WO2011101992A1 - 非水電解液型二次電池及び非水電解液型二次電池用非水電解液 - Google Patents
非水電解液型二次電池及び非水電解液型二次電池用非水電解液 Download PDFInfo
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- WO2011101992A1 WO2011101992A1 PCT/JP2010/052647 JP2010052647W WO2011101992A1 WO 2011101992 A1 WO2011101992 A1 WO 2011101992A1 JP 2010052647 W JP2010052647 W JP 2010052647W WO 2011101992 A1 WO2011101992 A1 WO 2011101992A1
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0045—Room temperature molten salts comprising at least one organic ion
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte for a non-aqueous electrolyte secondary battery.
- lithium-air batteries are attracting attention as lithium secondary batteries for electric vehicles and hybrid vehicles that require high energy density.
- Lithium-air batteries use oxygen in the air as the positive electrode active material. Therefore, the capacity can be increased as compared with a conventional lithium secondary battery incorporating a transition metal oxide such as lithium cobalt oxide as a positive electrode active material.
- the following reaction is known as a reaction of a lithium-air battery using metallic lithium as the negative electrode active material, although it varies depending on the electrolytic solution used.
- Negative electrode Li ⁇ Li + + e ⁇ Positive electrode: 2Li + + O 2 + 2e ⁇ ⁇ Li 2 O 2 Or 4Li + + O 2 + 4e ⁇ ⁇ 2Li 2 O [When charging] Negative electrode: Li + + e ⁇ ⁇ Li Positive electrode: Li 2 O 2 ⁇ 2Li + + O 2 + 2e ⁇ Or 2Li 2 O ⁇ 4Li + + O 2 + 4e ⁇
- lithium ions Li +
- Oxygen O 2
- Patent Document 1 discloses a negative electrode having the ability to release metal ions, a positive electrode containing a carbon material, and a [—O— (C ⁇ O) —O—] skeleton sandwiched between the negative electrode and the positive electrode.
- a nonaqueous electrolyte battery comprising a nonaqueous electrolyte solution containing an organic carbonate compound and a storage case in which an air hole for taking in oxygen into the positive electrode is formed.
- the carbon material surface of the positive electrode is decomposed and formed on the carbon material surface of the positive electrode
- a non-aqueous electrolyte battery coated with an object film is disclosed.
- the non-aqueous electrolyte battery of Patent Document 1 is intended to prevent the volatilization of the organic electrolyte from the air holes and improve the battery life and discharge capacity.
- Patent Document 2 discloses a positive electrode, a negative electrode that absorbs and releases lithium ions, a non-aqueous electrolyte-containing layer disposed between the positive electrode and the negative electrode, and at least the positive electrode, the negative electrode, and the non-aqueous electrolyte.
- a non-aqueous electrolyte air battery comprising a layer and a case having an air hole for supplying oxygen to the positive electrode, wherein the non-aqueous electrolyte in the non-aqueous electrolyte-containing layer has a specific chemical formula
- a non-aqueous electrolyte air battery characterized by being a room temperature molten salt containing at least one of the represented cations and lithium ions is disclosed.
- the decomposition product of the organic carbonate compound in the above-mentioned Patent Document 1 is such that the oxygen radical (O 2 ⁇ ) generated by the reduction of oxygen (O 2 ) on the positive electrode carbon and the catalyst is It was found to be produced by reacting with a carbonate compound. Furthermore, research by the present inventors has newly found that with the technique of Patent Document 1, the battery resistance after discharge is remarkably increased and full charge is difficult. Considering these disadvantages, it is considered that the merit obtained by the positive film formation in Patent Document 1 is low.
- oxygen (O 2 ) is mixed into the organic solvent in the manufacturing process.
- Oxygen mixed into an organic solvent in the manufacturing process (O 2) is reduced oxygen radicals in the positive electrode - to generate oxygen radicals (O 2) - cause side reactions due to (O 2).
- oxygen radicals (O 2 ⁇ ) can be generated.
- oxygen radicals As a side reaction by oxygen radicals (O 2 ⁇ ), there are a decomposition reaction of a solvent such as an organic carbonate compound as described above, and a decomposition reaction of other materials constituting the battery. In a secondary battery that is repeatedly charged and discharged and used for a long period of time, the side reaction due to oxygen radicals is one of the major factors that lower the durability of the battery.
- the air battery which supplies oxygen which is a positive electrode active material to the positive electrode from air (outside air) like the battery of patent document 1 and 2 the water and carbon dioxide in air are also supplied with oxygen.
- oxygen radicals (O 2 ⁇ ) generated from oxygen as the positive electrode active material react with water and carbon dioxide in addition to organic solvents such as organic carbonate compounds. Therefore, a chain radical reaction occurs in addition to the decomposition reaction of the organic solvent as described above.
- a characteristic (inherent) reaction in which the oxygen radical (O 2 ⁇ ) generated from oxygen as the positive electrode active material decomposes the organic solvent easily occurs.
- the present invention has been accomplished in view of the above circumstances, and aims to provide a non-aqueous electrolyte secondary battery that improves the resistance to oxygen radicals of a non-aqueous electrolyte and is excellent in durability and capacity characteristics.
- the non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte interposed between the positive electrode and the negative electrode,
- the positive electrode, the negative electrode, and the non-aqueous electrolyte, and at least carbon dioxide and water have a closed structure that is blocked,
- the discharge voltage is 3 V or less with respect to the lithium electrode
- the non-aqueous electrolyte contains two or more kinds of anions.
- oxygen radical generation potential the potential at which oxygen radicals (O 2 ⁇ ) are generated from oxygen (O 2 ) in the nonaqueous electrolytic solution
- oxygen radical generation potential the potential at which oxygen radicals (O 2 ⁇ ) are generated from oxygen (O 2 ) in the nonaqueous electrolytic solution
- the battery of the present invention does not generate oxygen radicals (O 2 ⁇ ) of the non-aqueous electrolyte in a potential region of 3 V or less with reference to a lithium electrode (hereinafter sometimes referred to as “vs. Li / Li +”). Since the potential window is wide, the oxygen radical resistance of the electrolyte in the non-aqueous electrolyte secondary battery with a discharge potential of 3 V or less (vs. Li / Li +) can be improved.
- non-aqueous electrolyte type secondary battery is a non-aqueous electrolyte type lithium secondary battery.
- the non-aqueous electrolyte secondary battery is a lithium-air battery in which the positive electrode uses oxygen as an active material, the effect obtained by the present invention is particularly high. This is because a metal-air battery typified by a lithium-air battery has a high dissolved oxygen concentration in the non-aqueous electrolyte and is particularly susceptible to problems caused by oxygen radicals (O 2 ⁇ ).
