WO2010047327A1 - 硫化リチウム鉄の製造方法及び硫化リチウム遷移金属の製造方法 - Google Patents
硫化リチウム鉄の製造方法及び硫化リチウム遷移金属の製造方法 Download PDFInfo
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- WO2010047327A1 WO2010047327A1 PCT/JP2009/068061 JP2009068061W WO2010047327A1 WO 2010047327 A1 WO2010047327 A1 WO 2010047327A1 JP 2009068061 W JP2009068061 W JP 2009068061W WO 2010047327 A1 WO2010047327 A1 WO 2010047327A1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Definitions
- the present invention relates to a production method for producing lithium iron sulfide and a lithium transition metal used as a positive electrode active material for a lithium ion secondary battery.
- Lithium ion secondary batteries are often used as power sources for mobile phones and laptop computers.
- oxide-based and sulfide-based materials are known.
- oxide materials include LiCoO 2 , LiMnO 2 , and LiNiO 2, which are currently widely used.
- examples of the sulfide-based material include LiTiS 2 , LiMoS 2 , LiNbS 2 , and Li 2 FeS 2 . Since sulfide-based materials can provide high-capacity secondary batteries, research is being conducted as alternative materials to oxide-based materials.
- lithium iron sulfide Li 2 FeS 2
- FeS ferrous sulfide
- Patent Document 1 discloses a method in which iron sulfide and lithium sulfide are mixed and the mixture is packed in a quartz tube and fired in an argon stream.
- Patent Document 2 discloses a method of reacting lithium sulfide and iron sulfide in a molten salt of lithium halide under an argon atmosphere.
- Patent Document 3 discloses that iron sulfide is reacted with lithium sulfide in a solvent containing molten sulfur.
- Non-Patent Document 1 discloses a method in which a mixture is placed in a carbon crucible, and the crucible is placed in a quartz tube, sealed, and fired. In addition to these, there have been disclosed lithium iron sulfide and a method for producing the same (Patent Documents 4 to 6, Non-Patent Document 1).
- an object of the present invention is to provide a method for producing single-phase lithium iron sulfide (Li 2 FeS 2 ) in XRD analysis.
- Another object of the present invention is to provide a method for producing a single-phase lithium sulfide transition metal in XRD analysis.
- the present inventors have (1) mixing and firing iron sulfide and sulfur, so that the composition is substantially single phase and the composition ratio of Fe / S is molar ratio. (2) When the iron sulfide having the Fe / S molar ratio thus obtained is reacted with lithium sulfide in a specific range, single-phase sulfide is obtained in XRD analysis. The inventors have found that lithium iron (Li 2 FeS 2 ) can be produced, and have completed the present invention.
- iron sulfide (a) and sulfur are mixed to obtain a mixture of iron sulfide (a) and sulfur, and then the mixture of iron sulfide (a) and sulfur is obtained.
- Sulfurized by firing in an inert gas atmosphere and having a substantially single phase in X-ray diffraction analysis and a composition ratio (Fe / S) of iron element to sulfur element in a molar ratio of 0.90 or more and less than 1.00
- the first step of obtaining iron (b), the iron sulfide (b), and lithium sulfide are mixed to obtain a mixture of the iron sulfide (b) and lithium sulfide, and then the iron sulfide (b)
- a second step of obtaining a lithium iron sulfide represented by Li 2 FeS 2 by firing a mixture of lithium sulfide and lithium sulfide under an inert gas atmosphere, and providing a method for producing lithium iron sulfide
- the transition metal sulfide (A) and sulfur are mixed to obtain the mixture of the transition metal sulfide (A) and sulfur, and then the transition metal sulfide (A) ) And sulfur are calcined under an inert gas atmosphere, and the following general formula (1), which is almost a single phase in X-ray diffraction analysis: M (a) S (b) (1) (In the formula, M is one or more of Fe, Ti, V, Cr, Mn, Co, Ni, Cu and Zn.)
- the sulfur-treated product (B) of the transition metal sulfide (A) and lithium sulfide are mixed to obtain a mixture of the sulfur-treated product (B) of the transition metal sulfide (A) and lithium sulfide,
- the present invention provides a method for producing a lithium sulfide transition metal characterized by satisfying the above.
- the present invention can provide a method for producing single-phase lithium iron sulfide (Li 2 FeS 2 ) in XRD analysis. Further, according to the present invention, it is possible to provide a method for producing a single-phase lithium sulfide transition metal in XRD analysis.
- FIG. 2 is an XRD chart of iron sulfide (b1) obtained in the first step of Example 1.
- FIG. 2 is an XRD chart of lithium iron sulfide obtained in the second step of Example 1.
- FIG. 3 is an XRD chart of iron sulfide (b2) obtained in the first step of Example 2.
- FIG. 3 is an XRD chart of lithium iron sulfide obtained in the second step of Example 2.
- FIG. 4 is an XRD chart of lithium iron sulfide obtained in Comparative Example 1.
- 4 is an XRD chart of iron sulfide (c1) used in Comparative Example 2.
- 4 is an XRD chart of lithium iron sulfide obtained in Comparative Example 2.
- iron sulfide (a) and sulfur are mixed to obtain a mixture of iron sulfide (a) and sulfur, and then a mixture of iron sulfide (a) and sulfur is obtained.
- iron sulfide (a) and sulfur are mixed to obtain a mixture of iron sulfide (a) and sulfur, and then iron sulfide (a). And a mixture of sulfur and calcining in an inert gas atmosphere to obtain iron sulfide (b).
- the iron sulfide (a) according to the first step is a substance that is sulfurized by sulfur, it is an iron sulfide having a lower composition ratio of elemental sulfur than the iron sulfide (b) obtained by performing the first step.
- the molar ratio (Fe / S) of the iron element content to the sulfur element content of iron sulfide (a) depends on the composition ratio of the iron element to the sulfur element of iron sulfide (b). However, it is preferably 1.00 or more and 2.00 or less, particularly preferably 1.10 or more and 1.90 or less, and further preferably 1.2 or more and 1.6 or less.
