WO2023181542A1 - ハロゲン化物材料の製造方法およびハロゲン化物材料 - Google Patents

ハロゲン化物材料の製造方法およびハロゲン化物材料 Download PDF

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WO2023181542A1
WO2023181542A1 PCT/JP2022/046923 JP2022046923W WO2023181542A1 WO 2023181542 A1 WO2023181542 A1 WO 2023181542A1 JP 2022046923 W JP2022046923 W JP 2022046923W WO 2023181542 A1 WO2023181542 A1 WO 2023181542A1
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compound
halide
manufacturing
mechanochemical
halide material
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French (fr)
Japanese (ja)
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英一 古賀
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202280093019.8A priority Critical patent/CN118829612A/zh
Priority to JP2024509762A priority patent/JPWO2023181542A1/ja
Priority to EP22933670.6A priority patent/EP4501856A1/en
Publication of WO2023181542A1 publication Critical patent/WO2023181542A1/ja
Priority to US18/826,242 priority patent/US20240425383A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/002—Compounds containing titanium, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/50—Fluorides
    • C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/02—Halides of titanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • 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
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/008—Halides
    • 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 disclosure relates to a method for producing a halide material and a halide material.
  • Patent Document 1 describes the formula: Li 6-(4-x)b (Ti 1-x M x ) b F 6 (where 0 ⁇ x ⁇ 1 and 0 ⁇ b ⁇ 1.5). Discloses a halide solid electrolyte.
  • Patent Document 2 discloses a method for producing a halide using M 2 O 3 (here, M is at least one element selected from the group consisting of Y, lanthanoids, and Sc) as a raw material.
  • An object of the present disclosure is to provide a manufacturing method for manufacturing a halide material having high ionic conductivity in a short time.
  • a method for producing a halide material includes (A) mechanochemically treating a mixed material containing a first compound containing Li, M1, and X1, and a second compound containing M2. , wherein M1 and M2 are each independently one type of element selected from metal elements and metalloid elements, and X1 is at least one type of element selected from the group consisting of F, Cl, Br, and I. There is one.
  • FIG. 1 is a flowchart showing a first example of the manufacturing method of the present disclosure.
  • FIG. 2 is a flowchart showing a second example of the manufacturing method of the present disclosure.
  • FIG. 3 is a graph showing the X-ray diffraction pattern of Sample 1 after the preparation process and before the mechanochemical process.
  • FIG. 4 is a graph showing the X-ray diffraction pattern of Sample 1-4 after the mechanochemical process.
  • FIG. 5 is a graph showing the X-ray diffraction pattern of Sample 5 after the preparation process.
  • FIG. 6 is a graph showing the X-ray diffraction pattern of sample 5-2 after the mechanochemical process.
  • the manufacturing method according to the first aspect of the present disclosure includes: (A) mechanochemically treating a mixed material containing a first compound containing Li, M1, and X1 and a second compound containing M2;
  • M1 and M2 are each independently one type of element selected from metal elements and metalloid elements
  • X1 is at least one selected from the group consisting of F, Cl, Br, and I.
  • the manufacturing method according to the first aspect allows a halide material having high ionic conductivity to be manufactured in a short time.
  • the first compound may be particles.
  • the ionic conductivity of the halide material can be further improved.
  • the mixed material may be subjected to mechanochemical treatment using a ball mill.
  • a halide material having higher ionic conductivity can be produced in a shorter time.
  • the first compound may include a crystalline phase.
  • the impact resistance of the halide material can be improved.
  • M1 may be Al or Ti.
  • the ionic conductivity of the halide material can be further improved.
  • X1 may include F.
  • the environmental resistance of the halide material can be improved.
  • the first compound has the formula: Li 6-ab M1 b X1 6 (where a is M1 (0 ⁇ b ⁇ 1.5 is satisfied).
  • the ionic conductivity of the halide material can be further improved.
  • M2 may be Al or Ti.
  • the ionic conductivity of the halide material can be further improved.
  • the second compound further includes X2, where X2 is F, Cl, Br, and I.
  • the ionic conductivity of the halide material can be further improved.
  • the manufacturing method according to any one of the first to ninth aspects further includes (B) synthesizing the first compound; It may be performed before A).
  • a halide material having higher ionic conductivity can be produced in a shorter time.
  • the first compound may be synthesized by firing a mixture of raw materials.
  • a halide material having higher ionic conductivity can be produced in a shorter time.
  • the first compound may be synthesized by mechanochemically treating the raw material.
  • the halide material according to the thirteenth aspect of the present disclosure is: Contains a compound A consisting of Li, M1, M2, and X,
  • M1 and M2 are each independently one type of element selected from metal elements and metalloid elements
  • X is at least one selected from the group consisting of F, Cl, Br, and I
  • the compound A contains an amorphous phase.
  • the halide material according to the thirteenth aspect can achieve high ionic conductivity.
  • the halide material according to the thirteenth aspect is substantially free of LiX, M1X m , and M2X n , where m represents the valence of M1 and n represents M2 It may also represent the valence of
  • ionic conductivity can be further improved.
  • the halide material according to the thirteenth aspect may further include a compound B containing a compound consisting of Li, M1, and X.