- a specific combination of anions contained in the non-aqueous electrolyte includes at least a combination of a first anion having a relatively high molecular weight and a second anion having a relatively low molecular weight.
- the molar ratio of the first anion to the second anion [(first anion) :( second anion)] is preferably in the range of 95: 5 to 65:35.
- Examples of the combination of the first anion and the second anion include a combination in which the first anion is at least bistrifluoromethanesulfonylimide and the second anion is at least trifluoromethanesulfonate. Can be mentioned.
- the non-aqueous electrolyte includes acetonitrile, dimethyl sulfoxide, dimethoxyethane, N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide, and N-methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl). It is preferable that the electrolyte salt is dissolved in at least one non-aqueous solvent selected from imides. This is because the decomposition of the nonaqueous electrolytic solution by oxygen radicals (O 2 ⁇ ) can be more effectively suppressed.
- oxygen radicals O 2 ⁇
- the positive electrode, the negative electrode, and the non-aqueous electrolyte, and the closed structure in which at least carbon dioxide and water are blocked are the positive electrode, the negative electrode, and the non-aqueous battery.
- a closed structure in which the electrolytic solution and the atmosphere are shut off can be given.
- the non-aqueous electrolyte of the present invention is a non-aqueous electrolyte for a non-aqueous electrolyte type secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte interposed between the positive electrode and the negative electrode, Containing two or more anions
- the non-aqueous electrolyte type secondary battery has a closed structure in which the positive electrode, the negative electrode, the non-aqueous electrolyte, and at least carbon dioxide and water are blocked, and the discharge voltage is 3 V or less based on a lithium electrode. It is characterized by being.
- non-aqueous electrolyte type secondary battery examples include a non-aqueous electrolyte type lithium secondary battery, and more specifically, a lithium-air battery in which the positive electrode uses oxygen as an active material. .
- a specific combination of anions contained in the non-aqueous electrolyte includes at least a combination of a first anion having a relatively high molecular weight and a second anion having a relatively low molecular weight.
- the molar ratio of the first anion to the second anion [(first anion) :( second anion)] is preferably in the range of 95: 5 to 65:35.
- Examples of the combination of the first anion and the second anion include a combination in which the first anion is at least bistrifluoromethanesulfonylimide and the second anion is at least trifluoromethanesulfonate. Can be mentioned.
- the non-aqueous electrolyte includes acetonitrile, dimethyl sulfoxide, dimethoxyethane, N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide, and N-methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl). It is preferable that the electrolyte salt is dissolved in at least one non-aqueous solvent selected from imides. This is because a metal-air battery typified by a lithium-air battery has a high dissolved oxygen concentration in the non-aqueous electrolyte and is particularly susceptible to problems caused by oxygen radicals (O 2 ⁇ ).
- the positive electrode, the negative electrode, and the non-aqueous electrolyte, and the closed structure in which at least carbon dioxide and water are blocked are the positive electrode, the negative electrode, and the non-aqueous battery.
- a closed structure in which the electrolytic solution and the atmosphere are blocked can be given.
- oxygen radical (O 2 ⁇ ) resistance of an electrolytic solution Therefore, according to the present invention, it is possible to improve the durability and capacity characteristics of the nonaqueous electrolyte secondary battery.
- the non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte interposed between the positive electrode and the negative electrode,
- the positive electrode, the negative electrode, and the non-aqueous electrolyte, and at least carbon dioxide and water have a closed structure that is blocked,
- the discharge voltage is 3 V or less with respect to the lithium electrode
- the non-aqueous electrolyte contains two or more kinds of anions.
- non-aqueous electrolyte solution for the non-aqueous electrolyte type secondary battery hereinafter sometimes simply referred to as a secondary battery
- a secondary battery the non-aqueous electrolyte type secondary battery of the present invention
- the secondary battery of the present invention is characterized in that a non-aqueous electrolyte is used as an electrolyte that intervenes between a positive electrode and a negative electrode and conducts ions between these electrodes.
- the secondary battery of the present invention is characterized in that the discharge voltage is 3 V or less (vs. Li / Li +).
- oxygen (O 2) oxygen radical from (O 2 -) generated reaction occurs in the potential range of 2 ⁇ 3V (vs.Li/Li+).
- the battery of the present invention if oxygen is present in the battery, oxygen radicals upon discharge from the oxygen (O 2) (O 2 - ) which is the reaction-prone environment generated by the.
- the secondary battery of the present invention has a closed structure in which the positive electrode, the negative electrode, and the nonaqueous electrolytic solution interposed between these electrodes are blocked from at least carbon dioxide and water.
- oxygen radicals (O 2 ⁇ ) are liable to cause a chain reaction with carbon dioxide and water. Therefore, in the battery of the present invention, a reaction in which oxygen (O 2 ) is reduced to generate oxygen radicals (O 2 ⁇ ) occurs more easily than a battery in which carbon dioxide and water are present together with oxygen.
- oxygen (O 2) oxygen radical from (O 2 -) in the secondary battery reaction are aligned easily condition progresses to generate, in order to improve oxygen radical resistance of the nonaqueous electrolyte solution, the present invention
- oxygen reduction peak potential the potential for oxygen radicals (O 2 ⁇ ) to be generated from oxygen (O 2 ) by incorporating two or more types of anions in the nonaqueous electrolyte
- the oxygen radicals can be suppressed side reactions caused by the (O 2 - -) decomposition of an organic solvent of the nonaqueous electrolytic solution, oxygen radical (O 2). Therefore, according to the present invention, it is possible to selectively advance a target electrode reaction. As a result, battery performance such as capacity characteristics and durability characteristics can be improved.
- the closed structure in which the positive electrode, the negative electrode, and the non-aqueous electrolyte are blocked from at least carbon dioxide and water prevents carbon dioxide and water from entering the battery from the outside.
- the negative electrode and the non-aqueous electrolyte can avoid contact with carbon dioxide and water.
- a sealed structure that does not have a communication structure with the outside, or a supply source or discharge port of the active material to the electrode, but there is no communication with the outside, and the supply source or discharge port Closed structure in which the intrusion of carbon dioxide and water from is prevented.
- oxygen in the outside air can be supplied into the battery in communication with the outside, but intrusion of carbon dioxide and water from the outside air is possible.
- examples thereof include a structure that is selectively blocked.
- a method for selectively preventing the intrusion of carbon dioxide and water for example, a method of disposing a carbon dioxide-absorbing material and a water-absorbing material at a communication port with the outside can be cited.