- the molar ratio (Fe / S) of the iron element content to the sulfur element content of the iron sulfide (a) is in the above range, iron sulfide (b) can be easily obtained.
- the molar ratio of the content of iron element to the content of sulfur element in iron sulfide (a) is the iron sulfide (a) obtained by ICP emission spectroscopic analysis, chelate titration method, precipitation weight method or the like.
- the number of moles of each element is calculated from the mass% of the iron element and the sulfur element therein, and the value is obtained from the number of moles of iron element / number of moles of sulfur element.
- Iron sulfide (a) may be a commercially available product or one obtained by a known synthesis method.
- Examples of the method for synthesizing iron sulfide (a) include a method of melting iron powder and sulfur in a crucible. In this method, since a part of sulfur used as a synthetic raw material is volatilized, the molar ratio (Fe / S) of the content of iron element to the content of sulfur element in the obtained iron sulfide (a) is 1.00 or more. It becomes.
- the average particle diameter of iron sulfide (a) is preferably 5 ⁇ m or more and 100 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 75 ⁇ m or less.
- the content of coarse particles having a particle diameter of more than 150 ⁇ m in iron sulfide (a) is preferably 15% by mass or less, particularly preferably 5% by mass or less.
- the content of coarse particles in iron sulfide (a) is within the above range, the reactivity between iron sulfide (a) and sulfur is increased in the first step.
- the content of coarse particles is a value determined by laser scattering particle size distribution measurement
- the average particle size is an average particle size (D50) determined by laser scattering particle size distribution measurement.
- the sulfur related to the first step is not particularly limited and may be a commercially available product.
- iron sulfide (a) and sulfur are mixed to obtain a mixture of iron sulfide (a) and sulfur. Since sulfur is easily volatilized, a desired composition ratio of Fe / S is obtained. It is desirable to charge sulfur in an excess state than the theoretical amount for obtaining the iron sulfide (b). At this time, iron sulfide (a) so that the molar ratio (Fe / S) of the content of iron element to the content of elemental sulfur in the mixture of iron sulfide (a) and sulfur is 0.50 or more and less than 1.00.
- the molar ratio (Fe / S) of the content of iron element to the content of elemental sulfur in the mixture of iron sulfide (a) and sulfur is ICP emission spectroscopic analysis, chelate titration method, precipitation weight. It is a value calculated from the number of moles of sulfur element contained in iron sulfide (a) and the number of moles of sulfur element obtained from the analysis results of the method and the like, and the number of moles of sulfur mixed with iron sulfide (a).
- the method of mixing iron sulfide (a) and sulfur is not particularly limited, and examples thereof include a method of mixing using a coffee mill, a bead mill, a Henschel mixer, a cutter mixer, or the like.
- the inert gas in the first step examples include argon gas, helium gas, nitrogen gas, and the like. These inert gases are preferably higher in purity in order to prevent impurities from being mixed into the product, and in order to avoid contact with moisture, the dew point is preferably ⁇ 50 ° C. or lower, and ⁇ 60 It is particularly preferable that the temperature is not higher than ° C.
- the method of introducing the inert gas into the reaction system is not particularly limited as long as the reaction system is filled with an inert gas atmosphere, but a method of purging the inert gas, introducing a certain amount of inert gas. There is a way to continue.
- the firing temperature when firing the mixture of iron sulfide (a) and sulfur is preferably 500 ° C. or higher and 1200 ° C. or lower, particularly preferably 700 ° C. or higher and 1000 ° C. or lower.
- the iron sulfide (b) is easily obtained when the firing temperature when firing the mixture of iron sulfide (a) and sulfur is in the above range.
- the firing time for firing the mixture of iron sulfide (a) and sulfur is preferably 1 hour to 24 hours, particularly preferably 2 hours to 12 hours.
- the iron sulfide (b) is easily obtained when the firing time when firing the mixture of iron sulfide (a) and sulfur is in the above range.
- iron sulfide (b) is obtained.
- Iron sulfide (b) is substantially single phase in XRD analysis and the composition ratio (Fe / S) of iron element to sulfur element is The molar ratio is 0.90 or more and less than 1.00.
- the iron sulfide (b) is substantially single-phase Fe 0.96 S.
- a peak pattern of Fe 0.96 S is obtained. It is. At this time, it is preferable that the iron sulfide (b) has only a peak derived from Fe 0.96 S in the XRD analysis, but it may be substantially single-phase Fe 0.96 S.
- the almost single-phase iron sulfide (b) in the XRD analysis means that the iron sulfide (b) exists as a single phase in the XRD analysis, or the single-phase rate defined above is 95. % Or more.
- the iron sulfide (b) is substantially single-phase Fe 0.96 S
- other iron sulfide (b) for example, substantially single-phase Fe 0.94 S is used.
- the iron sulfide (b) has a peak pattern of Fe 0.94 S when XRD analysis is performed.
- the iron sulfide (b) has only a peak derived from Fe 0.94 S in the XRD analysis, but it may be substantially single-phase Fe 0.94 S. There may be peaks derived from others to the extent that the effect is not impaired.
- the composition ratio (Fe / S) of iron element to sulfur element of iron sulfide (b) is 0.90 or more and less than 1.00, preferably 0.91 or more and 0.99 or less, particularly preferably 0. It is 0.93 or more and 0.97 or less, More preferably, it is 0.94 or more and 0.96 or less, More preferably, it is 0.94 or 0.96.
- iron sulfide (b) examples include substantially single phase Fe 0.96 S, almost single phase Fe 0.94 S, almost single phase Fe 0.95 S, and almost single phase Fe 0. .975 S, almost single phase Fe 0.985 S, almost single phase Fe 0.91 S, almost single phase Fe 0.95 S 1.05 , almost single phase Fe 9 S 10, etc. Is mentioned.
