WO2010016472A1 - 六フッ化リン酸塩の製造方法 - Google Patents
六フッ化リン酸塩の製造方法 Download PDFInfo
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- WO2010016472A1 WO2010016472A1 PCT/JP2009/063778 JP2009063778W WO2010016472A1 WO 2010016472 A1 WO2010016472 A1 WO 2010016472A1 JP 2009063778 W JP2009063778 W JP 2009063778W WO 2010016472 A1 WO2010016472 A1 WO 2010016472A1
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- hexafluorophosphate
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D13/00—Compounds of sodium or potassium not provided for elsewhere
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/005—Lithium hexafluorophosphate
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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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—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
- 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 method for producing hexafluorophosphate and an apparatus for producing the same, and more specifically, a method for producing hexafluorophosphate that can be applied to an electrolytic solution of a storage element, and hexafluorophosphate.
- the present invention relates to an electrolyte solution including the same and a power storage element including the electrolyte solution.
- Lithium ion secondary batteries are positioned as key devices in hybrid vehicles and electric vehicles that are expected as trump cards for reducing CO 2 emissions.
- As an electrolyte of the lithium ion secondary battery lithium hexafluorophosphate having high safety and excellent electrical characteristics can be given.
- the hexafluorophosphate containing lithium hexafluorophosphate is manufactured using phosphorus pentafluoride “PF 5 ” as a starting material.
- the phosphorus pentafluoride is used as a fluorinating agent for various chemical reactions in the chemical industry and is a gaseous substance at room temperature.
- silver hexafluorophosphate “AgPF 6 ” and potassium hexafluorophosphate “KPF 6 ” which are a kind of hexafluorophosphate are counters that generate an acid necessary for the initiation and proliferation reaction of photopolymerization. It is attracting attention as an ion.
- ammonium hexafluorophosphate “NH 4 PF 6 ” is useful as a raw material used in the production of pharmaceutical intermediates.
- quaternary ammonium salts such as triethylmethylammonium hexafluoride phosphate and tetraethylammonium hexafluoride phosphate are useful as an electrolyte for an electric double layer capacitor that is expected as a high-power storage element.
- hexafluorophosphate is used as an indispensable substance according to functions required in various fields.
- a high-quality hexafluorophosphate that can be used as an electrolyte for a lithium ion secondary battery is extremely expensive.
- Non-Patent Document 1 describes that LiPF 6 is produced by dissolving lithium chloride in HF and adding phosphorus pentachloride thereto.
- Patent Document 1 discloses that hexafluorophosphate is obtained by reacting phosphorus pentachloride with HF gas in the range of 60 to 165 ° C., and adding the obtained PF 5 to an anhydrous HF solution of an alkali metal fluoride. There is a description of manufacturing.
- Non-Patent Document 1 and Patent Document 1 phosphorus pentachloride is a solid with high hygroscopicity, and therefore, due to its poor handling property, the raw material is charged into the manufacturing facility. However, the workability is poor and it is difficult to mechanize. In addition, when a phosphorus halide represented by phosphorus pentachloride is used as a raw material, a large amount of hydrogen halide is by-produced. For this reason, there is an inconvenience that a long exhaust gas treatment facility is required.
- Patent Document 2 discloses the following manufacturing method.
- PF 5 is produced by reacting phosphorus pentachloride with anhydrous HF.
- the mixed gas of PF 5 and hydrogen chloride is cooled to a temperature not higher than the boiling point of phosphorus oxyfluoride and not lower than the boiling point of PF 5 , specifically, -40 ° C. to ⁇ 84 ° C.
- After separating phosphorus it is reacted with lithium fluoride dissolved in anhydrous HF.
- a small amount of phosphorus oxyfluoride is separated from a mixed gas of a large excess of hydrogen chloride and PF 5 .
- the above-described method for producing hexafluorophosphate has various problems such as poor workability, reaction under severe conditions, use of expensive raw materials, and treatment of by-products. For this reason, the manufacturing cost is high.
- the present invention has been made in view of the above problems, and its purpose is to produce a hexafluorophosphate capable of easily producing an inexpensive and high-quality hexafluorophosphate while suppressing the production cost.
- the object is to provide a method, an electrolytic solution containing hexafluorophosphate, and an electricity storage device including the electrolytic solution.
- the inventors of the present application have studied a method for producing hexafluorophosphate, an electrolytic solution containing hexafluorophosphate, and a power storage device including the electrolytic solution. As a result, the inventors have found that the object can be achieved by adopting the following configuration, and have completed the present invention.
- the method for producing hexafluorophosphate according to the present invention includes at least a phosphorus compound and MF s ⁇ r (HF) (where 0 ⁇ r ⁇ 6, 1 ⁇ s) in order to solve the above-described problems.
- M is at least one selected from the group consisting of Li, Na, K, Rb, Cs, NH 4 , Ag, Mg, Ca, Ba, Zn, Cu, Pb, Al, and Fe.
- M is at least one selected from the group consisting of Li, Na, K, Rb, Cs, NH 4 , Ag, Mg, Ca, Ba, Zn, Cu, Pb, Al, and Fe.
- the phosphorus compound solution it is preferable to prepare the phosphorus compound solution by dissolving the phosphorus compound in a solvent and then add the fluoride to the phosphorus compound solution.
- fluorides are generally poorly soluble in solvents with low relative dielectric constants, organic solvents, and the like.
- the reaction in the solvent can be facilitated by adding the fluoride after dissolving the phosphorus compound in the solvent in advance.
- the amount of fluoride added to the phosphorus compound solution is preferably stoichiometrically equivalent to or smaller than the amount of phosphorus atoms in the phosphorus compound.
