V (vs. Li) as described above. Above all, the average voltage of the positive electrode active material is preferably 1.8 V (vs. Li) or less, and more preferably in the range of 0.5 V (vs. Li) to 1.6 V (vs. Li) preferable. By clearly separating the operating voltage range, generation of unnecessary Li oxide can be further suppressed.
- a positive electrode active material for example, graphite, a layered spinel material such as Li 4 Ti 5 O 12 , and a conversion material such as CoO, SnS, Fe 3 P, and the like can be mentioned.
- the average voltage of the positive electrode active material is in a range larger than 2.9 V (vs. Li).
- the average voltage of the positive electrode active material is preferably 3.1 V (vs. Li) or more, and more preferably in the range of 3.3 V (vs. Li) to 4.4 V (vs. Li). preferable.
- a positive electrode active material for example, 4V class positive electrode material such as LiCoO 2 , LiFePO 4 , FePO 4 , LiMn 2 O 4 and 5V class positive electrode such as LiNi 0.5 Mn 1.5 O 4 or LiCoPO 4 Materials etc. can be mentioned.
- the second positive electrode layer in the present invention may contain a binder for immobilizing the positive electrode active material. About the kind and content of a binder, it is the same as that of the content described in said "(1) 1st positive electrode layer".
- the second positive electrode layer in the present invention may contain a conductive material. This is because the conductivity of the second positive electrode layer can be improved. Examples of the conductive material include carbon materials such as carbon black, ketjen black, acetylene black and furnace black.
- the content of the conductive material in the second positive electrode layer is preferably set appropriately in accordance with the type of the positive electrode active material and the like.
- the thickness of the second positive electrode layer varies depending on the use of the lithium air battery and the like, but is preferably in the range of 2 ⁇ m to 500 ⁇ m, and more preferably in the range of 5 ⁇ m to 300 ⁇ m.
- the positive electrode layer in the present invention has the first positive electrode layer and the second positive electrode layer described above.
- the positional relationship between the first positive electrode layer and the second positive electrode layer is not particularly limited, and can be designed arbitrarily.
- the first positive electrode layer and the second positive electrode layer may be stacked or arranged in parallel on the same plane.
- the first positive electrode layer and the second positive electrode layer can be formed in an arbitrary pattern.
- the lithium-air battery of the present invention preferably has a positive electrode current collector for collecting current in the positive electrode layer.
- the material of the positive electrode current collector include metal materials and carbon materials. Among them, carbon materials are preferable. It is because it is excellent in corrosion resistance. As such a carbon material, for example, carbon fiber (carbon fiber) is preferable. Electrons can be conducted through the fiber and the electron conductivity is high.
- the positive electrode current collector using carbon fiber include carbon cloth and carbon paper.
- examples of the metal material include stainless steel, nickel, aluminum, iron and titanium. A metal mesh etc. can be mentioned as a positive electrode collector using a metal material.
- the structure of the positive electrode current collector in the present invention is not particularly limited as long as desired electron conductivity can be secured, and may be a porous structure having gas diffusivity, and a dense structure having no gas diffusivity. It may be. Among them, in the present invention, the positive electrode current collector preferably has a porous structure having gas diffusibility. This is because oxygen can be diffused quickly.
- the porosity of the porous structure is not particularly limited, but is preferably in the range of, for example, 20% to 99%.
- the thickness of the positive electrode current collector is, for example, preferably in the range of 10 ⁇ m to 1000 ⁇ m, and more preferably in the range of 20 ⁇ m to 400 ⁇ m.
- a member composed of the positive electrode layer and the positive electrode current collector is referred to as a "positive electrode".
- the method of forming the positive electrode in the present invention is not particularly limited as long as the above-described positive electrode layer can be obtained.
- a method of forming a positive electrode a method of preparing a composition for forming a first positive electrode layer and a composition for forming a second positive electrode layer, respectively, applying these compositions sequentially to a positive electrode current collector and drying be able to.
- the composition for forming the first positive electrode layer contains, for example, a solvent in addition to the above-mentioned conductive material, binder and catalyst.
- the composition for forming a second positive electrode layer contains, for example, a solvent in addition to the positive electrode active material, the binder, and the conductive material described above.
- the solvent used for these compositions preferably has a boiling point of 200 ° C. or less. It is because drying becomes easy.
- the solvent include acetone, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMA), N, N-dimethylformamide (DMF), methyl ethyl ketone (MEK) and tetrahydrofuran (THF). It can be mentioned.