  • ionic conductivity can be further improved.
  • the compound B includes a first component having a first melting point and a second component having a second melting point different from the first melting point. It may include.
  • the reliability of a battery using a halide material can be improved.
  • the first melting point is higher than the second melting point
  • the compound B contains the first component as a main component. Good too.
  • the reliability of a battery using a halide material can be improved.
  • the ionic conductivity of the first component is higher than the ionic conductivity of the second component, and the compound B is The first component may be included as a main component.
  • a halide material having high ionic conductivity and excellent heat resistance and environmental resistance can be realized.
  • Patent Document 1 has the formula: Li 6-(4-x)b (Ti 1-x M x ) b F 6 (where 0 ⁇ x ⁇ 1, and Discloses a halide solid electrolyte represented by 0 ⁇ b ⁇ 1.5).
  • the halide solid electrolyte is synthesized by mechanochemical milling of a mixture using a single cation fluoride as a raw material using a planetary ball mill.
  • Patent Document 2 discloses that raw materials M 2 O 3 , NH 4 X, and LiZ (where M is at least one element selected from the group consisting of Y, lanthanoids, and Sc, and Discloses a method for producing a halide using at least one element selected from the group consisting of Cl, Br, I, and F.
  • the manufacturing method is a technique in which a mixture of raw materials is fired in an inert atmosphere. After firing, no mechanochemical treatment was performed in the manufacturing method of the present disclosure.
  • the method for manufacturing a halide material according to the first embodiment includes: (A) Mechanochemically treating a mixed material containing a first compound containing Li, M1, and X1 and a second compound containing M2.
  • M1 and M2 are each independently one type of element selected from metal elements and metalloid elements, and
  • X1 is at least one selected from the group consisting of F, Cl, Br, and I.
  • a halide material containing Li, M1, M2, and X and having high ionic conductivity can be manufactured in a short time.
  • high ionic conductivity means relatively high ionic conductivity when comparing halide materials formed from the same element.
  • the halide material obtained by the manufacturing method according to the first embodiment has ionic conductivity that is practical for use in batteries, for example. Practical ionic conductivity is, for example, 1 ⁇ S/cm or more near room temperature.
  • a halide material containing an amorphous phase can be manufactured.
  • "containing an amorphous phase” includes including an amorphous structure and a distorted crystal structure.
  • a halide material by mechanochemical treatment using a composite cation halide containing Li, a cation other than Li, and a halogen element, such as the first compound, Li, a cation other than Li, and a different cation are used as raw materials. It is possible to efficiently obtain halides containing halides. This is because the compositional components of the first compound, which is a raw material, are close to the target halide, and compositional fluctuations during synthesis are suppressed. Furthermore, the halide containing the above-mentioned different cations obtained using the first compound as a raw material has ionic conductivity by distorting its crystal structure (atomic arrangement) or by including an amorphous structure.
  • Halides with soft properties increase the number of contact points between particles due to plastic deformation in the compacted powder structure, thereby improving ionic conductivity.
  • the effect of imparting such soft properties is more pronounced in halides than in oxides or sulfides containing oxygen or sulfur as anions. This is because the electronegativity of the halogen element is about twice or more greater than that of oxygen and sulfur. This effect is particularly effective for halides containing F or Cl, which have high electronegativity, among halogen elements.
  • a halide material is produced by mechanochemical treatment using a composite cation halide such as the first compound as a raw material
  • the soft properties described above can be efficiently imparted to the halide. This is because the fluctuation in the composition of the resulting halide is suppressed compared to when only a single cation halide is used as a raw material, so a homogeneous halide can be obtained quickly, and the mechanochemical treatment removes the halide. This is because crystallization progresses sufficiently. Therefore, when the first compound is used as a raw material for mechanochemical treatment, a halide material containing a halide containing an amorphous phase can be obtained in a short time.
  • a halide material with improved ionic conductivity can be obtained in a short time. Moreover, since the particles constituting the halide material can be strongly fixed to each other over a wide area by plastic deformation, structural defects such as minute cracks and voids in the compacted powder structure are reduced. As a result, the reliability of ionic conductivity against external stress such as cooling/heating cycles is improved.
  • the manufacturing method of the present disclosure residual single cation halide in the obtained halide material is suppressed.
  • the halogen element has a high electronegativity, so the Li ion and the halogen element can form a strong bond.
  • lithium ion conductivity becomes low. Ionic conductivity can be improved by suppressing or eliminating such residual single cation halides.
  • composite cation halide means a compound containing Li, a cation other than Li, and a halogen element.
  • Single cation halide means a compound consisting of one type of cation and a halogen element.
  • FIG. 1 is a flowchart showing a first example of the manufacturing method of the present disclosure.
  • the manufacturing method according to the first embodiment includes a mechanochemical step S200.
  • the mixed material is mechanochemically treated.
  • the mixed material includes a first compound containing Li, M1, and X1, and a second compound containing M2.
  • a halide material with improved ionic conductivity can be produced in a short time.
  • the manufacturing method according to the first embodiment may further include (B) synthesizing the first compound.
  • FIG. 2 is a flowchart showing a second example of the manufacturing method of the present disclosure.
  • the manufacturing method according to the first embodiment may further include a preparation step S100.