- a non-slurry hexafluorophosphate solution produced by reacting the phosphorus compound and fluoride in the solvent may be used as a solvent for preparing the phosphorus compound solution.
- the hexafluorophosphate solution is produced by reacting a phosphorus compound with a fluoride that is stoichiometrically equivalent to or smaller than the amount of phosphorus atoms in the phosphorus compound. As such, it is in a non-slurry state. For this reason, the hexafluorophosphate solution can be circulated and used as a solvent for preparing the phosphorus compound solution in place of the initial solvent. As a result, continuous operation becomes possible and the productivity of hexafluorophosphate can be improved.
- the phosphorus compound is at least PF 6 in the solvent - preferably forms an ion.
- an organic solvent can be used as the solvent.
- the organic solvent is preferably at least one of a non-aqueous organic solvent and a non-aqueous ionic liquid.
- hydrolysis can be prevented like an anhydrous HF solvent.
- insoluble components such as oxyfluorophosphate and phosphate are generated with respect to acidic substances such as oxyfluorophosphoric acid, HF and phosphoric acid, or the solvent.
- an electrolytic solution containing these acidic substances and insoluble components is used in a power storage element, it has adverse effects such as corrosion of the power storage element and deterioration of electrical characteristics.
- the water concentration of the solvent is preferably 100 ppm by weight or less, more preferably 10 ppm by weight or less, and particularly preferably 1 ppm by weight or less.
- the electrolytic solution according to the present invention includes hexafluorophosphate obtained by the method for producing hexafluorophosphate described above.
- a power storage device includes the above-described electrolytic solution.
- a lithium ion secondary battery etc. are mentioned as an electrical storage element of this invention.
- the present invention has the following effects by the means described above. That is, according to the present invention, it is possible to easily produce an inexpensive and high-quality hexafluorophosphate using a low-quality raw material without requiring a complicated processing operation or special equipment. Furthermore, by applying the high-grade hexafluorophosphate obtained by the present invention to the electrolytic solution, a power storage device having high safety and excellent electrical characteristics can be obtained.
- the method for producing hexafluorophosphate according to the present embodiment includes at least a phosphorus compound, MF s ⁇ r (HF) (where 0 ⁇ r ⁇ 6, 1 ⁇ s ⁇ 3, M is Li, Na, And at least one selected from the group consisting of K, Rb, Cs, NH 4 , Ag, Mg, Ca, Ba, Zn, Cu, Pb, Al, and Fe. This is done by reacting.
- the raw material containing the phosphorus compound and fluoride may be in a liquid, gas, or solid state. Moreover, it is good also as a solution by dissolving in water, an anhydrous hydrogen fluoride solvent, and an organic solvent.
- the phosphorus compound is not particularly limited.
- white phosphorus, red phosphorus, black phosphorus, phosphorus trichloride (PCl 3 ), phosphorus tribromide (PBr 3 ), phosphine (PH 3 ), phosphorous acid, pentoxide Phosphorus (P 2 O 5 ), orthophosphoric acid (H 3 PO 4 ), polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, isophosphoric acid, phosphonic acid, phosphinic acid, phosphenic acid, diphophonic acid, cyanophosphoric acid, Cyanophosphonic acid, diethyldithiophosphinic acid, chlorophenylphosphonic acid, trimethyl phosphate, phenylselenophosphinic acid o-methyl, pyrophosphonic acid, phosphorus oxychloride (POCl 3 ), phosphorus oxybromide (POBr 3 ), phosphorus oxyio
- the fluoride is MF s ⁇ r (HF) (where 0 ⁇ r ⁇ 6, 1 ⁇ s ⁇ 3, M is Li, Na, K, Rb, Cs, NH 4 , Ag, Mg, Ca, Ba, And at least one selected from the group consisting of Zn, Cu, Pb, Al, and Fe.
- Fluoride MF s ⁇ r (HF) is used by excessively reacting HF with an oxide, hydroxide, carbonate, chloride, etc. containing at least one selected from the group consisting of (0 ⁇ r ⁇ 6).
- MF s ⁇ r (HF) by-produced by the reaction of the following chemical reaction formula may be reused.
- a high concentration HF aqueous solution of 50% by weight or more is used. It is preferable to use anhydrous HF. Hydrate formation can be prevented by using a high concentration HF aqueous solution. Moreover, when anhydrous HF is used, the production
- LiF, LiF ⁇ (HF), NaF, NaF ⁇ (HF), KF ⁇ (HF), RbF ⁇ (HF), or CsF is a crystal that has no hygroscopicity and excellent fluidity. is there. In the case where it is put into a production facility for mixing, the workability is remarkably improved, and mechanization can be easily achieved. This naturally improves the productivity of hexafluorophosphate.
- the fluoride when the fluoride is mixed with the hydrogen fluoride solution in advance, it generates a little heat. For this reason, it is preferable that the fluoride is slowly added with stirring after cooling the hydrogen fluoride solution within a range of 5 to 15 ° C. Thereby, a solution of fluoride is obtained.
- the content of phosphorus atoms contained in the raw material is not particularly limited, but is preferably 0.01% by weight to 25% by weight, more preferably 0.01% by weight to 15% by weight, The weight percentage is particularly preferably 10% by weight or more. If the phosphorus atom content is less than 0.01% by weight, the yield of phosphorus pentafluoride may decrease. On the other hand, when the content of phosphorus atoms exceeds 25% by weight, the viscosity increases when the raw material is a solution. As a result, there may be inconveniences when transporting the liquid. In addition, gas may be generated to cause inconvenience.
- Ratio of the number of fluorine atoms to the number of phosphorus atoms in the feedstock, PF 6 - is preferably present over the stoichiometry of when to form an ion.