- the method for forming the positive electrode a method using differences in the size of the opening of the conductive material, the positive electrode active material, and the positive electrode current collector can be mentioned.
- This method makes the size of one of the conductive material and the positive electrode active material larger than the size of the opening of the positive electrode current collector, and the other size smaller than the size of the opening of the positive electrode current collector.
- the first positive electrode layer and the second positive electrode layer are formed by one application.
- a composition for forming a positive electrode layer containing both a conductive material and a positive electrode active material can be used.
- the catalyst and the conductive material can be contained in the target layer by similarly adjusting the size.
- the negative electrode layer in the present invention usually contains a negative electrode active material.
- the negative electrode active material is not particularly limited as long as it can release Li ions, but among them, materials capable of absorbing and releasing Li ions are preferable. It is because it can be used for a lithium air secondary battery.
- the negative electrode active material examples include lithium metal, lithium alloy, lithium oxide, lithium nitride and the like.
- a lithium alloy a lithium aluminum alloy, a lithium tin alloy, a lithium lead alloy, a lithium silicon alloy etc.
- a lithium oxide a lithium titanium oxide etc.
- lithium nitride lithium cobalt nitride, lithium iron nitride, lithium manganese nitride etc. can be mentioned, for example.
- the negative electrode layer in the present invention may contain only the negative electrode active material, and may contain at least one of a conductive material and a binder in addition to the negative electrode active material.
- the negative electrode layer can contain only the negative electrode active material.
- the negative electrode active material when it is in the form of powder, it can be a negative electrode layer having a conductive material and a binder.
- the conductive material and the binder are the same as the contents described in “1. Positive electrode layer” described above, and thus the description thereof is omitted here.
- the thickness of the negative electrode layer is preferably selected appropriately in accordance with the configuration of the target lithium-air battery.
- the lithium-air battery of the present invention preferably has a negative electrode current collector for collecting current in the negative electrode layer.
- the material of the negative electrode current collector is not particularly limited as long as it has conductivity, and examples thereof include copper, stainless steel, nickel and the like.
- As a shape of the said negative electrode collector foil shape, plate shape, mesh (grid) shape etc. can be mentioned, for example.
- a battery case described later may have the function of a negative electrode current collector.
- the thickness of the negative electrode current collector is preferably selected appropriately in accordance with the configuration of the target lithium-air battery.
- a member composed of the negative electrode layer and the negative electrode current collector is referred to as a "negative electrode".
- the method of forming the negative electrode in the present invention is not particularly limited as long as it can form the above-described negative electrode.
- positioning the negative electrode active material of foil shape on a negative electrode collector, and pressurizing can be mentioned.
- a composition for forming a negative electrode layer containing a negative electrode active material and a binder is prepared, and then this composition is applied on a negative electrode current collector. And drying methods.
- the electrolyte layer in the present invention is a layer which is formed between the positive electrode layer and the negative electrode layer to conduct Li ions.
- the form of the electrolyte layer is not particularly limited as long as it has Li ion conductivity, and examples thereof include non-aqueous electrolytic solutions, non-aqueous gel electrolytes, polymer electrolytes, and inorganic solid electrolytes.
- the non-aqueous electrolyte usually contains a lithium salt and an organic solvent (non-aqueous solvent).
- the lithium salt include inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 and LiAsF 6 ; and LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , Organic lithium salts such as LiC (CF 3 SO 2 ) 3 and the like can be mentioned.
- the organic solvent examples include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), butylene carbonate, ⁇ -butyrolactone, sulfolane, acetonitrile, And 2-dimethoxymethane, 1,3-dimethoxypropane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and mixtures thereof.
- the said organic solvent is a solvent with high oxygen solubility. It is because dissolved oxygen can be efficiently used for reaction.
- the concentration of the lithium salt in the non-aqueous electrolytic solution is, for example, in the range of 0.5 mol / L to 3 mol / L.
- a low volatility liquid such as an ionic liquid may be used as the non-aqueous electrolytic solution.
- the non-aqueous gel electrolyte is usually gelled by adding a polymer to the non-aqueous electrolytic solution.
- the non-aqueous gel electrolyte can be obtained by adding a polymer such as polyethylene oxide (PEO), polyacrylonitrile (PAN) or polymethyl methacrylate (PMMA) to the above-mentioned non-aqueous electrolyte and gelling it.
