WO2010061451A1 - 空気二次電池 - Google Patents
空気二次電池 Download PDFInfo
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- WO2010061451A1 WO2010061451A1 PCT/JP2008/071542 JP2008071542W WO2010061451A1 WO 2010061451 A1 WO2010061451 A1 WO 2010061451A1 JP 2008071542 W JP2008071542 W JP 2008071542W WO 2010061451 A1 WO2010061451 A1 WO 2010061451A1
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- WIPO (PCT)
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- air
- negative electrode
- secondary battery
- electrode layer
- air electrode
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
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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
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to an air secondary battery using a non-aqueous electrolyte, and more particularly to an air secondary battery capable of reducing a charging voltage.
- An air secondary battery using a non-aqueous electrolyte is a secondary battery using air (oxygen) as a positive electrode active material, and has advantages such as high energy density and easy miniaturization and weight reduction. For this reason, it has attracted attention as a high-capacity secondary battery that exceeds the widely used lithium secondary battery.
- Such an air secondary battery includes, for example, an air electrode layer having a conductive material (for example, carbon black), a catalyst (for example, manganese dioxide) and a binder (for example, polyvinylidene fluoride), and a current collector for the air electrode layer.
- a conductive material for example, carbon black
- a catalyst for example, manganese dioxide
- a binder for example, polyvinylidene fluoride
- a negative electrode layer containing a negative electrode active material for example, metal Li
- a negative electrode current collector for collecting the current of the negative electrode layer
- a non-charger that conducts metal ions (for example, Li ions)
- an aqueous electrolyte for example, Li ions
- Patent Document 1 discloses an air electrode of an air battery using a nonaqueous electrolyte, in which a mixture of carbon, a catalyst, and a binder is pressed or applied to a mesh-shaped metal current collector. Furthermore, metals such as stainless steel, nickel, aluminum, iron, and titanium are disclosed as materials for the air electrode current collector.
- Patent Document 2 an aluminum air battery using an aqueous electrolyte instead of a non-aqueous electrolyte is disclosed. There, it is disclosed that carbon paper is used as the base material of the cathode catalyst electrode.
- Patent Document 3 also discloses an aluminum air battery using an aqueous electrolyte instead of a nonaqueous electrolyte. There, it is disclosed that a thin conductive carbon cloth is used as an air electrode current collector.
- a metal air electrode current collector has been used for an air secondary battery using a non-aqueous electrolyte.
- the metal air cathode current collector has a problem of being easily corroded.
- the present inventor has confirmed that the problem of corrosion can be solved by using an air electrode current collector made of a carbon material instead of a metal air electrode current collector.
- a carbon material air electrode current collector is used, a new problem has arisen in that the charging voltage becomes higher than when a metal air electrode current collector is used.
- the present invention has been made in view of the above problems, and it is a main object of the present invention to provide an air secondary battery that can reduce the charging voltage in an air secondary battery using a non-aqueous electrolyte. .
- an air electrode having an air electrode layer containing a conductive material and an air electrode current collector for collecting the air electrode layer, a negative electrode layer containing a negative electrode active material, and the negative electrode layer
- An air secondary battery comprising: a negative electrode having a negative electrode current collector for collecting current; and the air electrode layer and a non-aqueous electrolyte that conducts metal ions between the negative electrode layer,
- an air secondary battery characterized in that the electric body is made of a carbon material, and the non-aqueous electrolyte contains a sulfonimide salt.
- the charge voltage can be lowered by using a combination of an air electrode current collector made of a carbon material and a nonaqueous electrolytic solution containing a sulfonimide salt.
- the sulfonimide salt is preferably a compound represented by the following general formula (1). This is because the charging voltage can be effectively reduced.
- M is an alkali metal element
- R 1 and R 2 are each independently a functional group containing a fluorine element and a carbon element.
- R 1 and R 2 may be bonded to each other to form a ring structure.
- the carbon material is preferably carbon fiber. This is because electrons can be conducted through the fiber and the electron conductivity is high.
- the air electrode current collector is preferably carbon paper or carbon cloth using the carbon fiber. This is because it has excellent gas diffusibility and oxygen can be diffused quickly.
- the metal ion is preferably Li ion. This is because a battery having a high energy density can be obtained.