- a material having water absorbability for example, a material generally used as a desiccant, for example, a material having deliquescence such as calcium chloride, potassium peroxide, potassium carbonate, or water adsorbability such as silica gel
- a material having deliquescence such as calcium chloride, potassium peroxide, potassium carbonate, or water adsorbability
- the carbon dioxide-absorbing material include lithium silicate, zinc oxide, zeolite, activated carbon, and alumina.
- the non-aqueous electrolyte contains at least a non-aqueous solvent containing an organic solvent and / or an ionic liquid and an electrolyte salt.
- the nonaqueous electrolytic solution of the present invention is characterized by containing two or more types of anions, but the supply source (origin) of these anions is not particularly limited.
- electrolyte salt and an ionic liquid are mentioned, for example.
- As a specific configuration of the nonaqueous electrolytic solution of the present invention for example, (1) at least two kinds of electrolyte salts containing different anions are dissolved in an organic solvent, and (2) at least in an organic solvent.
- the organic solvent is not particularly limited as long as the electrolyte salt to be used can be dissolved, and examples thereof include those that can be used for an electrolytic solution for a lithium secondary battery. Specifically, propylene carbonate, ethylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, isopropiomethyl carbonate, ethyl propionate, methyl propionate, ⁇ -butyrolactone, ethyl acetate, methyl acetate , Tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol didiethyl ether, acetonitrile, dimethyl sulfoxide, diethoxyethane, dimethoxyethane and the like.
- the ionic liquid is not particularly limited as long as the electrolyte salt to be used can be dissolved, and examples thereof include those that can be used for an electrolyte for a lithium secondary battery.
- N, N, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide [abbreviation: TMPA-TFSI], N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide
- PP13-TFSI N-methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide
- P13-TFSI N-methyl-N-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide
- P14-TFSI aliphatic quaternary ammonium salt; 1-methyl-3-ethylimida
- organic solvents and ionic liquids since they are difficult to react with oxygen radicals (O 2 ⁇ ), organic solvents such as acetonitrile, dimethyl sulfoxide, and dimethoxyethane, and N-methyl-N-propylpiperidinium bis ( At least one selected from ionic liquids such as trifluoromethanesulfonyl) imide and N-methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide is preferred. From the viewpoint of becoming an anion source in the nonaqueous electrolytic solution, the ionic liquid is a preferable solvent. In addition, only 1 type may be used for the organic solvent and ionic liquid which are nonaqueous solvents, and it may use it in combination of 2 or more type.
- the electrolyte salt is not particularly limited as long as it can conduct ions to be conducted between the positive electrode and the negative electrode, and can be appropriately selected according to the form of the secondary battery.
- concentration of the electrolyte salt in the non-aqueous electrolyte depends on the electrolyte salt used, but is usually preferably in the range of 0.1 to 3.0 mol / L, particularly 0.5 to 1.5 mol. / L is preferable.
- the anion contained in the electrolyte salt is not particularly limited.
- perchlorate ion (ClO 4 over) [molecular weight of about 100
- hexafluorophosphate ion (PF 6 chromatography) molecular weight of about 145
- tetrafluoroborate ion (BF 4 over) molecular weight of about 87
- m is 1 or more and 8 or less, preferably 1 or more and 4 or less.
- Specific examples of the anion represented by the formula (1) include trifluoromethanesulfonate [abbreviation: TfO, molecular weight: about 149].
- n and p are each 1 or more and 8 or less, preferably 1 or more and 4 or less, and may be the same or different from each other.
- anion represented by the formula (2) include bistrifluoromethanesulfonylimide ([N (CF 3 SO 2 ) 2 )] ⁇ ) [abbreviation: TFSA, molecular weight: about 280], bispentafluoro Ethanesulfonylimide ([N (C 2 F 5 SO 2 ) 2 )] ⁇ ), trifluoromethanesulfonyl nonafluorobutanesulfonyl imide ([N (CF 3 SO 2 ) (C 4 F 9 SO 2 ))] ⁇ ) and the like Is mentioned.
- the specific combination of two or more kinds of anions contained in the nonaqueous electrolytic solution is not particularly limited, and can be appropriately selected and combined.
- combinations include combinations of two or more anions having different molecular weights. That is, at least a first anion having a relatively large molecular weight (hereinafter sometimes simply referred to as a first anion) and a second anion having a relatively small molecular weight (hereinafter simply referred to as a second anion).
- a combination This is because it is presumed that the effect of suppressing the oxygen reduction reaction by the interaction as described above can be obtained by combining anions having different molecular weights, that is, different molecular sizes.
- the anions having different molecular weights used in combination are not limited to two kinds of the first anion and the second anion, and three or more kinds of anions having different molecular weights may be used.
- the ratio of each anion in the non-aqueous electrolyte is not particularly limited and can be determined as appropriate.
- the molar ratio of the first anion to the second anion [(first anion) :( second anion)] is preferably in the range of 95: 5 to 65:35, particularly 92: The range is preferably 8 to 65:35, more preferably 92: 8 to 88:12, and most preferably 90:10.
- the cation which is a counter ion of these anions is not particularly limited, and may be appropriately selected according to, for example, the ion conductive species required for the nonaqueous electrolytic solution.
- the present invention relates to general non-aqueous electrolysis such as lithium secondary battery, sulfur battery, metal-air battery (eg, sodium-air battery, magnesium-air battery, calcium-air battery, potassium-air battery). It can be applied to a secondary battery using a liquid.
- the present invention is preferably applied to a lithium secondary battery.
- a lithium-air battery is a secondary battery that is particularly effective when the present invention is applied because oxygen dissolves in the non-aqueous electrolyte during discharge.
- the lithium secondary battery operates as a secondary battery by moving lithium ions from the negative electrode to the positive electrode during discharging and moving from the positive electrode to the negative electrode during charging, and is made of metallic lithium.
- Those using a negative electrode and those using a negative electrode made of a material capable of intercalating and deintercalating lithium ions such as graphite are also included.
- lithium-air batteries are also included in lithium secondary batteries.
- specific configurations of various secondary batteries for example, a positive electrode, a negative electrode, current collectors, a separator, a battery case, and the like are not particularly limited, and a general configuration can be adopted.
- FIG. 1 is a cross-sectional view showing an embodiment of a non-aqueous electrolyte secondary battery (lithium-air battery) according to the present invention.
- the secondary battery (lithium-air battery) 1 includes a positive electrode (air electrode) 2 containing oxygen as an active material, a negative electrode 3 containing a negative electrode active material, a non-aqueous battery that conducts lithium ions between the positive electrode 2 and the negative electrode 3.
