WO2012176907A1 - オキシフルオロライト系正極活物質の製造方法およびオキシフルオロライト系正極活物質 - Google Patents
オキシフルオロライト系正極活物質の製造方法およびオキシフルオロライト系正極活物質 Download PDFInfo
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- WO2012176907A1 WO2012176907A1 PCT/JP2012/066071 JP2012066071W WO2012176907A1 WO 2012176907 A1 WO2012176907 A1 WO 2012176907A1 JP 2012066071 W JP2012066071 W JP 2012066071W WO 2012176907 A1 WO2012176907 A1 WO 2012176907A1
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- positive electrode
- electrode active
- feof
- active material
- fef
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000013543 active substance Substances 0.000 title abstract 6
- IYOHHZVNHNCZNL-UHFFFAOYSA-N [Fe].FOF Chemical compound [Fe].FOF IYOHHZVNHNCZNL-UHFFFAOYSA-N 0.000 title 2
- 229910015182 FeOF Inorganic materials 0.000 claims abstract description 88
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims abstract description 37
- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
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- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims description 69
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 238000010791 quenching Methods 0.000 claims description 27
- 230000000171 quenching effect Effects 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
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- 238000007578 melt-quenching technique Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 2
- 238000000034 method Methods 0.000 description 24
- 239000002994 raw material Substances 0.000 description 24
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
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- 239000003792 electrolyte Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 125000006850 spacer group Chemical group 0.000 description 6
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
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- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
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- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
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- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/24—Oxygen compounds of fluorine
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Definitions
- the present invention belongs to the technical field of non-aqueous electrolyte secondary batteries, and particularly relates to a novel manufacturing method and a novel cathode active material for efficiently producing a cathode active material for a non-aqueous electrolyte secondary battery at low cost.
- non-aqueous electrolyte secondary batteries using non-aqueous electrolyte are actively used as secondary batteries that can simultaneously achieve high voltage and energy density. It has been studied.
- a positive electrode active material made of fluoride or oxide is widely used.
- FeF 3 see Non-Patent Document 1
- Fe 2 O 3 see Non-Patent Document 2
- FeF 3 has a high average discharge voltage of about 1.7 V with respect to the lithium negative electrode and shows a theoretical capacity of 712 mAh / g (theoretical energy density 1210 mWh / g) in a three-electron reaction, whereas Fe 2 O 3 Although the average discharge voltage is about 1V, the theoretical capacity is 1007 mAh / g (theoretical energy density 1006 mWh / g) in a 6-electron reaction. Compared to these FeF 3 and Fe 2 O 3 , FeOF has an average discharge voltage of about 1.4 V and a theoretical capacity of 885 mAh / g in a three-electron reaction.
- the integrated value that is, the energy density that can be used as a battery is 1239 mWh / g, which is the highest of these. Therefore, as an interesting positive electrode active material having these significant features, a positive electrode active material made of FeOF, which is an oxyfluorolite-based iron compound containing both a fluorine element and an oxygen element, has attracted attention.
- a positive electrode active material composed of an oxyfluorolite-based iron compound a material containing lithium element is disclosed (see Patent Document 1), but there are few examples using FeOF as a positive electrode active material.
- FeOF is synthesized from a compound containing its constituent elements by solid-phase firing, which is generally used conventionally, damage to the heating furnace and FeOF itself will be caused. Therefore, FeOF is synthesized by solid-phase firing. So far, no reports have been reported.
- a positive electrode active material mainly composed of FeOF that is used in a nonaqueous electrolyte secondary battery and has excellent charge / discharge characteristics is not found.
- Non-Patent Document 3 As an alternative to solid-phase firing for obtaining FeOF as a positive electrode active material, for example, an ion exchange method in which the chlorine element of FeOCl is replaced with a fluorine element (see Non-Patent Document 3), or silicon containing in an oxygen atmosphere compound (FeSiF 6 ⁇ 6H 2 O) thermal decomposition method using a thermal decomposition (see non-Patent Document 4) have been proposed. In addition to this, a method of obtaining a single crystal of FeOF under high temperature and high pressure simply to obtain FeOF (see Non-Patent Document 5) is found.