- FIG. 1 It is a schematic sectional drawing which shows an example of the air secondary battery of this invention. 2 is a schematic cross-sectional view showing an evaluation cell used in Example 1. FIG.
- the air secondary battery of the present invention includes an air electrode having an air electrode layer containing a conductive material and an air electrode current collector for collecting the air electrode layer, a negative electrode layer containing a negative electrode active material, and the negative electrode.
- An air secondary battery comprising: a negative electrode having a negative electrode current collector for collecting current of the layer; and the air electrode layer and a non-aqueous electrolyte solution that conducts metal ions between the negative electrode layer, the air
- the electrode current collector is made of a carbon material, and the non-aqueous electrolyte contains a sulfonimide salt.
- the charge voltage can be lowered by using a combination of an air electrode current collector made of a carbon material and a nonaqueous electrolytic solution containing a sulfonimide salt.
- an air electrode current collector made of a carbon material when used, corrosion of the air electrode current collector can be prevented, but there is a problem that a charging voltage becomes high.
- the charging voltage can be lowered and charging can be performed efficiently.
- the reason why the charging voltage is low is not yet clear, but the non-aqueous electrolyte containing a sulfonimide salt has a low surface tension, and therefore the wettability of the surface of the carbon material constituting the air electrode current collector. This is thought to be due to the fact that the charging reaction (decomposition reaction of the discharge product) is likely to occur due to the improvement of the flow rate and the smooth movement of ions.
- a discharge product such as Li 2 O 2 is generated by discharge, but if the wettability of the surface of the carbon material is improved during charging to decompose the discharge product, It is considered that the movement of Li ions in the vicinity of the product becomes smooth and the charge reaction is likely to occur.
- the sulfonimide salt contains a fluorine element, a nonaqueous electrolytic solution having a high dissolved oxygen amount is usually obtained. In this case, since a large amount of oxygen can be dissolved in the nonaqueous electrolytic solution, oxygen generated during charging can be smoothly excluded from the reaction field of the charging reaction, and the charging reaction is likely to occur.
- FIG. 1 is a schematic cross-sectional view showing an example of the air secondary battery of the present invention.
- An air secondary 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.
- the air electrode current collector 5 is made of a carbon material, and the nonaqueous electrolytic solution 7 contains a sulfonimide salt.
- the air secondary battery of the present invention will be described for each configuration.
- the air electrode used in the present invention has an air electrode layer containing a conductive material and an air electrode current collector that collects the air electrode layer.
- Air electrode current collector The air electrode current collector used in the present invention collects current in the air electrode layer. Furthermore, the air electrode current collector used in the present invention is usually composed of a carbon material. Carbon materials have the advantage of being excellent in corrosion resistance, the advantage of being excellent in electronic conductivity, and the advantage of being higher in energy density per weight because they are lighter than metals. Examples of such a carbon material include carbon fiber (carbon fiber), activated carbon (what activated a carbon plate), and the like. Among these, carbon fiber is preferable. This is because electrons can be conducted through the fiber and the electron conductivity is high. Examples of the type of carbon fiber include PAN carbon fiber and pitch carbon fiber.
- the structure of the air electrode current collector in the present invention is not particularly limited as long as the desired electron conductivity can be ensured, and may be a porous structure having gas diffusibility, or a dense structure having no gas diffusibility. It may be. Among them, in the present invention, the air current collector preferably has a porous structure having gas diffusibility. Specific examples of the porous structure include a mesh structure, a non-woven fabric structure, and a three-dimensional network structure having connecting holes. The porosity of the porous structure is not particularly limited, but is preferably in the range of 20% to 99%, for example.
- Examples of the air electrode current collector using the carbon fiber described above include carbon cloth and carbon paper.
- the carbon cloth generally refers to a material in which carbon fibers are regularly knitted (corresponding to the mesh structure described above).
- carbon paper generally refers to a carbon fiber randomly arranged (corresponding to the above-mentioned nonwoven fabric structure). Further, the carbon cloth and the carbon paper may be sintered or activated. In the present invention, carbon cloth and carbon fiber may be used in an overlapping manner. This is because an air electrode current collector with improved mechanical strength can be obtained.
- the thickness of the air electrode current collector in the present invention 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.