- the iron sulfide (b) is almost single phase in the X-ray diffraction analysis and the composition ratio (Fe / S) of the iron element to the sulfur element is in the above range, so that it is represented by single phase Li 2 FeS 2 . Lithium iron sulfide is obtained.
- iron sulfide (b) is substantially single phase in X-ray diffraction analysis and has a composition of Fe 0.96 S, or is almost single phase in X-ray diffraction analysis and Fe 0.94. It is preferably any of iron sulfides having a composition of S.
- the first step is a step of sulfiding the iron sulfide (a) to increase the composition ratio of the sulfur element to the iron element and converting it to single-phase iron sulfide.
- the amount of sulfur required for the reaction with iron sulfide (a) is the iron to the sulfur element of iron sulfide (b) after baking. It depends on how many elemental composition ratios are used, how many molar ratios of the content of iron element to the content of sulfur element in iron sulfide (a) are used.
- the first step is performed by appropriately selecting the mixing amount, firing temperature, firing time and the like.
- iron sulfide ( b) by appropriately selecting the molar ratio of the content of iron element to the content of elemental sulfur in iron sulfide (a), the amount of sulfur mixed, the firing temperature, the firing time, etc., iron sulfide ( b) can be obtained.
- the average particle diameter of iron sulfide (b) is preferably 5 ⁇ m or more and 150 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 100 ⁇ m or less. When the average particle diameter of iron sulfide (b) is within the above range, the reactivity between iron sulfide (b) and lithium sulfide is increased.
- the content of coarse particles having a particle diameter of more than 100 ⁇ m in iron sulfide (b) is preferably 15% by mass or less, particularly preferably 5% by mass or less.
- the content of coarse particles in iron sulfide (b) is in the above range, the reactivity between iron sulfide (b) and lithium sulfide according to the second step is increased.
- the content of coarse particles is a value determined by laser scattering particle size distribution measurement
- the average particle size is an average particle size (D50) determined by laser scattering particle size distribution measurement.
- iron sulfide (b) and lithium sulfide are mixed to obtain a mixture of iron sulfide (b) and lithium sulfide, and then iron sulfide (b ) And a mixture of lithium sulfide is fired under an inert gas atmosphere to obtain lithium iron sulfide represented by Li 2 FeS 2 .
- the molar ratio of the lithium element content to the sulfur element content in the lithium sulfide according to the second step is 1.90 to 2.10, preferably 1.95 to 2.05. Since the molar ratio of the lithium element to the sulfur element in the lithium sulfide according to the second step is within the above range, single-phase lithium iron sulfide (Li 2 FeS 2 ) is easily obtained.
- the molar ratio of lithium element to sulfur element in lithium sulfide in the second step is the mass of lithium element and sulfur element in lithium sulfide obtained by ICP emission spectroscopy, neutralization titration method, precipitation weight method, etc.
- the number of moles of each element is calculated from%, and is a value determined by the number of moles of lithium element / number of moles of sulfur element.
- the maximum particle diameter of the lithium sulfide according to the second step is preferably 200 ⁇ m or less.
- the content of coarse particles having a particle diameter exceeding 200 ⁇ m in the lithium sulfide according to the second step is preferably 10% by mass or less, particularly preferably 5% by mass or less.
- the average particle diameter of the lithium sulfide according to the second step is preferably 20 ⁇ m or more and 100 ⁇ m or less, and particularly preferably 40 ⁇ m or more and 80 ⁇ m or less.
- the average particle diameter of lithium sulfide in the second step is within the above range, the reactivity between iron sulfide (b) and lithium sulfide in the second step is increased.
- iron sulfide (b) and lithium sulfide are mixed to obtain a mixture of iron sulfide (b) and lithium sulfide.
- the mixing ratio of iron sulfide (b) and lithium sulfide is preferably 0.9 mol or more and 1.1 mol or less of lithium sulfide with respect to 1 mol of iron sulfide (b). It is particularly preferably 94 mol or more and 1.00 mol or less.
- the mixing ratio of iron sulfide (b) and lithium sulfide in the second step is in the above range, single-phase lithium iron sulfide (Li 2 FeS 2 ) is easily obtained.
- the mixing method for mixing iron sulfide (b) and lithium sulfide is not particularly limited as long as it is a mixing method capable of uniformly mixing iron sulfide (b) and lithium sulfide. It is preferable to carry out by chemical treatment because it is easy to obtain single-phase lithium iron sulfide (Li 2 FeS 2 ).
- the mixing in the second step is preferably performed in an inert gas atmosphere because lithium sulfide is unstable in the air.
- the mixing method by mechanochemical treatment according to the second step is a mixing method in which mechanical energy such as shear force, collision force or centrifugal force is added to the powder to be mixed.
- a pulverizing apparatus such as a bead mill, a planetary ball mill, a vibration mill, or the like, that is, a granular medium is present in the powder to be mixed.
- Equipment that can flow at high speed. And by making them flow at high speed, mechanical energy is added to the powder to be mixed by the granular medium.
- the gravitational acceleration applied to the mixture of iron sulfide (b) and lithium sulfide is 5G to 40G, preferably 8G to 30G.
- the particle diameter of the granular medium is 1 mm or more and 20 mm or less, preferably 5 mm or more and 15 mm or less, and the filling ratio of the granular medium is 10% or more and 50% or less, preferably 20% or more and 40%. It is as follows.
- a mixture of iron sulfide (b) and lithium sulfide is then fired under an inert gas atmosphere to obtain lithium iron sulfide represented by Li 2 FeS 2 .
- the inert gas in the second step examples include argon gas, helium gas, nitrogen gas, and the like. These inert gases are preferably higher in purity in order to prevent impurities from being mixed into the product, and in order to avoid contact with moisture, the dew point is preferably ⁇ 50 ° C. or lower, and ⁇ 60 It is particularly preferable that the temperature is not higher than ° C.
- the method of introducing the inert gas into the reaction system is not particularly limited as long as the reaction system is filled with an inert gas atmosphere, but a method of purging the inert gas, introducing a certain amount of inert gas. There is a way to continue.