- the synthesis of hexafluorophosphate is preferably performed, for example, by dissolving the phosphorus compound in a solvent to prepare a phosphorus compound solution and then adding the fluoride to the phosphorus compound solution.
- the method for adding the phosphorus compound to the solvent is not particularly limited, and it can be carried out either continuously or batchwise.
- the solvent may be charged after the phosphorus compound is put in the mixing tank, or the phosphorus compound may be charged after the solvent is first put in the mixing tank.
- it can also be carried out by reacting a fluoride (MF s ⁇ r (HF)) solution with a phosphorus compound. In this case, little heat is generated during the reaction. As a result, for example, there is no need to perform cooling or the like, and the mixing method is not particularly limited.
- the amount of fluoride added to the phosphorus compound solution is preferably stoichiometrically equivalent to or smaller than the amount of phosphorus atoms in the phosphorus compound. Thereby, all the fluorides can be reacted with phosphorus atoms. As a result, unreacted fluoride does not remain, and a non-slurry hexafluorophosphate solution can be produced. Furthermore, when it is a non-slurry hexafluorophosphate solution, it can be used as a solvent for preparing the phosphorus compound solution. As a result, continuous operation becomes possible and the productivity of hexafluorophosphate can be improved.
- HF may be by-produced with the progress of the reaction between the phosphorus compound and the fluoride.
- the by-product HF can be used as a solvent. Therefore, it is not always necessary to add a solvent, and the hexafluorophosphate can be synthesized simply by putting a phosphorus compound and a fluoride in a reaction vessel and stirring them.
- an anhydrous HF solution of hexafluorophosphate is generated in the reaction vessel as a result, a phosphorus compound and a fluoride may be further added.
- the phosphorus compound contains an oxygen atom and a hydrogen atom
- water and HF may be by-produced as the reaction with the fluoride proceeds.
- the by-produced water and HF can be used as a solvent. Therefore, it is not always necessary to add a solvent, and the hexafluorophosphate can be easily synthesized only by putting a phosphorus compound and a fluoride in a reaction vessel and stirring them.
- the by-product water concentration is low.
- the water concentration of the solution in the reaction vessel including the by-product water is preferably 100 ppm by weight or less, more preferably 10 ppm by weight or less, and particularly preferably 1 ppm by weight or less.
- the solvent for dissolving the phosphorus compound is not particularly limited, and for example, a hydrogen fluoride solution or an organic solvent can be used.
- a hydrogen fluoride solution When a hydrogen fluoride solution is used as the solvent, it may be used as anhydrous hydrogen fluoride, or may be used after being dissolved in water, an organic solvent, or a mixed solvent of water and an organic solvent. Moreover, it does not specifically limit as hydrogen fluoride, For example, commercially available hydrofluoric acid, such as an industrial grade, a general grade, and a semiconductor grade, can be used as it is, or it can adjust density
- the concentration of polyatomic ions containing phosphorus atoms and fluorine atoms present in the solution is 0.03% by weight to 50% by weight, preferably 0.5% by weight to 20% by weight. It is good to use it in a liquid state within the range of%. Further, the phosphorus compound does not need to be completely dissolved in the solution, and may be in a suspended state.
- the temperature at which the phosphorus compound is mixed with the hydrogen fluoride solution is not particularly limited, but is preferably in the range of ⁇ 50 to 200 ° C. When the temperature is lower than ⁇ 50 ° C., the composition containing the phosphorus compound and fluoride may solidify. On the other hand, if the temperature exceeds 200 ° C., a special device is required in terms of heat resistance and the like, which may not be preferable.
- the organic solvent is preferably at least one of a non-aqueous organic solvent and a non-aqueous ionic liquid.
- aprotic is preferable. Since it is not capable of donating hydrogen ions when it is aprotic, the solution of hexafluorophosphate obtained by the production method of the present invention is applied as it is to the electrolyte of a storage element such as a lithium ion secondary battery. be able to.
- the non-aqueous organic solvent is not particularly limited, and examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl acetate, ethyl acetate, ⁇ -butyl lactone, acetonitrile, Examples include dimethylformamide, 1,2-dimethoxyethane, methanol, isopropanol and the like.
- the produced hexafluorophosphate is difficult to precipitate, that is, the hexafluorophosphate is highly soluble in ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, Methyl ethyl carbonate, acetonitrile and 1,2-dimethoxyethane are preferred.
- These organic solvents may be used alone or in combination of two or more.
- non-aqueous and aprotic organic solvent examples include a cyclic carbonate ester, a chain carbonate ester, a carboxylic acid ester, a nitrile, an amide, or an ether compound. These non-aqueous aprotic organic solvents may be used alone or in combination of two or more.
- non-aqueous ionic liquid is not particularly limited.
- a fluoride complex salt or fluoride salt such as quaternary ammonium or quaternary phosphonium, among others, a quaternary ammonium cation includes a tetraalkylammonium cation, Examples include imidazolium cation, pyrazolium cation, pyridinium cation, triazolium cation, pyridazinium cation, thiazolium cation, oxazolium cation, pyrimidinium cation, and pyrazinium cation.
- examples of the quaternary phosphonium cation include a tetraalkylphosphonium cation.
- These non-aqueous ionic liquids may be used alone or in combination of two or more, or may be used by dissolving in the non-aqueous organic solvent.
- the organic solvent may be a non-aqueous organic solvent or a non-aqueous ionic liquid, or a mixture of two or more.
- the reaction temperature of the phosphorus compound and fluoride is not particularly limited, but is preferably in the range of ⁇ 40 ° C. to 100 ° C., and in consideration of the productivity of hexafluorophosphate, it is ⁇ 20 ° C. to + 50 ° C. More preferably within the range.
