WO2016199358A1 - シリコン材料およびその製造方法 - Google Patents
シリコン材料およびその製造方法 Download PDFInfo
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- WO2016199358A1 WO2016199358A1 PCT/JP2016/002477 JP2016002477W WO2016199358A1 WO 2016199358 A1 WO2016199358 A1 WO 2016199358A1 JP 2016002477 W JP2016002477 W JP 2016002477W WO 2016199358 A1 WO2016199358 A1 WO 2016199358A1
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- silicon material
- alloy
- silicon
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- xat
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Images
Classifications
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- C01B33/00—Silicon; Compounds thereof
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- C01B33/021—Preparation
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/04—Hydrides of silicon
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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- H—ELECTRICITY
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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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 silicon material and a manufacturing method thereof.
- Silicon materials are known to be used as components of semiconductors, solar cells, secondary batteries and the like, and in recent years, research on silicon materials has been actively conducted.
- Non-Patent Document 1 describes that layered polysilane is synthesized by reacting CaSi 2 with an acid.
- Patent Document 1 describes that CaSi 2 is reacted with an acid to synthesize layered polysilane, and that a lithium ion secondary battery including the layered polysilane as an active material exhibits a suitable capacity. ing.
- Patent Document 2 a layered silicon compound composed mainly of a layered polysilane obtained by reacting CaSi 2 with an acid to remove Ca and synthesizing the layered silicon compound and heating the layered silicon compound at 300 ° C. or more to release hydrogen is disclosed. It is described that the material was manufactured and that a lithium ion secondary battery including the silicon material as an active material exhibits a suitable capacity maintenance rate.
- JP 2011-090806 A International Publication No. 2014/080608
- the present invention has been made in view of such circumstances, and an object thereof is to provide a manufacturing method capable of manufacturing a silicon material of a desired size without requiring a pulverizing action by a pulverizer.
- the silicon material is produced after converting the starting material CaSi 2 into a precursor layered silicon compound.
- the present inventor thought that if the crystal grain size of CaSi 2 contained in the starting material was reduced, the resulting silicon material would be finely divided.
- the present inventor has found that there is a correlation between the crystal grain size of CaSi 2 contained in the starting material and the particle diameter of the obtained silicon material. The inventor has completed the present invention based on such findings.
- the method for producing the silicon material of the present invention comprises: A melt preparation step of preparing a Ca-xat% Si alloy (42 ⁇ x ⁇ 75) melt, A solidification step of cooling the molten metal with a rapid cooling device to solidify the Ca-xat% Si alloy; A synthesis step of obtaining a layered silicon compound by reacting a solidified Ca-xat% Si alloy with an acid; A heating step of heating the layered silicon compound at 300 ° C. or higher; It is characterized by including.
- the silicon material manufacturing method of the present invention can manufacture a silicon material of a desired size without requiring a pulverizing action by a pulverizer.
- FIG. 2 is a powder X-ray diffraction chart of a first solid material of Comparative Example 1 and solidified CaSi 2 after pulverization of Comparative Example 1.
- FIG. 2 is an SEM image of solidified CaSi 2 of Example 1.
- FIG. 4 is a SEM image of massive solidified CaSi 2 of Comparative Example 1.
- 3 is an X-ray diffraction chart of solidified CaSi 2 of Example 2.
- FIG. 3 is an X-ray diffraction chart of the silicon material of Example 2.
- the numerical range “x to y” described in this specification includes the lower limit x and the upper limit y.
- the numerical range can be configured by arbitrarily combining these upper limit value and lower limit value and the numerical values listed in the examples.
- numerical values arbitrarily selected from the numerical value range can be used as upper and lower numerical values.
- the method for producing the silicon material of the present invention comprises: A melt preparation step of preparing a Ca-xat% Si alloy (42 ⁇ x ⁇ 75) melt, A solidification step of cooling the molten metal with a rapid cooling device to solidify the Ca-xat% Si alloy; A synthesis step of obtaining a layered silicon compound by reacting a solidified Ca-xat% Si alloy with an acid; A heating step of heating the layered silicon compound at 300 ° C. or higher; It is characterized by including.
- the silicon material produced by the method for producing a silicon material of the present invention may be referred to as “silicon material of the present invention”.
- the Ca-xat% Si alloy means an alloy containing Ca and Si, and the element% of Si with respect to the total number of elements of Ca and Si is x.
- the alloy may contain inevitable impurities, or may contain an element M selected from Group 3 to Group 9 elements.
- the element M can combine with Si in the alloy to form MSi a (1/3 ⁇ a ⁇ 3) such as MSi 2 or MSi. Then, MSi a, since the silicon material of the present invention can function as a buffer when to expand and contract, a secondary battery having a silicon material of the present invention containing MSi a as a negative electrode active material is durable It can be said that it is excellent.
- the element M may be a single element selected from Group 3 to Group 9 elements or a plurality of elements.
- As the element M Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Sc, and Fe are preferable.
- the ratio of the element M contained in the Ca-xat% Si alloy is preferably in the range of 0.01 to 10% by mass, more preferably in the range of 0.1 to 7% by mass, and 1 to 5% by mass. Within the range is more preferable.