- Non-patent Document 4 when producing FeOF as a positive electrode active material by using a thermal decomposition method (Non-patent Document 4), there is a problem that the production cost increases because the synthesis time requires a long time of 10 hours or more. Furthermore, for a synthesis product obtained, it is generated oxygen element and fluorine element mixing ratio sparse oxy fluoro lights (FeO x F 2? X) (0 ⁇ x ⁇ 1), until it produced a pure FeOF Has not reached. Further, the raw material FeSiF 6 remains in the composite as an impurity, and the performance as an electrode is degraded. For example, as shown also from the experimental results of discharge capacity with respect to the number of cycles shown in FIG.
- the discharge capacity decreases as the number of cycles increases, it remains at the maximum at about 380 mAh / g at the maximum.
- Non-patent Document 5 iron oxide Fe 2 O 3 and iron fluoride FeF 3 are used as starting materials, but fluorine atoms derived from fluorine atoms contained in the raw materials are volatilized. In order to prevent this, an extremely high gas pressure of 6 GPa (60 kbar) is required, which is not very suitable for mass production. Further, this method is exclusively for the production of a single crystal of FeOF, and no mention is made as to whether or not the single crystal FeOF is used as a positive electrode active material for a non-aqueous electrolyte secondary battery. There is also no proven data regarding battery properties as a material.
- the present invention has been proposed in order to solve the above-described problems, and can be easily manufactured in a shorter time than a conventional method, and a positive electrode active material mainly composed of FeOF having a sufficient charge-discharge capacity. And a positive electrode active material mainly composed of FeOF.
- the present inventors have newly found a method for producing a positive electrode active material mainly composed of FeOF suitable for a secondary battery using a non-aqueous electrolyte and a positive electrode active material mainly composed of FeOF. It was. Furthermore, it has been found that a non-aqueous electrolyte secondary battery with high operational stability can be constructed by selecting a negative electrode active material and combining it with a positive electrode active material mainly composed of FeOF.
- a method for producing a positive electrode active material containing FeOF as a main component in which both iron oxide Fe 2 O 3 and iron fluoride FeF 3 are mixed in a solid state, and an inert gas atmosphere is used.
- a method for producing a positive electrode active material is provided, which includes a step of melting and quenching at the same time.
- a positive electrode active material characterized in that FeOF is 50% or more and the balance is FeOF composed mainly of iron fluoride FeF 3 and / or iron oxide Fe 2 O 3. Is done.
- Fe 2 O 3: FeF 3 1: shows the XRD pattern results and discharge-charge result of the positive electrode active material composed mainly of FeOF produced according to the present invention the raw material molar ratio of 2.33.
- Fe 2 O 3: FeF 3 1: shows a 2.33 volume relationship to the current density of the positive electrode active material FeOF a main component produced by the present invention the raw material molar ratio, and capacity relationship to the number of cycles.
- a positive electrode active material mainly composed of FeOF can be produced by mixing iron oxide and iron fluoride together in a solid state and melting and quenching in an inert gas atmosphere. That is, by mixing iron oxide and iron fluoride as raw materials and melting and quenching in an inert gas atmosphere, fluorine is combined with solid iron oxide as much as possible, and the target oxygen element and fluorine A product containing the positive electrode active material FeOF containing the element is obtained.
- the target positive electrode active material is produced by melt quenching (method). That is, the target FeOF is obtained by cooling as quickly as possible so that the constituent components (particularly fluorine) are not volatilized from the state in which the raw iron oxide and iron fluoride are melted and mixed. To obtain a product containing as a main component.
- melt quenching various types of conventionally known melting (heating) means and quenching means can be used in combination.
- a known melting method such as a high frequency induction heating method or an arc melting method can be used.
- a known quenching method such as a single roll quenching method, a twin roll quenching method, an atomizing quenching method, or a splat quenching method can be used.
- the above-described known melting method and quenching method may be combined. Good.
- the raw material metal previously charged in the reaction vessel is melted with an induction coil, and then the molten raw metal is injected from the melting nozzle onto the surface of the single roll.
- the product can be obtained by rapid cooling at The heating temperature may be a temperature at which the raw iron oxide melts (for example, 1300 ° C.).
- the melting and quenching treatment according to the present invention is cooled as quickly as possible to suppress desorption due to vaporization of fluorine from the raw material metal.
- the high-frequency induction heating / single roll quenching apparatus used in the present invention includes a quartz tube 1 and a crucible 2 with a pilot hole placed inside the quartz tube 1 as shown in FIG.
- a copper tube coil 3 made of copper wound around the quartz tube 1 and a copper roll 4 as a solid cooling medium can be used.