- the reaction temperature exceeds 100 ° C., HF may be scattered.
- the reaction temperature is less than ⁇ 40 ° C., the reaction rate may be slow.
- the synthesized M (PF 6 ) s is preferably taken out as a crystal by a crystallization method.
- the crystallization temperature is not particularly limited.
- the yield is improved as the crystallization temperature is lower, but the production cost is increased in terms of incidental facilities or productivity. Therefore, it is preferably ⁇ 40 ° C. or higher and + 100 ° C. or lower, more preferably ⁇ 30 ° C. or higher and + 50 ° C. or lower, and particularly preferably ⁇ 20 ° C. or higher and + 20 ° C. or lower.
- the reaction time or crystallization time in the above is not particularly limited, and is, for example, 0.5 hours to less than 72 hours, preferably 1 hour to 48 hours, more preferably 1.5 hours to 8 hours, Particularly preferably, it is 2 hours or more and 6 hours or less. If the reaction time or crystallization time is less than 0.5 hour, the yield of hexafluorophosphate may be reduced. On the other hand, if the reaction time or crystallization time is 72 hours or more, the productivity of hexafluorophosphate may be reduced.
- the crystallized M (PF 6 ) s is solid-liquid separated.
- the method for solid-liquid separation is not particularly limited, and examples thereof include filtration.
- a filtration method conventionally well-known various filtration methods, such as natural filtration, pressure filtration, and centrifugal filtration, are employable.
- washing operation it is preferable to wash the filtrate after solid-liquid separation.
- the purity of M (PF 6 ) s can be increased.
- a known method such as a method in which M (PF 6 ) s is again dispersed in the washing agent, a method in which the washing agent is directly introduced into the separation apparatus and brought into contact with M (PF 6 ) s , or the like is used. It can be performed alone or in combination.
- the filtrate after solid-liquid separation may contain a large amount of excess M (PF 6 ) s salt solution or acid.
- PF 6 excess M
- the filtrate is subjected to distillation or the like and the MPF 6 salt solution or the acid is recovered, the cost can be reduced and the valuable material can be recovered by reducing the load of the wastewater treatment, and a double effect can be obtained.
- the cleaning agent is not particularly limited, and any of anhydrous HF, high concentration HF, dilute HF, pure water, and the like may be used. Furthermore, in order to neutralize the acid (for example KPF 6 synthesis, K 2 using CO 3 or KHCO 3 and the like) an alkali salt of the same cation may be washed with. By performing alkali neutralization in this way, it is possible to suppress the effects of acid corrosion and metal impurity contamination on the product in the subsequent steps.
- the temperature of the crystallized M (PF 6 ) s crystal itself during solid-liquid separation is not particularly limited, but it is usually preferably ⁇ 40 ° C. or higher and + 30 ° C. or lower, and preferably ⁇ 20 ° C. or higher and + 20 ° C. or lower. Is more preferably ⁇ 5 ° C. or higher and + 20 ° C. or lower.
- the temperature of the cleaning agent at the time of washing the filtrate after solid-liquid separation is not particularly limited. Is more preferably ⁇ 5 ° C. or higher and + 20 ° C. or lower.
- M (PF 6 ) s obtained by solid-liquid separation is preferably dried. It does not specifically limit as a drying method, For example, air drying, heat drying, vacuum drying, etc. are mentioned.
- the drying time is not particularly limited, and is generally preferably 0.5 to 72 hours.
- the drying temperature is preferably less than 120 ° C. If it is performed at a temperature of 120 ° C. or higher, the drying equipment becomes expensive, a large amount of heat is required, and the production cost is increased.
- M (PF 6 ) s may be decomposed by a small amount of moisture as the temperature increases. Therefore, the drying temperature is particularly preferably 85 to 110 ° C.
- M (PF 6 ) s having a water content of 50 ppm by weight or less can be easily produced.
- this method can use inexpensive raw materials, and the manufacturing method is simple, so that the manufacturing cost can be reduced.
- hexafluorophosphate obtained by the above method may be further subjected to salt exchange according to the following chemical formula B.
- the ratio of JF t ⁇ k (HF) to M (PF 6 ) s is preferably 1 to 2 equivalents, and more preferably 1.0 to 1.1 equivalents.
- the ratio is less than 1 equivalent, there is a disadvantage that unsubstituted M (PF 6 ) s remains and is mixed.
- unreacted JF t ⁇ k (HF) may be mixed into the product J (PF 6 ) t .
- the solvent used in the salt exchange is not particularly limited, and examples thereof include anhydrous HF, high concentration HF having a concentration of 50% by weight or more, dilute HF, pure water, and an organic solvent. Of these solvents, anhydrous HF and high-concentration HF are preferably used from the viewpoint of preventing the formation of oxyfluoride and the like.
- the amount of the solvent used is not particularly limited, and is preferably 0.5 to 10 times, more preferably 1 to 5 times the weight of hexafluorophosphate. When the amount used exceeds 10 times, the amount of hexafluorophosphate dissolved increases and the yield may decrease. On the other hand, if the amount used is less than 0.5 times, unreacted JF t ⁇ k (HF) or by-product MF s ⁇ r (HF) may be mixed into J (PF 6 ) t. .
- the addition method of the raw material in the salt exchange is not particularly limited.
- a solution in which M (PF 6 ) s or JF t ⁇ k (HF) is dissolved in a solvent is added all at once or by dropwise addition.
- a method of adding one to the other may be used.
- the reaction vessel may be filled with a solvent, and M (PF 6 ) s or JF t ⁇ k (HF) may be slowly added to the solvent.
- the solvent may be slowly added to M (PF 6 ) s or JF t ⁇ k (HF).