- Electrolyte 4 a separator 5 disposed between the positive electrode 2 and the negative electrode 3 to ensure electrical insulation between these electrodes, a positive electrode current collector 6 for collecting the positive electrode 2, and a collection of the negative electrode 3
- a negative electrode current collector 7 for conducting electricity is accommodated in a battery case 8.
- the separator 5 has a porous structure, and the nonaqueous electrolytic solution 4 is impregnated in the porous body. The nonaqueous electrolytic solution 4 is impregnated into the positive electrode 2 and further into the negative electrode 3 as necessary.
- a positive electrode current collector 6 that collects current from the positive electrode 2 is electrically connected to the positive electrode 2.
- the positive electrode current collector 6 has a porous structure capable of supplying oxygen to the positive electrode 2.
- a negative electrode current collector 7 that collects current from the negative electrode 3 is electrically connected to the negative electrode 3.
- One of the ends of the positive electrode current collector 6 and the negative electrode current collector 7 protrudes from the battery case 8 and functions as a positive electrode terminal 9 and a negative electrode terminal 10, respectively.
- the secondary battery 1 has a structure in which water and carbon dioxide are prevented from entering the battery case 8 from the outside.
- the positive electrode usually has a porous structure containing a conductive material, and contains a binder and a catalyst that promotes the positive electrode reaction as necessary.
- the conductive material is not particularly limited as long as it has conductivity, and examples thereof include a carbon material. Specific examples of the carbon material include mesoporous carbon, graphite, acetylene black, carbon nanotube, and carbon fiber.
- the content of the conductive material in the positive electrode is preferably in the range of 10 wt% to 99 wt%, for example, with respect to the total amount of the positive electrode constituent material.
- the positive electrode preferably contains a binder. It is because a catalyst and an electroconductive material are fixed by containing a binder, and the positive electrode excellent in cycling characteristics can be obtained.
- the binder include polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), polyethylene, polypropylene, and styrene butadiene rubber.
- the content of the binder in the positive electrode is, for example, preferably 40% by weight or less, particularly 1 to 10% by weight, based on the total amount of the positive electrode constituent materials.
- the positive electrode preferably contains a catalyst in order to increase the reaction rate of the electrochemical reaction of oxygen.
- a catalyst such as cobalt phthalocyanine, manganese phthalocyanine, nickel phthalocyanine, tin phthalocyanine oxide, titanyl phthalocyanine, dilithium phthalocyanine, and the like; cobalt naphthocyanine Naphthocyanine compounds such as iron porphyrin; MnO 2 , Co 3 O 4 , NiO, V 2 O 5 , Fe 2 O 3 , ZnO, CuO, LiMnO 2 , Li 2 MnO 3 , LiMn 2 O 4, Li 4 Ti 5 O 12 , Li 2 TiO 3, LiNi 1/3 Co 1/3 Mn 1/3 O 2, LiNiO 2, LiVO
- the content of the catalyst in the positive electrode is preferably in the range of 1% by weight to 90% by weight, for example, with respect to the total amount of the positive electrode constituent materials. If the catalyst content is too low, sufficient catalytic function may not be achieved. On the other hand, if the catalyst content is too high, the content of the conductive material is relatively reduced, resulting in a decrease in the reaction field. This is because the battery capacity may be reduced.
- the positive electrode composed of the above materials can be produced by the following method. For example, a method in which a positive electrode mixture in which a conductive material, a binder, and a catalyst are mixed is press-molded on the surface of a positive electrode current collector, or a paste in which the positive electrode mixture is dispersed in a solvent is prepared. The method of apply
- the thickness of the positive electrode varies depending on the use of the lithium-air battery, but is preferably in the range of 2 ⁇ m to 500 ⁇ m, particularly preferably in the range of 5 ⁇ m to 300 ⁇ m.
- the positive electrode current collector has a function of collecting the positive electrode current.
- Examples of the material for the air electrode current collector include stainless steel, nickel, aluminum, iron, titanium, and carbon.
- Examples of the shape of the positive electrode current collector include a foil shape, a plate shape, and a mesh (grid) shape.
- the shape of the positive electrode current collector is preferably a porous shape such as a mesh shape. This is because the oxygen supply efficiency to the positive electrode is excellent.
- the current collection efficiency of the positive electrode can be increased by arranging the mesh air electrode current collector inside the positive electrode layer.
- the electrical power collector edge part which functions as a positive electrode terminal may be made into foil shape, plate shape, etc. from a viewpoint of current collection efficiency.
- the negative electrode contains at least a negative electrode active material.
- a negative electrode active material the negative electrode active material of a general air battery can be used, and it is not specifically limited.
- the negative electrode active material is usually capable of intercalating and deintercalating (occluding and releasing) lithium ions (metal ions).
- Examples of negative electrode active materials for lithium-air batteries include: lithium metal; lithium alloys such as lithium aluminum alloy, lithium tin alloy, lithium lead alloy, lithium silicon alloy; tin oxide, silicon oxide, lithium titanium oxide, niobium oxide , Metal oxides such as tungsten oxide; metal sulfides such as tin sulfide and titanium sulfide; metal nitrides such as lithium cobalt nitride, lithium iron nitride and lithium manganese nitride; and carbon materials such as graphite Among them, metallic lithium and carbon materials are preferable, and metallic lithium is more preferable from the viewpoint of increasing capacity.
- the negative electrode only needs to contain at least a negative electrode active material, but may contain a binder for immobilizing the negative electrode active material, if necessary.
- a binder for immobilizing the negative electrode active material, if necessary.
- the negative electrode current collector has a function of 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 carbon.
- Examples of the shape of the negative electrode current collector include a foil shape, a plate shape, and a mesh (grid) shape.
- the separator is installed between the positive electrode and the negative electrode.
- the separator is not particularly limited as long as it has a function of electrically insulating the positive electrode and the negative electrode and has a porous structure that can be impregnated with a nonaqueous electrolytic solution. Examples thereof include porous films such as polyethylene and polypropylene; nonwoven fabrics such as resin nonwoven fabrics and glass fiber nonwoven fabrics; and polymer materials used in lithium polymer batteries.
- the electrolyte used in the lithium-air battery of the present invention is a non-aqueous electrolyte containing two or more types of anions, in which an electrolyte (lithium salt) is dissolved in a non-aqueous solvent. Since the organic solvent and ionic liquid which are non-aqueous solvents are the same as those described above, description thereof is omitted here.
- the lithium salt include those containing the anion exemplified above as the anion contained in the electrolyte salt and lithium ion.
- an inorganic lithium salt such as lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ) and LiAsF 6 ; and LiCF 3 SO 3
- Organic lithium salts such as LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ) Can be mentioned.