- a method for preparing the molten Ca—xat% Si alloy for example, a method of heating purchased or synthesized CaSi 2 with a heating device to form a molten metal, A method in which a mixture in which a Si source is mixed at a molar ratio of about 1: 4/3 to 1: 3 is heated with a heating device to form a molten metal may be used.
- a Ca-xat% Si alloy (42 ⁇ x ⁇ 75) molten metal may be prepared by a method in which a Ca source is charged into the Si-containing molten metal.
- a heating apparatus a high frequency induction heating apparatus, an electric furnace, and a gas furnace can be used, for example.
- the molten metal preparation step may be performed under pressure or reduced pressure, or in an inert gas atmosphere such as argon.
- the Ca source and Si source may be each simple substance, an alloy, or a compound containing each element. From the standpoint of obtaining a high-purity target product, the Ca source and the Si source are preferably each simple substance and / or Ca—Si alloy.
- the molten metal may be prepared using the M source in addition to the Ca source and the Si source. Moreover, the molten metal may be prepared using a Ca source and / or Si source containing the element M in advance, or the molten metal may be prepared using CaSi 2 containing the element M in advance.
- purchased CaSi 2 often contains impurities, and the molar ratio of Ca to Si is often not exactly 1: 2. Usually, the purchased CaSi 2 contains more Si than the theoretical value.
- the melting point of the Ca-xat% Si alloy (42 ⁇ x ⁇ 75) is 1030 to 1300 ° C., and considering the handling after melting, the temperature of the molten metal is preferably 50 ° C. or more higher than the melting point. On the other hand, if the molten metal temperature is too higher than the melting point, the cooling efficiency is lowered, so that the crystal grain size of the Ca—xat% Si alloy obtained after cooling tends to be large.
- preferable molten metal temperature ranges include melting point +50 to + 350 ° C., melting point +50 to + 250 ° C., melting point +50 to + 150 ° C.
- the rapid cooling device described in the present specification does not include a device that cools the molten metal by leaving it, and means a device that forcibly cools the molten metal.
- a rapid cooling device for example, 100 ° C./sec or more, preferably 1000 ° C./sec
- the crystal grain size is relatively Small CaSi 2 is produced.
- the crystal grain size of CaSi 2 generated in the solidification step determines the particle size of the target silicon material.
- Examples of the range of the average diameter of the CaSi 2 crystal grain size generated in the solidification step include 0.1 to 100 ⁇ m, 0.1 to 50 ⁇ m, 0.1 to 20 ⁇ m, 0.5 to 15 ⁇ m, and 1 to 10 ⁇ m.
- the average diameter of the crystal grain size of CaSi 2 means the average value of the obtained diameters in the following manner.
- a solidified Ca-xat% Si alloy is obtained in a powder state.
- each particle in a powder state may be obtained as a single crystal.
- the value of D50 when measured with a general laser diffraction particle size distribution measuring device may be adopted as the average diameter of the CaSi 2 crystal grain size generated in the solidification step.
- the molten metal is injected by a cooling means (so-called melt span method, strip cast method, or melt spinning method) for injecting molten metal onto a rotating cooling roll, or a method of spraying a fluid to a trickled molten metal.
- a cooling device using a cooling means such as an atomizing method for powdering can be exemplified.
- the atomizing method include a gas atomizing method, a water atomizing method, a centrifugal atomizing method, and a plasma atomizing method.
- Specific rapid cooling devices include a liquid rapid solidification device, a rapid cooling flake production device, a submerged spinning device, a gas atomizing device, a water atomizing device, a rotating disk device, a rotating electrode method device (above, Nisshin Giken Co., Ltd.), liquid Examples include a quenching device, a gas atomizing device (Makabe Giken Co., Ltd.), and a centrifugal powder manufacturing device (Ducol Co., Ltd.).
- the rapid cooling device a cooling device using an atomizing method for pulverizing molten metal is preferable.
- the reason is that the Ca-xat% Si alloy is obtained in a powder state such as a spherical shape or an ellipsoidal shape, so that the fluidity of the alloy is good and the handling is excellent, and the alloy is obtained in a powder state. Therefore, the reaction time in the following synthesis process can be shortened.
- the cooling rate of the solidification process may be increased. Specifically, the number of rotations of the cooling roll or rotating disk is increased, the temperature of the cooling roll or rotating disk is decreased, the temperature of the cooling fluid is decreased, the supply amount of the cooling fluid is increased, per unit time What is necessary is just to employ
- the molten metal preparation step and the solidification step may be collectively referred to as a preparation step of preparing a Ca—xat% Si alloy (42 ⁇ x ⁇ 75) containing CaSi 2 crystal grains of a desired size.
- a synthesis process for obtaining a layered silicon compound by reacting a solidified Ca-xat% Si alloy with an acid will be described.
- Si forms an Si—H bond while Ca is replaced with acid H.
- the layered silicon compound is layered because the basic skeleton of the Si layer made of CaSi 2 constituting the raw material Ca—xat% Si alloy is maintained.
- Acids include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, methanesulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluoroarsenic acid And fluoroantimonic acid, hexafluorosilicic acid, hexafluorogermanic acid, hexafluorotin (IV) acid, trifluoroacetic acid, hexafluorotitanic acid, hexafluorozirconic acid, trifluoromethanesulfonic acid, and fluorosulfonic acid. These acids may be used alone or in combination.
- an acid capable of generating a fluorine anion as the acid.