- Air electrode layer used in the present invention contains at least a conductive material. Furthermore, you may contain at least one of a catalyst and a binder as needed.
- the conductive material used for the air electrode layer is not particularly limited as long as it has conductivity, and examples thereof include a carbon material. Further, the carbon material may have a porous structure or may not have a porous structure. However, in the present invention, the carbon material preferably has a porous structure. This is because the specific surface area is large and many reaction fields can be provided. Specific examples of the carbon material having a porous structure include mesoporous carbon. On the other hand, specific examples of the carbon material having no porous structure include graphite, acetylene black, carbon nanotube, and carbon fiber.
- the content of the conductive material in the air electrode layer is preferably in the range of 10% by weight to 99% by weight, for example. If the content of the conductive material is too small, the reaction field may decrease and the battery capacity may decrease. If the content of the conductive material is too large, the content of the catalyst or binder is relatively high. This is because the desired air electrode layer may not be obtained.
- the air electrode layer used in the present invention may contain a catalyst that promotes the reaction. This is because the electrode reaction is performed more smoothly.
- the conductive material preferably carries a catalyst.
- the catalyst include oxide catalysts such as manganese dioxide (MnO 2 ) and cerium dioxide (CeO 2 ), macrocyclic compounds such as phthalocyanine and porphyrin, and transition metals (eg, Co) coordinated with the macrocyclic compounds. A complex etc. can be mentioned.
- the catalyst content in the air electrode layer is, for example, preferably in the range of 1% by weight to 30% by weight, and more preferably in the range of 5% by weight to 20% by weight. If the catalyst content is too low, sufficient catalytic function may not be achieved. If the catalyst content is too high, the content of the conductive material is relatively reduced, the reaction field is reduced, and the battery capacity is reduced. This is because there is a possibility that a decrease in the number of times will occur.
- the air electrode layer used in the present invention may contain a binder for fixing the conductive material.
- the binder include fluorine-containing binders such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- the content of the binder in the air electrode layer is, for example, preferably 40% by weight or less, and more preferably in the range of 1% by weight to 10% by weight.
- the thickness of the air electrode layer varies depending on the use of the air secondary battery, 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 formation method of the air electrode in this invention will not be specifically limited if it is a method which can form the air electrode mentioned above.
- a method for forming an air electrode first, a composition for forming an air electrode layer containing a conductive material, a catalyst, and a binder is prepared, and then this composition is placed on the air electrode current collector.
- coating to and drying can be mentioned.
- the nonaqueous electrolyte used in the present invention conducts metal ions between the negative electrode layer and the air electrode layer. Furthermore, the non-aqueous electrolyte usually contains a sulfonimide salt and an organic solvent (non-aqueous solvent). Examples of the sulfonimide salt used in the present invention include compounds represented by the following general formula (1).
- M is an alkali metal element
- R 1 and R 2 are each independently a functional group containing a fluorine element and a carbon element. R 1 and R 2 may be bonded to each other to form a ring structure.
- M is an alkali metal element, and usually this alkali metal ion becomes a conduction ion of the air secondary battery.
- alkali metal ion Li ion, Na ion, K ion etc. can be mentioned, for example, Li ion is especially preferable. This is because a battery having a high energy density can be obtained.
- R 1 and R 2 are functional groups containing a fluorine element and a carbon element, and among them, a functional group composed of only a fluorine element and a carbon element is preferable.
- R 1 and R 2 are —C n F 2n + 1 . This is because the charging voltage can be sufficiently lowered.
- the value of n is preferably 1 to 6, and more preferably 1 to 4.
- Specific examples of the sulfonimide salt in which M is Li and R 1 and R 2 are —C n F 2n + 1 include (CF 3 SO 2 ) 2 NLi (sometimes referred to as LiTFSI), (C 2 F 5 SO 2) (CF 3 SO 2) NLi, ( sometimes C 2 F 5 SO 2) referred to as 2 NLi (LiBETI), (C 3 F 7 SO 2) (CF 3 SO 2) NLi, (C 3 F 7 SO 2) (C 2 F 5 SO 2) NLi, (C 3 F 7 SO 2) 2 NLi, (C 4 F 9 SO 2) (CF 3 SO 2) NLi, (C 4 F 9 SO 2 ) (C 2 F 5 SO 2 ) NLi, (C 4 F 9 SO 2 ) (C 3 F 7 SO 2 ) NLi, etc., among which LiTFSI and LiBETI Is preferred.