- the firing temperature when firing the mixture of iron sulfide (b) and lithium sulfide is preferably 450 ° C. or higher and 1500 ° C. or lower, particularly preferably 600 ° C. or higher and 1200 ° C. or lower.
- the firing temperature when firing the mixture of iron sulfide (b) and lithium sulfide is within the above range, single-phase lithium iron sulfide (Li 2 FeS 2 ) is easily obtained.
- the firing time when firing the mixture of iron sulfide (b) and lithium sulfide is preferably 1 hour to 24 hours, particularly preferably 1 hour to 18 hours.
- lithium iron sulfide (Li 2 FeS 2 ) is easily obtained.
- the lithium iron sulfide obtained by performing the method for producing lithium iron sulfide of the present invention is a lithium iron sulfide represented by single-phase Li 2 FeS 2 in which no heterogeneous peak is observed in the XRD analysis.
- the lithium iron sulfide obtained by carrying out the method for producing lithium iron sulfide of the present invention can be pulverized and classified as necessary.
- the pulverization performed as necessary is not particularly limited, and examples thereof include known pulverization methods using a mortar, a rotary mill, a coffee mill, and the like. Moreover, it does not restrict
- the average particle size of lithium iron sulfide to be pulverized and classified as required is preferably 1 ⁇ m or more and 100 ⁇ m or less, particularly preferably 10 ⁇ m or more and 90 ⁇ m or less, although it depends on the purpose of use.
- Lithium iron sulfide obtained by carrying out the method for producing lithium iron sulfide of the present invention is highly crystalline Li 2 FeS 2 having no heterogeneous phase, and therefore is suitably used as a positive electrode material for lithium ion secondary batteries.
- iron sulfide since the sulfur component is easily volatilized during the production of iron sulfide, it usually contains metal Fe or iron sulfide having a different phase, and the molar amount of iron element relative to the content of sulfur element. The ratio is greater than 1. Therefore, by performing the first step according to the method for producing lithium iron sulfide of the present invention, the metal Fe or iron sulfide contained in the iron sulfide is sulfided to be substantially single-phase and iron against the sulfur element. Iron sulfide having an elemental composition ratio (Fe / S) in a molar ratio of 0.90 or more and less than 1.00, that is, iron sulfide (b) is obtained.
- Fe / S elemental composition ratio
- the iron sulfide to be reacted with lithium sulfide is used as iron sulfide (b), and substantially single-phase iron sulfide is used, and iron with respect to elemental sulfur.
- the target lithium iron sulfide Li 2
- the target lithium iron sulfide Li 2
- single-phase lithium iron sulfide Li 2 FeS 2
- the transition metal element is iron
- a transition metal sulfide having such a composition ratio is obtained, and then the obtained transition metal sulfide and lithium sulfide are reacted to obtain a single-phase lithium sulfide transition metal. Can be obtained.
- the transition metal sulfide (A) and sulfur are mixed to obtain a mixture of the transition metal sulfide (A) and sulfur, and then the transition The mixture of metal sulfide (A) and sulfur is calcined under an inert gas atmosphere, and the following general formula (1), which is almost a single phase in X-ray diffraction analysis: M (a) S (b) (1) (In the formula, M is one or more of Fe, Ti, V, Cr, Mn, Co, Ni, Cu and Zn.)
- the sulfur-treated product (B) of the transition metal sulfide (A) and lithium sulfide are mixed to obtain a mixture of the sulfur-treated product (B) of the transition metal sulfide (A) and lithium sulfide,
- the method for producing a transition metal lithium sulfide of the present invention differs from the method for producing lithium iron sulfide of the present invention in that the transition metal element is different, and for that reason, depending on the type of transition metal element, the transition metal valence and the transition to the sulfur element This is the same except that the composition ratios of the metal elements are different.
- x is 0.5 or more and 4.0 or less, preferably 1.0 or more and 3.0 or less
- y is 0.5 or more and 4.0 or less, preferably 1.0. It is 3.0 or less.
- the above formula (3) is obtained from the theoretical amount of sulfur necessary for reacting with lithium sulfide to obtain the target lithium sulfide transition metal. It shows that the composition ratio of sulfur element to transition metal element in transition metal sulfide to be reacted with lithium is increased.
- ICP emission spectroscopic analysis Using an ICP emission spectroscopic analyzer (LibertySeries II, manufactured by Varian, Inc.), measurement was performed by ICP emission spectroscopic analysis to determine the mass% of each element, and based on this, the molar ratio was calculated.
- the particle size distribution was measured by a laser scattering particle size distribution measuring method using a particle size distribution measuring device (Microtrack X-100, manufactured by Nikkiso Co., Ltd.).
- Example 1 The molar ratio of the content of iron element to the content of sulfur element by ICP emission spectroscopic analysis (Fe / S) is 1.53, the maximum particle size is 150 ⁇ m (content of coarse particles exceeding 150 ⁇ m is 0% by mass), average 22 g of iron sulfide (a1) (manufactured by Hosoi Chemical Co., Ltd.) having a particle size (D50) of 10 ⁇ m and 3.76 g of sulfur (manufactured by Kanto Chemical Co., Ltd.) were mixed using a coffee mill. At this time, the Fe / S molar ratio in the mixture was 0.94 (calculated from the results of ICP emission spectroscopic analysis and the amount of sulfur mixed).
- this mixture is put in an alumina container, which is set in a quartz horizontal tubular furnace, and is baked at 950 ° C. for 3 hours while flowing nitrogen at a flow rate of 0.1 L / min from the vent of the tubular furnace. did.
- the mixture was cooled to room temperature to obtain iron sulfide (b1) as a fired product.
- the obtained iron sulfide (b1) was subjected to X-ray diffraction analysis, and the X-ray diffraction chart is shown in FIG. From the obtained X-ray diffraction chart, it was confirmed to be a single phase of Fe 0.96 S. In the X-ray diffraction chart shown in FIG. 1, no peak derived from a substance other than Fe 0.96 S was observed.