- a non-aqueous gel electrolyte of LiTFSI (LiN (CF 3 SO 2 ) 2 ) -PEO type is preferable.
- the inorganic solid electrolyte for example, a Li-La-Ti-O-based inorganic solid electrolyte can be mentioned.
- the inorganic solid electrolyte can be formed into a solid electrolyte membrane and disposed between the positive electrode layer and the negative electrode layer.
- the lithium-air battery of the present invention preferably has a separator between the positive electrode layer and the negative electrode layer. It is because a highly safe battery can be obtained.
- the separator include porous films such as polyethylene and polypropylene; and nonwoven fabrics such as resin nonwoven fabric and glass fiber nonwoven fabric.
- the shape of the battery case in the present invention is not particularly limited as long as the above-described positive electrode layer, negative electrode, and electrolyte can be stored. Specifically, coin shape, flat shape, cylindrical shape, laminate type, etc. It can be mentioned. Further, the battery case may be an open-air battery case or a closed battery case. As shown in FIG. 1 described above, the open-air battery case is a battery case that can be in contact with the air. On the other hand, when the battery case is a sealed battery case, it is preferable to provide a gas (air) supply pipe and a discharge pipe in the sealed battery case. In this case, the gas to be supplied / discharged preferably has a high oxygen concentration, and more preferably pure oxygen. Further, it is preferable to increase the oxygen concentration at the time of discharge and lower the oxygen concentration at the time of charge.
- the lithium-air battery of the present invention may be a primary battery or a secondary battery, but among them, a secondary battery is preferable. It is because it can be used for a wide range of applications. Examples of applications of the lithium-air battery of the present invention include vehicle-mounted applications, stationary power applications, household power applications, and the like.
- the method for producing the lithium-air battery of the present invention is not particularly limited, and is the same as a general method for producing a metal-air battery. Further, in the present invention, there is provided a method of using the lithium air battery described above, wherein the lithium air battery and the lithium ion battery are selectively used by adjusting the current load. can do.
- the present invention is not limited to the above embodiment.
- the above embodiment is an exemplification, and it has substantially the same configuration as the technical idea described in the claims of the present invention, and any one having the same function and effect can be used. It is included in the technical scope of the invention.
- Example 1 Carbon black (size of primary particle 100 nm or less, size of secondary particle aggregate about several ⁇ m), graphite (central particle size 11.5 ⁇ m), and PVDF-HFP by weight ratio 25: 42 It weighed and mixed so that it might become: 33. Next, the mixture and acetone were mixed and stirred (2000 rpm, 30 minutes) to obtain a composition for forming a positive electrode layer. In addition, the average voltage of the graphite calculated by the method mentioned above was about 0.2 V (vs. Li).
- a carbon paper (TGP-H-090 manufactured by Toray Industries, Inc .; thickness 0.28 mm) having an opening diameter of 8 ⁇ m was prepared as a positive electrode current collector.
- the above composition for forming a positive electrode layer was applied to the carbon paper with a doctor blade.
- drying was performed under an Ar atmosphere at 80 ° C. for 1 hour, and then vacuum drying was performed at 60 ° C. overnight.
- a positive electrode was obtained in which the positive electrode current collector, the first positive electrode layer (layer containing carbon black) and the second positive electrode layer (layer containing graphite) were arranged in this order.
- a lithium air battery element was manufactured using the above-mentioned positive electrode.
- the element was assembled in an argon box.
- an F-type electrochemical cell manufactured by Hokuto Denko was used for the battery case of the element.
- metal Li manufactured by Honjo Metal Co., Ltd., ⁇ 18 mm, thickness 0.25 mm
- a polyethylene separator ⁇ 18 mm, thickness 25 ⁇ m
- the above positive electrode positive electrode layer was disposed so as to face the separator and sealed, to obtain a lithium air battery element.
- the obtained element was placed in a desiccator filled with oxygen (oxygen concentration 99.99% by volume, internal pressure 1 atm, desiccator volume 1 L) to obtain a cell for evaluation.
- the average voltage of MnO 2 calculated by the above-described method was about 2.7 V (vs. Li).
- Discharge Test A discharge test was performed using the evaluation cell obtained in Example 1. Discharge, large current discharge (current density 0.2 mA / cm 2, less than 0.01 V (Vs.Li) is cut) and small current discharge (current density 0.02mA / cm 2, 2.0V (vs.Li ) Less than a cut was performed under the conditions. The results are shown in FIG. As shown in FIG. 4, it was confirmed that the evaluation cell of Example 1 functions as a lithium ion battery at the time of large current discharge and functions as a lithium air battery at the small current discharge. Thereby, it was confirmed that batteries of different characteristics can be used properly depending on the current density at the time of discharge.