- R 1 and R 2 may be bonded to each other to form a ring structure.
- cyclic sulfoimide salts include CF 2 (CF 2 SO 2 ) 2 NLi.
- concentration of the sulfonimide salt in the non-aqueous electrolyte is, for example, preferably in the range of 0.3 mol / L to 3 mol / L, and more preferably in the range of 0.5 mol / L to 2 mol / L.
- 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, , 2-dimethoxymethane, 1,3-dimethoxypropane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran and mixtures thereof.
- the organic solvent is preferably a solvent having high oxygen solubility. This is because dissolved oxygen can be used efficiently in the reaction.
- an ionic liquid room temperature molten salt
- room temperature molten salt may be used as the solvent.
- non-aqueous electrolyte used in the present invention may be used as a non-aqueous gel electrolyte by adding a polymer.
- a non-aqueous gel electrolyte of a lithium-air secondary battery is gelled by adding a polymer such as polyethylene oxide (PEO), polyacrylonitrile (PAN), or polymethyl methacrylate (PMMA) to the non-aqueous electrolyte described above. By doing so, it can be obtained.
- a polymer such as polyethylene oxide (PEO), polyacrylonitrile (PAN), or polymethyl methacrylate (PMMA)
- the negative electrode used in the present invention has a negative electrode layer containing a negative electrode active material and a negative electrode current collector that collects current from the negative electrode layer.
- the negative electrode layer used in the present invention contains at least a negative electrode active material.
- the negative electrode active material is not particularly limited as long as it can occlude and release metal ions, and examples thereof include simple metals, alloys, metal oxides, and metal nitrides.
- an alkali metal ion can be mentioned, for example.
- examples of the alkali metal ions include Li ions, Na ions, K ions, and the like, and among them, Li ions are preferable. This is because a battery having a high energy density can be obtained.
- examples of the alloy containing lithium element include a lithium aluminum alloy, a lithium tin alloy, a lithium lead alloy, and a lithium silicon alloy.
- examples of a metal oxide which has a lithium element lithium titanium oxide etc. can be mentioned, for example.
- examples of the metal nitride containing a lithium element include lithium cobalt nitride, lithium iron nitride, and lithium manganese nitride.
- the negative electrode layer in the present invention may contain only the negative electrode active material, or may contain at least one of a conductive material and a binder in addition to the negative electrode active material.
- a negative electrode layer containing only the negative electrode active material can be obtained.
- a negative electrode layer having a conductive material and a binder can be obtained.
- the thickness of the negative electrode layer is preferably selected as appropriate according to the configuration of the target air secondary battery.
- Negative electrode current collector used in the present invention collects current from the negative electrode layer.
- the material for the negative electrode current collector is not particularly limited as long as it has conductivity, and examples thereof include copper, stainless steel, and nickel.
- Examples of the shape of the negative electrode current collector include a foil shape, a plate shape, and a mesh (grid) shape.
- a battery case which will be described later, may have the function of a negative electrode current collector.
- the thickness of the negative electrode current collector is preferably appropriately selected according to the configuration of the target air secondary battery.
- the formation method of the negative electrode in this invention will not be specifically limited if it is a method which can form the negative electrode mentioned above.
- a method for forming the negative electrode a method in which a foil-like negative electrode active material is placed on a negative electrode current collector and pressurized can be exemplified.
- 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 onto a negative electrode current collector. And a method of drying.
- the shape of the battery case used in the present invention is not particularly limited as long as it can accommodate the air electrode, the negative electrode, and the non-aqueous electrolyte described above, but specifically, a coin type, a flat plate type, a cylindrical type And a laminate type.
- the battery case may be an open-air battery case or a sealed battery case. As shown in FIG. 1 described above, the open-air battery case is a battery case that can come into contact with the atmosphere.
- the battery case is a sealed battery case, it is preferable to provide a gas (air) introduction pipe and an exhaust pipe in the sealed battery case.
- the gas to be introduced / exhausted preferably has a high oxygen concentration, and more preferably pure oxygen.