- the shape of the battery case is not particularly limited as long as it can hold the positive electrode, the negative electrode, and the non-aqueous electrolyte described above. Specifically, a coin type, a flat plate type, a cylindrical type, a laminate type, etc. Can be mentioned.
- Example 1 Preparation of non-aqueous electrolyte>
- a first nonaqueous electrolytic solution TEATFSA concentration
- TEATFSA tetraethylammonium bistrifluoromethanesulfonylimide
- AN acetonitrile
- TEATfO tetraethylammonium trifluoromethanesulfonate
- the oxygen reduction peak potential (O 2 ⁇ generation potential) in the prepared nonaqueous electrolytic solution was measured as follows. That is, after a nonaqueous electrolyte was bubbled with pure oxygen (99.99%, 1 atm) for 30 minutes to saturate oxygen, cyclic voltammogram (CV) measurement was performed under the following scanning conditions using a triode cell having the following configuration. Went. The results are shown in Table 1. Table 1 shows the potential converted from the Ag electrode (Ag / Ag +) standard to the Li electrode (Li / Li +) standard.
- Working electrode / counter electrode / reference electrode rod-shaped glassy carbon electrode (manufactured by BAS) / Ni ribbon (manufactured by Nilaco) / Ag / Ag + type (manufactured by BAS) Scanning conditions: The potential was scanned from a natural potential to -1.7 V (Ag electrode reference) and then to 0.3 V (Ag electrode reference) at a scanning speed of 100 mV / sec.
- Example 2 In Example 1, a non-aqueous electrolyte containing two types of anions was prepared in the same manner except that the first non-aqueous electrolyte and the second non-aqueous electrolyte were mixed at a volume ratio of 92: 8. CV measurement was performed. The results are shown in Table 1.
- Example 3 In Example 1, a non-aqueous electrolyte containing two types of anions was prepared in the same manner except that the first non-aqueous electrolyte and the second non-aqueous electrolyte were mixed at a volume ratio of 90:10. CV measurement was performed. The results are shown in Table 1 and FIG. As in Table 1, FIG. 2 shows the potential converted from the Ag electrode (Ag / Ag +) standard to the Li electrode (Li / Li +) standard.
- Example 4 In Example 1, a nonaqueous electrolyte containing two types of anions was prepared in the same manner except that the first nonaqueous electrolyte and the second nonaqueous electrolyte were mixed at a volume ratio of 88:12. CV measurement was performed. The results are shown in Table 1.
- Example 5 In Example 1, a non-aqueous electrolyte containing two types of anions was prepared in the same manner except that the first non-aqueous electrolyte and the second non-aqueous electrolyte were mixed at a volume ratio of 85:15. CV measurement was performed. The results are shown in Table 1.
- Example 6 In Example 1, a non-aqueous electrolyte containing two types of anions was prepared in the same manner except that the first non-aqueous electrolyte and the second non-aqueous electrolyte were mixed at a volume ratio of 75:25. CV measurement was performed. The results are shown in Table 1.
- Example 7 In Example 1, a non-aqueous electrolyte containing two types of anions was prepared in the same manner except that the first non-aqueous electrolyte and the second non-aqueous electrolyte were mixed at a volume ratio of 65:35. CV measurement was performed. The results are shown in Table 1.
- Example 8 In Example 1, a non-aqueous electrolyte containing two types of anions was prepared in the same manner except that the first non-aqueous electrolyte and the second non-aqueous electrolyte were mixed at a volume ratio of 50:50. CV measurement was performed. The results are shown in Table 1.
- Example 9 In Example 1, a nonaqueous electrolyte containing two types of anions was prepared in the same manner except that the first nonaqueous electrolyte and the second nonaqueous electrolyte were mixed at a volume ratio of 25:75. CV measurement was performed. The results are shown in Table 1.
- Example 10 In Example 1, a non-aqueous electrolyte containing two types of anions was prepared in the same manner except that the first non-aqueous electrolyte and the second non-aqueous electrolyte were mixed at a volume ratio of 10:90. CV measurement was performed. The results are shown in Table 1.
- Example 11 In Example 3, except that a second nonaqueous electrolytic solution (TEPF6 concentration 0.1 M) in which tetraethylammonium hexafluorophosphate (hereinafter sometimes abbreviated as TEAPF6) was dissolved in AN was prepared, Similarly, a nonaqueous electrolytic solution containing two types of anions was prepared and CV measurement was performed. The results are shown in Table 1.
- TEPF6 concentration 0.1 M tetraethylammonium hexafluorophosphate
- Example 12 In Example 3, except that a second nonaqueous electrolytic solution (TEABF4 concentration of 0.1 M) in which tetraethylammonium tetrafluoroborate (hereinafter sometimes abbreviated as TEABF4) was dissolved in AN was prepared, Similarly, a nonaqueous electrolytic solution containing two types of anions was prepared and CV measurement was performed. The results are shown in Table 1.
- TEABF4 concentration of 0.1 M tetraethylammonium tetrafluoroborate
- Example 3 The second non-aqueous electrolyte of Example 11 was used as an electrolyte without mixing, and CV measurement was performed in the same manner as in Example 1. The results are shown in Table 1.
- Example 4 (Comparative Example 4) CV measurement was performed in the same manner as in Example 1 except that the second nonaqueous electrolytic solution of Example 12 was used as an electrolytic solution without mixing. The results are shown in Table 1.
- the non-aqueous electrolytes of Examples 1 to 10 containing a plurality of anions are compared with the non-aqueous electrolytes of Comparative Examples 1 to 2 containing only one kind of anion.
- the reduction peak potential of oxygen decreased.
- the ratio (molar ratio) of a relatively high molecular weight anion (bis (trifluoromethanesulfonyl) imide) to a relatively low molecular weight anion (trimethanesulfonate) is in the range of 95: 5 to 65:35.
- Examples 1 to 7 and particularly in Examples 2 to 4 in the range of 92: 8 to 88:12, and in Example 3 of 90:10 the oxygen reduction peak potential was greatly reduced.
- Example 11 in comparison between Example 11 and Comparative Example 3, the nonaqueous electrolytic solution of Example 11 containing two types of anions is the same as the nonaqueous electrolytic solution of Comparative Example 3 containing only one type of anions. In comparison, the reduction peak potential of oxygen decreased.
- Example 12 and Comparative Example 4 the nonaqueous electrolytic solution of Example 12 containing two kinds of anions is similar to the nonaqueous electrolytic solution of Comparative Example 4 containing only one kind of anions. In comparison, the reduction peak potential of oxygen decreased.