- the acid Si—O bonds that can be generated in the layered silicon compound and bonds between Si and anions of other acids (for example, Si—Cl bond in the case of hydrochloric acid) can be reduced.
- Si—O bonds or Si—Cl bonds may exist in the silicon material even after the next step.
- a lithium ion secondary battery employing a silicon material having a Si—O bond or Si—Cl bond as a negative electrode active material, it is estimated that the Si—O bond or Si—Cl bond inhibits the movement of lithium ions. .
- the acid used in the synthesis step may be used in an amount capable of supplying a proton equivalent to 2 equivalents or more with respect to Ca of the Ca—xat% Si alloy. Therefore, a monovalent acid may be used in an amount of 2 mol or more with respect to 1 mol of Ca in the Ca-xat% Si alloy.
- this step may be performed without a solvent, it is preferable to employ water as a solvent from the viewpoint of separation of a target product and removal of by-products such as CaCl 2 .
- the reaction conditions in this step are preferably reduced pressure conditions such as vacuum or an inert gas atmosphere, and are preferably temperature conditions of room temperature or lower such as an ice bath. What is necessary is just to set the reaction time of the same process suitably.
- Si 6 H 6 corresponds to polysilane which is an ideal layered silicon compound.
- the synthesis step it is preferable to be carried out in the presence of water, and since Si 6 H 6 can react with water, usually, the layered silicon compound is hardly obtained only with a compound of Si 6 H 6 , Contains elements derived from oxygen and acids.
- a filtration step for filtering the layered silicon compound After the synthesis step, it is preferable to appropriately perform a filtration step for filtering the layered silicon compound, a washing step for washing the layered silicon compound, and a drying step for drying the layered silicon compound as necessary.
- the layered silicon compound is heated at 300 ° C. or higher to release hydrogen, water, and the like, thereby obtaining a silicon material.
- the chemical reaction of this step is represented by an ideal reaction formula as follows. Si 6 H 6 ⁇ 6Si + 3H 2 ⁇
- the layered silicon compound actually used in the heating process contains oxygen and acid-derived elements and also contains unavoidable impurities
- the actually obtained silicon material also contains oxygen and acid-derived elements and is unavoidable. It also contains impurities.
- the heating step is preferably performed in a non-oxidizing atmosphere having a lower oxygen content than in normal air.
- the non-oxidizing atmosphere include a reduced pressure atmosphere including a vacuum and an inert gas atmosphere.
- the heating temperature is preferably in the range of 350 ° C. to 1100 ° C., more preferably in the range of 400 ° C. to 1000 ° C. If the heating temperature is too low, hydrogen may not be released sufficiently, and if the heating temperature is too high, energy is wasted. What is necessary is just to set a heating time suitably according to heating temperature. It is preferable to determine the heating time while measuring the amount of hydrogen or the like that escapes from the reaction system.
- the heating temperature and the heating time By appropriately selecting the heating temperature and the heating time, the ratio of amorphous silicon and silicon crystallites contained in the silicon material to be manufactured, and the size of the silicon crystallites can also be adjusted. By appropriately selecting the heating temperature and the heating time, the shape of a nano-level layer containing amorphous silicon and silicon crystallites contained in the manufactured silicon material can be prepared.
- the size of the silicon crystallite is preferably nano-sized.
- the silicon crystallite size is preferably in the range of 0.5 nm to 300 nm, more preferably in the range of 1 nm to 100 nm, further preferably in the range of 1 nm to 50 nm, and particularly in the range of 1 nm to 10 nm. preferable.
- the silicon crystallite size is calculated from Scherrer's equation using X-ray diffraction measurement (XRD measurement) on the silicon material and using the half width of the diffraction peak of the Si (111) plane of the obtained XRD chart.
- the silicon material having a structure in which a plurality of plate-like silicon bodies are laminated in the thickness direction can be obtained by the heating step. This structure can be confirmed by observation with a scanning electron microscope or the like.
- the plate-like silicon body has a thickness in the range of 10 nm to 100 nm for efficient insertion and removal of lithium ions. Are preferred, and those in the range of 20 nm to 50 nm are more preferred.
- the length of the plate-like silicon body in the major axis direction is preferably in the range of 0.1 ⁇ m to 50 ⁇ m.
- the plate-like silicon body preferably has a (length in the long axis direction) / (thickness) range of 2 to 1000.
- amorphous silicon is used as a matrix and silicon crystallites are scattered in the matrix.
- the element M When the element M is included in the silicon material of the present invention, it can exist as MSi a (1/3 ⁇ a ⁇ 3). Specific MSi a, TiSi 2, TiSi, ZrSi 2, HfSi 2, VSi 2, NbSi 2, TaSi 2, CrSi 2, CrSi 1/3, MoSi 2, MoSi 1/3, MoSi 3/5, WSi 2 , FeSi 2 , and FeSi.
- the shape of MSi a, spherical, needle, plate, disc-shaped, annular be exemplified.
- the element M when the element M is Fe, cyclic FeSi 2 covering the outer surface of the silicon material body may be observed.
- the silicon material of the present invention can be obtained as a powder without using a special pulverizer. Moreover, even if a lump exists in the silicon material of the present invention, the lump becomes a powder state by applying a slight pressure. For this reason, the silicon material of the present invention does not have cracks or strains on the particle surface due to the use of a pulverizer, which seems to have occurred in the conventional powdered silicon material. Therefore, it can be said that the silicon material of the present invention is excellent in durability against various uses.