  • Preparation step S100 is performed before mechanochemical step S200.
  • the first compound includes Li, M1, and X1.
  • the first compound may consist of Li, M1, and X1.
  • the first compound may be particles. This allows the production of halide materials in the form of particles, either by distorting the crystalline structure on the surface of the particles or by incorporating an amorphous structure into the particles (mainly at the wide joint surface of the particle surface). , it is possible to form a tissue with improved ionic conductivity and softness. Furthermore, the surface layer of the particles has high ionic conductivity and is soft, resulting in a network (mesh-like) structure having high ionic conductivity and interparticle bonding properties. Therefore, by the manufacturing method according to the first embodiment, a halide material having high ionic conductivity and excellent bonding reliability can be obtained.
  • the first compound may include a crystalline phase.
  • the first compound may include multiple crystal phases.
  • the first compound may be crystalline.
  • the manufacturing method according to the first embodiment places a crystalline compound having ion conductivity in the core region of the particle, creating a region with disordered crystallinity that has higher ion conductivity and is softer than the core region.
  • a particulate halide material contained on the surface side can be obtained.
  • a halide material having high ionic conductivity and excellent mechanical reliability can be realized by such an aggregate of particles (such as a compacted powder structure).
  • the core region and the surface side region of the particle have similar chemical composition and crystal phase, problems caused by differences in thermal expansion are reduced, and bondability within and between particles is excellent. Therefore, the resulting halide material also has excellent impact resistance (eg, resistance to stress and thermal stress).
  • M1 may be Al or Ti. Thereby, the halide obtained by the reaction in the mechanochemical step S200 has high ionic conductivity.
  • X1 may include F.
  • Complex cation halides containing F tend to have excellent atmospheric stability. Therefore, it can achieve higher environmental resistance than sulfides, which are weak against moisture. Therefore, deterioration of characteristics due to moisture during the manufacturing process can be suppressed. Also. As the manufacturing environment does not require sophisticated dew point control such as an argon atmosphere, productivity is excellent and the industrial ripple effect is large.
  • X1 may be F.
  • the first compound may be a material represented by the formula: Li 6-ab M1 b X1 6 (where a represents the valence of M1, and 0 ⁇ b ⁇ 1.5 is satisfied) .
  • the compound that is included the most is defined as the first compound.
  • the most abundant compound means a compound having the strongest peak in an X-ray diffraction pattern obtained by X-ray diffraction measurement.
  • the second compound includes M2.
  • M2 may be Al or Ti.
  • M2 may contain an element different from M1. When M1 is Al, M2 may be Ti. When M1 is Ti, M2 may be Al.
  • the second compound may further contain X2.
  • X2 is at least one selected from the group consisting of F, Cl, Br, and I. That is, the second compound may contain M2 and X2.
  • the second compound is, for example, a compound consisting only of M2 and a halogen element.
  • the second compound may be, for example, a compound consisting only of Li, M2, and a halogen element.
  • the second compound is a material represented by the formula: Li 6-cd M2 d X2 6 (where c represents the valence of M2, and 0 ⁇ d ⁇ 1.5 is satisfied). It's okay.
  • X2 may include F.
  • X2 may be F.
  • X2 may contain the same element as the element contained in X1.
  • X1 and X2 may contain F.
  • X1 and X2 may be F.
  • preparation step S100 In the preparation step S100, a first compound is synthesized.
  • a plurality of single cation halides are prepared as raw materials.
  • a mixture of these may be prepared as a raw material.
  • a plurality of raw materials may be uniformly mixed.
  • the raw material for the first compound is prepared so that the first compound has a desired composition ratio.
  • the raw materials for the first compound are, for example, LiZ1 and a compound consisting of M1 and Z2.
  • Z1 and Z2 are each independently at least one selected from the group consisting of F, Cl, Br, and I.
  • Specific examples of the raw materials for the first compound are LiF and AlF 3 or LiF and TiF 4 .
  • the raw material for the first compound may be a precursor of LiZ1 and a precursor of a compound consisting of M1 and Z2.
  • the raw material for the first compound may be a powder.
  • the raw material for the first compound may have an average particle diameter of, for example, 0.5 ⁇ m or more and 10 ⁇ m or less.
  • the raw material may be prepared in an atmosphere with a humidity of less than 60%.
  • the humidity in the atmosphere is less than 60%, it is possible to suppress deliquescence of the surface of the raw material, thereby suppressing a decrease in weighing accuracy or a fluctuation in composition.
  • the crystalline first compound may be obtained by subjecting a mixture of raw materials to a solid phase reaction.
  • the mixture of raw materials may be heat-treated (baked), for example. That is, the first compound may be synthesized by firing a mixture of raw materials.
  • a wide range of solid-phase reaction conditions such as temperature and atmosphere control can be applied, so a composite cation halide (i.e., the first compound) with excellent ionic conductivity and environmental resistance can be synthesized by a process with excellent mass productivity.
  • the mixture of raw materials may be mechanochemically treated, for example. That is, the first compound may be synthesized by mechanochemically treating the raw material.
  • Mechanochemical processing is a process that generates a reaction by applying a mechanical impact, such as the impact caused by a crushing process. For example, the material to be treated is mixed and crushed while applying mechanical energy using an impact crushing device. It is processing.