- Example 1 (2) Impedance Evaluation
- the evaluation cells obtained in Example 1 and Comparative Example 1 were used to evaluate changes in impedance of the positive electrode layer due to charge and discharge.
- the charge and discharge are large current charge and discharge (current density 0.2 mA / cm 2 , 0.01 V to 1.5 V (vs. Li)) and small current discharge (current density 0.02 mA / cm 2 , 2.0 V to 4 It carried out on the conditions of .3V (vs. Li).
- the results are shown in FIG.
- FIG. 5 in the large current charge and discharge (0.2 mA / cm 2 ), the cell for evaluation of Example 1 is inhibited from increasing in impedance as compared with the cell for evaluation of Comparative Example 1. That was confirmed.
- Example 1 functions as a lithium ion battery at the time of high current discharge, thereby suppressing the generation of Li oxide generated by the discharge reaction of the lithium air battery.
- small current charge / discharge (0.02 mA / cm 2 )
- no significant difference was observed in the increase in impedance between the evaluation cell of Example 1 and the evaluation cell of Comparative Example 1. This is considered to be due to the fact that both function as a lithium air battery in small current charge and discharge.
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Abstract
Description
1b … 正極ケース
2 … 負極集電体
2a … 負極リード
3 … 負極層
4 … 正極層
4a … 第一正極層
4b … 第二正極層
5 … 正極集電体
5a … 正極リード
6 … セパレータ
7 … 非水電解液
8 … 微多孔膜
9 … パッキン
以下、本発明のリチウム空気電池について、構成ごとに説明する。
まず、本発明における正極層について説明する。本発明における正極層は、少なくとも酸素還元能を有する第一正極層と、少なくともLiイオン吸蔵能を有する第二正極層とを有する。
本発明における第一正極層は、少なくとも酸素還元能を有する層であり、通常、リチウム空気電池の正極層として機能する層である。また、本発明のリチウム空気電池が二次電池である場合、第一正極層は、通常、放電反応で生じたLi酸化物(LiO2、Li2O2)を分解するLi酸化物分解能を有する。
次に、本発明における第二正極層について説明する。本発明における第二正極層は、少なくともLiイオン吸蔵能を有する層であり、通常、リチウムイオン電池の正極層として機能する層である。また、本発明のリチウム空気電池が二次電池である場合、通常、第二正極層は、Liイオン放出能を有する。
本発明における正極層は、上述した第一正極層および第二正極層を有するものである。本発明において、第一正極層および第二正極層の位置関係は、特に限定されるものではなく、任意に設計することができる。本発明においては、第一正極層および第二正極層が、積層配置されていても良く、同一平面上に並列配置されていても良い。積層配置の場合、第一正極層および第二正極層は、負極層側から、第二正極層および第一正極層の順で積層配置されていることが好ましい(図1参照)。酸素の取り込みが容易になるからである。一方、並列配置の場合、任意のパターンで、第一正極層および第二正極層を形成することができる。
次に、本発明における負極層について説明する。本発明における負極層は、通常、負極活物質を含有するものである。上記負極活物質としては、Liイオンを放出できるものであれば特に限定されるものではないが、中でもLiイオンを吸蔵・放出できるものであることが好ましい。リチウム空気二次電池に用いることができるからである。