- Examples of the preferable average particle diameter range of the silicon material of the present invention include 1 to 100 ⁇ m, 1 to 50 ⁇ m, 1 to 20 ⁇ m, 1 to 15 ⁇ m, and 3 to 10 ⁇ m.
- the average particle diameter of the silicon material of the present invention means D50 when measured with a general laser diffraction particle size distribution measuring apparatus.
- Examples of the shape of the silicon material of the present invention include spherical and ellipsoidal shapes.
- the silicon material of the present invention can be used as a negative electrode active material for power storage devices such as secondary batteries such as lithium ion secondary batteries, electric double layer capacitors, and lithium ion capacitors.
- the silicon material of the present invention can be used as a material such as a CMOS, a semiconductor memory and a solar cell, or a photocatalytic material.
- the lithium ion secondary battery of the present invention comprises the silicon material of the present invention as a negative electrode active material.
- the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode including the silicon material of the present invention as a negative electrode active material, an electrolytic solution, and a separator.
- the positive electrode has a current collector and a positive electrode active material layer bound to the surface of the current collector.
- a current collector refers to a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharge or charging of a lithium ion secondary battery.
- the current collector at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, and stainless steel, etc. Metal materials can be exemplified.
- the current collector may be covered with a known protective layer. What collected the surface of the electrical power collector by the well-known method may be used as an electrical power collector.
- the current collector can take the form of a foil, a sheet, a film, a linear shape, a rod shape, a mesh, or the like. Therefore, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.
- a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.
- the thickness is preferably in the range of 1 ⁇ m to 100 ⁇ m.
- the positive electrode active material layer contains a positive electrode active material and, if necessary, a conductive additive and / or a binder.
- a positive electrode active material a solid solution composed of a spinel such as LiMn 2 O 4 and a mixture of a spinel and a layered compound, LiMPO 4 , LiMVO 4 or Li 2 MSiO 4 (wherein M is Co, Ni, Mn, And a polyanionic compound represented by (selected from at least one of Fe).
- tavorite compound the M a transition metal
- LiMPO 4 F such as LiFePO 4 F represented by, Limbo 3 such LiFeBO 3 (M is a transition metal
- Limbo 3 such LiFeBO 3 (M is a transition metal
- M is a transition metal
- any metal oxide used as the positive electrode active material may have the above-described composition formula as a basic composition, and those obtained by substituting the metal elements contained in the basic composition with other metal elements can also be used as the positive electrode active material.
- a positive electrode active material a positive electrode active material that does not contain lithium ions that contribute to charge / discharge, for example, sulfur alone, a compound in which sulfur and carbon are combined, a metal sulfide such as TiS 2 , V 2 O 5 , MnO 2 and other oxides, polyaniline and anthraquinone, compounds containing these aromatics in the chemical structure, conjugated materials such as conjugated diacetate-based organic substances, and other known materials can also be used.
- a compound having a stable radical such as nitroxide, nitronyl nitroxide, galvinoxyl, phenoxyl, etc. may be adopted as the positive electrode active material.
- a positive electrode active material that does not contain lithium it is necessary to add ions to the positive electrode and / or the negative electrode in advance by a known method.
- a metal or a compound containing the ion may be used.
- Conductive aid is added to increase the conductivity of the electrode. Therefore, the conductive auxiliary agent may be added arbitrarily when the electrode conductivity is insufficient, and may not be added when the electrode conductivity is sufficiently excellent.
- the conductive auxiliary agent may be a chemically inert electronic high conductor, such as carbon black, graphite, vapor grown carbon fiber (Vapor Grown Carbon Fiber: VGCF), and various metal particles. Illustrated. Examples of carbon black include acetylene black, ketjen black (registered trademark), furnace black, and channel black. These conductive assistants can be added to the active material layer alone or in combination of two or more.
- the binder serves to hold the active material and the conductive auxiliary agent on the surface of the current collector and maintain the conductive network in the electrode.
- the binder include fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene, and fluororubber, thermoplastic resins such as polypropylene and polyethylene, imide resins such as polyimide and polyamideimide, alkoxysilyl group-containing resins, poly ( Examples include acrylic resins such as (meth) acrylic acid, styrene-butadiene rubber (SBR), alginate such as carboxymethylcellulose, sodium alginate, ammonium alginate, water-soluble cellulose ester crosslinked product, starch-acrylic acid graft polymer. it can. These binders may be used singly or in plural.
- the negative electrode has a current collector and a negative electrode active material layer bound to the surface of the current collector. What is necessary is just to employ
- the negative electrode active material layer includes a negative electrode active material and, if necessary, a conductive additive and / or a binder.
- the silicon material of the present invention may be used, and only the silicon material of the present invention may be employed, or the silicon material of the present invention and a known negative electrode active material may be used in combination.
- a material obtained by coating the silicon material of the present invention with carbon may be used as the negative electrode active material.
- a current collecting method such as a roll coating method, a die coating method, a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method
- An active material may be applied to the surface of the body.
- an active material, a solvent, and, if necessary, a binder and / or a conductive aid are mixed to prepare a slurry.
- the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water.
- the slurry is applied to the surface of the current collector and then dried. In order to increase the electrode density, the dried product may be compressed.