  • a ball mill may be used for mechanochemical treatment. That is, the first compound may be synthesized by reacting raw materials using a ball mill. This makes it possible to synthesize complex cation halides that are difficult to synthesize by solid-phase reaction by calcination.
  • a planetary ball mill or a common pot mill may be used for mechanochemical processing.
  • single cation halide with low conductivity can be reduced to below the detection limit of X-ray diffraction measurement or removed.
  • the conductivity of the single cation halide is, for example, 1 ⁇ 10 ⁇ 9 S/cm or less at room temperature.
  • the single cation halide that is the raw material for the first compound may be reduced to below the detection limit of X-ray diffraction measurement or removed. Thereby, single cation halide can be further reduced or removed in the halide material obtained after the mechanochemical step S200.
  • the first compound synthesized in the preparation step S100 is, for example, a molten body, a sintered body, a powder, or a block-shaped mass of solidified powder.
  • a uniform mixture of the raw materials for the first compound is placed in a heat-resistant alumina container (i.e., a pod), and an alumina lid is placed on top of the mixture. and seal tightly.
  • a firing furnace in an inert gas atmosphere such as argon and nitrogen.
  • the alumina heat-resistant container is thick (for example, 10 mm thick), and the contact surfaces between the lid and the shell are each mirror-polished. Note that if the pod is sealed and fired, the mass reduction rate can be reduced. Therefore, when the pod is sealed and fired, it is easy to aim for the desired composition even if there are evaporated components.
  • a mechanism may be provided that can discharge reactive gas when it is generated while nitrogen is flowing into the firing furnace during the firing process.
  • the reaction gas includes, for example, moisture, chlorine, ammonium, hydrogen chloride, and the like.
  • a plate larger than the gas inlet may be placed between the gas inlet and the sheath.
  • the thickness of the plate may be such that it will not be damaged by gas flow or handling.
  • it may be partially shielded by leaning a board such as an alumina board.
  • the gas inlet is preferably installed at the bottom of the firing furnace, and the exhaust port is preferably installed at the upper side (for example, on the ceiling or above the side wall).
  • the reaction gas can be smoothly discharged out of the furnace along with the flow of convection inside the firing furnace from the bottom to the top, so that unnecessary residual components can be reduced.
  • the introduced gas may be heated before being introduced into the firing furnace. This can prevent the temperature distribution within the pod from becoming non-uniform. As a result, the reaction distribution within the pod can be homogenized, so that a more homogeneous first compound can be obtained. Therefore, it is effective in reducing or removing raw materials with low conductivity.
  • the firing temperature may be 300°C or higher and 900°C or lower, or 550°C or higher and 800°C or lower.
  • the block of the first compound may be coarsely ground using a mortar, pestle, or the like. It may be pulverized to the extent that coarse particles are no longer felt to the touch.
  • the blocks may be ground to have an average particle size of about 10 ⁇ m.
  • the firing time may be 0.5 hours or more and 40 hours, or 0.5 hours or more and 20 hours or less.
  • the firing conditions for example, firing temperature and firing time
  • the firing conditions can be determined while taking into consideration the synthesis state of the first compound and handling including post-processes. For example, the determination may be made taking into consideration the possibility that the material may stick to the pod.
  • a known atmosphere firing furnace can be used.
  • the inert gas may be flowed after vacuum displacement. Thereby, it is possible to suppress the raw material from reacting with moisture, etc. in the atmosphere. Vacuum replacement may be performed repeatedly.
  • the mixture of raw materials may be treated in advance under the same conditions (atmosphere and firing profile) as those for firing, before firing. This can reduce variations in the reaction of moisture-sensitive raw materials.
  • the temperature distribution within the pod may be within the temperature distribution width of a commonly used firing furnace, for example, within 30°C. Note that the temperature distribution within the pod is the difference between the maximum temperature and the minimum temperature within the pod.
  • the sheath used may be, for example, a heat-resistant container made of dense alumina without air permeability.
  • SSA-H purity 95%, density 3.9 g/cm 3 , water absorption 0%
  • the first compound can be synthesized and taken out without the molten component penetrating into the wall of the pod.
  • a grade of pod has a high thermal conductivity of approximately 20 W/m ⁇ k, so it is possible to suppress uneven temperature distribution within the pod and is suitable for a homogeneous reaction.
  • the blocks of the first compound can be recovered with reduced loss.
  • the material of the sheath is not limited to alumina.
  • the material of the sheath may be, for example, a refractory material that has a thermal conductivity equal to or higher than that of alumina, and that does not easily react with the first compound. In this way, by using a high heat conductive refractory for the pod, the first compound can be synthesized while reducing non-uniformity of temperature distribution within the pod.
  • sheath materials include SSA-S, SSA-T, or SSA-995 grades of alumina, or high thermal conductivity refractories such as SiC, which has a thermal conductivity of approximately 17 W/m ⁇ k. It will be done.
  • the powder may be sprayed and heat treated using a rotary kiln or spray drying.
  • the firing may be performed under high pressure that can suppress evaporation.
  • a first compound containing multiple crystal phases can be synthesized.