- Air Secondary Battery The air secondary battery of the present invention preferably has a separator that holds a non-aqueous electrolyte between the air electrode layer and the negative electrode layer. This is because a safer air secondary battery can be obtained.
- the separator include porous films such as polyethylene and polypropylene; and nonwoven fabrics such as a resin nonwoven fabric and a glass fiber nonwoven fabric. The thickness of the separator is preferably selected as appropriate according to the use of the air secondary battery.
- the type of the air secondary battery of the present invention differs depending on the type of metal ions that become conductive ions.
- an alkali metal ion can be mentioned, for example.
- examples of the alkali metal ions include Li ions, Na ions, K ions, and the like, and among them, Li ions are preferable.
- examples of the type of the air secondary battery of the present invention include a lithium air secondary battery, a sodium air secondary battery, and a potassium air secondary battery, and among them, a lithium air secondary battery is preferable. This is because a battery having a high energy density can be obtained.
- the air secondary battery of this invention a vehicle mounting use, a stationary power supply use, a household power supply use etc. can be mentioned, for example.
- the method for producing the air secondary battery of the present invention is not particularly limited, and is the same as the method for producing a general air secondary battery.
- the present invention is not limited to the above embodiment.
- the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
- Example 1 (Production of air electrode) First, 85 parts by weight of ketjen black (manufactured by ketjen black international), 15 parts by weight of electrolytic manganese dioxide (manufactured by High Purity Chemical Laboratory), and 100 parts by weight of PVDF solution (manufactured by Kureha) are mixed. NMP (N-methylpyrrolidone, manufactured by Kanto Chemical Co., Inc.) was added to and mixed with a kneader to obtain an air electrode layer forming paste. Thereafter, the air electrode layer forming paste was applied onto carbon paper (air electrode current collector, manufactured by Toray Industries, Inc., TGP-H-090, thickness 0.28 mm), and NMP was removed by drying. Thereafter, punching was performed at ⁇ 18 mm to obtain an air electrode.
- NMP N-methylpyrrolidone, manufactured by Kanto Chemical Co., Inc.
- the lithium air secondary battery 20 includes battery cases 11a and 11b made of Teflon (registered trademark) and a battery case 11c made of SUS.
- the battery case 11b and the battery case 11c are joined by bolts 12.
- the battery case 11a has an opening for supplying oxygen, and a hollow current extraction portion 13 is provided in the opening.
- the air electrode obtained by the above method is used as the air electrode 14, and non-aqueous electrolysis in which (CF 3 SO 2 ) 2 NLi is dissolved in propylene carbonate (PC) at a concentration of 1 M is used as the non-aqueous electrolyte 15.
- a liquid lithium was used for the negative electrode layer 16 (made by Honjo Metal Co., Ltd., thickness: 200 ⁇ m, diameter: 19 mm).
- the non-aqueous electrolyte 15 was added to such an extent that the upper part of the air electrode 14 was immersed.
- the air electrode lead 23 is connected to the current extraction unit 13 made of SUS, the negative electrode lead 25 is connected to the battery case 11c made of SUS, and the lithium air secondary battery 20 is stored in the glass container 21 having a capacity of 1000 cc. . Thereafter, the glass container 21 was sealed, and the sealed glass container 21 was taken out from the argon box. Next, oxygen was introduced from a gas cylinder of oxygen through the gas introduction part 22 and, at the same time, the gas exhaust part 24 was evacuated to replace the inside of the glass container with an oxygen atmosphere from an argon atmosphere. Thereby, the cell for evaluation was obtained.
- Example 2 An evaluation cell was obtained in the same manner as in Example 1 except that (C 2 F 5 SO 2 ) 2 NLi was used in place of (CF 3 SO 2 ) 2 NLi in the nonaqueous electrolytic solution 15.
- the charge capacity at the fifth cycle is substantially the same (almost 100%) as the charge capacity at the first cycle, and the air secondary battery of the present invention is As a result, it has been revealed that it exhibits good cycle characteristics.