- the electrolytic solution contains a non-aqueous solvent and an electrolyte dissolved in the non-aqueous solvent.
- cyclic esters examples include ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, and gamma valerolactone.
- chain esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, ethyl methyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester.
- ethers examples include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane.
- non-aqueous solvent a compound in which part or all of hydrogen in the chemical structure of the specific solvent is substituted with fluorine may be employed.
- Examples of the electrolyte include lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 .
- a lithium salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 in a nonaqueous solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, and diethyl carbonate.
- a solution dissolved at a concentration of about / L can be exemplified.
- the separator separates the positive electrode and the negative electrode and allows lithium ions to pass while preventing a short circuit due to contact between the two electrodes.
- natural resins such as polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polymer), polyester, polyacrylonitrile, etc., polysaccharides such as cellulose, amylose, fibroin, keratin, lignin, suberin, etc. Examples thereof include porous bodies, nonwoven fabrics, and woven fabrics using one or more electrically insulating materials such as polymers and ceramics.
- the separator may have a multilayer structure.
- a separator is sandwiched between the positive electrode and the negative electrode as necessary to form an electrode body.
- the electrode body may be either a stacked type in which the positive electrode, the separator and the negative electrode are stacked, or a wound type in which the positive electrode, the separator and the negative electrode are sandwiched.
- the shape of the lithium ion secondary battery of the present invention is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a laminate shape can be adopted.
- the lithium ion secondary battery of the present invention may be mounted on a vehicle.
- the vehicle may be a vehicle that uses electric energy from a lithium ion secondary battery for all or a part of its power source, and may be, for example, an electric vehicle or a hybrid vehicle.
- a lithium ion secondary battery is mounted on a vehicle, a plurality of lithium ion secondary batteries may be connected in series to form an assembled battery.
- devices equipped with lithium ion secondary batteries include various home appliances driven by batteries such as personal computers and portable communication devices, office devices, and industrial devices in addition to vehicles.
- the lithium ion secondary battery of the present invention includes wind power generation, solar power generation, hydroelectric power generation, and other power system power storage devices and power smoothing devices, power supplies for ships and / or auxiliary power supplies, aircraft, Power supply for spacecraft and / or auxiliary equipment, auxiliary power supply for vehicles that do not use electricity as a power source, power supply for mobile home robots, power supply for system backup, power supply for uninterruptible power supply, You may use for the electrical storage apparatus which stores temporarily the electric power required for charge in the charging station for electric vehicles.
- Example 1 The solidified CaSi 2 , the layered silicon compound, the silicon material, and the lithium ion secondary battery of Example 1 were manufactured as follows.
- the solidification step the melt, cooled with liquid rapid solidification device (Nisshin Engineering Inc.), to obtain a solidified CaSi 2 of Example 1 of the thin strip.
- a liquid rapid solidification apparatus (Nisshin Giken Co., Ltd.) is an apparatus provided with a cooling means for injecting molten metal onto a rotating cooling roll.
- Example 1 - 36 wt% HCl aqueous solution 100mL synthetic steps ice bath, solidification of the Example 1 in an argon gas stream CaSi 2 10 g was added and stirred for 90 minutes. The reaction solution was filtered, the residue was washed with distilled water and acetone, and further dried under reduced pressure at room temperature for 12 hours or more to obtain 8 g of a layered silicon compound. This was used as the layered silicon compound of Example 1.
- Heating step 8 g of the layered silicon compound of Example 1 was heated at 900 ° C. for 1 hour in an argon gas atmosphere to obtain a powdery silicon material of Example 1.
- -Lithium ion secondary battery manufacturing process 45 parts by mass of the silicon material of Example 1 as the negative electrode active material, 40 parts by mass of graphite as the negative electrode active material, 10 parts by mass of polyamideimide as the binder, and acetylene as the conductive auxiliary agent 5 parts by mass of black and an appropriate amount of N-methyl-2-pyrrolidone were mixed to form a slurry.
- An electrolytic copper foil having a thickness of 20 ⁇ m was prepared as a current collector.
- the slurry was applied to the surface of the copper foil using a doctor blade so as to form a film.
- the copper foil coated with the slurry was dried at 80 ° C. for 20 minutes to remove N-methyl-2-pyrrolidone by volatilization.
- a copper foil having a negative electrode active material layer formed on the surface was obtained.
- the copper foil was compressed with a roll press so that the negative electrode active material layer had a thickness of 20 ⁇ m to obtain a bonded product. This joined product was dried by heating under reduced pressure at 200 ° C. for 2 hours to obtain an electrode.
- the electrode was cut into a diameter of 11 mm to obtain an evaluation electrode.
- a metal lithium foil was cut into a diameter of 15 mm to obtain a counter electrode.
- a separator a glass filter (Hoechst Celanese) and celgard 2400 (Polypore Corporation), which is a single-layer polypropylene, were prepared. It was also prepared an electrolyte solution obtained by dissolving LiPF 6 at 1 mol / L in a solvent obtained by mixing 50 parts by volume of ethylene carbonate and diethyl carbonate 50 parts by volume. Two kinds of separators were sandwiched between the counter electrode and the evaluation electrode in the order of the counter electrode, the glass filter, celgard 2400, and the evaluation electrode, thereby forming an electrode body. This electrode body was accommodated in a coin-type battery case CR2032 (Hosen Co., Ltd.), and an electrolyte was further injected to obtain a coin-type battery. This was designated as the lithium ion secondary battery of Example 1.