- reaction temperature and reaction time in salt exchange can be performed under the same conditions as in the synthesis of hexafluorophosphate described above.
- the crystallization method, solid-liquid separation, washing, and drying can be performed under the same conditions as described above.
- the reactor used in the present invention is not particularly limited as long as it is made of a material having resistance to the composition, and stainless steel or carbon steel is preferably used.
- stainless steel or carbon steel is preferably used.
- the reactor is corroded, the resulting product is also contaminated by the corroded material, which causes the metal content of the product to increase.
- Example 1 A 5 L fluororesin reaction tank was filled with 1000 g of ultrapure water, and the reaction tank was heated in an oil bath to keep the ultrapure water at 40 ° C. While stirring this ultrapure water with a rotor, 800 g of commercially available acidic ammonium fluoride (NH 4 F ⁇ (HF)) was added little by little and dissolved.
- NH 4 F ⁇ (HF) acidic ammonium fluoride
- the reaction vessel was heated again with an oil bath, and the solution in the reaction vessel was evaporated to dryness. Crystals remaining in the reaction vessel were collected, washed with 750 g of 75% aqueous HF solution, and then filtered off with suction filtration. The liquid temperature of the 75% HF aqueous solution during washing was 0 ° C., and the liquid temperature during suction filtration was 5 ° C.
- Example 2 100 g of acidic potassium fluoride (KF ⁇ (HF)) and 500 g of a semiconductor grade 75 wt% hydrogen fluoride (HF) solution are placed in a 3 L fluororesin (PFA) reaction vessel together with a rotor and stirred in an ice bath. KF (HF) was dissolved. Furthermore, 140 g of an 85 wt% phosphoric acid (H 3 PO 4 ) solution was weighed into a separatory funnel, slowly dropped over 30 minutes in an ice bath, and reacted for 6 hours with stirring.
- KF ⁇ (HF) acidic potassium fluoride
- PFA fluororesin
- H 3 PO 4 85 wt% phosphoric acid
- this solution was cooled at ⁇ 5 ° C. for 24 hours for crystallization. Thereby, the hydrogen fluoride solution in which the precipitate was precipitated was obtained.
- This hydrogen fluoride solution was separated by suction filtration. The liquid temperature of the hydrogen fluoride solution at this time was ⁇ 5 ° C.
- the HF concentration of the filtrate was quantified to be 46% by weight.
- the recovered crystals were washed with 600 g of a semiconductor grade 75 wt% hydrogen fluoride (HF) solution.
- the liquid temperature of the hydrogen fluoride solution at this time was 0 ° C.
- the washed residue was transferred to a 3 L fluororesin (PFA) bottle and air-dried at 80 ° C. for 6 hours while blowing high-purity nitrogen gas at 3 L / min. Thereafter, the drying temperature was raised to 105 ° C., and drying was performed for 12 hours.
- PFA fluororesin
- the obtained crystal was measured by XRD, it was confirmed to be KPF 6 .
- the yield of KPF 6 obtained was 137 g, and the yield was 61%.
- the water content of the obtained KPF 6 was measured by the Karl Fischer method, it was 50 ppm by weight or less.
- the free hydrofluoric acid concentration was 50 ppm by weight or less.
- Example 3 210 g of cesium fluoride (CsF) and 700 g of a semiconductor grade 75 wt% hydrogen fluoride (HF) solution were placed in a 3 L-PFA reaction vessel together with a rotor, and CsF was dissolved while stirring in an ice bath. Furthermore, 175 g of 85 wt% phosphoric acid (H 3 PO 4 ) solution was weighed into a separatory funnel, slowly dropped over 30 minutes in an ice bath, and reacted for 12 hours with stirring.
- CsF cesium fluoride
- HF hydrogen fluoride
- this solution was cooled at ⁇ 5 ° C. for 36 hours for crystallization. Thereby, a solution in which a precipitate was precipitated was obtained. Furthermore, this solution was separated by suction filtration. The temperature of the phosphoric acid solution at this time was ⁇ 5 ° C. The HF concentration of the filtrate was quantified and found to be 55% by weight.
- the recovered crystals were washed with 400 g of anhydrous hydrofluoric acid cooled to 0 ° C. Subsequently, the washed residue was transferred to a 3 L fluororesin bottle, and air-dried at 80 ° C. for 5 hours while blowing high purity N 2 gas at 3 L / min. Thereafter, the drying temperature was raised to 105 ° C., and drying was performed for 12 hours.
- the obtained crystal was measured by XRD, it was confirmed to be CsPF 6 .
- the yield of CsPF 6 obtained was 352 g, and the yield was 92%.
- the water content of the obtained CsPF 6 was measured by the Karl Fischer method, it was 50 ppm by weight or less.
- the free hydrofluoric acid concentration was 50 ppm by weight or less.
- Example 4 500 g of an industrial grade anhydrous hydrogen fluoride solution and a rotor were placed in a 3 L fluororesin reaction vessel, and 60 g of sodium fluoride (NaF) was slowly added and dissolved while stirring in an ice bath. Further, 120 g of phosphorus oxyfluoride (POF 3 ) was absorbed into this solution.
- NaF sodium fluoride
- POF 3 phosphorus oxyfluoride
- this solution was cooled at ⁇ 20 ° C. for 48 hours for crystallization. Thereby, a solution in which a precipitate was precipitated was obtained.
- This solution was filtered off by suction filtration. When the HF concentration of the filtrate at this time was quantified, it was 94% by weight.