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Abstract
Description
1b … 空気極ケース
2 … 負極集電体
2a … 負極リード
3 … 負極層
4 … 空気極層
5 … 空気極集電体
5a … 空気極リード
6 … セパレータ
7 … 非水電解液
8 … 微多孔膜
9 … パッキン
以下、本発明の空気二次電池について、構成ごとに説明する。
まず、本発明に用いられる空気極について説明する。本発明に用いられる空気極は、導電性材料を含有する空気極層と、上記空気極層の集電を行う空気極集電体と、を有するものである。
本発明に用いられる空気極集電体は、空気極層の集電を行うものである。さらに、本発明に用いられる空気極集電体は、通常、カーボン材料から構成されている。カーボン材料は、耐腐食性に優れるという利点、電子伝導性に優れているという利点、金属に比べて軽いため重量当たりのエネルギー密度が高くなるという利点を有する。このようなカーボン材料としては、例えばカーボンファイバー(炭素繊維)、賦活カーボン(カーボン板を賦活したもの)等を挙げることができ、中でもカーボンファイバーが好ましい。電子が繊維を通じて伝導することができ、電子伝導性が高いからである。カーボンファイバーの種類としては、例えばPANカーボンファイバー、ピッチカーボンファイバー等を挙げることができる。
本発明に用いられる空気極層は、少なくとも導電性材料を含有するものである。さらに、必要に応じて、触媒および結着材の少なくとも一方を含有していても良い。
本発明における空気極の形成方法は、上述した空気極を形成することができる方法であれば特に限定されるものではない。空気極の形成方法の一例としては、まず、導電性材料、触媒および結着材を含有する空気極層形成用の組成物を作製し、次に、この組成物を、空気極集電体上に塗布して、乾燥する方法等を挙げることができる。
次に、本発明に用いられる非水電解液について説明する。本発明に用いられる非水電解液は、負極層および空気極層の間で金属イオンの伝導を行うものである。さらに、非水電解液は、通常、スルホンイミド塩および有機溶媒(非水溶媒)を含有する。本発明に用いられるスルホンイミド塩としては、例えば、下記一般式(1)で表される化合物を挙げることができる。一般式(1)において、Mはアルカリ金属元素であり、R1およびR2は、それぞれ独立に、フッ素元素および炭素元素を含む官能基である。また、R1およびR2は、互いに結合し環構造を形成していても良い。
次に、本発明に用いられる負極について説明する。本発明に用いられる負極は、負極活物質を含有する負極層と、上記負極層の集電を行う負極集電体と、を有するものである。
本発明に用いられる負極層は、少なくとも負極活物質を含有する。負極活物質は、金属イオンを吸蔵・放出することができるものであれば特に限定されるものではないが、例えば金属単体、合金、金属酸化物、金属窒化物等を挙げることができる。上記金属イオンとしては、例えばアルカリ金属イオンを挙げることができる。さらに、上記アルカリ金属イオンとしては、例えばLiイオン、NaイオンおよびKイオン等を挙げることができ、中でもLiイオンが好ましい。エネルギー密度の高い電池を得ることができるからである。
本発明に用いられる負極集電体は、負極層の集電を行うものである。負極集電体の材料としては、導電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、銅、ステンレス、ニッケル等を挙げることができる。上記負極集電体の形状としては、例えば箔状、板状およびメッシュ(グリッド)状等を挙げることができる。本発明においては、後述する電池ケースが負極集電体の機能を兼ね備えていても良い。また、負極集電体の厚さについては、目的とする空気二次電池の構成に応じて適宜選択することが好ましい。
本発明における負極の形成方法は、上述した負極を形成することができる方法であれば特に限定されるものではない。負極の形成方法の一例としては、箔状の負極活物質を、負極集電体上に配置して、加圧する方法を挙げることができる。また、負極の形成方法の他の例としては、負極活物質および結着材を含有する負極層形成用の組成物を作製し、次に、この組成物を、負極集電体上に塗布して、乾燥する方法等を挙げることができる。
次に、本発明に用いられる電池ケースについて説明する。本発明に用いられる電池ケースの形状としては、上述した空気極、負極、非水電解液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)の導入管および排気管を設けることが好ましい。この場合、導入・排気する気体は、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。