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Abstract
Description
使用する電解液等によっても異なるが、負極活物質として金属リチウムを用いたリチウム-空気電池の反応としては、下記反応が知られている。
負極 : Li → Li+ + e-
正極 : 2Li+ + O2 + 2e- → Li2O2
又は
4Li+ + O2 + 4e- → 2Li2O
[充電時]
負極 : Li+ + e- → Li
正極 : Li2O2 → 2Li+ + O2 + 2e-
又は
2Li2O → 4Li+ + O2 + 4e-
例えば、特許文献1には、金属イオンを放出する能力を有する負極と、炭素材料を含有する正極と、前記負極及び正極に挟まれた[-O-(C=O)-O-]骨格を有する有機カーボネート化合物を含有する非水電解液と、前記正極に酸素を取り込む空気孔が形成された収納ケースを具備した非水電解質電池において、前記正極の炭素材料表面を前記有機カーボネート化合物の分解生成物の皮膜で被覆した非水電解液電池が開示されている。
特許文献1の非水電解質電池は、空気孔からの有機電解液の揮発を防止し、電池寿命及び放電容量を向上させることを目的としている。
酸素ラジカル(O2 -)による副反応としては、上記したような有機カーボネート化合物等の溶媒の分解反応の他、電池を構成する他の材料の分解反応等がある。充電と放電を繰り返し、長期間使用される二次電池では、酸素ラジカルによる上記副反応は電池の耐久性を低下させる大きな要因の1つとなる。
前記正極、前記負極及び前記非水電解液と、少なくとも二酸化炭素及び水とが、遮断された閉鎖構造を有し、
放電電圧がリチウム電極基準で3V以下であり、
前記非水電解液が、2種以上のアニオンを含むことを特徴とする。
前記第1のアニオンと前記第2のアニオンとのモル比[(第1のアニオン):(第2のアニオン)は、95:5~65:35の範囲内であることが好ましい。
前記第1のアニオンと前記第2のアニオンとの組合せとしては、例えば、前記第1のアニオンが、少なくともビストリフルオロメタンスルホニルイミドであり、前記第2のアニオンが、少なくともトリフルオロメタンスルホネートである組み合わせが挙げられる。
2種以上のアニオンを含み、
前記非水電解液型二次電池は、前記正極、前記負極及び前記非水電解液と、少なくとも二酸化炭素及び水と、が遮断された閉鎖構造を有すると共に、放電電圧がリチウム電極基準で3V以下であることを特徴とする。
前記第1のアニオンと前記第2のアニオンとのモル比[(第1のアニオン):(第2のアニオン)は、95:5~65:35の範囲内であることが好ましい。
前記第1のアニオンと前記第2のアニオンとの組合せとしては、例えば、前記第1のアニオンが、少なくともビストリフルオロメタンスルホニルイミドであり、前記第2のアニオンが、少なくともトリフルオロメタンスルホネートである組み合わせが挙げられる。
前記正極、前記負極及び前記非水電解液と、少なくとも二酸化炭素及び水とが、遮断された閉鎖構造を有し、
放電電圧がリチウム電極基準で3V以下であり、
前記非水電解液が、2種以上のアニオンを含むことを特徴とする。
また、本発明の二次電池は、放電電圧が3V以下(vs.Li/Li+)であることを特徴とする。上記したように、酸素(O2)から酸素ラジカル(O2 -)が生成する反応は、2~3V(vs.Li/Li+)の電位範囲で生じる。従って、本発明の電池は、電池内に酸素が存在すれば、放電時に酸素(O2)から酸素ラジカル(O2 -)が生成する反応が起こりやすい環境である。
さらに、本発明の二次電池は、正極、負極及びこれら電極間に介在する非水電解液が、少なくとも二酸化炭素及び水と遮断された閉鎖構造を有している。上記したように、酸素ラジカル(O2 -)は、二酸化炭素や水とも連鎖的な反応を起こしやすい。従って、本発明の電池は、酸素と共に二酸化炭素や水が存在する電池と比較して、酸素(O2)が還元されて酸素ラジカル(O2 -)を生成する反応が起こり易い。
酸素還元ピーク電位が低下することは、非水電解液の酸素ラジカル(O2 -)に対して安定な電位窓が広くなることを意味する。すなわち、本発明によれば、酸素ラジカル(O2 -)による非水電解液中の有機溶媒の分解等、酸素ラジカル(O2 -)に起因する副反応を抑制することができる。従って、本発明によれば、狙いの電極反応を選択的に進行させることが可能である。その結果、容量特性や耐久特性等の電池性能を向上させることができる。
ここで、二酸化炭素及び水の浸入を選択的に阻止する方法としては、例えば、二酸化炭素吸収性を有する材料及び水吸収性を有する材料を外部との連通口に配置する方法等が挙げられる。水吸収性を有する材料としては、例えば、乾燥剤として一般的に使用されている材料、例えば、塩化カルシウム、過酸化カリウム、炭酸カリウム等の潮解性を有する材料、或いは、シリカゲル等の水吸着性を有する材料が挙げられる。また、二酸化炭素吸収性を有する材料としては、例えば、リチウムシリケート、酸化亜鉛、ゼオライト、活性炭、アルミナ等が挙げられる。
非水電解液中の電解質塩の濃度は、使用する電解質塩にもよるが、通常、0.1~3.0モル/Lの範囲であることが好ましく、特に0.5~1.5モル/Lの範囲であることが好ましい。
式中、mは、1以上8以下であり、好ましくは1以上4以下である。
(1)式で表される具体的なアニオンとしては、例えば、トリフルオロメタンスルホネート[略称:TfO、分子量:約149]等が挙げられる。
式中、n及びpはそれぞれ1以上8以下、好ましくは1以上4以下であり、互いに同じであっても異なっていてもよい。
式(2)で表される具体的なアニオンとしては、例えば、ビストリフルオロメタンスルホニルイミド([N(CF3SO2)2)]-)[略称:TFSA、分子量:約280]、ビスペンタフルオロエタンスルホニルイミド([N(C2F5SO2)2)]-)、トリフルオロメタンスルホニルノナフルオロブタンスルホニルイミド([N(CF3SO2)(C4F9SO2))]-)等が挙げられる。
尚、組み合わせて用いる、分子量の異なるアニオンは、第1のアニオン及び第2のアニオンの2種に限定されるものではなく、3種以上の分子量の異なるアニオンを用いてもよい。
ここで、リチウム二次電池とは、放電時に負極から正極へリチウムイオンが移動し、充電時に正極から負極へリチウムイオンが移動することによって、二次電池として作動するものであり、金属リチウムからなる負極を用いるもの、グラファイト等のリチウムイオンのインターカレート及びデインターカレートが可能な材料からなる負極を用いるものも含む。さらには、リチウム-空気電池もリチウム二次電池に含まれる。
尚、本発明において、各種二次電池の具体的な構成、例えば、正極、負極、各集電体、セパレータ、電池ケース等は、特に限定されず、一般的な構成を採用することができる。
図1は、本発明の非水電解液型二次電池(リチウム-空気電池)の一形態例を示す断面図である。二次電池(リチウム-空気電池)1は、酸素を活物質とする正極(空気極)2、負極活物質を含有する負極3、正極2及び負極3の間でリチウムイオンの伝導を担う非水電解液4、正極2と負極3との間に配置され、これら電極間の電気的絶縁を確保するためのセパレータ5、正極2の集電を行う正極集電体6、並びに、負極3の集電を行う負極集電体7が、電池ケース8に収容されている。