  • the first compound includes, for example, a main component crystalline phase having relatively high ionic conductivity and a high melting point, and a subcomponent crystalline phase having a lower melting point than the main component phase. Melting point may vary depending on composition or crystal structure. According to the above configuration, for example, when a halide obtained by the manufacturing method according to the first embodiment and containing the first compound is used in a battery, when the battery generates heat, The crystalline phase of the subcomponent is preferentially degraded, and damage to the crystalline phase of the main component is reduced. Therefore, reliability of the battery can be improved.
  • the first compound may be synthesized by a reaction using mechanochemical treatment.
  • the mechanochemical treatment may be performed by ball milling using an ordinary pot mill.
  • the raw material of the first compound is put into a planetary ball mill or a pot mill together with a grinding medium such as zirconia balls, and the grinding process is performed. Due to repeated impacts from the grinding media, the reaction between the raw materials progresses and the first compound is synthesized.
  • Reactions using mechanochemical processing are effective for materials that are difficult to synthesize by calcination. Furthermore, since the synthesis is carried out in a closed space, there is no evaporation of the composition, and all the raw materials contained in the container can be recovered, making it easy to obtain a compound having the desired composition.
  • Partially stabilized zirconia may be used as the grinding media. Partially stabilized zirconia has excellent wear resistance. Therefore, contamination of impurities due to wear can be reduced.
  • zirconia balls of 10% to 60% of the volume of the container are placed in a mill container, sealed with an inert gas (nitrogen, argon, etc.), and the mill container is rotated and stirred.
  • an inert gas nitrogen, argon, etc.
  • Compounds with high atmospheric stability may be processed in the atmosphere.
  • compounds containing Li, Al, Ti, F, etc. as main components have high atmospheric stability.
  • industrial mass synthesis of the first compound can be realized.
  • the shape of the grinding medium may be spherical with a diameter of 1 mm or more and 30 mm or less.
  • the grinding media are, for example, zirconia balls.
  • the crushability (for example, synthesis rate) is selected as appropriate.
  • the inner walls of the ball mill may also be made of hard materials such as zirconia and alumina to enhance grindability.
  • the shape of the inner wall of the ball mill may be cylindrical or polygonal such as a rectangle. When the inner wall of the ball mill is polygonal and cylindrical, the grindability is enhanced and the synthesis rate is accelerated. For example, when a hexagonal cylindrical mill container is used, the synthesis time can be reduced to 1/3 to 1/2 of the synthesis time when a cylindrical mill container is used.
  • the inner wall of the ball mill may have an uneven shape. Thereby, it is also possible to further improve the crushability.
  • the synthesis time may be, for example, 1 hour or more and 80 hours or less, or 10 hours or more and 20 hours or less.
  • the synthesis rate may be improved by heating the ball mill from the outside to activate the reaction. This allows synthesis in a short time. That is, mass productivity can be improved.
  • the first compound is a material whose crystallinity is disturbed by mechanochemical milling or whose amorphization progresses, it is not suitable for synthesis in a state of good crystallinity. Therefore, in the above case, a synthesis method in which impact action, such as firing, is less likely to act on the powder is suitable for the preparatory step S100.
  • the raw material mixture may be fired twice.
  • the two firings are performed under different reaction conditions, for example. This allows the solid phase reaction to proceed more homogeneously. Therefore, since the contamination of the single cation halide that is the raw material can be suppressed, it is possible to produce a highly conductive halide and shorten the processing time of the mechanochemical step S200.
  • the mixed material is mechanochemically treated.
  • the mixed material includes a first compound and a second compound.
  • the mechanochemical step S200 distorted crystals or amorphous properties are introduced into the first compound, which is a complex cation halide, by mechanochemical treatment. Since conditions of mechanochemical treatment are easy to adjust, appropriate treatment can be performed depending on the required amount of halide material, the scale of manufacturing equipment, etc.
  • the mechanochemical treatment method may be the same as the method described in the preparation step S100.
  • the mixed material may be subjected to mechanochemical treatment using a ball mill.
  • the crystal structure on the surface of the first compound can be treated in a short time using a method that is excellent in mass production.
  • powder can be used as the mixed material.
  • the mechanochemical processing device, grinding medium, etc. used in the mechanochemical step S200 may be the same as those used in the preparatory step S100.
  • a halide is synthesized and crystallinity is reduced. That is, in the mechanochemical step S200, the halide is made amorphous. In particular, it reduces the crystallinity of the surface layer region of the halide powder or particles.
  • the mechanochemical treatment in the mechanochemical step S200 may require a shorter treatment time and be performed under conditions of lower crushing and collision energy than the mechanochemical treatment for synthesizing the first compound from a single cation halide in the preparation step S100. It may be.
  • the softness of the powder particles can be increased. That is, crystallinity can be reduced.
  • the softness of powder particles can be comparatively evaluated by micro-Vickers evaluation for each particle or powder structure. Changes in the softness of powder particles can also be confirmed from changes in the yield of mechanochemical treatment. This is because as the ball milling time increases, the crystallinity changes, i.e. the softness of the powder particles increases, and the amount of powder adhering to the inner wall of the ball mill container and the zirconia balls also increases correspondingly. This is because the yield decreases in proportion to the amount of powder adhering to the wall surface and zirconia balls.