- a raw material is put into a crucible 2 with a prepared hole placed inside a quartz tube 1, and a raw material metal falling from the prepared hole of the crucible with a prepared hole is induction-heated by a copper tube coil 3 (indicated by A in the figure). And the induction-heated raw material metal becomes a glass ribbon-like sample B and is rapidly cooled by coming into contact with a copper roll 4 as a metal water-cooled roll.
- the melting and quenching treatment according to the present invention is generally performed in an inert gas atmosphere such as nitrogen gas or argon gas, but it is preferable to use argon gas for ease of handling.
- an inert gas atmosphere such as nitrogen gas or argon gas, but it is preferable to use argon gas for ease of handling.
- the conditions of the melt quenching process such as the processing time, the rotation speed of the metal water cooling roll (copper roll), the induction heating speed, the cooling speed, etc., are analyzed and confirmed by XRD etc. What is necessary is just to determine so that the crystal
- FeOF which is a main component of the positive electrode active material for a non-aqueous electrolyte secondary battery is generated by the following reaction.
- FeOF can be obtained by setting the ratio of iron fluoride FeF 3 and iron oxide Fe 2 O 3 as raw materials to a stoichiometric ratio (equal molar ratio).
- fluorine has the property of being easily vaporized and desorbed from iron fluoride during melting and quenching, so that the ratio of iron fluoride to iron oxide is more fluorine than the stoichiometric ratio. It is preferable to make it.
- the ratio depends on the melting (heating) means and quenching means employed and the experimental conditions.
- the molar ratio of iron fluoride to iron oxide is 1 (stoichiometric ratio) or more but preferably 10 or less.
- iron fluoride is excessively added, the initial discharge capacity of the obtained positive electrode active material tends to decrease.
- a positive electrode active material that is produced by, for example, the above-described method and mainly contains FeOF. According to the finding of the present inventor, if 50% or more of FeOF is contained as a main component, even if the balance is iron fluoride (FeF 3 ) and / or iron oxide (Fe 2 O 3 ) What has sufficient battery characteristics as a positive electrode active material for water electrolyte secondary batteries is obtained. As described above, from the viewpoint of increasing the energy density that can be used as a battery, the higher the content of FeOF, the better the battery characteristics. Therefore, 60% or more is preferable, but it is excellent even if it is not 100%. A positive electrode active material exhibiting battery characteristics has been obtained. That is, according to the embodiment of the present invention, FeOF is 50% or more, preferably 60% or more, 99% or less, particularly preferably 96% or less, and the balance is FeF 3 and / or Fe 2 O 3. A positive electrode active material is provided.
- the positive electrode active material of the present invention containing FeOF as a main component has an intensity ratio of the diffraction peak of FeOF (110) plane to (101) plane of 2 or more in X-ray diffraction measurement using CuK ⁇ rays.
- the intensity ratio of the diffraction peak which is also characterized by this, is preferably 2 or more and 20 or less, more preferably 2 or more and 10 or less.
- the positive electrode active material mainly composed of FeOF according to the present invention as described above has a charge / discharge characteristic whose initial discharge capacity is approximately 900 mAh / g, which is almost equal to the theoretical capacity (see the examples described later).
- the positive electrode active material mainly composed of FeOF according to the present invention may be used as it is as a positive electrode of a non-aqueous electrolyte secondary battery.
- a composite with a known conductive material is used. It may be formed.
- the cathode active material mainly composed of FeOF according to the present invention is carbon coated by pulverizing and mixing together with carbon fine particles in an inert gas atmosphere.
- the carbon fine particles furnace black, channel black, acetylene black, thermal black, and the like can be used, but acetylene black is preferred because of its high conductivity when used as an electrode.
- the inert gas nitrogen gas, argon gas, or the like can be used.
- argon gas can be used.
- Specific means applied to the pulverization / mixing at the time of carbon coating are not particularly limited, and various means conventionally used for the purpose of pulverization / mixing of solid substances can be applied, A ball mill is preferable, and among these, a planetary ball mill is preferable because the raw materials can be sufficiently pulverized and mixed.
- a positive electrode active material mainly composed of FeOF for a nonaqueous electrolyte secondary battery a secondary battery positive electrode including the positive electrode active material, and a secondary battery in which the negative electrode is combined with the positive electrode.
- the positive electrode active material described above is used.