- Comparative Example 1 The solidified CaSi 2 , layered silicon compound, silicon material, and lithium ion secondary battery of Comparative Example 1 were produced as follows.
- the said molten metal was cooled by pouring into a predetermined casting_mold
- the first solid material contains impurities such as crystalline silicon and Ca 14 Si 19 . Therefore, in order to reduce these impurities, the first solid was heated at 900 ° C. for 12 hours in an argon gas atmosphere. Subsequently, the mixture was allowed to cool to obtain massive solidified CaSi 2 of Comparative Example 1.
- Lumped solid CaSi 2 was pulverized into a powder by a mortar and passed through a sieve having an opening of 53 ⁇ m. The powder that passed through the sieve was designated as solidified CaSi 2 after pulverization in Comparative Example 1.
- a powder X-ray diffraction chart of the first solid material and a powder X-ray diffraction chart of solidified CaSi 2 after pulverization in Comparative Example 1 are shown in FIG.
- Synthetic Step A layered silicon compound of Comparative Example 1 was obtained in the same manner as in Example 1 except that the solidified CaSi 2 after pulverization of Comparative Example 1 was used.
- pulverization process 8g of layered silicon compounds of the said comparative example 1 were heated at 900 degreeC by argon gas atmosphere for 1 hour, and the silicon material was obtained.
- the silicon material was pulverized with a jet mill to obtain the silicon material of Comparative Example 1.
- Lithium ion secondary battery manufacturing process A lithium ion secondary battery of Comparative Example 1 was obtained in the same manner as in Example 1 except that the silicon material of Comparative Example 1 was used instead of the silicon material of Example 1. .
- D50 of the silicon material of Example 1 is a level equivalent to the average diameter of the solidified CaSi 2 crystal grains of Example 1. It was confirmed that the silicon material manufacturing method of the present invention can manufacture a silicon material of a suitable size without requiring a pulverizing action by a pulverizer.
- Evaluation Example 3 letting the evaluation electrode occlude Li is referred to as discharging, and discharging Li from the evaluation electrode is referred to as charging.
- the capacity maintenance rate of the lithium ion secondary battery of Example 1 was superior to the capacity maintenance rate of the lithium ion secondary battery of Comparative Example 1. From this result, since the silicon material used for the lithium ion secondary battery of Comparative Example 1 was cracked or distorted by jet mill grinding, the life of the lithium ion secondary battery including the silicon material of Comparative Example 1 was short. On the other hand, since the silicon material used in the lithium ion secondary battery of Example 1 did not have any particular cracks or strains, the life of the lithium ion secondary battery comprising the silicon material of Example 1 was It is thought that it was long.
- Example 2 As follows, the solidified CaSi 2 , layered silicon compound, silicon material, and lithium ion secondary battery of Example 2 were manufactured.
- the composition formula of Ca, Fe, and Si in the Fe-containing CaSi 2 molten metal is Ca 1.08 Fe 0.08 Si 1.9 .
- the solidification step the melt, cooled in a centrifugal powder production apparatus (Deyukoru Ltd.), to obtain a solidified CaSi 2 Example 2 is a spherical powder.
- the centrifugal powder manufacturing device (Ducol Co., Ltd.) is a device that manufactures powder by cooling the droplet-like molten metal by flowing the molten metal onto a rotating disk and scattering the molten metal into droplets. It corresponds to the cooling device using the centrifugal atomization method.
- Synthesis step, heating step, and lithium ion secondary battery manufacturing step The layered silicon compound, silicon material, and lithium ion secondary material of Example 2 were the same as Example 1 except that the solidified CaSi 2 of Example 2 was used. A secondary battery was manufactured.
- Comparative Example 2 The solidified CaSi 2 , layered silicon compound, silicon material, and lithium ion secondary battery of Comparative Example 2 were produced as follows.
- D50 of the silicon material of Example 2 is at a level equivalent to D50 of the crystal grains of solidified CaSi 2 of Example 2. It was confirmed that the solidified CaSi 2 particles of Example 2 were single crystals. It was confirmed that the silicon material production method of the present invention can produce a silicon material of a suitable size without requiring a crushing action.
- the silicon material of Example 2 was analyzed by SEM and SEM-EDX (energy dispersive X-ray analysis). As a result, the silicon material of Example 2 is formed of an ellipsoidal silicon material main body mainly composed of Si and an annular FeSi 2 that covers the circumference of the minor axis of the ellipsoid of the main body. There was found.
- the capacity retention rate of the lithium ion secondary battery of Example 2 was superior to the capacity retention rate of the lithium ion secondary battery of Comparative Example 2. From this result, since the silicon material used for the lithium ion secondary battery of Comparative Example 2 had an adverse effect due to pulverization on the solidified CaSi 2 in the comparative solidification step, the lithium ion having the silicon material of Comparative Example 2 was obtained. It is thought that the life of the secondary battery was short. On the other hand, since the silicon material used for the lithium ion secondary battery of Example 2 did not have any particular cracks or strains, it is considered that the life of the lithium ion secondary battery including the silicon material of Example 2 was long. .