  • a general ball mill using a pot mill that is commonly used in mass production processes may be used. Pots of various capacities can be used, from tens of mL to large volumes of several hundred liters, and it is possible to treat reactants in quantities of several grams to several hundred kilograms.
  • Planetary ball mills with strong impact resistance are often used for mechanochemical processing, but when large containers are used, internal heat generation due to strong impact and frictional effects becomes a problem.
  • Pot mills have a weaker mechanochemical effect than planetary ball mills, so it is generally not possible to obtain the desired reaction, and the processing time may be several times to about 10 times longer than that of a planetary ball mill. . For these reasons, it has been difficult to achieve high quality and large-scale synthesis in a short time by mechanochemical processing.
  • a halide material having high conductivity can be obtained at the mechanochemical action level of a ball mill used in general ceramic synthesis.
  • the amount of grinding media may be smaller in the mechanochemical treatment in the mechanochemical step S200 than in the mechanochemical treatment in the preparation step S100. Further, the amount of powder to be introduced may be increased.
  • the mechanochemical treatment time may be, for example, 1 hour or more and 30 hours or less, or 3 hours or more and 12 hours or less.
  • the rotation speed may be 60 rpm or more and 80 rpm or less.
  • the mechanochemical process S200 has simpler equipment and higher productivity than general mechanochemical synthesis.
  • a container made of zirconia is used to mechanochemically mill the mixed material by placing zirconia balls in an amount of 10% or more and 60% or less based on the volume of the container.
  • the zirconia balls may be of any size. Usually, a diameter of 1 mm or more and 30 mm or less is used, but it may be smaller or larger than this.
  • an appropriate amount of an additive such as ethanol may be added.
  • the additive one is used that does not adversely affect the properties of the resulting halide.
  • the manufacturing method according to the first embodiment may further include firing the first compound before the mechanochemical step S200. This allows the solid phase reaction to proceed more homogeneously. This makes it possible to suppress contamination of the raw material for the first compound, that is, the single cation halide, thereby achieving higher conductivity of the halide material and shortening the processing time of the preparatory step S100.
  • the obtained fired product is in a state where the particles are necked together due to a solid phase reaction between the contacting particles.
  • the particle size suitable for use is, for example, from 1 ⁇ m to 10 ⁇ m.
  • the conductivity is low.
  • crystallinity is disturbed and a soft region, that is, a region with deformability is not formed.
  • the manufacturing method according to the first embodiment includes a mechanochemical step S200 with a mechanochemical action, such as pulverization or disturbing crystallinity, and is therefore suitable for manufacturing a halide material used as a solid electrolyte, for example. .
  • the halide material obtained by the manufacturing method of the first embodiment has good lithium ion conductivity, it can be used as a solid electrolyte.
  • the halide material according to the second embodiment includes a compound A consisting of Li, M1, M2, and X.
  • M1 and M2 are each independently one type of element selected from metal elements and metalloid elements
  • X is at least one element selected from the group consisting of F, Cl, Br, and I. It is.
  • Compound A contains an amorphous phase.
  • the halide material according to the second embodiment can have high lithium ion conductivity because the compound A includes an amorphous phase.
  • the halide material according to the second embodiment is obtained, for example, by the manufacturing method according to the first embodiment.
  • the fact that the halide material contains an amorphous phase can be confirmed by an X-ray diffraction pattern obtained by X-ray diffraction measurement.
  • the X-ray diffraction pattern can be measured by the ⁇ -2 ⁇ method using Cu-K ⁇ radiation (wavelengths of 1.5405 ⁇ and 1.5444 ⁇ ) as the X-ray source.
  • a region having a distorted crystal structure that is, a region with disordered crystallinity, can be observed by a transmission electron microscope (TEM) as an image of highly regular regions and disordered regions.
  • TEM transmission electron microscope
  • the halide material according to the second embodiment may consist of only Li, M1, M2, and X.
  • the halide material may contain two or more types of distorted crystal structures.
  • the two or more types of distorted crystal structures may have different compositions or may have different atomic arrangements. This allows the halide material to contain a mixed structure with different softness. Then, since the fracture limits of stress resistance and thermal shock resistance at the bonding interface between particles differ depending on the amorphous structure, these limit levels are dispersed within the compacted powder structure. As a result, when strong stress or external thermal stress is applied to the halide material, sudden destruction or breakage can be prevented. Therefore, when the halide material according to the second embodiment is used in a device such as a battery, the problem that the device suddenly stops working is reduced.
  • the halide material according to the second embodiment may be substantially free of LiX, M1X m and M2X n .
  • m represents the valence of M1
  • n represents the valence of M2.
  • substantially free of means that trace amounts of LiX, M1X m , and M2X n are allowed to be mixed in. In this case, LiX, M1X m and M2X n mixed into the halide material are below the detection limit of X-ray diffraction measurement.
  • the halide material according to the second embodiment may be free of LiX, M1X m and M2X n . According to the above configuration, the ionic conductivity can be further improved.
  • the halide material according to the second embodiment may include a compound A consisting of Li, M1, M2, and X.