- the active material powder is mixed with a known binder such as polyethylene, if necessary, and a known conductive material such as acetylene black, if necessary, and the resulting mixed powder is made of stainless steel or the like. It can be pressure-molded on the support or filled into a metal container.
- An example of such a positive electrode is a pellet electrode.
- a pellet electrode as shown in FIG.1 (b), it can be comprised from the pellet electrode 10a, the spacer 11a, the coin cell container (lower lid) 12, and the nickel mesh 13 made from nickel, for example.
- the pellet electrode 10a can have a thickness of 10 mm, for example.
- the spacer 11 a mounts the nickel mesh 13, and the pellet electrode 10 a is mounted on the nickel mesh 13.
- the positive electrode of the present invention can also be produced by a method such as applying a slurry obtained by mixing the mixed powder with an organic solvent such as toluene onto a metal substrate such as aluminum, nickel, stainless steel, or copper. Can do.
- An example of such a positive electrode is a coated electrode.
- the application electrode for example, as shown in FIG. 1 (c), the application electrode 10 b, a spacer 11 b, and a coin cell container (lower lid) 12 can be configured.
- the coating electrode 10b can have an electrode diameter of 10 mm, for example.
- the spacer 11b the coating electrode 10b is spot-welded in the center part of the upper surface.
- a lithium compound or an alloy thereof can be used as the negative electrode (negative electrode active material) used in combination with the above positive electrode.
- the negative electrode may be manufactured by a known method, for example, by the same method as described above in relation to the positive electrode. That is, for example, if necessary, the negative electrode active material powder is mixed with the known binder described above and, if necessary, the known conductive material, and then the mixed powder is formed into a sheet. Then, this may be pressure-bonded to a conductor network (current collector) such as stainless steel or copper. Moreover, for example, it can also be produced by applying a slurry obtained by mixing the above mixed powder with the above-mentioned known organic solvent on a metal substrate such as copper.
- a conductor network current collector
- those used for known nonaqueous electrolyte secondary batteries can be used as components.
- the following can be illustrated.
- the electrolytic solution usually contains an electrolyte and a solvent.
- the solvent of the electrolytic solution is not particularly limited as long as it is non-aqueous, for example, carbonates, ethers, ketones, sulfolane compounds, lactones, nitriles, chlorinated hydrocarbons, ethers, amines, Esters, amides, phosphate ester compounds and the like can be used.
- Examples of these include 1,2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene carbonate (EC), vinylene carbonate, methyl formate, dimethyl sulfoxide, propylene carbonate, acetonitrile, ⁇ Butyrolactone, dimethylformamide, dimethyl carbonate (DMC), diethyl carbonate, sulfolane, ethyl methyl carbonate, 1,4-dioxane, 4-methyl-2-pentanone, 1,3-dioxolane, 4-methyl-1,3-dioxolane , Diethyl ether, sulfolane, methyl sulfolane, propionitrile, benzonitrile, butyronitrile, valeronitrile, 1,2-dichloroethane, trimethyl phosphate, triethyl phosphate, etc. . These can be used by 1 type (s)
- an electrolyte substance capable of performing migration for lithium ions in the negative electrode active material to electrochemically react with the positive electrode active material or the positive electrode active material and the negative electrode active material in the solvent for example, LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiAsF 6 , LiB (C 6 H 5 ) 4 , LiCl, LiBr, CH 3 SO 3 Li, CF 3 SO 3 Li, LiN (SO 2 CF 3) 2, LiN (SO 2 C 2 F 5) 2, LiC (SO 2 CF 3) 3, LiN (SO 3 CF 3) can be used 2 or the like, can be used LiPF 6, for example.
- non-aqueous electrolyte secondary battery conventionally known various materials can be used for elements such as a separator, a battery case, and other structural materials, and there is no particular limitation. What is necessary is just to assemble the non-aqueous electrolyte secondary battery which concerns on this invention according to a well-known method using said battery element.
- the shape of the battery is not particularly limited, and various shapes and sizes such as a cylindrical shape, a square shape, and a coin shape can be appropriately employed.
- Example 1 Iron oxide Fe 2 O 3 ( Soekawa Rika ) and iron fluoride FeF 3 ( Soekawa Rika ) were used as starting materials for the synthesis of a positive electrode active material mainly composed of FeOF by the melt quenching method .
