WO2010134161A1 - 空気電池 - Google Patents
空気電池 Download PDFInfo
- Publication number
- WO2010134161A1 WO2010134161A1 PCT/JP2009/059186 JP2009059186W WO2010134161A1 WO 2010134161 A1 WO2010134161 A1 WO 2010134161A1 JP 2009059186 W JP2009059186 W JP 2009059186W WO 2010134161 A1 WO2010134161 A1 WO 2010134161A1
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- WO
- WIPO (PCT)
- Prior art keywords
- oxygen
- solvent
- air
- air battery
- negative electrode
- Prior art date
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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
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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
Definitions
- the present invention relates to an air battery.
- An air battery is a battery using oxygen as a positive electrode active material, and takes in air from the outside during discharge. Therefore, it is possible to increase the proportion of the negative electrode active material in the battery container as compared with other batteries having positive and negative electrode active materials in the battery. Therefore, in principle, the electric capacity that can be discharged is large, and it is easy to reduce the size and weight. Further, since the oxidizing power of oxygen used as the positive electrode active material is strong, the battery electromotive force is relatively high. Furthermore, since oxygen has a feature that it is a clean material without resource restrictions, the air battery has a small environmental load. As described above, the air battery has many advantages and is expected to be used for a battery for a portable device, a battery for an electric car, a battery for a hybrid car, a battery for a fuel cell car, and the like.
- Patent Document 1 discloses that a non-aqueous electrolyte is made of a room temperature molten salt, for example, trimethylpropylammonium bis (trifluoromethylsulfonyl) imide. A technique for suppressing contact between the negative electrode and moisture is disclosed.
- the non-aqueous electrolyte is made hydrophobic as in the technique disclosed in Patent Document 1 above, the non-aqueous electrolyte must naturally have ionic conductivity. It had to be conductive and hydrophobic. However, it has been difficult to achieve both ionic conductivity and hydrophobicity in the nonaqueous electrolyte.
- an object of the present invention is to provide an air battery capable of suppressing the mixing of moisture into the housing while maintaining the battery performance.
- the present invention relates to a power generation unit comprising an air electrode, a negative electrode containing an alkali metal, and an electrolyte layer that conducts ions between the air electrode and the negative electrode, an oxygen solvent having hydrophobicity and oxygen solubility, and a power generation unit An oxygen battery, and an oxygen battery disposed between the oxygen supply unit and the electrolyte layer.
- the air battery includes a housing for storing the oxygen solvent and an oxygen supply unit for supplying oxygen gas to the oxygen solvent.
- the “oxygen supply part” means an opening through which an oxygen-containing gas such as air can be taken into the casing.
- an oxygen-containing gas such as air
- the installation location and the number of installations are not particularly limited.
- the oxygen supply part and the electrolyte layer are separated from each other, and a hydrophobic oxygen solvent is disposed between the oxygen supply part and the electrolyte layer, thereby preventing moisture from entering the electrolyte layer from the oxygen supply part. can do.
- the oxygen supply unit includes an oxygen supply means for supplying oxygen gas by bubbling.
- an oxygen supply means for supplying oxygen gas by bubbling.
- the casing has an oxygen solvent inlet and outlet, and a circulation path for circulating the oxygen solvent from the outlet to the inlet is provided outside the casing. And it can be set as the form which circulates through a circulation path. By adopting such a form, oxygen dissolved in the oxygen solvent can be used efficiently.
- the power generation unit is provided such that the electrolyte layer is incompatible with the oxygen solvent and has a specific gravity smaller than that of the oxygen solvent, and the negative electrode is disposed vertically above the oxygen solvent. It can be made into the form currently provided. In such a form, it is preferable that the interface between the electrolyte and the oxygen solvent is in the air electrode.
- An oxygen supply unit is provided at the other end of the oxygen supply pipe having one end connected to the lower part of the housing, and an interface between the oxygen solvent and the oxygen-containing gas is formed in the oxygen supply pipe. Is preferably provided at a position higher than the interface.
- an exhaust port is provided in the upper part of the housing, and it is more preferable that a pressure regulating valve that opens at a predetermined pressure is provided in the exhaust port, and the gas in the housing is guided to the exhaust port. It is further preferred that a guiding means is provided.
- the air battery of the present invention it is preferable that a plurality of power generation units are accommodated in the housing.
- an air battery capable of suppressing the mixing of moisture into the housing while maintaining the battery performance.
- FIG. 1 is a cross-sectional view showing an example of a form of an air battery 10.
- 2 is a cross-sectional view showing an example of a configuration of an air battery 20.
- FIG. 2 is a cross-sectional view showing an example of a configuration of an air battery 30.
- FIG. 3 is a cross-sectional view showing an example of a configuration of an air battery 40. It is sectional drawing which shows the example of a form of a guidance means.
- the air battery When the water enters the power generation part of the air battery and the negative electrode and the water come into contact with each other, the air battery deteriorates.
- the air batteries proposed so far to suppress contact between the negative electrode and moisture while maintaining the performance of the air battery.