- the average particle diameter of iron sulfide (b1) was 50 ⁇ m, and the content of coarse particles exceeding 100 ⁇ m was 2% by mass.
- this mixture is put in an alumina container, which is set in a quartz horizontal tubular furnace, and baked at 950 ° C. for 12 hours while flowing nitrogen at a flow rate of 0.1 L / min from the vent of the tubular furnace. did.
- the mixture was cooled to room temperature to obtain lithium iron sulfide as a fired product.
- the obtained lithium iron sulfide was subjected to X-ray diffraction analysis, and the X-ray diffraction chart is shown in FIG. From the obtained X-ray diffraction chart, it was confirmed to be a single phase of Li 2 FeS 2 . Incidentally, the X-ray diffraction chart shown in FIG.
- Example 2 (First step) Instead of 3.76 g of sulfur (manufactured by Kanto Chemical Co., Inc.), 4.46 g of sulfur (manufactured by Kanto Chemical Co., Ltd.), the Fe / S molar ratio in the mixture was 0.87 (result of ICP emission spectroscopic analysis and amount of sulfur mixed)
- the calculation was performed in the same manner as in Example 1 except that the iron sulfide (b2) as a fired product was obtained.
- the obtained iron sulfide (b2) was subjected to X-ray diffraction analysis, and the X-ray diffraction chart thereof is shown in FIG.
- Li was 10.4% by mass
- Fe was 41.8% by mass
- S was 47.8% by mass.
- the Fe / Li molar ratio was 0.50
- the Fe / S molar ratio was 0.50. Also from this result, it was confirmed that it was a single phase of Li 2 FeS 2 .
- the obtained lithium iron sulfide was pulverized with a mortar and classified with a sieve having an opening of 100 ⁇ m to obtain Li 2 FeS 2 having an average particle diameter of 50 ⁇ m.
- a mechanochemical treatment was performed for 1 hour under an atmosphere to obtain a mixture.
- this mixture is put in an alumina container, which is set in a quartz horizontal tubular furnace, and baked at 950 ° C. for 12 hours while flowing nitrogen at a flow rate of 0.1 L / min from the vent of the tubular furnace. did.
- the mixture was cooled to room temperature to obtain lithium iron sulfide as a fired product.
- the obtained lithium iron sulfide was subjected to X-ray diffraction analysis, and the X-ray diffraction chart is shown in FIG. From the obtained X-ray diffraction chart, a peak of Li 3 Fe 2 S 4 was confirmed in addition to Li 2 FeS 2 .
- the obtained lithium iron sulfide was subjected to X-ray diffraction analysis, and the X-ray diffraction chart is shown in FIG. From the resulting X-ray diffraction chart, the peak of Li 2 S was confirmed in addition to Li 2 FeS 2. Further, ICP emission spectroscopic analysis was performed, and as a result, Li was 11.1% by mass, Fe was 45.1% by mass, and S was 43.8% by mass. When the molar ratio was calculated from this result, the Fe / Li molar ratio was 0.51, and the Fe / S molar ratio was 0.59. Also from this result, it was confirmed that substances other than Li 2 FeS 2 were present.
- Li 2 FeS 2 suitably used as a positive electrode material of a lithium ion secondary battery is produced at low cost. be able to.
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Abstract
Description
M(a)S(b) (1)
(式中、Mは、Fe、Ti、V、Cr、Mn、Co、Ni、Cu及びZnのうちの1種又は2種以上である。)