- the starting material was weighed in a glove box so that Fe 2 O 3 and FeF 3 were in a molar ratio of 1: 2.33 (Fe 2 O 3 : FeF 3 ), and thoroughly mixed in an agate mortar.
- the mixed precursor starting material is put into a platinum crucible with a pilot hole (height 50 mm, hole diameter 12 mm) until the height is about 1/3, and then the platinum crucible is put into a quartz tube (height about 100 mm, The inner wall having a diameter of about 15 mm and a gap (wall spacing) of about 1 mm were introduced into the quartz tube and set in a single roll melting and quenching apparatus. The air inside the quartz tube was deaerated for about 10 minutes to a pressure of 10.sup.- 3 torr and then sealed as an argon gas atmosphere. Inductively heated and heated to about 1300 ° C.
- the obtained positive electrode active material sample was subjected to X-ray diffraction measurement (using Rigaku TTRIII) using CuK ⁇ rays. (As a result of the measurement)
- the result obtained by the XRD diffraction measurement is shown in FIG.
- the sample was assigned to the previously reported FeOF of the space group P4 2 / mnm (rutile tetragonal structure). From this result, it was shown that FeOF was synthesized by the melt quenching method.
- the charge / discharge measurement mode was CCV mode.
- the measurement conditions were such that the theoretical capacity for 1Li desorption was 1 C rate for the current density for charging and discharging in 1 hour, the current density was 0.2 mA / cm 2 , and the voltage range was 1.3 V to 4.0 V.
- FIG. 2B shows the results of the charge / discharge characteristics in the first cycle and the second cycle. From the results in the figure, it was shown that the discharge capacity reached 404 mAh / g.
- FIG. 3A shows the results of FeOF current density and discharge capacity for lithium metal. From the result of FIG. 9A, it was shown that 350 mAh / g was maintained even when the current density was 1/4 C (horizontal axis 0.25 in the figure). Furthermore, the same figure (b) shows the result of the charging / discharging capacity
- 6B are the results of charge / discharge capacity and voltage (2) measured by 1 Li constant current discharge (constant current 60 mA / g; current density 0.11 mA / cm 2 ), respectively.
- the results of the charge / discharge capacity measured at 0.0 to 4.0 V) are shown. From these results, a constant capacity was maintained even after 10 cycles without any decrease in capacity due to charge / discharge. It was shown that.
- Example 2 Synthesis of Positive Electrode Active Material with FeOF as Main Component at Different Raw Material Ratios
- the X-ray diffraction measurement was performed on the positive electrode active material sample obtained by changing the melting time from Example 1 with a melting time of 45 seconds.
- compositions and calculation of intensity ratio of diffraction peak were calculated from the results of X-ray diffraction measurement using the above-described CuK ⁇ ray. That is, the composition (%) of FeOF and the remaining components (FeF 3 and Fe 2 O 3 ) in the obtained positive electrode active material sample was determined when the obtained positive electrode active material sample was measured by X-ray diffraction using CuK ⁇ rays. It calculated from the intensity ratio (peak height ratio) of the main peak derived from each of the appearing FeOF, FeF 3 and Fe 2 O 3 (see Table 1 described later).
- the intensity ratio of the diffraction peaks is based on the intensity ratio (peak height ratio) of the main peak derived from each of the (110) plane and (101) plane of FeOF that appears when X-ray diffraction measurement is performed using CuK ⁇ rays. It calculated (refer Table 2 mentioned later).
- the XRD measurement result (chart) of the obtained positive electrode active material sample is shown.
- the peak indicated by a is the main peak derived from FeF 3
- the peak indicated by b is the main peak derived from Fe 2 O 3
- the peak indicated by c Is the main peak derived from the (110) plane of FeOF
- the peak indicated by d is the main peak derived from the (101) plane of FeOF.
- the main component is FeOF, which has a high intensity ratio of the diffraction peak of (110) face to (101) face of FeOF and is 2 or more. It was found that a positive electrode active material was obtained.
- Example 4B when the melting time of Example 1 was changed to 45 seconds, the raw material iron oxide Fe 2 O 3 that did not remain in Example 1 tends to remain in the product. there were. For this reason, it turned out that it is suitable for the experimental conditions of Example 1 that the melting time is 40 seconds.