セパレータ5は、多孔質構造を有しており、非水電解液4がその多孔質内に含浸されている。非水電解液4は、正極2の内部、さらには必要に応じて負極3の内部にも含浸されている。
正極2には、該正極2の集電を行う正極集電体6が電気的に接続されている。正極集電体6は、正極2への酸素供給が可能な多孔質構造を有している。負極3には、該負極3の集電を行う負極集電体7が電気的に接続されている。正極集電体6及び負極集電体7の端部のうち一方は、電池ケース8から突出しており、それぞれ、正極端子9、負極端子10として機能する。
図1には図示していないが、二次電池1は、外部から電池ケース8内への水及び二酸化炭素の侵入が阻止された構造を有している。
導電性材料としては、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、例えば炭素材料等を挙げることができる。炭素材料として、具体的には、メソポーラスカーボン、グラファイト、アセチレンブラック、カーボンナノチューブ、カーボンファイバ等を挙げることができる。正極における導電性材料の含有量は、例えば、正極構成材料の合計量に対して、10重量%~99重量%の範囲内であることが好ましい。
触媒としては、リチウム-空気電池の正極(空気極)で使用可能なもの、例えば、コバルトフタロシアニン、マンガンフタロシアニン、ニッケルフタロシアニン、スズフタロシアニンオキサイド、チタニルフタロシアニン、ジリチウムフタロシアニン等のフタロシアニン系化合物;コバルトナフトシアニン等のナフトシアニン系化合物;鉄ポルフィリン等のポリフィリン系化合物;MnO2、Co3O4、NiO、V2O5、Fe2O3、ZnO、CuO、LiMnO2、Li2MnO3、LiMn2O4、Li4Ti5O12、Li2TiO3、LiNi1/3Co1/3Mn1/3O2、LiNiO2、LiVO3、Li5FeO4、LiFeO2、LiCrO2、LiCoO2、LiCuO2、LiZnO2、Li2MoO4、LiNbO3、LiTaO3、Li2WO4、Li2ZrO3、NaMnO2、CaMnO3、CaFeO3、MgTiO3、KMnO2等の金属酸化物等が挙げられる。
正極の厚さは、リチウム-空気電池の用途等により異なるものであるが、例えば2μm~500μmの範囲内、特に5μm~300μmの範囲内であることが好ましい。
負極は、少なくとも負極活物質を含有してればよいが、必要に応じて、負極活物質を固定化する結着材を含有していてもよい。結着材の種類、使用量等については、上述した正極と同様であるため、ここでの説明は省略する。
<非水電解液の調製>
まず、アセトニトリル(以下、ANと略する場合がある)に、テトラエチルアンモニウムビストリフルオロメタンスルホニルイミド(以下、TEATFSAと略する場合がある)を溶解させた第1の非水電解液(TEATFSAの濃度:0.1M)を調製した。
一方、ANに、テトラエチルアンモニウムトリフルオロメタンスルホネート(以下、TEATfOと略する場合がある)を0.1M溶解させた第2の非水電解液を調製した。
第1の非水電解液と第2の非水電解液とを、体積比95:5の割合で混合し、2種のアニオンを含む非水電解液を調製した。
調製した非水電解液における酸素還元ピーク電位(O2 -の発生電位)を、以下のようにして測定した。すなわち、非水電解液を純酸素(99.99%、1atm)で30分間バブリングして酸素を飽和させた後、下記構成の三極セルを用いて下記走査条件でサイクリックボルタモグラム(CV)測定を行った。結果を表1に示す。尚、表1には、Ag電極(Ag/Ag+)基準からLi電極(Li/Li+)基準に換算した電位を示す。
・走査条件 : 走査速度100mV/secで、自然電位から-1.7V(Ag電極基準)まで、その後0.3V(Ag電極基準)まで電位を走査した。
実施例1において、第1の非水電解液と第2の非水電解液とを、体積比92:8で混合した以外は同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1に示す。
実施例1において、第1の非水電解液と第2の非水電解液とを、体積比90:10で混合した以外は同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1及び図2に示す。尚、表1同様、図2には、Ag電極(Ag/Ag+)基準からLi電極(Li/Li+)基準に換算した電位を示す。
実施例1において、第1の非水電解液と第2の非水電解液とを、体積比88:12で混合した以外は同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1に示す。
実施例1において、第1の非水電解液と第2の非水電解液とを、体積比85:15で混合した以外は同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1に示す。
実施例1において、第1の非水電解液と第2の非水電解液とを、体積比75:25で混合した以外は同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1に示す。
実施例1において、第1の非水電解液と第2の非水電解液とを、体積比65:35で混合した以外は同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1に示す。
実施例1において、第1の非水電解液と第2の非水電解液とを、体積比50:50で混合した以外は同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1に示す。
実施例1において、第1の非水電解液と第2の非水電解液とを、体積比25:75で混合した以外は同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1に示す。
実施例1において、第1の非水電解液と第2の非水電解液とを、体積比10:90で混合した以外は同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1に示す。
実施例3において、ANに、六フッ化リン酸テトラエチルアンモニウム(以下、TEAPF6と略する場合がある)を溶解させた第2の非水電解液(TEAPF6濃度0.1M)を調製した以外は、同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1に示す。
実施例3において、ANに、四フッ化ホウ酸テトラエチルアンモニウム(以下、TEABF4と略する場合がある)を溶解させた第2の非水電解液(TEABF4濃度0.1M)を調製した以外は、同様にして、2種のアニオンを含む非水電解液を調製し、CV測定を行った。結果を表1に示す。
実施例1の第1の非水電解液を混合せずに電解液として用い、実施例1と同様にしてCV測定を行った。結果を表1及び図2に示す。
実施例1の第2の非水電解液を混合せずに電解液として用い、実施例1と同様にしてCV測定を行った。結果を表1及び図2に示す。
実施例11の第2の非水電解液を混合せずに電解液として用い、実施例1と同様にしてCV測定を行った。結果を表1に示す。
実施例12の第2の非水電解液を混合せずに電解液として用い、実施例1と同様にしてCV測定を行った。結果を表1に示す。