で表わされる遷移金属硫化物(A)の硫黄処理物(B)を得る第一工程と、
該遷移金属硫化物(A)の硫黄処理物(B)と、硫化リチウムと、を混合して、該遷移金属硫化物(A)の硫黄処理物(B)と硫化リチウムとの混合物を得、次いで、該遷移金属硫化物(A)の硫黄処理物(B)と硫化リチウムとの混合物を、不活性ガス雰囲気下で焼成して、下記一般式(2):
LixMSy (2)
(式中、Mは、Fe、Ti、V、Cr、Mn、Co、Ni、Cu及びZnのうちの1種又は2種以上である。xは0.5以上4.0以下であり、yは0.5以上4.0以下である。)
で表わされる硫化リチウム遷移金属を得る第二工程を有し、
下記式(3):
a/b<1/(y-(x/2)) (3)
を満たすこと
を特徴とする硫化リチウム遷移金属の製造方法を提供するものである。
本発明の硫化リチウム鉄の製造方法は、硫化鉄(a)と、硫黄と、を混合して、硫化鉄(a)及び硫黄の混合物を得、次いで、硫化鉄(a)及び硫黄の混合物を、不活性ガス雰囲気下で焼成して、X線回折分析においてほぼ単一相であり且つ硫黄元素に対する鉄元素の組成比(Fe/S)がモル比で0.90以上1.00未満である硫化鉄(b)を得る第一工程と、
硫化鉄(b)と、硫化リチウムと、を混合して、硫化鉄(b)及び硫化リチウムの混合物を得、次いで、硫化鉄(b)及び硫化リチウムの混合物を、不活性ガス雰囲気下で焼成して、Li2FeS2で表わされる硫化リチウム鉄を得る第二工程と
を有する硫化リチウム鉄の製造方法である。
単一相率(%)=(P1/(P1+P2))×100
(式中、P1は、硫化鉄(b)のXRDチャートにおいて、Fe0.96Sに由来するピークのうち、最もピーク強度が高いピークのピーク強度であり、P2は、硫化鉄(b)のXRDチャートにおいて、Fe0.96Sに由来するピーク以外のピークのうち、最もピーク強度が高いピークのピーク強度を指す。)
に示す単一相率が、95%以上であればよい。即ち、本発明においてXRD分析でほぼ単一相の硫化鉄(b)とは、XRD分析において、硫化鉄(b)が単一相として存在するか、又は前記で定義した単一相率が95%以上であることを示す。
単一相率(%)=(P1/(P1+P2))×100
(式中、P1は、硫化鉄(b)のXRDチャートにおいて、Fe0.94Sに由来するピークのうち、最もピーク強度が高いピークのピーク強度であり、P2は、硫化鉄(b)のXRDチャートにおいて、Fe0.94Sに由来するピーク以外のピークのうち、最もピーク強度が高いピークのピーク強度を指す。)
に示す単一相率が、95%以上であればよい。
そして、本発明の硫化リチウム鉄の製造方法に係る第二工程で、硫化リチウムと反応させる硫化鉄を、硫化鉄(b)として、ほぼ単一相の硫化鉄を用い、且つ、硫黄元素に対する鉄元素の組成比(Fe/S)をモル比で0.90以上1.00未満とのように、硫化鉄中の硫黄の組成比を高くすることで、目的物である硫化リチウム鉄(Li2FeS2)を得るために必要な理論量よりも硫黄の量を多くし、その結果、単一相の硫化リチウム鉄(Li2FeS2)を得ることができる。
M(a)S(b) (1)
(式中、Mは、Fe、Ti、V、Cr、Mn、Co、Ni、Cu及びZnのうちの1種又は2種以上である。)
で表わされる遷移金属硫化物(A)の硫黄処理物(B)を得る第一工程と、
該遷移金属硫化物(A)の硫黄処理物(B)と、硫化リチウムと、を混合して、該遷移金属硫化物(A)の硫黄処理物(B)と硫化リチウムとの混合物を得、次いで、該遷移金属硫化物(A)の硫黄処理物(B)と硫化リチウムとの混合物を、不活性ガス雰囲気下で焼成して、下記一般式(2):
LixMSy (2)
(式中、Mは、Fe、Ti、V、Cr、Mn、Co、Ni、Cu及びZnのうちの1種又は2種以上である。xは0.5以上4.0以下であり、yは0.5以上4.0以下である。)
で表わされる硫化リチウム遷移金属を得る第二工程を有し、
下記式(3):
a/b<1/(y-(x/2)) (3)
を満たす硫化リチウム遷移金属の製造方法である。
前記一般式(2)中、xは、0.5以上4.0以下、好ましくは1.0以上3.0以下であり、yは、0.5以上4.0以下、好ましくは1.0以上3.0以下である。
ICP発光分光分析装置(バリアン社製、LibertySeriesII)を用いて、ICP発光分光分析法により測定し、各元素の質量%を求め、それに基づいて、モル比を計算した。
粒度分布測定装置(日機装社製、マイクロトラックX-100)を用いて、レーザー散乱粒度分布測定法により求めた。
X線回折装置(ブルカー社製、D8 ADVANCE)を用いて、X線回折分析法により求めた。
(第一工程)
ICP発光分光分析による硫黄元素の含有量に対する鉄元素の含有量のモル比(Fe/S)が1.53、最大粒子径が150μm(150μmを超える粗粒子の含有量が0質量%)、平均粒子径(D50)が10μmの硫化鉄(a1)(細井化学工業社製)22gと、硫黄(関東化学社製)3.76gとを、コーヒーミルにより混合した。このとき、混合物中のFe/Sモル比は0.94(ICP発光分光分析の結果及び硫黄の混合量から算出)であった。
次いで、この混合物を、アルミナ製容器に入れ、これを石英製の横型管状炉にセットして、管状炉の通気口より窒素を0.1L/分の流量で流しながら、950℃で3時間焼成した。焼成後、室温まで冷却し、焼成物である硫化鉄(b1)を得た。得られた硫化鉄(b1)を、X線回折分析し、そのX線回折チャートを図1に示す。得られたX線回折チャートからは、Fe0.96Sの単一相であることが確認された。なお、図1に示すX線回折チャートには、Fe0.96S以外の物質に由来するピークは見られなかった。なお、硫化鉄(b1)の平均粒子径は50μmで、100μmを超える粗粒子の含有量は2質量%であった。
上記のようにして得られた硫化鉄(b1)3.66gと、ICP発光分光分析によるLi/Sのモル比が2.00であり、平均粒子径70μm、200μmを超える粗粒子の含有量が0質量%である硫化リチウム(日本化学工業社製)1.84gとを、遊星ボールミル(フリッチュジャパン社製、P-7)に投入し、以下の条件で、アルゴン雰囲気下で1時間メカノケミカル処理して、混合物を得た。
次いで、この混合物を、アルミナ製容器に入れ、これを石英製の横型管状炉にセットして、管状炉の通気口より窒素を0.1L/分の流量で流しながら、950℃で12時間焼成した。焼成後、室温まで冷却し、焼成物である硫化リチウム鉄を得た。得られた硫化リチウム鉄を、X線回折分析し、そのX線回折チャートを図2に示す。得られたX線回折チャートからは、Li2FeS2の単一相であることが確認された。なお、図2に示すX線回折チャートには、Li2FeS2以外の物質に由来するピークは見られなかった。また、ICP発光分光分析を行ったところ、Liが10.5質量%、Feが41.7質量%、Sが47.8質量%との結果を得た。この結果からモル比を算出したところ、Fe/Liモル比が0.50、Fe/Sモル比が0.50となった。この結果からも、Li2FeS2の単一相であることが確認された。得られた硫化リチウム鉄を乳鉢により粉砕し、目開き100μmの篩により分級して、平均粒子径50μmのLi2FeS2を得た。
粒状媒体:平均粒子径10mm、充填率30%
回転数:400rpm
重力加速度:10.9G
(第一工程)