- FIG. 5B shows that the initial discharge capacity has reached about 800 mAh / g, and that a positive electrode active material mainly composed of FeOF having a sufficient quality as a positive electrode of a secondary battery is obtained. It was. In particular, it was found that the discharge curve was flat at 3.2 V, which is an insertion potential derived from FeF 3, and 2.5 V, which is an insertion potential derived from FeOF. From this, it was found that an unprecedented positive electrode active material having both excellent characteristics of FeF 3 and FeOF can be obtained.
- the positive electrode active material according to the present invention containing FeOF as a main component and the balance being iron fluoride FeF 3 and / or iron oxide Fe 2 O 3 exhibits extremely good battery characteristics.
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Abstract
Description
となる酸化鉄とフッ化鉄とが溶融して混合している状態から、構成成分(特にフッ素)の
揮散がないように可及的速やかに冷却を行うことにより、目的となるFeOFを主成分とする生成物を得る。このような溶融急冷には、従来から知られている各種の溶融(加熱)手段と急冷手段とを組み合わせて用いることができる。
Fe2O3+FeF3→ 3FeOF
溶融急冷法によるFeOFを主成分とする正極活物質の合成
出発物質には、酸化鉄Fe2O3(添川理化学)とフッ化鉄FeF3 (添川理化学)を使用した。出発物質はグローブボックス内で、Fe2O3とFeF3がモル比で1:2.33(Fe2O3:FeF3)になるよう秤量し、瑪瑙乳鉢により充分に混合した。混合した前駆体出発物質は下穴付き白金坩堝(高さ50 mm, 穴直径12 mm)の高さ約1/3となるまで入れた後、当該白金坩堝を石英管(高さ約100 mm, 直径約15 mm)の内壁と約1mmのギャップ(壁間隔)で、石英管の内部に導入し、単ロール溶融急冷装置にセットした。石英管内部の空気を約10分間脱気して圧力を10?3torrとした後、アルゴンガス雰囲気として封鎖した。誘導加熱し、約5秒間で約1300℃(石英管の長手方向に長さ15mmで石英管の周囲に巻かれたチューブコイルの隙間から石英管に光を照射することで測定)に昇温させた。この温度を約40秒間維持した。原料が溶融した後に上記下穴から滴下したのを見計らって、アルゴンガスを石英管に約1分間追加注入し、2000rpmで回転する銅ロール上に上記下穴から射出させてガラスリボン状のサンプルを得た。試料の大気暴露を避けるため、得られたサンプルはグローブボックス内で瑪瑙乳鉢を用いて粉末状にして正極活物質とした。なお、試料の合成における大気暴露は単ロール急冷装置への白金坩堝の設置およびその後の試料回収時のみとした。
(測定の方法)
得られた正極活物質サンプルをCuKα線を用いてX線回折測定(リガクTTRIIIを使用)した。
(測定の結果)
XRD回折測定により得られた結果を図2(a)に示す。サンプルは、既に報告されている空間群P42/mnm(ルチル型正方晶系構造)のFeOFに帰属された。この結果から、溶融急冷法によってFeOFが合成されたことが示された。
溶融急冷により得られた正極活物質サンプルを瑪瑙乳鉢で粉砕後、重量比でFeOF:アセチレンブラック:PTFE結着剤を70:25:5で秤量し、f10mmディスク(約30mg)に収納してペレットに成型して正極とした。この正極に、リチウム金属を負極として、電解液に1 mol dm-3 ヘキサフルオロリン酸リチウム/エチレンカーボネート+ジメチルカーボネート[LiPF6 / EC+DMC(体積比EC:DMC=1:1)]を用いてステンレス製の2032型コインセル(直径20×3.2mm)を作成し、以下の放充電試験を行った。
充放電測定モードはCCVモードで行った。測定条件は、1Li脱離の理論容量を1時間で充放電する電流密度を1Cレートとし、電流密度0.2 mA/cm2、電圧範囲1.3 V?4.0 Vで行った。第1サイクルと第2サイクルにおける放充電特性の結果を図2(b)に示す。同図の結果から、放電能力は404mAh/gに達したことが示された。
異なる原料比でのFeOFを主成分とする正極活物質の合成
上述の実施例1と原料のモル比を変えて正極活物質を作製した。すなわち、Fe2O3とFeF3のモル比を変えて(具体的には、酸化鉄Fe2O3:フッ化鉄FeF3=(1:2.13)、(1:1.86)、(1:5)、(1:10)を選定)秤量し、上記の実施例1と同様の手順でFeOFを主成分とする正極活物質を作製した。
(算出の方法)
得られた正極活物質サンプルの組成および回折ピークの強度比は、上述のCuKα線を用いたX線回折測定の結果から算出した。
すなわち、得られた正極活物質サンプルにおけるFeOFおよび残部成分(FeF3およびFe2O3)の組成(%)は、得られた正極活物質サンプルをCuKα線を用いてX線回折測定した際に現れるFeOF、FeF3およびFe2O3のそれぞれに由来するメインピークの強度比(ピークハイト比)から算出した(後述の表1参照)。