- the inventors have arranged an oxygen solvent having hydrophobicity and oxygen solubility between the oxygen supply unit and the electrolyte layer, thereby maintaining moisture in the casing while maintaining battery performance. It was found that the contamination of can be suppressed. It is considered that the deterioration of the air battery can be suppressed by suppressing the mixing of moisture into the housing.
- the present invention has been made based on such knowledge. This invention makes it a main point to provide the air battery which can suppress that a water
- FIG. 1 is a cross-sectional view schematically showing an embodiment of an air battery 10 of the present invention.
- an air battery 10 includes an air electrode 1, a negative electrode 2, and a power generation unit 4 including an electrolyte layer 3 disposed between the air electrode 1 and the negative electrode 2, an oxygen solvent 5, and a plurality of , And a housing 6 that accommodates the oxygen solvent 5.
- the hydrophobic oxygen solvent 5 is filled in the housing 6, it is possible to prevent moisture from entering the housing 6.
- the oxygen solvent 5 is disposed between the oxygen supply unit 9 and the electrolyte layer 3, and the oxygen solvent 5 has oxygen solubility in addition to hydrophobicity.
- FIG. 1 shows a form in which the air electrode 1 is disposed so as to be in contact with the oxygen solvent 5, in the air battery of the present invention, oxygen dissolved in the oxygen solvent can be taken into the electrolyte layer. If present, the oxygen solvent may not be in contact with the air electrode. This is because since the air electrode is in contact with the electrolyte layer, the battery reaction can be performed at the positive electrode using oxygen that has moved from the oxygen solvent to the electrolyte layer.
- the air battery 10 will be described for each configuration.
- the power generation unit 4 includes an air electrode 1 disposed on the side in contact with the oxygen solvent 5, a negative electrode 2 disposed in the center, and an electrolyte layer 3 disposed between the air electrode 1 and the negative electrode 2.
- the electrode 1 and the electrode 2 are in contact with the electrolyte layer 3.
- FIG. 1 schematically shows a cross section of the power generation unit 4.
- the power generation unit 4 is in the form of a laminate in which the negative electrode 2 is sandwiched between the electrolyte layers 3 and 3 and further sandwiched between the positive electrode layers 1 and 1.
- it may be in the form of a columnar body in which the electrolyte layer 3 is wound around the negative electrode 2 and the positive electrode layer 1 is wound around the outer peripheral surface thereof. By setting it as this form, it becomes easy to improve the output (power density) per unit volume of the power generation unit 4.
- the air electrodes 1, 1, ... and the negative electrodes 2, 2, ... may be electrically connected in series or may be connected in parallel.
- the partition wall 7 is not particularly limited as long as it can isolate the negative electrode 2 and the electrolyte layer 3 from the oxygen solvent 5 and does not inhibit the battery reaction.
- an engineering plastic such as polycarbonate can be used as a specific example of the material constituting the partition wall 7, an engineering plastic such as polycarbonate can be used.
- Air electrode 1 contains a conductive material, a catalyst, and a binder for binding them.
- the air electrode 1 is provided with an air electrode current collector that collects the air electrode 1 in contact with the inside or the outer surface of the air electrode 1.
- the conductive material contained in the air electrode 1 is not particularly limited as long as it can withstand the environment when the air battery 10 is used and has conductivity.
- Examples of the conductive material contained in the air electrode 1 include carbon materials such as carbon black and mesoporous carbon.
- the content of the conductive material in the air electrode 1 is preferably 10% by mass or more.
- Examples of the catalyst contained in the air electrode 1 include cobalt phthalocyanine and manganese dioxide. From the viewpoint of providing a form capable of exhibiting a sufficient catalytic function, the content of the catalyst in the air electrode 1 is preferably 1% by mass or more. Further, from the viewpoint of suppressing a decrease in reaction field and a decrease in battery capacity, the content of the catalyst in the air electrode 1 is preferably 90% by mass or less.
- binder contained in the air electrode 1 examples include polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE).
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- content of the binder in the air electrode 1 is not specifically limited, For example, it is preferable to set it as 10 mass% or less, and it is more preferable to set it as 1 mass% or more and 5 mass% or less.
- the air electrode 1 can be produced by, for example, a method of applying a paint composed of carbon black, a catalyst, and a binder to the surface of an air electrode current collector described later by a doctor blade method. In addition, it can also be produced by a method such as thermocompression bonding of mixed powder containing carbon black and a catalyst.
- the air electrode current collector has a function of collecting the air electrode 1.
- the material of the air electrode current collector is not particularly limited as long as it is a conductive material.
- the material for the air electrode current collector include stainless steel, nickel, aluminum, iron, titanium, and carbon.
- the shape of such an air electrode current collector include a mesh (grid) shape.
- the negative electrode 2 contains an alkali metal that functions as a negative electrode active material.
- the negative electrode 2 is provided with a negative electrode current collector (not shown) that contacts the inside or the outer surface of the negative electrode 2 and collects the current of the negative electrode 2.
- Examples of simple alkali metals that can be contained in the negative electrode 2 include Li, Na, and K. Moreover, as an alkali metal compound which can be contained in the negative electrode 2, a Li alloy etc. can be illustrated.