  • the halide material according to the second embodiment may further include a compound B containing a compound consisting of Li, M1, and X.
  • Compound B may include an amorphous phase.
  • a component having excellent ionic conductivity and atmospheric stability can be formed on the surface layer of the particles of the halide material or between the particles.
  • the halide material according to the second embodiment has high ionic conductivity and excellent mechanical reliability.
  • Compound B may further include a compound consisting of Li, M2, and X.
  • Compound B may include a first component having a first melting point and a second component having a second melting point different from the first melting point. This results in a distribution of different melting points within the halide material. Therefore, for example, when the halide material according to the second embodiment is used in a battery, thermal runaway during abnormal heat generation or current concentration can be suppressed from proceeding all at once within the device. Therefore, reliability of the battery can be improved.
  • a compound consisting of Li, M1, and X may be the first component, and a compound consisting of Li, M2, and X may be the second component.
  • the first component and the second component may both be compounds consisting of Li, M1, and X, and may have different compositions.
  • the first component and the second component may both be compounds with the same composition, but have different crystal structures.
  • the first melting point may be higher than the second melting point, and compound B may contain the first component as a main component.
  • the main component is the component contained in the largest amount in terms of molar ratio.
  • the ionic conductivity of the first component is higher than the ionic conductivity of the second component, and the compound B may contain the first component as a main component.
  • a halide having high ionic conductivity and excellent heat resistance and environmental resistance can be obtained.
  • Samples 1-1 to 8 of halide materials were produced.
  • Samples 1-1 to 2 correspond to comparative examples, in which the material to be mechanochemically treated in the mechanochemical process did not contain the first compound.
  • Samples 3 to 8 correspond to Examples, and in the mechanochemical process, a mixed material containing the first compound and the second compound was mechanochemically treated. The manufacturing method implemented in this example will be described in detail below.
  • the prepared raw material powder was mixed uniformly for about 30 minutes using an alumina porcelain mortar and pestle.
  • Samples 1-2 to 1-4> A halide material of Sample 1-2 was obtained in the same manner as Sample 1-1 except that the ball milling time was 7 hours.
  • a halide material of Sample 1-3 was obtained in the same manner as Sample 1-1 except that the ball mill processing time was 12 hours.
  • a halide material of Sample 1-4 was obtained in the same manner as Sample 1-1 except that the ball mill processing time was 40 hours.
  • the obtained raw material powder mixture (approximately 5 g) was placed in a high purity (SSA-H) alumina pod (diameter 40 mm, height 45 mm). Next, a high purity (SSA-H) alumina lid was placed and sealed in order to suppress evaporation of the components due to calcination.
  • SSA-H high purity alumina pod
  • the pod containing the raw material powder was placed in the center of the kiln to improve temperature uniformity.
  • the pod was placed on three supports (i.e., pegs) so that heater heat (i.e., radiant heat) and inert gas could reach the bottom of the pod.
  • the pot is made of mullite and has a porosity of about 20%, so it has a small heat capacity.
  • the dimensions of the plug were 10 mm in length, 11 mm in width, and 10 mm in height.
  • the mass reduction rate after firing was approximately 0.1% by mass to 1.0% by mass, and evaporation was almost suppressed.
  • the block body (about 5 g) of the fired product in the pod was coarsely ground in advance using an alumina porcelain mortar and pestle so that the average particle size was about 10 ⁇ m.
  • the coarsely ground fired product and 15 mm diameter zirconia balls (approximately 1000 g) were placed in a 1 L cylindrical ball mill container having an inner wall made of zirconia, and the ball mill was heated at a rotation speed of 60 rpm to 80 rpm at room temperature for the time shown in Table 2. processed. Thereafter, the treated powder and zirconia balls were taken out from the ball mill container, and passed through a mesh without any load to separate the powder and zirconia balls.
  • sample evaluation The composition, crystal phase, and ionic conductivity of each sample after the preparation process and the sample after the mechanochemical process were evaluated.
  • the evaluation results of the samples after the preparation process are shown in Table 1.
  • the evaluation results of the samples after the mechanochemical process are shown in Table 2.
  • the composition was evaluated by inductively coupled plasma (ICP) emission spectrometry using an inductively coupled plasma emission spectrometer (manufactured by ThermoFisher Scientific, iCAP7400).
  • ICP inductively coupled plasma
  • the coarse particles of the obtained sample were uniformly ground in an alumina mortar. For example, it was ground until it became a powder with an average particle diameter of 3 ⁇ m or less, and then the crystal phase was evaluated by powder X-ray diffraction.
  • An X-ray diffraction device (MiniFlex600, manufactured by RIGAKU) was used for the measurement.
  • Cu-K ⁇ radiation (wavelengths 1.5405 ⁇ and 1.5444 ⁇ ) was used as the X-ray source.
  • the order of the crystal phases listed in the column of crystal phases is determined by comparing the strongest peaks of each crystal phase in the X-ray diffraction patterns obtained by X-ray diffraction measurements. It is.
  • the phase listed on the leftmost side is the main component in the material.
  • the ionic conductivity is determined by the area, thickness, and The ionic conductivity was calculated from the impedance characteristics at room temperature.