また、回折ピークの強度比については、CuKα線を用いてX線回折測定した際に現れるFeOFの(110)面および(101)面のそれぞれに由来するメインピークの強度比(ピークハイト比)から算出した(後述の表2参照)。
図中、横軸の2θの値について、aで示されるピークがFeF3に由来するメインピークであり、bで示されるピークがFe2O3に由来するメインピークであり、cで示されるピークがFeOFの(110)面に由来するメインピークであり、dで示されるピークがFeOFの(101)面に由来するメインピークである。例えば、図4(a)から、原料の組成比がFe2O3:FeF3=1:10の場合については、FeOF、FeF3およびFe2O3のそれぞれに由来するメインピークの強度比(ピークハイト比)がFeF3:Fe2O3:FeOF=a:b:c=4:0:6となっていることから、その組成比については、FeOFが60%でありFeF3が40%であると算出した。また、図4(a)から、当該原料の組成比の場合について、FeOFの(110)面および(101)面のそれぞれに由来するメインピークの強度比(ピークハイト比)は、FeOF(110):FeOF(101)=5.9:1を算出した。
上述のように、得られたFeOFを主成分とする正極活物質に含まれる各成分の組成(%)について、XRD回折測定により算出した以下の結果が得られた。
得られた正極活物質について実施例1と同様に充放電試験を実施した。その結果を図5に示す。
先ず、酸化鉄Fe2O3:フッ化鉄FeF3=(1:1.86)、(1:2.13)、(1:2.33)から得られた正極活物質に関して、1.3V?4.0V(0.2mA/cm2、1 M LiPF6、 EC:DMC=1:1)の放充電特性を図5(a)に示す。同図から、いずれの原料の場合においても二次電池の正極として十分な品質のFeOFを主成分とする正極活物質が得られている。
2 下穴付き坩堝
3 銅チューブコイル
4 銅ロール
10a ペレット電極
10b 塗布電極
11a スペーサー
11b スペーサー
12 コインセル容器(下蓋)
13 ニッケルメッシュ
Claims (4)
- FeOFを主成分とする正極活物質の製造方法であって、酸化鉄Fe2O3とフッ化鉄FeF3とを共に固体状態で混合し、不活性ガス雰囲気下で溶融急冷する工程を含むことを特徴とする正極活物質の製造方法。
- 高周波誘導加熱と単ロール急冷を用いて溶融急冷を行い、酸化鉄Fe2O3に対するフッ化鉄FeF3のモル比を1以上10以下とすることを特徴とする請求項1に記載の正極活物質の製造方法。
- FeOFが50%以上であり、残部がフッ化鉄FeF3および/または酸化鉄Fe2O3から成るFeOFを主成分とすることを特徴とする正極活物質。
- FeOFが50%以上であり、残部がフッ化鉄FeF3および/または酸化鉄Fe2O3から成り、CuKα線を用いるX線回折測定において、FeOFの(110)面の(101)面に対する回折ピークの強度比が2以上である、FeOFを主成分とすることを特徴とする正極活物質。
Priority Applications (5)
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KR1020137033270A KR20140024920A (ko) | 2011-06-22 | 2012-06-22 | 옥시플루오로라이트계 양극 활물질의 제조 방법 및 옥시플루오로라이트계 양극 활물질 |
US14/128,470 US9312538B2 (en) | 2011-06-22 | 2012-06-22 | Method for producing iron oxyfluoride positive electrode active substance and iron oxyflouride positive electrode active substance |
JP2013521648A JP5991680B2 (ja) | 2011-06-22 | 2012-06-22 | オキシフルオロライト系正極活物質の製造方法およびオキシフルオロライト系正極活物質 |
EP12802330.6A EP2725643B1 (en) | 2011-06-22 | 2012-06-22 | Method for producing iron oxyfluoride positive electrode active substance |
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Cited By (6)
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JP2014220203A (ja) * | 2013-05-10 | 2014-11-20 | 国立大学法人九州大学 | ナトリウムイオン電池用の正極活物質およびその製造方法 |
EP2973800A4 (en) * | 2013-03-13 | 2016-10-05 | Quantumscape Corp | IRON, FLUOROUS AND SULFUR COMPOUNDS FOR CATHODES |
US10326135B2 (en) | 2014-08-15 | 2019-06-18 | Quantumscape Corporation | Doped conversion materials for secondary battery cathodes |
US10511012B2 (en) | 2012-07-24 | 2019-12-17 | Quantumscape Corporation | Protective coatings for conversion material cathodes |
JPWO2019004288A1 (ja) * | 2017-06-30 | 2020-04-23 | 株式会社村田製作所 | 非水系二次電池用の正極活物質、およびそれを用いた非水系二次電池 |