- the air battery 10 is a lithium air secondary battery, it is preferable that Li is contained from the viewpoint of providing the air battery 10 that can easily increase the capacity.
- the negative electrode 2 only needs to contain at least a negative electrode active material, and may further contain a conductive material that improves conductivity, or a binder that fixes an alkali metal or the like. From the viewpoint of suppressing a decrease in reaction field and a decrease in battery capacity, the content of the conductive material in the negative electrode 2 is preferably 10% by mass or less. Further, the content of the binder in the negative electrode 2 is not particularly limited, but is preferably 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less. The kind of conductive material and binder that can be contained in the negative electrode 2, the amount used, and the like can be the same as in the air electrode 1.
- a negative electrode current collector is provided in contact with the inside or the outer surface of the negative electrode 2.
- the negative electrode current collector has a function of collecting the negative electrode 2.
- the material for the negative electrode current collector is not particularly limited as long as it is a conductive material. Examples of the material for the negative electrode current collector 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.
- the negative electrode 2 can be produced by the same method as that for the air electrode 1, for example.
- the electrolyte layer 3 contains an electrolyte (liquid or solid) that conducts ions (alkali metal ions) between the air electrode 1 and the negative electrode 2.
- electrolyte liquid electrolyte
- electrolyte solution that can be used for the electrolyte layer 3 include the following non-aqueous electrolyte solutions.
- the type of electrolyte used for the electrolyte layer 3 is preferably selected as appropriate according to the type of metal ions to be conducted. For example, in the case of a lithium-air battery, a non-aqueous electrolyte containing a lithium salt and an organic solvent is used. Can be used.
- Lithium salts include LiPF 6 , LiBF 4 , LiClO 4 , LiBOB, LiAsF 6 and other inorganic lithium salts, as well as LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2.
- An organic lithium salt such as LiC (CF 3 SO 2 ) 3 can be exemplified.
- organic solvent examples include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), butylene carbonate, ⁇ -butyrolactone (GBL), sulfolane, Examples include acetonitrile, 1,2-dimethoxymethane, 1,3-dimethoxypropane, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and mixtures thereof.
- an organic solvent is a solvent with high oxygen solubility from a viewpoint of making it the form in which dissolved oxygen is used for reaction efficiently.
- the concentration of the lithium salt in the non-aqueous electrolyte is, for example, not less than 0.2 mol / L and not more than 3 mol / L.
- a low volatile liquid such as an ionic liquid can be used as the nonaqueous electrolytic solution.
- the electrolyte layer 3 is preferably in a form in which the electrolyte solution is held by a separator or a gel polymer.
- the separator include porous membranes such as polyethylene and polypropylene, and nonwoven fabrics such as resin nonwoven fabrics and glass fiber nonwoven fabrics.
- the gel polymer include acrylate polymer compounds, ether polymer compounds such as polyethylene oxide, and crosslinked polymers containing these, methacrylate polymer compounds such as polymethacrylate, polyvinylidene fluoride, and polyvinylidene fluoride.
- Fluorine polymer compounds such as a copolymer of styrene and hexafluoropropylene can be used.
- the form of the gel polymer is not particularly limited as long as it is a form that can hold the electrolytic solution, such as a particulate form. Although it does not specifically limit about preparation of the electrolyte layer 3, By making the separator and a gel polymer hold
- the housing 6 contains at least the power generation unit 4 and is filled with the oxygen solvent 5.
- the casing 6 is provided with an inlet 6 a and an outlet 6 b for the oxygen solvent 5, and the inlet 6 a and the outlet 6 b are connected by a circulation path 8 outside the casing 6.
- a material that can be used for the housing of the air battery can be appropriately used.
- the oxygen solvent 5 is a liquid having hydrophobicity and oxygen solubility.
- the oxygen solvent 5 is not compatible with the electrolyte solution provided in the electrolyte layer 3.
- Specific examples of the oxygen solvent 5 that can be used in the present invention include a fluorine solvent.
- chain fluorinated carbon such as C 6 F 14 , C 7 F 16 , C 8 F 18 , and C 9 F 20 , HFB (hexafluorobenzene), and C 4 F 9 OCH 3 (Trade name “7100” manufactured by 3M), C 4 F 9 OC 2 H 5 (same “7200”), C 6 F 13 OCH 3 (same “7300”), and C 3 HF 6 —CH (CH 3 ) HFE (hydrofluoroether) such as O—C 3 HF 6 (same as “7600”).
- the oxygen solvent 5 flows in the direction of the arrow shown in FIG. That is, the oxygen solvent 5 flows into the housing 6 from the inlet 6a, is discharged from the outlet 6b, flows through the circulation path 8, and flows again into the housing 6 from the inlet 6a.
- the oxygen solvent 5 is supplied with oxygen gas from an oxygen supply means 11 provided in the oxygen supply unit 9 during circulation.
- oxygen dissolved in the oxygen solvent 5 can be efficiently used by circulating the oxygen gas while supplying it to the oxygen solvent 5.
- the air battery 10 includes an oxygen supply unit 9 that supplies oxygen gas to the oxygen solvent 5.
- the oxygen supply part 9 will not be specifically limited if it is a form which can supply oxygen to an oxygen solvent.