硫黄(関東化学社製)3.76gに代えて、硫黄(関東化学社製)4.46gとして、混合物中のFe/Sモル比を0.87(ICP発光分光分析の結果及び硫黄の混合量から算出)とすること以外は、実施例1と同様に行い、焼成物である硫化鉄(b2)を得た。得られた硫化鉄(b2)を、X線回折分析し、そのX線回折チャートを図3に示す。得られたX線回折チャートからは、Fe0.94Sの単一相であることが確認された。なお、図3に示すX線回折チャートには、Fe0.94S以外の物質に由来するピークは見られなかった。なお、硫化鉄(b2)の平均粒子径は50μmで、100μmを超える粗粒子の含有量は1質量%であった。
硫化鉄(b1)3.66gに代えて、硫化鉄(b2)4.46gとすること以外は、実施例1と同様の方法で行い、焼成物である硫化リチウム鉄を得た。得られた硫化リチウム鉄を、X線回折分析し、そのX線回折チャートを図4に示す。得られたX線回折チャートからは、Li2FeS2の単一相であることが確認された。なお、図4に示すX線回折チャートには、Li2FeS2以外の物質に由来するピークは見られなかった。また、ICP発光分光分析を行ったところ、Liが10.4質量%、Feが41.8質量%、Sが47.8質量%との結果を得た。この結果からモル比を算出したところ、Fe/Liモル比が0.50、Fe/Sモル比が0.50となった。この結果からも、Li2FeS2の単一相であることが確認された。得られた硫化リチウム鉄を乳鉢により粉砕し、目開き100μmの篩により分級して、平均粒子径50μmのLi2FeS2を得た。
ICP発光分光分析による硫黄元素の含有量に対する鉄元素の含有量のモル比(Fe/S)が1.43、最大粒子径が320μm(150μmを超える粗粒子の含有量は8質量%)、平均粒子径(D50)が60μmの硫化鉄(添川化学工業社製)5.27gと、ICP発光分光分析によるLi/Sのモル比が2.00であり、平均粒子径70μm、200μmを超える粗粒子の含有量が0質量%である硫化リチウム(日本化学工業社製)2.76gとを、遊星ボールミル(フリッチュジャパン社製、P-7)に投入し、実施例1と同様の条件で、アルゴン雰囲気下で1時間メカノケミカル処理して、混合物を得た。
次いで、この混合物を、アルミナ製容器に入れ、これを石英製の横型管状炉にセットして、管状炉の通気口より窒素を0.1L/分の流量で流しながら、950℃で12時間焼成した。焼成後、室温まで冷却し、焼成物である硫化リチウム鉄を得た。得られた硫化リチウム鉄を、X線回折分析し、そのX線回折チャートを図5に示す。得られたX線回折チャートからは、Li2FeS2の他にLi3Fe2S4のピークが確認された。また、ICP発光分光分析を行ったところ、Liが10.4質量%、Feが40.4質量%、Sが49.2質量%との結果を得た。この結果からモル比を算出したところ、Fe/Liモル比が0.48、Fe/Sモル比が0.47となった。この結果からも、Li2FeS2以外の物質が存在していることが確認された。
ICP発光分光分析による硫黄元素の含有量に対する鉄元素の含有量のモル比(Fe/S)が0.97、最大粒子径が200μm(150μmを超える粗粒子の含有量は1質量%)、平均粒子径(D50)が10μmの硫化鉄(c1)(添川化学工業社製)5.27gと、ICP発光分光分析によるLi/Sのモル比が2.00であり、平均粒子径70μm、200μmを超える粗粒子の含有量が0質量%である硫化リチウム(日本化学工業社製)2.76gとを、遊星ボールミル(フリッチュジャパン社製、P-7)に投入し、実施例1と同様の条件で、アルゴン雰囲気下で1時間メカノケミカル処理して、混合物を得た。なお、ここで用いた硫化鉄(c1)をX線回折分析した結果を図6に示すが、そのX線回折チャートからは、Feの異相をもつことが確認された。
次いで、この混合物を、アルミナ製容器に入れ、これを石英製の横型管状炉にセットして、管状炉の通気口より窒素を0.1L/分の流量で流しながら、950℃で12時間焼成した。焼成後、室温まで冷却し、焼成物である硫化リチウム鉄を得た。得られた硫化リチウム鉄を、X線回折分析し、そのX線回折チャートを図7に示す。得られたX線回折チャートからは、Li2FeS2の他にLi2Sのピークが確認された。また、ICP発光分光分析を行ったところ、Liが11.1質量%、Feが45.1質量%、Sが43.8質量%との結果を得た。この結果からモル比を算出したところ、Fe/Liモル比が0.51、Fe/Sモル比が0.59となった。この結果からも、Li2FeS2以外の物質が存在していることが確認された。
Claims (8)
- 硫化鉄(a)と、硫黄と、を混合して、硫化鉄(a)及び硫黄の混合物を得、次いで、該硫化鉄(a)及び硫黄の混合物を、不活性ガス雰囲気下で焼成して、X線回折分析においてほぼ単一相であり且つ硫黄元素に対する鉄元素の組成比(Fe/S)がモル比で0.90以上1.00未満である硫化鉄(b)を得る第一工程と、
該硫化鉄(b)と、硫化リチウムと、を混合して、該硫化鉄(b)及び硫化リチウムの混合物を得、次いで、該硫化鉄(b)及び硫化リチウムの混合物を、不活性ガス雰囲気下で焼成して、Li2FeS2で表わされる硫化リチウム鉄を得る第二工程と
を有することを特徴とする硫化リチウム鉄の製造方法。 - 前記硫化鉄(a)の硫黄元素の含有量に対する鉄元素の含有量のモル比(Fe/S)が1.00以上2.00以下であることを特徴とする請求項1記載の硫化リチウム鉄の製造方法。
- 前記第一工程において、前記硫化鉄(a)及び硫黄の混合物中の硫黄元素の含有量に対する鉄元素の含有量のモル比(Fe/S)が0.50以上1.00未満となるように、前記硫化鉄(a)と硫黄とを混合することを特徴とする請求項1又は2いずれか1項記載の硫化リチウム鉄の製造方法。
- 前記第一工程において、前記硫化鉄(a)及び硫黄の混合物の焼成を、500~1200℃で行うことを特徴とする請求項1~3いずれか1項記載の硫化リチウム鉄の製造方法。
- 前記硫化鉄(b)が、X線回折分析においてほぼ単一相であり且つFe0.96Sの組成を有することを特徴とする請求項1~4いずれか1項記載の硫化リチウム鉄の製造方法。
- 前記硫化鉄(b)が、X線回折分析においてほぼ単一相であり且つFe0.94Sの組成を有することを特徴とする請求項1~4いずれか1項記載の硫化リチウム鉄の製造方法。
- 前記第二工程において、前記硫化鉄(b)と硫化リチウムとの混合を、メカノケミカル処理により行うことを特徴とする請求項1~6いずれか1項記載の硫化リチウム鉄の製造方法。
- 遷移金属硫化物(A)と、硫黄と、を混合して、該遷移金属硫化物(A)及び硫黄の混合物を得、次いで、該遷移金属硫化物(A)及び硫黄の混合物を、不活性ガス雰囲気下で焼成して、X線回折分析においてほぼ単一相である下記一般式(1):
M(a)S(b) (1)
(式中、Mは、Fe、Ti、V、Cr、Mn、Co、Ni、Cu及びZnのうちの1種又は2種以上である。)
で表わされる遷移金属硫化物(A)の硫黄処理物(B)を得る第一工程と、
該遷移金属硫化物(A)の硫黄処理物(B)と、硫化リチウムと、を混合して、該遷移金属硫化物(A)の硫黄処理物(B)と硫化リチウムとの混合物を得、次いで、該遷移金属硫化物(A)の硫黄処理物(B)と硫化リチウムとの混合物を、不活性ガス雰囲気下で焼成して、下記一般式(2):
LixMSy (2)
(式中、Mは、Fe、Ti、V、Cr、Mn、Co、Ni、Cu及びZnのうちの1種又は2種以上である。xは0.5以上4.0以下であり、yは0.5以上4.0以下である。)
で表わされる硫化リチウム遷移金属を得る第二工程を有し、
下記式(3):
a/b<1/(y-(x/2)) (3)