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Abstract
Description
Ca-xat%Si合金(42≦x≦75)溶湯を準備する溶湯準備工程、
急速冷却装置にて前記溶湯を冷却して、Ca-xat%Si合金を固化させる固化工程、
固化させたCa-xat%Si合金と酸とを反応させて、層状シリコン化合物を得る合成工程、
前記層状シリコン化合物を300℃以上で加熱する加熱工程、
を含むことを特徴とする。
Ca-xat%Si合金(42≦x≦75)溶湯を準備する溶湯準備工程、
急速冷却装置にて前記溶湯を冷却して、Ca-xat%Si合金を固化させる固化工程、
固化させたCa-xat%Si合金と酸とを反応させて、層状シリコン化合物を得る合成工程、
前記層状シリコン化合物を300℃以上で加熱する加熱工程、
を含むことを特徴とする。
以下、本発明のシリコン材料の製造方法で製造されたシリコン材料を「本発明のシリコン材料」ということがある。
2)SEM像において、CaSi2の結晶粒の全体が観察される結晶粒すべてにつき、EBSD(Electron Back Scatter Diffracion Patterns)法を用いて、各結晶粒の面積をそれぞれ算出する。
3)各結晶粒を真円と仮定した場合の直径をそれぞれ算出する。
4)直径の平均値を算出する。
3CaSi2+6HCl→Si6H6+3CaCl2
Si6H6→6Si+3H2↑
以下のとおり、実施例1の固化CaSi2、層状シリコン化合物、シリコン材料及びリチウムイオン二次電池を製造した。
Ca及びSiを1:2のモル比で炭素坩堝に秤量した。高周波誘導加熱装置にて、アルゴンガス雰囲気下、当該坩堝を1150℃で加熱してCaSi2溶湯とした。
前記溶湯を、液体急冷凝固装置(日新技研株式会社)で冷却し、薄帯状の実施例1の固化CaSi2を得た。なお、液体急冷凝固装置(日新技研株式会社)は、回転する冷却ロール上に溶湯を噴射する冷却手段を具備する装置である。
氷浴中の36質量%HCl水溶液100mLに、アルゴンガス気流中にて実施例1の固化CaSi210gを加え、90分間撹拌した。反応液を濾過し、残渣を蒸留水及びアセトンで洗浄し、さらに、室温で12時間以上減圧乾燥して8gの層状シリコン化合物を得た。これを実施例1の層状シリコン化合物とした。
上記実施例1の層状シリコン化合物8gをアルゴンガス雰囲気下、900℃で1時間加熱し、粉末状の実施例1のシリコン材料を得た。
負極活物質として実施例1のシリコン材料を45質量部、さらに負極活物質として黒鉛を40質量部、結着剤としてポリアミドイミドを10質量部、導電助剤としてアセチレンブラックを5質量部及び適量のN-メチル-2-ピロリドンを混合してスラリーとした。
以下のとおり、比較例1の固化CaSi2、層状シリコン化合物、シリコン材料及びリチウムイオン二次電池を製造した。
Ca及びSiを1:2のモル比で炭素坩堝に秤量した。高周波誘導加熱装置にて、アルゴンガス雰囲気下、当該坩堝を1150℃で加熱してCaSi2溶湯とした。
前記溶湯を所定の鋳型に注湯して放置することにより冷却し、第1固形物を得た。第1固形物には、結晶性シリコンやCa14Si19などの不純物が含まれている。そこで、これらの不純物を減量するために、第1固形物をアルゴンガス雰囲気下、900℃で12時間加熱した。引き続き、放冷して、比較例1の塊状の固化CaSi2を得た。塊状の固化CaSi2を乳鉢で粉砕して粉末とし、目開き53μmの篩を通過させた。篩を通過した粉末を比較例1の粉砕後の固化CaSi2とした。参考までに、第1固形物の粉末X線回折チャートと、比較例1の粉砕後の固化CaSi2の粉末X線回折チャートを、図1に示す。
比較例1の粉砕後の固化CaSi2を用いた以外は、実施例1と同様の方法で、比較例1の層状シリコン化合物を得た。
上記比較例1の層状シリコン化合物8gをアルゴンガス雰囲気下、900℃で1時間加熱し、シリコン材料を得た。当該シリコン材料をジェットミルで粉砕し、比較例1のシリコン材料とした。
実施例1のシリコン材料に換えて比較例1のシリコン材料を用いた以外は、実施例1と同様の方法で、比較例1のリチウムイオン二次電池を得た。
実施例1の固化CaSi2及び比較例1の塊状の固化CaSi2の断面をSEMで観察した。実施例1の固化CaSi2のSEM像を図2に示し、比較例1の塊状の固化CaSi2のSEM像を図3に示す。さらに、図2のSEM像において、CaSi2の結晶粒の全体が観察される結晶粒すべてにつき、EBSD法を用いて各結晶粒の面積をそれぞれ算出し、各結晶粒を真円と仮定した場合の直径をそれぞれ算出し、算出された直径の平均値を算出した。その結果、平均値は3.42μmであった。この値を、実施例1のCaSi2の結晶粒サイズの平均径とした。
レーザー回折式粒度分布測定装置を用いて実施例1及び比較例1のシリコン材料の粒度分布を測定し、それぞれD50の値を算出した。結果を表1に示す。