- FIG. 1 shows a form in which the oxygen supply means 11 for supplying oxygen gas by bubbling is provided in the oxygen supply unit 9, the present invention is not limited to such a form, and the oxygen solvent 5 is simply air (oxygen-containing gas). It is good also as a form provided with the opening part provided so that it may touch.
- the oxygen supply means 11 is provided with a pump and a flow pipe for circulating oxygen gas.
- a plurality of holes are provided on the side surface of the end of the flow pipe that is immersed in the oxygen solvent 5. Therefore, the oxygen gas can be dissolved in the oxygen solvent 5 by flowing the oxygen gas through the flow pipe using the pump and bubbling the oxygen gas into the oxygen solvent 5 from the hole.
- oxygen By bubbling oxygen gas into the oxygen solvent 5 and dissolving it, oxygen can be rapidly supplied into the oxygen solvent 5 even when the dissolved oxygen in the oxygen solvent 5 decreases due to the discharge reaction in the power generation unit 4. it can.
- oxygen gas supplied from the oxygen supply means 11 to the oxygen solvent 5 oxygen gas having a pressure of 1.01 ⁇ 10 5 Pa and an oxygen concentration of 99.99% can be used. Further, the oxygen supply means 11 may be provided with a filter (not shown) so that moisture and unnecessary gas are not taken into the oxygen solvent 5.
- the shape of the oxygen supply means 11 is not particularly limited. Moreover, the material which can be used for an air battery, such as being stable with respect to the oxygen solvent 5, can be used suitably also about the material of the oxygen supply means 11.
- FIG. 2 is sectional drawing which shows schematically the example of the form of the air battery 20 of this invention. 2, components having the same configuration as that of the air battery 10 are denoted by the same reference numerals as those used in FIG. 1, and description thereof is omitted as appropriate.
- the air battery 20 includes an air electrode 1, a negative electrode 2, and power generation units 4, 4,... Having an electrolyte layer 3 disposed between the air electrode 1 and the negative electrode 2, 5 and a housing 26 that accommodates the plurality of power generation units 4 and the oxygen solvent 5.
- the casing 26 is filled with the hydrophobic oxygen solvent 5, it is possible to prevent moisture from entering the casing 26.
- the power generation unit 4 is housed in the casing 26 so that the air electrode 1 is in contact with the oxygen solvent 5, and the oxygen solvent 5 has oxygen solubility in addition to hydrophobicity. Dissolved oxygen can be supplied to the air electrode 1, and moisture can be prevented from entering the negative electrode 2. Therefore, according to the air battery 20, deterioration of the battery due to the negative electrode 2 reacting with moisture can be suppressed while maintaining the battery performance.
- the air battery 20 will be described for each configuration.
- the housing 26 contains at least the power generation unit 4 and is filled with the oxygen solvent 5.
- the casing 26 is provided with an inlet 26a and an outlet 26b for the oxygen solvent 5.
- the constituent material of the housing 26 the same material as that of the housing 6 can be used.
- ⁇ Oxygen solvent 5> As the oxygen solvent 5 in the air battery 20, the same one as in the air battery 10 can be used. In the air battery 20, the oxygen solvent 5 flows in the direction of the arrow shown in FIG. That is, the oxygen solvent 5 flows into the casing 26 from the inlet 26a, passes through the flow paths 26x, 26x,..., And is discharged out of the casing 26 from the outlet 26b. By adopting such a configuration, since the oxygen solvent 5 can contact more air electrodes 1 at a time than the air battery 10, the unevenness of the oxygen concentration in the oxygen solvent 5 can be reduced.
- the air battery 20 is preferably provided with an oxygen supply unit and a circulation path.
- FIG. 3 is sectional drawing which shows schematically the example of the form of the air battery 30 of this invention. 3, components having the same configuration as that of the air battery 10 are denoted by the same reference numerals as those used in FIG. 1, and description thereof is omitted as appropriate.
- the air battery 30 includes an air electrode 31, a negative electrode 32, and a power generation unit 34 including an electrolyte layer 33 disposed between the air electrode 31 and the negative electrode 32, an oxygen solvent 5, And a housing 36 for housing the oxygen solvent 5.
- the specific gravity of the electrolyte solution provided in the electrolyte layer 33 is smaller than the specific gravity of the oxygen solvent 5, and the power generation unit 34 is provided so that the negative electrode 32 is disposed vertically above the oxygen solvent 5 in the vertical direction.
- the air battery 30 is provided with an oxygen supply unit 39 for supplying oxygen gas to the oxygen solvent 5.
- the hydrophobic oxygen solvent 5 is filled in the housing 36, it is possible to prevent moisture from entering the housing 36.
- the power generation unit 34 is housed in the housing 36 so that the air electrode 31 is in contact with the oxygen solvent 5, and the oxygen solvent 5 has oxygen solubility in addition to hydrophobicity. Dissolved oxygen can be supplied to the air electrode 31, and moisture can be prevented from entering the negative electrode 32. Therefore, according to the air battery 30, deterioration of the battery due to the negative electrode 32 reacting with moisture can be suppressed while maintaining the performance of the battery.