本発明の空気二次電池は、空気極層および負極層の間に、非水電解液を保持するセパレータを有することが好ましい。より安全性の高い空気二次電池を得ることができるからである。上記セパレータとしては、例えばポリエチレン、ポリプロピレン等の多孔膜;および樹脂不織布、ガラス繊維不織布等の不織布等を挙げることができる。また、セパレータの厚さは、空気二次電池の用途等に応じて、適宜選択することが好ましい。
(空気極の作製)
まず、ケッチェンブラック(ケッチェンブラックインターナショナル社製)85重量部と、電解二酸化マンガン(高純度化学研究所製)15重量部と、PVDF溶液(クレハ社製)100重量部とを混合し、これにNMP(N-メチルピロリドン、関東化学社製)を添加し、混練機で混合することにより、空気極層形成用ペーストを得た。その後、空気極層形成用ペーストを、カーボンペーパー(空気極集電体、東レ社製、TGP-H-090、厚さ0.28mm)上に塗布し、乾燥によりNMPを除去した。その後、φ18mmで打ち抜いて、空気極を得た。
次に、得られた空気極を用いたリチウム空気二次電池を作製した(図2参照)。なお、電池の組立はすべてアルゴンボックス内(露点-40℃以下)で行った。ここで、リチウム空気二次電池20は、テフロン(登録商標)製の電池ケース11a、11bと、SUS製の電池ケース11cと、を有している。なお、電池ケース11bおよび電池ケース11cは、ボルト12で接合されている。さらに、電池ケース11aには酸素を供給する開口部を有しており、その開口部には、中空状の電流取出し部13が設けられている。また、空気極14には上記の方法で得られた空気極を用い、非水電解液15には(CF3SO2)2NLiをプロピレンカーボネート(PC)に濃度1Mで溶解させた非水電解液を用い、負極層16には金属リチウム(本城金属社製、厚み200μm、直径19mm)を用いた。なお、非水電解液15は、空気極14の上部が浸る程度まで加えた。
次に、SUS製の電流取出し部13に空気極リード23を接続し、SUS製の電池ケース11cに負極リード25を接続し、リチウム空気二次電池20を、容積1000ccのガラス容器21に収納した。その後、ガラス容器21を密閉し、密封したガラス容器21をアルゴンボックス内から取出した。次に、酸素のガスボンベからガス導入部22を介して酸素を導入し、同時に、ガス排気部24から排気を行い、ガラス容器内を、アルゴン雰囲気から酸素雰囲気に置換した。これにより、評価用セルを得た。
非水電解液15において、(CF3SO2)2NLiの代わりに、(C2F5SO2)2NLi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。
非水電解液15において、(CF3SO2)2NLiの代わりに、LiClO4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。
非水電解液15において、(CF3SO2)2NLiの代わりに、LiPF6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。
実施例1、2および比較例1、2で得られた評価用セルを用いて、充放電試験を行った。下記に充放電の条件を示す。なお、充放電は放電スタートとし、25℃の恒温槽を用いて充放電を行った。
(1)100mA/(g-carbon)の電流で電池電圧2Vになるまで放電を行う
(2)放電後、1時間休止する。
(3)休止後、100mA/(g-carbon)の電流で電池電圧4.3Vになるまで充電を行う
ここで「g-carbon」は、粉末カーボン重量を表す。得られた結果を表1に示す。
Claims (5)
- 導電性材料を含有する空気極層および前記空気極層の集電を行う空気極集電体を有する空気極と、負極活物質を含有する負極層および前記負極層の集電を行う負極集電体を有する負極と、前記空気極層および前記負極層の間で金属イオンの伝導を担う非水電解液と、を有する空気二次電池であって、
前記空気極集電体がカーボン材料から構成されており、前記非水電解液がスルホンイミド塩を含有することを特徴とする空気二次電池。 - 前記カーボン材料が、カーボンファイバーであることを特徴とする請求の範囲第1項または第2項に記載の空気二次電池。
- 前記空気極集電体が、前記カーボンファイバーを用いた、カーボンペーパーまたはカーボンクロスであることを特徴とする請求の範囲第3項に記載の空気二次電池。
- 前記金属イオンが、Liイオンであることを特徴とする請求の範囲第1項から第4項までのいずれかに記載の空気二次電池。
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JP2014238985A (ja) * | 2013-06-07 | 2014-12-18 | スズキ株式会社 | リチウム空気電池の正極構造及び正極製造方法 |
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