- the recovered crystals were transferred to a 3 L fluororesin bottle, and 100 g of an anhydrous hydrogen fluoride solution that had been cooled to 5 ° C. in advance was added to disperse the crystals. At this time, the reaction vessel was stirred for 30 minutes while ice bathing. Then, standing, from withdrawn supernatant, the high-purity N 2 gas while blowing with 3L / min, it was air-dried for 6 hours at 80 ° C.. Thereafter, the drying temperature was raised to 105 ° C., and drying was performed for 6 hours.
- the resulting crystal was measured by XRD, it was confirmed that a NaPF 6.
- the yield of NaPF 6 obtained was 148 g, and the yield was 76% (however, the yield of NaPF 6 dissolved in the anhydrous hydrogen fluoride solution as the washing liquid was not included). Further, when the water content of the obtained NaPF 6 was measured by the Karl Fischer method, it was 50 ppm by weight or less. As a result of measuring the free hydrofluoric acid concentration by neutralization titration, the free hydrofluoric acid concentration was 50 ppm by weight or less.
- Example 5 A semiconductor-grade 75% by weight hydrogen fluoride solution 2000 g and a rotor were placed in a 5 L fluororesin reaction vessel and held under stirring in an ice bath. Furthermore, 420 g of 85 wt% phosphoric acid solution was weighed into a separatory funnel, slowly dropped over 15 minutes in an ice bath, and reacted for 3 hours with stirring.
- this solution was cooled at ⁇ 40 ° C. for 48 hours for crystallization. Thereby, a solution in which a precipitate was precipitated was obtained. Furthermore, this solution was separated by suction filtration. The weight of crystals separated by filtration before drying was measured and found to be 1080 g. In the case of HPF 6 (without water of crystallization), the crystal weight when the yield is 100% is 532 g. Therefore, it was confirmed that the actual measured weight was large even when the water content and the HF content were added. Thereby, it was estimated that the crystals before drying separated by filtration were in the form of HPF 6 ⁇ qH 2 O having water of crystallization.
- the supernatant liquid of the 3L-PFA reaction tank was slowly extracted, and solid-liquid separation was performed. After separation, air drying was performed at 80 ° C. for 6 hours while blowing high purity N 2 gas at 3 L / min. Thereafter, the drying temperature was increased to 105 ° C., and drying was performed for 3 hours.
- the resulting crystal was measured by XRD, it was confirmed that a NaPF 6.
- the yield of NaPF 6 obtained was 205 g, and the yield was 33%. Further, when the water content of the obtained NaPF 6 was measured by the Karl Fischer method, it was 420 ppm by weight or less.
- Example 6 In order to reuse HF, 700 g of the 71 wt% HF filtrate recovered in Example 5 was placed in a 3 L fluororesin reaction vessel, and 140 g of anhydrous HF was further added to prepare 840 g of a hydrogen fluoride solution having a concentration of 75 wt%. did.
- this solution was cooled at ⁇ 20 ° C. for 24 hours for crystallization. Thereby, a solution in which a precipitate was precipitated was obtained.
- This solution was filtered off by suction filtration. The weight of the crystals separated by filtration before drying was measured and found to be 250 g. The HF concentration of the filtrate was quantified to be 72% by weight. All the crystals before drying were transferred to a 1 L fluororesin reaction vessel containing a rotor.
- the HF solution after the reaction of KPF 6 + HF ⁇ PF 5 + KF ⁇ (HF) was completely concentrated and dried to recover 125 g of white powder.
- XRD analysis of this powder was performed, it was a mixture of KPF 6 and KF ⁇ (HF), and 90% by weight was KF ⁇ (HF).
- the obtained KPF 6 / KF ⁇ (HF) mixture was slowly added to the 1 L fluororesin reaction vessel and reacted at 20 ° C. for 48 hours. Stirring was difficult at the beginning of the reaction because it was a reaction between solids, but after 30 minutes of reaction, H 2 O / HF was gradually generated from the crystal to form a liquid and could be easily stirred.
- the precipitate obtained by the above reaction was separated by suction filtration.
- the recovered crystals were washed with 400 g of pure water at 5 ° C. Further, drying was performed at 105 ° C. for 24 hours.
- the yield of the obtained KPF 6 was 105 g, and the yield was 55% (the yield of KPF 6 dissolved in pure water as a washing liquid was not included). Further, when the water content of the obtained KPF 6 was measured by the Karl Fischer method, it was 400 ppm by weight.
- Example 7 In this embodiment, the apparatus shown in FIG. 1 was used. That is, 250 g of commercial battery grade diethyl carbonate (water concentration 9 ppm by weight) and 250 g of ethylene carbonate (water concentration 7 ppm by weight) are put in a second tank 6 made of fluororesin, and the top of the second absorption tower 5 is pumped 7. And circulated. The second tank 6 was kept constant at 20 ° C. using a cooler 8. Next, PF 5 was supplied to the bottom of the second absorption tower 5 at a flow rate of 0.5 L / min for 25.5 minutes, and 64.3 g was introduced (first step).
- the diethyl carbonate / ethyl carbonate solution of lithium hexafluorophosphate thus obtained had an insoluble component of 10 ppm by weight or less, a free acid of 10 ppm by weight or less, and a water content of 10 ppm by weight or less.
- a coin-type non-aqueous electrolyte lithium secondary battery as shown in FIG. 2 was produced using the solution thus obtained, and the performance as an electrolyte was evaluated by a charge / discharge test. Specifically, the procedure was as follows.
- ⁇ Creation of negative electrode 22 Natural graphite and binder polyvinylidene fluoride (PVdF) were mixed at a weight ratio of 9: 1, and N-methylpyrrolidone was added thereto to obtain a paste. This paste was uniformly applied onto a copper foil having a thickness of 22 ⁇ m using an electrode applicator. This was vacuum-dried at 120 ° C. for 8 hours, and a negative electrode 22 having a diameter of 16 mm was obtained with an electrode punching machine.