- the air battery 30 will be described for each configuration.
- the power generation unit 34 includes an air electrode 31 disposed on the side in contact with the oxygen solvent 5, an electrolyte layer 33 provided on the upper surface side of the air electrode 31, and a negative electrode 32 provided on the upper surface side of the electrolyte layer 33.
- the air electrode 31 and the negative electrode 32 are in contact with the electrolyte layer 33.
- FIG. 3 schematically shows a cross section of the power generation unit 34, and the power generation unit 34 is a laminate in which the electrolyte layer 33 is sandwiched between the air electrode 31 and the negative electrode 32.
- the material constituting the positive electrode 31 can be the same as that of the positive electrode 1, and the function of the positive electrode 31 is the same as that of the positive electrode 1.
- the material constituting the negative electrode 32 can be the same as that of the negative electrode 2, and the function of the negative electrode 32 is the same as that of the negative electrode 2.
- the material constituting the electrolyte layer 33 may be the same as that of the electrolyte layer 3, and the function of the electrolyte layer 33 is the same as that of the electrolyte layer 3.
- the specific gravity of the electrolyte provided in the electrolyte layer 33 is smaller than the specific gravity of the oxygen solvent 5, and the electrolyte solution and the oxygen solvent 5 are not compatible.
- the specific gravity of the electrolytic solution provided in the electrolyte layer 33 is smaller than the specific gravity of the oxygen solvent 5 and the electrolytic solution and the oxygen solvent 5 are not compatible with each other. It is supported.
- the other surface of the electrolyte layer 33 is covered with the negative electrode 2 or the housing 36. Therefore, volatilization of the electrolytic solution provided in the electrolyte layer 33 can be prevented.
- the electrolyte solution provided in the electrolyte layer 33 and the oxygen solvent 5 are not compatible, even if the electrolyte solution and the oxygen solvent 5 are temporarily mixed due to shaking of the air battery 30 or the like, they are naturally separated.
- the interface between the electrolytic solution and the oxygen solvent 5 is preferably located in the air electrode 31. The position of the interface between the electrolyte solution and the oxygen solvent 5 can be adjusted by adjusting the amount of the electrolyte solution and the oxygen solvent 5 accommodated in the housing 36 and the pressure applied to the oxygen solvent 5 from the interface 5a described later. it can.
- a connecting pipe 37 communicating with the oxygen supply unit 39 is connected to the lower portion of the housing 36.
- the air battery 30 includes an oxygen supply unit 39 that supplies oxygen gas to the oxygen solvent 5.
- the oxygen supply part 39 is formed at the other end of an oxygen supply pipe 37 whose one end is connected to the lower part of the housing 36.
- the oxygen solvent 5 can flow between the oxygen supply pipe 37 and the housing 36, and an interface 5 a between the oxygen solvent 5 and the oxygen-containing gas is formed in the oxygen supply pipe 37.
- Oxygen can be taken into the housing 36 from the interface 5a through the oxygen solvent 5.
- the oxygen supply unit 39 may be opened to form an interface between the atmosphere and the oxygen solvent 5, and an oxygen cylinder or the like may be attached to the oxygen supply unit 39.
- the oxygen supply unit 39 is provided at a position higher than the interface 5a, and the oxygen solvent 5 can be prevented from leaking from the oxygen supply unit 39.
- the position of the interface 5 a is the pressure applied to the oxygen solvent 5 at the interface between the electrolyte solution and the oxygen solvent 5 in the housing 36 (pressure due to gravity acting on the electrolyte solution) and the size of the inner diameter of the oxygen supply pipe 37. It depends on things.
- FIG. 4 is sectional drawing which shows schematically the example of the form of the air battery 40 of this invention. 4, components having the same configuration as that of the air battery 30 are denoted by the same reference numerals as those used in FIGS. 1 and 3, and description thereof will be omitted as appropriate.
- the air battery 40 includes an air electrode 31, a negative electrode 42, and a power generation unit 44 including an electrolyte layer 43 disposed between the air electrode 31 and the negative electrode 42, an oxygen solvent 5, And a housing 46 that accommodates the portion 44 and the oxygen solvent 5.
- the specific gravity of the electrolyte solution provided in the electrolyte layer 43 is smaller than the specific gravity of the oxygen solvent 5, and the power generation unit 44 is provided so that the negative electrode 42 is disposed vertically above the oxygen solvent 5 in the vertical direction.
- the air battery 40 is provided with an oxygen supply unit 39 for supplying oxygen gas to the oxygen solvent 5.
- the air battery 40 is provided with an exhaust port 60 provided with a pressure regulating valve 61 that opens at a predetermined pressure, and guidance means that can induce gas to the exhaust port 60.
- the hydrophobic oxygen solvent 5 is filled in the casing 46, it is possible to prevent moisture from entering the casing 46.
- the power generation unit 44 is housed in the housing 46 so that the air electrode 31 is in contact with the oxygen solvent 5, and the oxygen solvent 5 has oxygen solubility in addition to hydrophobicity. Dissolved oxygen can be supplied to the air electrode 31, and moisture can be prevented from entering the negative electrode 42. Therefore, according to the air battery 40, deterioration of the battery due to the negative electrode 42 reacting with moisture can be suppressed while maintaining the performance of the battery.