また、実施例11と比較例3との対比においても同様に、2種のアニオンを含有する実施例11の非水電解液は、アニオンを1種のみ含有する比較例3の非水電解液と比較して、酸素の還元ピーク電位が低下した。
また、実施例12と比較例4との対比においても同様に、2種のアニオンを含有する実施例12の非水電解液は、アニオンを1種のみ含有する比較例4の非水電解液と比較して、酸素の還元ピーク電位が低下した。
2…正極
3…負極
4…非水電解液
5…セパレータ
6…正極集電体
7…負極集電体
8…電池ケース
9…正極端子
10…負極端子
Claims (16)
- 正極、負極、及び前記正極と前記負極との間に介在する非水電解液を備える非水電解液型二次電池であって、
前記正極、前記負極及び前記非水電解液と、少なくとも二酸化炭素及び水とが、遮断された閉鎖構造を有し、
放電電圧がリチウム電極基準で3V以下であり、
前記非水電解液が、2種以上のアニオンを含むことを特徴とする、非水電解液型二次電池。 - 前記非水電解液型二次電池が、非水電解液型リチウム二次電池である、請求の範囲第1項に記載の非水電解液型リチウム二次電池。
- 前記正極が酸素を活物質とするリチウム-空気電池である、請求の範囲第2項に記載の非水電解液型二次電池。
- 前記非水電解液が、少なくとも、相対的に分子量が大きい第1のアニオンと、相対的に分子量が小さい第2のアニオンと、を含む、請求の範囲第1項乃至第3項のいずれかに記載の非水電解液型二次電池。
- 前記第1のアニオンと前記第2のアニオンとのモル比[(第1のアニオン):(第2のアニオン)が、95:5~65:35である、請求の範囲第4項に記載の非水電解液型二次電池。
- 前記第1のアニオンが、少なくともビストリフルオロメタンスルホニルイミドであり、前記第2のアニオンが、少なくともトリフルオロメタンスルホネートである、請求の範囲第4項又は第5項に記載の非水電解液型二次電池。
- 前記非水電解液が、アセトニトリル、ジメチルスルホキシド、ジメトキシエタン、N-メチル-N-プロピルピペリジニウムビス(トリフルオロメタンスルホニル)イミド、及びN-メチル-N-プロピルピロリジニウムビス(トリフルオロメタンスルホニル)イミドから選ばれる少なくとも1種の非水溶媒に、電解質塩を溶解したものである、請求の範囲第1項乃至第6項のいずれかに記載の非水電解液型二次電池。
- 前記正極、前記負極及び前記非水電解液と、大気とが遮断された閉鎖構造を有する、請求の範囲第1項乃至第7項のいずれかに記載の非水電解液型二次電池。
- 正極、負極、及び前記正極と前記負極との間に介在する非水電解液を備える非水電解液型二次電池の非水電解液であって、
2種以上のアニオンを含み、
前記非水電解液型二次電池は、前記正極、前記負極及び前記非水電解液と、少なくとも二酸化炭素及び水と、が遮断された閉鎖構造を有すると共に、放電電圧がリチウム電極基準で3V以下であることを特徴とする非水電解液。 - 前記非水電解液型二次電池が、非水電解液型リチウム二次電池である、請求の範囲第9項に記載の非水電解液。
- 前記非水電解液型二次電池は、前記正極が酸素を活物質とするリチウム-空気電池である、請求の範囲第10に記載の非水電解液。
- 少なくとも、相対的に分子量が大きい第1のアニオンと、相対的に分子量が小さい第2のアニオンを含む、請求の範囲第9項乃至第11項のいずれかに記載の非水電解液。
- 前記第1のアニオンと前記第2のアニオンとのモル比[(第1のアニオン):(第2のアニオン)が、95:5~65:35である、請求の範囲第12項に記載の非水電解液。
- 前記第1のアニオンが、少なくともビストリフルオロメタンスルホニルイミドであり、前記第2のアニオンが、少なくともトリフルオロメタンスルホネートである、請求の範囲第12項又は第13項に記載の非水電解液。
- 前記非水電解液が、アセトニトリル、ジメチルスルホキシド、ジメトキシエタン、N-メチル-N-プロピルピペリジニウムビス(トリフルオロメタンスルホニル)イミド、及びN-メチル-N-プロピルピロリジニウムビス(トリフルオロメタンスルホニル)イミドから選ばれる少なくとも1種の非水溶媒に、電解質塩を溶解したものである、請求の範囲第9項乃至第14項のいずれかに記載の非水電解液。
- 前記非水電解液型二次電池は、前記正極、前記負極及び前記非水電解液と、大気とが遮断された閉鎖構造を有する、請求の範囲第9項乃至第15項のいずれかに記載の非水電解液。
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AU2010346157A AU2010346157B2 (en) | 2010-02-22 | 2010-02-22 | Non-aqueous electrolyte type secondary battery, and non-aqueous electrolyte for non-aqueous electrolyte type secondary battery |
JP2012500443A JP5397533B2 (ja) | 2010-02-22 | 2010-02-22 | 非水電解液型二次電池及び非水電解液型二次電池用非水電解液 |
EP10846128.6A EP2541665B1 (en) | 2010-02-22 | 2010-02-22 | Non-aqueous liquid electrolyte secondary battery |
CN2010800644386A CN102771000A (zh) | 2010-02-22 | 2010-02-22 | 非水电解液型二次电池以及非水电解液型二次电池用非水电解液 |
US13/575,330 US20120315553A1 (en) | 2010-02-22 | 2010-02-22 | Non-aqueous liquid electrolyte secondary battery and non-aqueous liquid electrolyte for non-aqueous liquid electrolyte secondary battery |
PCT/JP2010/052647 WO2011101992A1 (ja) | 2010-02-22 | 2010-02-22 | 非水電解液型二次電池及び非水電解液型二次電池用非水電解液 |
KR1020127021860A KR101376366B1 (ko) | 2010-02-22 | 2010-02-22 | 비수 전해액형 이차 전지 및 비수 전해액형 이차 전지용 비수 전해액 |
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CN102771000A (zh) | 2012-11-07 |
AU2010346157B2 (en) | 2013-06-27 |
KR20120118848A (ko) | 2012-10-29 |
EP2541665A4 (en) | 2014-03-19 |
KR101376366B1 (ko) | 2014-03-20 |
EP2541665A1 (en) | 2013-01-02 |
EP2541665B1 (en) | 2015-11-25 |
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