US11764398B1 (en) * | 2022-04-29 | 2023-09-19 | Toyota Motor Engineering & Manufacturing North America, Inc. | Inorganic precursors for ionic conductors |
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CN104282882B (zh) * | 2014-09-26 | 2017-01-11 | 江苏华东锂电技术研究院有限公司 | 正极复合材料及其制备方法 |
US20210249654A1 (en) * | 2018-06-13 | 2021-08-12 | Yadong Liu | Fast charge feof cathode for lithium ion batteries |
CN111129423B (zh) * | 2018-10-30 | 2021-08-06 | 深圳市比亚迪锂电池有限公司 | 一种锂离子电池负极材料及其制备方法、锂离子电池负极和锂离子电池 |
CN110508299B (zh) * | 2019-09-03 | 2022-04-19 | 北京邮电大学 | 一种迅速升温制备二维局域氧化的过渡族金属氟化物催化剂方法 |
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CN113871591B (zh) * | 2021-09-24 | 2023-04-11 | 中国科学院过程工程研究所 | 一种铁基电极材料及其制备方法和应用 |
WO2023184274A1 (zh) * | 2022-03-30 | 2023-10-05 | 宁德新能源科技有限公司 | 正极活性材料、电化学装置和电子设备 |
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- 2012-06-22 KR KR1020137033270A patent/KR20140024920A/ko not_active Application Discontinuation
- 2012-06-22 EP EP12802330.6A patent/EP2725643B1/en not_active Not-in-force
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Cited By (8)
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US10511012B2 (en) | 2012-07-24 | 2019-12-17 | Quantumscape Corporation | Protective coatings for conversion material cathodes |
EP2973800A4 (en) * | 2013-03-13 | 2016-10-05 | Quantumscape Corp | IRON, FLUOROUS AND SULFUR COMPOUNDS FOR CATHODES |
US9786905B2 (en) | 2013-03-13 | 2017-10-10 | Quantumscape Corporation | Iron, fluorine, sulfur compounds for battery cell cathodes |
JP2014220203A (ja) * | 2013-05-10 | 2014-11-20 | 国立大学法人九州大学 | ナトリウムイオン電池用の正極活物質およびその製造方法 |
US10326135B2 (en) | 2014-08-15 | 2019-06-18 | Quantumscape Corporation | Doped conversion materials for secondary battery cathodes |
JPWO2019004288A1 (ja) * | 2017-06-30 | 2020-04-23 | 株式会社村田製作所 | 非水系二次電池用の正極活物質、およびそれを用いた非水系二次電池 |
JP7047841B2 (ja) | 2017-06-30 | 2022-04-05 | 株式会社村田製作所 | 非水系二次電池用の正極活物質、およびそれを用いた非水系二次電池 |
US11764398B1 (en) * | 2022-04-29 | 2023-09-19 | Toyota Motor Engineering & Manufacturing North America, Inc. | Inorganic precursors for ionic conductors |
Also Published As
Publication number | Publication date |
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US9312538B2 (en) | 2016-04-12 |
JP5991680B2 (ja) | 2016-09-14 |
CN103718352B (zh) | 2016-12-14 |
EP2725643A1 (en) | 2014-04-30 |
JPWO2012176907A1 (ja) | 2015-02-23 |
EP2725643B1 (en) | 2019-01-02 |
CN103718352A (zh) | 2014-04-09 |
KR20140024920A (ko) | 2014-03-03 |
US20140291573A1 (en) | 2014-10-02 |
EP2725643A4 (en) | 2015-04-01 |
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