- the air battery 40 will be described for each configuration.
- the power generation unit 44 includes an air electrode 31 disposed on the side in contact with the oxygen solvent 5, an electrolyte layer 43 provided on the upper surface side of the air electrode 31, and a negative electrode 42 provided on the upper surface side of the electrolyte layer 43.
- the air electrode 31 and the negative electrode 42 are in contact with the electrolyte layer 43.
- FIG. 4 schematically shows a cross section of the power generation unit 44, and the power generation unit 44 is a laminate in which the electrolyte layer 43 is sandwiched between the air electrode 31 and the negative electrode 42.
- the material constituting the negative electrode 42 can be the same as that of the negative electrode 2, and the function of the negative electrode 42 is the same as that of the negative electrode 2.
- the material constituting the electrolyte layer 43 can be the same as that of the electrolyte layer 3, and the function of the electrolyte layer 43 is the same as that of the electrolyte layer 3.
- the specific gravity of the electrolytic solution provided in the electrolyte layer 43 is smaller than the specific gravity of the oxygen solvent 5, and the electrolytic solution and the oxygen solvent 5 are not compatible.
- the housing 46 accommodates at least the power generation unit 44 and the oxygen solvent 5.
- the casing 46 is provided with an exhaust port 60 at the top, and the exhaust port 60 is provided with a pressure regulating valve 61 that opens at a predetermined pressure.
- the pressure regulating valve 61 is provided.
- the pressure regulating valve 61 is opened when the pressure applied to the pressure regulating valve 61 from the inside of the housing 46 reaches a predetermined pressure, the gas generated from the air electrode 31 during charging can be discharged. It is possible to prevent outside air from being taken into the housing 46.
- casing of an air battery can be used for the constituent material of the housing
- the air battery 40 is provided with guiding means capable of guiding gas to the exhaust port 60.
- the negative electrode 46 constitutes a guiding means. That is, as shown in FIG. 4, the negative electrode 46 is inclined toward the exhaust port 60, whereby the gas generated from the air electrode 31 is guided to the exhaust port 60 along the lower surface of the negative electrode 46.
- exhaust gas can be efficiently exhausted by collecting the exhaust gas at a predetermined location.
- a guidance means is not limited to the said form, If it is a means which can collect the gas which generate
- a form as shown in FIG. 5 can be considered.
- FIG. 5 is a cross-sectional view schematically showing an example of the form of the guiding means (negative electrode).