- PVdF binder polyvinylidene fluoride
- This paste was uniformly applied onto a copper foil having a thickness of 22 ⁇ m using an electrode applicator. This was vacuum-dried at 120 ° C. for 8 hours, and a positive electrode 21 having a diameter of 16 mm was obtained with an electrode punching machine.
- Comparative Example 1 This comparative example was performed using the apparatus shown in FIG. That is, after 3L of commercially available battery grade diethyl carbonate (water concentration 9 ppm by weight) was charged into the first tank 2 and the second tank 6 made of fluororesin, the pumps 3 and 7 were used for each absorption tower and tank. Circulation operation started. At this time, the flow rates of the pump 3 and the pump 7 were both 1 L / min. Moreover, the 1st tank 2 and the 2nd tank 6 were made constant temperature of 20 degreeC using the coolers 4 and 8, respectively.
- a high-quality hexafluorophosphate having a low moisture concentration and a high purity can be produced using a low-quality raw material without requiring a complicated processing operation or special equipment.
- the high-quality hexafluorophosphate obtained by the present invention can be suitably used as an electrolyte solution for a storage element, a catalyst for an organic synthesis reaction, or the like.
- lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, etc. are electrolytes for power storage elements for personal computers, mobile phones, hybrid vehicles, etc.
- silver hexafluorophosphate is used as a counter ion for generating an acid necessary for the initiation / proliferation reaction of photopolymerization.
- ammonium hexafluorophosphate is useful as a raw material used in the production of pharmaceutical intermediates.
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Abstract
Description
例えば、非特許文献1には、HF中に塩化リチウムを溶解し、これに五塩化リンを加えてLiPF6を製造する旨の記載がある。また、特許文献1には、五塩化リンとHFガスを60~165℃の範囲で反応させ、得られるPF5をアルカリ金属フッ化物の無水HF溶液に添加することにより六フッ化リン酸塩を製造する旨の記載がある。
即ち、本発明によると、複雑な処理操作や特別な装置を必要とせず、低品位の原料を用いて安価で高品位な六フッ化リン酸塩を容易に製造することができる。更に、本発明により得られる高品位の六フッ化リン酸塩を電解液に適用することで、安全性が高く、電気特性にも優れた蓄電素子が得られる。
5Lフッ素樹脂製反応槽に超純水を1000g充填し、反応槽をオイルバスで加温してこの超純水を40℃に保った。この超純水を回転子にて攪拌をしながら市販の酸性フッ化アンモニウム(NH4F・(HF))800gを少量ずつ添加し溶解させた。
酸性フッ化カリウム(KF・(HF))100gと、半導体グレードの75重量%フッ化水素(HF)溶液500gを回転子と共に3Lフッ素樹脂(PFA)製反応槽に入れ、氷浴下で攪拌しながらKF(HF)を溶解させた。更に、分液ロートに85重量%リン酸(H3PO4)溶液140gを測りとり、氷浴下で30分かけてゆっくり滴下させ、撹拌しながら6時間反応させた。
フッ化セシウム(CsF)210gと、半導体グレードの75重量%フッ化水素(HF)溶液700gを回転子と共に3L-PFA製反応槽に入れ、氷浴下で攪拌しながらCsFを溶解させた。更に、分液ロートに85重量%リン酸(H3PO4)溶液175gを測りとり、氷浴下で30分かけてゆっくり滴下させ、撹拌しながら12時間反応させた。
工業用グレードの無水フッ化水素溶液500gと回転子を3Lフッ素樹脂製反応槽に入れ、氷浴下で攪拌しながらフッ化ナトリウム(NaF)60gをゆっくり添加し溶解させた。更に、この溶液にオキシフッ化リン(POF3)120gを吸収させた。
半導体グレードの75重量%フッ化水素溶液2000gと回転子を、5Lフッ素樹脂製反応槽に入れ、氷浴下で攪拌しながら保持した。更に、分液ロートに85重量%リン酸溶液420gを測りとり、氷浴下で15分かけてゆっくり滴下させ、攪拌しながら3時間反応させた。
HFの再利用を行うため、実施例5で回収した71重量%のHF濾液700gを3Lフッ素樹脂製反応槽に入れ、更に無水HF140gを加えて、濃度75重量%のフッ化水素溶液840gを調製した。
本実施例においては、図1に示す装置を用いて行なった。即ち、市販電池グレードのジエチルカーボネート250g(水分濃度9重量ppm)とエチレンカーボネート250g(水分濃度7重量ppm)をフッ素樹脂製の第2槽6に入れ、ポンプ7で第2吸収塔5の塔頂部に供給し、循環させた。第2槽6は冷却器8を用いて20℃の恒温にした。次に、第2吸収塔5の塔底部にPF5を流量0.5L/minで25.5分間供給し、64.3gを導入した(第1工程)。