を満たすこと
を特徴とする硫化リチウム遷移金属の製造方法。
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JP2017084812A (ja) * | 2011-05-24 | 2017-05-18 | シオン・パワー・コーポレーション | 電気化学電池および当該電気化学電池を含むバッテリー |
US10297827B2 (en) | 2004-01-06 | 2019-05-21 | Sion Power Corporation | Electrochemical cell, components thereof, and methods of making and using same |
US10468721B2 (en) | 2012-12-17 | 2019-11-05 | Sion Power Corporation | Lithium-ion electrochemical cell, components thereof, and methods of making and using same |
US10854921B2 (en) | 2011-09-07 | 2020-12-01 | Sion Power Corporation | Electrochemical cell including electrolyte having insoluble nitrogen-containing material and battery including the cell |
US10985403B2 (en) | 2004-01-06 | 2021-04-20 | Sion Power Corporation | Electrolytes for lithium sulfur cells |
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GB2464455B (en) * | 2008-10-14 | 2010-09-15 | Iti Scotland Ltd | Lithium-containing transition metal sulfide compounds |
EP2609646A1 (en) | 2010-08-24 | 2013-07-03 | Basf Se | Electrolyte materials for use in electrochemical cells |
JP6356020B2 (ja) * | 2014-09-11 | 2018-07-11 | 古河機械金属株式会社 | リチウムイオン電池用正極活物質、正極材料、正極、およびリチウムイオン電池 |
JP6723707B2 (ja) * | 2015-09-08 | 2020-07-15 | 古河機械金属株式会社 | リチウムイオン電池用正極活物質、正極材料、正極、およびリチウムイオン電池 |
JP6681211B2 (ja) * | 2016-02-09 | 2020-04-15 | 古河機械金属株式会社 | 正極活物質の製造方法、正極材料の製造方法、正極の製造方法およびリチウムイオン電池の製造方法 |
CN110589776B (zh) * | 2019-10-28 | 2022-11-08 | 南昌航空大学 | 一种机械球磨合成硫化镁的方法 |
CN113299895B (zh) * | 2021-05-24 | 2022-06-17 | 武汉纺织大学 | 一种饼状硫基化合物复合材料的可控合成及储能应用 |
WO2024057991A1 (ja) * | 2022-09-15 | 2024-03-21 | 株式会社Adeka | 硫黄含有材料の製造方法 |
US20240109786A1 (en) * | 2022-09-19 | 2024-04-04 | California Institute Of Technology | LITHIUM-RICH ALUMINUM IRON SULFIDE Li-ION BATTERY CATHODES |
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- 2009-10-20 CN CN2009801425398A patent/CN102196998A/zh active Pending
- 2009-10-20 KR KR1020117009176A patent/KR20110074754A/ko not_active Application Discontinuation
- 2009-10-20 US US13/125,164 patent/US20110193015A1/en not_active Abandoned
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Publication number | Priority date | Publication date | Assignee | Title |
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US10297827B2 (en) | 2004-01-06 | 2019-05-21 | Sion Power Corporation | Electrochemical cell, components thereof, and methods of making and using same |
US10985403B2 (en) | 2004-01-06 | 2021-04-20 | Sion Power Corporation | Electrolytes for lithium sulfur cells |
JP2017084812A (ja) * | 2011-05-24 | 2017-05-18 | シオン・パワー・コーポレーション | 電気化学電池および当該電気化学電池を含むバッテリー |
US10854921B2 (en) | 2011-09-07 | 2020-12-01 | Sion Power Corporation | Electrochemical cell including electrolyte having insoluble nitrogen-containing material and battery including the cell |
US10468721B2 (en) | 2012-12-17 | 2019-11-05 | Sion Power Corporation | Lithium-ion electrochemical cell, components thereof, and methods of making and using same |
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JP2010100475A (ja) | 2010-05-06 |
CN102196998A (zh) | 2011-09-21 |
US20110193015A1 (en) | 2011-08-11 |
KR20110074754A (ko) | 2011-07-01 |
JP5271035B2 (ja) | 2013-08-21 |
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