- gas can be induced to the exhaust port 62 by forming the negative electrode 63 into a truncated cone shape having a bottom surface on the side where the electrolyte layer is provided.
- the air battery of the present invention can be used as a power source for electric vehicles and portable information devices.
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Abstract
Description
本発明は、空気極と、アルカリ金属を含む負極と、空気極及び負極の間でイオンの伝導を担う電解質層と、を備えた発電部、疎水性及び酸素溶存性を有する酸素溶媒、発電部及び酸素溶媒を収容する筐体、並びに、酸素溶媒に酸素ガスを供給するための酸素供給部、を備えており、酸素供給部と電解質層との間に酸素溶媒が配置されている、空気電池とする。
2…負極
3…電解質層
4…発電部
5…酸素溶媒
6…筐体
6a…流入口
6b…排出口
7…隔壁
8…循環路
9…酸素供給部
11…酸素供給手段
10…空気電池
20…空気電池
30…空気電池
31…空気極
32…負極
33…電解質層
34…発電部
35…酸素溶媒
36…筐体
37…酸素供給管
39…酸素供給部
40…空気電池
42…負極(誘導手段)
43…電解質層
44…発電部
46…筐体
図1は、本発明の空気電池10の形態例を概略的に示す断面図である。図1に示すように、空気電池10は、空気極1、負極2、並びに、空気極1及び負極2の間に配設された電解質層3を備える発電部4と、酸素溶媒5と、複数の発電部4、4、…及び酸素溶媒5を収容する筐体6と、を具備している。空気電池10では、疎水性を有する酸素溶媒5が筐体6内に満たされているため、筐体6内に水分が混入することを抑制できる。また、酸素溶媒5は、酸素供給部9と電解質層3との間に配置されており、酸素溶媒5は疎水性に加えて酸素溶存性を備えているため、酸素溶媒5に溶存した酸素を空気極1に供給することができるとともに、負極2まで水分が浸入することを抑制できる。したがって、空気電池10によれば、電池の性能を維持しつつ、負極2が水分と反応することによる電池の劣化を抑制することができる。なお、図1では空気極1が酸素溶媒5に接するように配置されている形態を示しているが、本発明の空気電池では、酸素溶媒に溶存する酸素を電解質層に取り込むことができる形態であれば、酸素溶媒は空気極に接していなくてもよい。空気極は電解質層に接しているため、酸素溶媒から電解質層に移動した酸素を利用して正極で電池反応を行うことができるからである。以下、空気電池10について、構成ごとに説明する。
発電部4は、酸素溶媒5に接する側に配置された空気極1、中央に配置された負極2、及び、空気極1と負極2との間に配置された電解質層3を有し、空気極1及び負極2は電解質層3と接触している。また、図1では発電部4の断面を概略的に示しており、発電部4は、負極2を電解質層3、3で挟持し、さらにそれらを正極層1、1で挟持した積層体の形態でもよく、負極2の周りに電解質層3を捲回し、さらにその外周面側に正極層1を巻回した柱状体の形態であっても良い。かかる形態とすることにより、発電部4の単位体積当たりの出力(出力密度)を向上させることが容易になる。空気電池10において、空気極1、1、…及び負極2、2、…は、電気的に直列に接続されていてもよく、並列に接続されていても良い。
空気極1は、導電性材料、触媒、および、これらを結着させる結着材を含有している。また、空気極1には、空気極1の内部または外面に当接して、空気極1の集電を行う空気極集電体が設けられる。
負極2は、負極活物質として機能するアルカリ金属を含有している。また、負極2には、負極2の内部又は外面に当接して、負極2の集電を行う負極集電体(不図示)が設けられる。
電解質層3には、空気極1及び負極2の間でイオン(アルカリ金属のイオン)の伝導を担う電解質(液体又は固体)が収容される。
筐体6にはすくなくとも発電部4が収容され、酸素溶媒5で満たされている。また、筐体6には酸素溶媒5の流入口6a及び排出口6bが備えられており、筐体6外において流入口6a及び排出口6bは循環路8によって結ばれている。筐体6の構成材料は、空気電池の筐体に使用可能な材料を適宜用いることができる。
酸素溶媒5は、疎水性と酸素溶存性とを有する液体である。また、酸素溶媒5には、電解質層3に備えられる電解液と相溶しないものを用いる。本発明に用いることができる酸素溶媒5の具体例としては、フッ素溶媒が挙げられる。より具体的には、C6F14、C7F16、C8F18、及びC9F20などの鎖状のフッ素化カーボン、HFB(ヘキサフルオロベンゼン)、並びに、C4F9OCH3(3M社製、商品名「7100」)、C4F9OC2H5(同「7200」)、C6F13OCH3(同「7300」)、及びC3HF6-CH(CH3)O-C3HF6(同「7600」)などのHFE(ハイドロフルオロエーテル)を挙げることができる。
空気電池10には、酸素溶媒5に酸素ガスを供給する酸素供給部9が備えられている。酸素供給部9は、酸素溶媒に酸素を供給できる形態であれば特に限定されない。図1では、酸素ガスをバブリングにより供給する酸素供給手段11が酸素供給部9に備えられる形態を示しているが、本発明はかかる形態に限定されず、単に酸素溶媒5を空気(酸素含有ガス)に触れさせるように設けられた開口部を備える形態としてもよい。
酸素供給手段11には、ポンプと酸素ガスを流通させる流通管が備えられている。また、該流通管の酸素溶媒5に浸漬された側の端部の側面には、複数の孔が設けられている。したがって、上記ポンプを利用して酸素ガスを上記流通管に流通させ、上記孔から酸素溶媒5内に酸素ガスをバブリングさせて、酸素溶媒5に酸素ガスを溶解させることができる。酸素溶媒5に酸素ガスをバブリングさせて溶解させることによって、発電部4での放電反応に伴い酸素溶媒5中の溶存酸素が減少する場合でも、酸素溶媒5中に酸素を急速に供給することができる。
図2は、本発明の空気電池20の形態例を概略的に示す断面図である。図2において、空気電池10と同様の構成を採るものには、図1で使用した符号と同一の符号を付し、その説明を適宜省略する。
筐体26にはすくなくとも発電部4が収容され、酸素溶媒5で満たされている。また、筐体26には酸素溶媒5の流入口26a及び排出口26bが備えられている。筐体26の構成材料は、筐体6と同様の材料を用いることができる。