実施例1及び比較例1のリチウムイオン二次電池につき、評価極の対極に対する電圧が0.01Vになるまで0.25Cレートで放電を行い、評価極の対極に対する電圧が1Vになるまで0.25Cレートで充電を行う充放電サイクルを30サイクル行った。(30サイクル目の充電容量/初回充電容量)×100を容量維持率(%)として算出した。結果を表2に示す。
以下のとおり、実施例2の固化CaSi2、層状シリコン化合物、シリコン材料及びリチウムイオン二次電池を製造した。
Feを3.8質量%含有するCaSi2の10質量部及びCaの1質量部を、炭素坩堝に秤量した。高周波誘導加熱装置にて、アルゴンガス雰囲気下、当該坩堝を1150℃で加熱してFe含有CaSi2溶湯とした。なお、Fe含有CaSi2溶湯におけるCa、Fe及びSiの組成式はCa1.08Fe0.08Si1.9である。
前記溶湯を、遠心粉末製造装置(株式会社デュコル)で冷却し、球状の粉末状である実施例2の固化CaSi2を得た。なお、遠心粉末製造装置(株式会社デュコル)は、回転するディスク上に溶湯を流下し、溶湯を液滴状に飛散させることで、液滴状の溶湯を冷却して粉末を製造する装置であり、遠心力アトマイズ法を利用した冷却装置に該当する。
実施例2の固化CaSi2を用いた以外は、実施例1と同様の方法で、実施例2の層状シリコン化合物、シリコン材料及びリチウムイオン二次電池を製造した。
以下のとおり、比較例2の固化CaSi2、層状シリコン化合物、シリコン材料及びリチウムイオン二次電池を製造した。
実施例2と同様の方法で、Fe含有CaSi2溶湯を製造した。
前記溶湯を所定の鋳型に注湯して放置することにより冷却し、塊状の固化CaSi2を得た。塊状の固化CaSi2を乳鉢で粉砕して粉末とし、目開き53μmの篩を通過させた。篩を通過した粉末を比較例2の粉砕後の固化CaSi2とした。
比較例2の粉砕後の固化CaSi2を用いた以外は、実施例2と同様の方法で、比較例2の層状シリコン化合物、シリコン材料及びリチウムイオン二次電池を製造した。
レーザー回折式粒度分布測定装置を用いて実施例2の固化CaSi2、並びに、実施例2及び比較例2のシリコン材料の粒度分布を測定し、それぞれD50の値を算出した。結果を表3に示す。
粉末X線回折装置を用いて、実施例2の固化CaSi2及びシリコン材料を分析した。得られたX線回折チャートを図4及び図5に示す。図4から、実施例2の固化CaSi2には、CaSi2とFeSi2が存在することが裏付けられた。図5から、実施例2のシリコン材料には、SiとFeSi2が存在することが裏付けられた。
実施例2のシリコン材料を、SEM及びSEM-EDX(エネルギー分散型X線分析)にて分析した。その結果、実施例2のシリコン材料が、Siと主体とする楕円体形状のシリコン材料本体と、当該本体の楕円体における短径の円周付近を覆う環状のFeSi2とで形成されていることが判明した。
実施例2及び比較例2のリチウムイオン二次電池につき、評価例3と同様の方法で、評価した。結果を表4に示す。
Claims (6)
- Ca-xat%Si合金(42≦x≦75)溶湯を準備する溶湯準備工程、
急速冷却装置にて前記溶湯を冷却して、Ca-xat%Si合金を固化させる固化工程、
固化させたCa-xat%Si合金と酸とを反応させて、層状シリコン化合物を得る合成工程、
前記層状シリコン化合物を300℃以上で加熱する加熱工程、
を含むことを特徴とするシリコン材料の製造方法。 - 前記急速冷却装置が、回転する冷却ロール上に前記溶湯を噴射する冷却手段を用いる冷却装置、又は、アトマイズ法を用いた冷却装置から選択される請求項1に記載のシリコン材料の製造方法。
- 前記急速冷却装置が、液体急冷凝固装置、急冷薄片製造装置、液中紡糸装置、ガスアトマイズ装置、水アトマイズ装置、回転ディスク装置、回転電極法装置、又は、遠心粉末製造装置から選択される請求項1又は2に記載のシリコン材料の製造方法。
- 平均径0.1~100μmのCaSi2結晶粒を含有するCa-xat%Si合金(42≦x≦75)を準備する準備工程、
前記Ca-xat%Si合金と酸とを反応させて層状シリコン化合物を得る合成工程、
前記層状シリコン化合物を300℃以上で加熱する加熱工程、
を含むことを特徴とするシリコン材料の製造方法。 - 前記準備工程が、請求項1に記載の溶湯準備工程及び固化工程である請求項4に記載のシリコン材料の製造方法。
- 請求項1~5のいずれか1項に記載のシリコン材料の製造方法で製造されたシリコン材料を用いる二次電池製造工程、を含む二次電池の製造方法。
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JP2020092100A (ja) * | 2020-03-11 | 2020-06-11 | トヨタ自動車株式会社 | 負極層およびリチウム全固体電池 |
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CN114105647A (zh) * | 2021-10-26 | 2022-03-01 | 广州大学 | 雾化急冻结晶法快速制备多尺度纳米复合结构β-FeSi2热电材料的方法 |
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