次に、本発明における電解質層について説明する。本発明における電解質層は、上記正極層および上記負極層の間に形成され、Liイオンの伝導を行う層である。電解質層の形態は、Liイオン伝導性を有するものであれば特に限定されるものではないが、例えば、非水電解液、非水ゲル電解質、ポリマー電解質および無機固体電解質等を挙げることができる。
次に、本発明における電池ケースについて説明する。本発明における電池ケースの形状としては、上述した正極層、負極、電解質を収納することができれば特に限定されるものではないが、具体的にはコイン型、平板型、円筒型、ラミネート型等を挙げることができる。また、電池ケースは、大気開放型の電池ケースであっても良く、密閉型の電池ケースであっても良い。大気開放型の電池ケースは、上述した図1に示すように、大気と接触可能な電池ケースである。一方、電池ケースが密閉型電池ケースである場合は、密閉型電池ケースに、気体(空気)の供給管および排出管を設けることが好ましい。この場合、供給・排出する気体は、酸素濃度が高いことが好ましく、純酸素であることがより好ましい。また、放電時には酸素濃度を高くし、充電時には酸素濃度を低くすることが好ましい。
本発明のリチウム空気電池は、一次電池であっても良く、二次電池であっても良いが、中でも二次電池であることが好ましい。幅広い用途に用いることができるからである。本発明のリチウム空気電池の用途としては、例えば車両搭載用途、定置型電源用途、家庭用電源用途等を挙げることができる。また、本発明のリチウム空気電池を製造する方法は、特に限定されるものではなく、一般的な金属空気電池の製造方法と同様である。また、本発明においては、上述したリチウム空気電池の使用方法であって、電流負荷を調節することで、リチウム空気電池とリチウムイオン電池とを使い分けることを特徴とするリチウム空気電池の使用方法を提供することができる。
(正極の作製)
カーボンブラック(一次粒子の大きさが100nm以下、二次粒子凝集体の大きさが数μm程度)と、グラファイト(中心粒径11.5μm)と、PVDF-HFPと、を重量比で25:42:33となるように秤量し、混合した。次に、これらの混合物およびアセトンを混合撹拌(2000rpm、30分)し、正極層形成用組成物を得た。なお、上述した方法により算出したグラファイトの平均電圧は、約0.2V(vs.Li)であった。
まず、上記の正極を用いて、リチウム空気電池素子を作製した。なお、素子の組立はアルゴンボックス内で行った。また、素子の電池ケースには、北斗電工製のF型電気化学セルを用いた。
グラファイトの代わりに、MnO2(d50=15μm)を用いたこと以外は、実施例1と同様にして評価用セルを得た。なお、上述した方法により算出したMnO2の平均電圧は、約2.7V(vs.Li)であった。
(1)放電試験
実施例1で得られた評価用セルを用いて、放電試験を行った。放電は、大電流放電(電流密度0.2mA/cm2、0.01V(vs.Li)未満はカット)および小電流放電(電流密度0.02mA/cm2、2.0V(vs.Li)未満はカット)の条件で行った。その結果を図4に示す。図4に示されるように、実施例1の評価用セルは、大電流放電の際にはリチウムイオン電池として機能し、小電流放電の際にはリチウム空気電池として機能することが確認された。これにより、放電時の電流密度に応じて、異なる特性の電池を使い分けることができることが確認された。
実施例1および比較例1で得られた評価用セルを用いて、充放電に伴う正極層のインピーダンスの変化について評価した。充放電は、大電流充放電(電流密度0.2mA/cm2、0.01V~1.5V(vs.Li))および小電流放電(電流密度0.02mA/cm2、2.0V~4.3V(vs.Li))の条件で行った。その結果を図5に示す。図5に示されるように、大電流充放電(0.2mA/cm2)において、実施例1の評価用セルは、比較例1の評価用セルに比べて、インピーダンスの増加が抑制されていることが確認できた。これは、実施例1の評価用セルが、大電流放電時にリチウムイオン電池として機能することで、リチウム空気電池の放電反応で生じるLi酸化物の生成が抑制されたためであると考えられる。一方、小電流充放電(0.02mA/cm2)においては、実施例1の評価用セルと、比較例1の評価用セルとは、インピーダンスの増加に大きな差は見られなかった。これは、小電流充放電では、共にリチウム空気電池として機能しているためであると考えられる。
Claims (4)
- 正極層と、負極層と、前記正極層および前記負極層の間に形成された電解質層とを有するリチウム空気電池であって、
前記正極層は、少なくとも酸素還元能を有する第一正極層と、少なくともLiイオン吸蔵能を有する第二正極層とを有し、
前記第二正極層が、2.0V(vs.Li)よりも小さい平均電圧、または、2.9V(vs.Li)よりも大きい平均電圧を有する正極活物質を含有することを特徴とするリチウム空気電池。 - 前記正極活物質が、グラファイトまたはLi4Ti5O12であることを特徴とする請求の範囲第1項に記載のリチウム空気電池。
- 前記正極活物質が、LiCoO2またはLiFePO4であることを特徴とする請求の範囲第1項に記載のリチウム空気電池。
- 前記第一正極層および前記第二正極層は、前記負極層側から、前記第二正極層および前記第一正極層の順で積層配置されていることを特徴とする請求の範囲第1項から第3項までのいずれかに記載のリチウム空気電池。
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