空気電池20における酸素溶媒5は、空気電池10と同様のものを用いることできる。空気電池20において、酸素溶媒5は図2に示した矢印の方向に流通する。すなわち、酸素溶媒5は流入口26aから筐体26内に流入し、流路26x、26x、…を通って、排出口26bから筐体26外に排出される。かかる形態とすることによって、空気電池10に比べて酸素溶媒5が一度に多くの空気極1に接触することができるため、酸素溶媒5内の酸素濃度のむらを少なくすることができる。
図2には示していないが、空気電池10と同様に、空気電池20にも酸素供給部、循環路が備えられていることが好ましい。
図3は、本発明の空気電池30の形態例を概略的に示す断面図である。図3において、空気電池10と同様の構成を採るものには、図1で使用した符号と同一の符号を付し、その説明を適宜省略する。
発電部34は、酸素溶媒5に接する側に配置された空気極31、空気極31の上面側に備えられた電解質層33、及び電解質層33の上面側に備えられた負極32を有しており、空気極31及び負極32は電解質層33と接触している。図3では発電部34の断面を概略的に示しており、発電部34は、空気極31と負極32とで電解質層33を挟持した積層体である。
筐体36にはすくなくとも発電部34および酸素溶媒5が収容されており、筐体36の下部には酸素供給部39に連通する連結管37が連結されている。筐体36の構成材料は、空気電池の筐体に使用可能な材料を適宜用いることができる。
空気電池30には、酸素溶媒5に酸素ガスを供給する酸素供給部39が備えられている。酸素供給部39は、一端が筐体36の下部に連結された酸素供給管37の他端に形成されている。酸素供給管37と筐体36との間では酸素溶媒5の流通が可能であり、酸素供給管37内には酸素溶媒5と酸素含有ガスとの界面5aが形成されている。界面5aから酸素溶媒5を介して筐体36内に酸素を取り込むことが可能である。界面5aを酸素溶媒5と酸素含有ガスとの界面にするには、例えば、酸素供給部39を開放することで大気と酸素溶媒5との界面としてもよく、酸素供給部39に酸素ボンベなどを連結することで酸素ガスと酸素溶媒5との界面としてもよい。また、酸素供給部39は界面5aより高い位置に備えられており、酸素供給部39から酸素溶媒5が漏洩することを防止できる。なお、界面5aの位置は、筐体36内の電解液と酸素溶媒5との界面において酸素溶媒5に加えられる圧力(電解液に働く重力などによる圧力)や酸素供給管37の内径の大きさなどによって変わる。
図4は、本発明の空気電池40の形態例を概略的に示す断面図である。図4において、空気電池30と同様の構成を採るものには、図1および図3で使用した符号と同一の符号を付し、その説明を適宜省略する。
発電部44は、酸素溶媒5に接する側に配置された空気極31、空気極31の上面側に備えられた電解質層43、及び電解質層43の上面側に備えられた負極42を有しており、空気極31及び負極42は電解質層43と接触している。図4では発電部44の断面を概略的に示しており、発電部44は、空気極31と負極42とで電解質層43を挟持した積層体である。
筐体46にはすくなくとも発電部44および酸素溶媒5が収容されている。また、筐体46には上部に排気口60が備えられており、排気口60には所定の圧力で開放する調圧弁61が備えられている。排気口60を備えていることによって、充電時に空気極31から発生した気体を排出することができる。ただし、排気口60を常に開放しておくと、水分などの不要なものを含んだ外気を筐体46内に取り込む虞があるため、調圧弁61が備えられている。筐体46の内側から調圧弁61にかかる圧力が所定の圧力に達したときに調圧弁61が開放される構成とすることによって、充電時に空気極31から発生した気体を排出することができるとともに、外気を筐体46に取り込むことを防止できる。なお、筐体46の構成材料は、空気電池の筐体に使用可能な材料を適宜用いることができる。
空気電池40には、排気口60に気体を誘導することができる誘導手段が備えられている。図4に示した形態では、負極46が誘導手段を構成している。すなわち、図4に示したように、負極46を排気口60に向けて傾斜させることによって、空気極31から発生した気体が負極46の下面に沿って、排気口60に誘導される。このようにして排出する気体を所定の箇所に集めることによって、効率よく排気することができる。
Claims (10)
- 空気極と、アルカリ金属を含む負極と、前記空気極及び前記負極の間でイオンの伝導を担う電解質層と、を備えた発電部、
疎水性及び酸素溶存性を有する酸素溶媒、
前記発電部及び前記酸素溶媒を収容する筐体、並びに、
前記酸素溶媒に酸素ガスを供給するための酸素供給部、を備えており、
前記酸素供給部と前記電解質層との間に前記酸素溶媒が配置されている、空気電池。 - 前記酸素供給部が、前記酸素ガスをバブリングにより供給する酸素供給手段を備えている、請求の範囲第1項に記載の空気電池。
- 前記筐体が前記酸素溶媒の流入口及び排出口を有するとともに、前記排出口から前記流入口に前記酸素溶媒を循環させる循環路が前記筐体外部に備えられており、
前記酸素溶媒が前記筐体内及び前記循環路を循環する、請求の範囲第1項または第2項に記載の空気電池。 - 前記電解質層が、前記酸素溶媒と相溶せず、かつ前記酸素溶媒より比重が小さく、
前記酸素溶媒の鉛直方向上方において、前記負極が鉛直方向上方に配置されるように前記発電部が備えられている、請求の範囲第1項から第3項のいずれかに記載の空気電池。 - 前記電解質と前記酸素溶媒との界面が前記空気極内にある、請求の範囲第4項に記載の空気電池。
- 前記酸素供給部が、一端が前記筐体の下部に連結された酸素供給管の他端に備えられており、
前記酸素供給管内に前記酸素溶媒と酸素含有ガスとの界面が形成され、前記酸素供給部が該界面より高い位置に備えられている、請求の範囲第4項または第5項に記載の空気電池。 - 前記筐体の上部に排気口が備えられている、請求の範囲第4項から第6項のいずれかに記載の空気電池。
- 所定の圧力で開放する調圧弁が前記排気口に備えられている、請求の範囲第7項に記載の空気電池。
- 前記筐体内の気体を前記排気口に誘導することができる誘導手段が備えられている、請求の範囲第7項または第8項に記載の空気電池。
- 前記筐体内に複数の前記発電部が収容されている、請求の範囲第1項から第9項のいずれかに記載の空気電池。
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