天然黒鉛と結着剤のポリフッ化ビニリデン(PVdF)を9:1の重量比で混合し、これにN-メチルピロリドンを加え、ペーストを得た。このペーストを厚さ22μmの銅箔上に電極塗工用アプリケーターを用いて均一に塗工した。これを120℃で8時間、真空乾燥し、電極打ち抜き機で直径16mmの負極22を得た。
LiCoO2粉末と導電助剤のアセチレンブラックと結着剤のPVdFを90:5:5の重量比で混合し、この混合物にN-メチルピロリドンを加え、ペーストを得た。このペーストを厚さ22μmの銅箔上に電極塗工用アプリケーターを用いて均一に塗工した。これを120℃で8時間、真空乾燥し、電極打ち抜き機で直径16mmの正極21を得た。
正極21を正極缶24の底面に載せ、その上にポリプロピレン製多孔質セパレーター23を載置した後、実施例2で調製した非水性電解液を注入し、ガスケット26を挿入した。その後、セパレーター23の上に負極22、スペーサー27、スプリング28及び負極缶25を順々に載置し、コイン型電池かしめ機を使用して、正極缶24の開口部を内方へ折り曲げることにより封口し、非水電解液リチウム二次電池を作成した。続いて、充電を0.4mAの一定電流で行い、電圧が4.1Vに到達した時点で4.1V、1時間定電圧充電した。放電は1.0mAの定電流で行い、電圧が3.0Vになるまで放電した。電圧が3.0Vに到達したら3.0V、1時間保持し充放電サイクルにより充放電試験を実施した。その結果、充放電効率はほぼ100%で、充放電を150サイクル繰り返した所、充電容量は変化しなかった。
本比較例は図1に示す装置を用いて行なった。即ち、市販電池グレードのジエチルカーボネート(水分濃度9重量ppm)をフッ素樹脂製の第1槽2及び第2槽6にそれぞれ3L仕込んだ後、ポンプ3及び7を用いて各吸収塔及び槽での循環運転を開始した。このとき、ポンプ3及びポンプ7の流量はともに1L/minとした。また、第1槽2及び第2槽6はそれぞれ冷却器4及び8を用いて20℃の恒温にした。
実施例1~7から明らかな通り、リン化合物とフッ化物を反応させることにより、安価で高品位の六フッ化リン酸塩(M(PF6)s)を、製造コストを抑制しつつ製造することが確認された。また、各実施例で使用したフッ化物は、Li、Na、K、Rb、Cs、NH4、Ag、Mg、Ca、Ba、Zn、Cu、Pb、Al若しくはFe、又はこれらを含んだ酸化物・水酸化物・炭酸塩・塩化物等とHFとを過剰に反応させることにより容易に合成することができるものである。このため、いずれのフッ化物も入手が容易であり、従来の六フッ化リン酸塩の製造方法と比較して、製造コストの低減が可能になるなど優れた方法である。
2 第1槽
3 ポンプ
4 冷却器
5 第2吸収塔
6 第2槽
7 ポンプ
8 冷却器
9 脱気塔
10 第3槽
12 エアーポンプ
13 凝縮器
21 正極
22 負極
23 多孔質セパレーター
24 正極缶
25 負極缶
26 ガスケット
27 スペーサー
28 スプリング
Claims (11)
- 少なくともリン化合物と、MFs・r(HF)(但し、0≦r≦6、1≦s≦3、MはLi、Na、K、Rb、Cs、NH4、Ag、Mg、Ca、Ba、Zn、Cu、Pb、Al及びFeからなる群より選択される少なくとも何れか1種である。)で表されるフッ化物とを反応させることにより、化学式M(PF6)sで表される六フッ化リン酸塩を生成させることを特徴とする六フッ化リン酸塩の製造方法。
- 前記リン化合物を溶媒に溶解させてリン化合物溶液を作製した後、前記リン化合物溶液に前記フッ化物を添加することを特徴とする請求項1に記載の六フッ化リン酸塩の製造方法。
- 前記リン化合物溶液に対するフッ化物の添加量は、リン化合物中のリン原子の量に対し化学量論的に等価又はそれより小さいことを特徴とする請求項2に記載の六フッ化リン酸塩の製造方法。
- 前記溶媒中で前記リン化合物とフッ化物とを反応させることにより生成した、非スラリー状態の六フッ化リン酸塩の溶液を、前記リン化合物溶液を作製するための溶媒として使用することを特徴とする請求項3に記載の六フッ化リン酸塩の製造方法。
- 前記リン化合物は前記溶媒中で少なくともPF6 -イオンを形成していることを特徴とする請求項2に記載の六フッ化リン酸塩の製造方法。
- 前記溶媒としてフッ化水素溶液を用いることを特徴とする請求項2に記載の六フッ化リン酸塩の製造方法。
- 前記溶媒として有機溶媒を用いることを特徴とする請求項2に記載の六フッ化リン酸塩の製造方法。
- 前記有機溶媒は、非水性有機溶媒又は非水性イオン液体の少なくとも何れか一方であることを特徴とする請求項7に記載の六フッ化リン酸塩の製造方法。
- 前記溶媒として水分濃度が100ppmw以下のものを使用することを特徴とする請求項2に記載の六フッ化リン酸塩の製造方法。
- 請求項1に記載の六フッ化リン酸塩の製造方法により得られた六フッ化リン酸塩を含む電解液。
- 請求項10に記載の電解液を備える蓄電素子。
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CN106536412A (zh) * | 2014-03-31 | 2017-03-22 | 南非核能源股份有限公司 | 六氟磷酸盐和五氟化磷的生产 |
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CN112394166A (zh) * | 2020-11-09 | 2021-02-23 | 广东希格生物科技有限公司 | 六氟磷酸盐在制备抑制elisa反应基质效应的制剂中的应用 |
Also Published As
Publication number | Publication date |
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EP2319800A4 (en) | 2012-04-04 |
JP2010042938A (ja) | 2010-02-25 |
CN102105395B (zh) | 2013-12-18 |
CN102105395A (zh) | 2011-06-22 |
TWI457274B (zh) | 2014-10-21 |
JP5351463B2 (ja) | 2013-11-27 |
KR20110040985A (ko) | 2011-04-20 |
US9059480B2 (en) | 2015-06-16 |
US20110097626A1 (en) | 2011-04-28 |
CA2732346A1 (en) | 2010-02-11 |
TW201022136A (en) | 2010-06-16 |
EP2319800A1 (en) | 2011-05-11 |
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