  • the impedance measurement was performed under pressure at room temperature. Note that the impedance measurement was performed at a measurement frequency of 10 Hz to 10 MHz, a measurement voltage of 1 Vrms, and under no DC bias, and the deviation in the electrical length of the cable and the measurement jig was evaluated by offset.
  • FIG. 3 is a graph showing the X-ray diffraction pattern of Sample 1 after the preparation process and before the mechanochemical process.
  • Samples 2 to 5-2 and 6 to 8 also contained Li 3 AlF 6 and Li 2 TiF 6 . That is, Samples 2 to 5-2 and 6 to 8 contained Compound B having Li 3 AlF 6 as a first component and Li 2 TiF 6 as a second component.
  • the melting point of Li 3 AlF 6 is approximately 800°C to 900°C
  • the melting point of Li 2 TiF 6 is approximately 700°C to 800°C.
  • the ionic conductivities of both Li 3 AlF 6 and Li 2 TiF 6 are approximately 1 ⁇ 10 ⁇ 10 S/cm to 1 ⁇ 10 ⁇ 9 S/cm.
  • the ionic conductivity of the halide material of Sample 2 was 0.6 ⁇ S/cm.
  • the ionic conductivity of the halide materials of Samples 3 to 8 was 2.1 ⁇ S/cm, which was higher than that of Samples 1 to 2. From this, when a mixed material containing the first compound which is a complex cation halide with conductivity is mechanochemically treated, a halide material with high ionic conductivity can be produced in a short time.
  • the halide material obtained after the mechanochemical process contained compounds with the composition Li 2.7 Ti 0.3 Al 0.7 F 6 .
  • Li 3 AlF 6 as the first compound which is a crystalline composite cation halide having ionic conductivity, was synthesized through the preparation process. Specifically, a fired product mainly containing crystalline Li 3 AlF 6 was obtained. Note that the fired product also contained crystalline Li 2 TiF 6 .
  • FIG. 5 is a graph showing the X-ray diffraction pattern of Sample 5 after the preparation process. On the other hand, in Sample 2, the first compound was not synthesized during the preparation process.
  • the mixed material to be mechanochemically treated may contain a raw material that is a single cation halide, as long as it contains the first compound that is a complex cation halide.
  • Sample 3 already showed a certain degree of ionic conductivity (0.6 ⁇ S/cm) after the preparation step, and then, by mechanochemical treatment in the mechanochemical step, Li 3 AlF 6 and Li 2 TiF 6 phases were replaced by Li. It is considered that the conductivity was further improved because a phase of 2.7 Ti 0.3 Al 0.7 F 6 (hereinafter referred to as "LTAF phase”) was formed as the main component. At this time, in addition to the LTAF phase, which is the main component, Li 3 AlF 6 phase and Li 2 TiF 6 phase were also detected.
  • LTAF phase 2.7 Ti 0.3 Al 0.7 F 6
  • the Li 3 AlF 6 phase generated by the solid phase reaction due to calcination in the preparation step progresses to transition to the LTAF phase by the mechanochemical step.
  • a small amount of AlF 3 confirmed by X-ray diffraction measurement after the preparation step disappeared after the mechanochemical step.
  • FIG. 6 is a graph showing the X-ray diffraction pattern of sample 5-2 after the mechanochemical process.
  • the arrow indicates the peak of LTAF. From FIG. 6, it can be seen that in the halide material of Sample 5-2, the LTAF phase is the main component phase, and Li 3 AlF 6 is contained in a smaller amount than LTAF.
  • the LTAF phase that appeared instead of the two-phase diffraction pattern of Li 3 AlF 6 and Li 2 TiF 6 showed a very broad characteristic peak.
  • the broad strongest peak (half width of about 3° to 8°) located in the diffraction angle 2 ⁇ range of about 21° to 22° and the intensity of about 40% to 60% of the strongest peak are and has a peak located in a diffraction angle 2 ⁇ range of about 41° to 42° (half width of about 3° to 6°) and an intensity of about 10% to 20% of the strongest peak,
  • a peak located at a diffraction angle 2 ⁇ of about 53° to 54° half width of about 2° to 4° was observed. Since the half-width of the peak is wide, the reflective surface spacing that contributes to diffraction has a wide distribution of surface spacings (different surface spacings) corresponding to the peak width.
  • the LTAF phase of the halide material of Sample 5-2 mainly contains components with disordered atomic arrangement and low Li-restricted properties, that is, distorted crystals or amorphous materials. Since distorted crystals or amorphous materials are formed by external stress, it is thought that the formation of distorted crystals or amorphous materials progresses from the particle surface to the inside through repeated impact. Therefore, it is thought that the surface of the particle contains the most disordered crystallinity or amorphousness, and that the disorder of crystallinity is reduced as it gets closer to the inside of the particle.
  • Samples 5-2 to 8 had higher ionic conductivity than samples 3 and 4 in the fired products obtained after the preparation process. This confirmed that when the firing temperature in the preparation step was 650° C. or higher, a halide with higher ionic conductivity could be produced. Although no raw material was detected in the X-ray diffraction measurement after the preparation step for sample 4, it is thought that a trace amount of raw material below the detection limit is present.
  • sample 8 in which the firing temperature was 800° C. in the preparation process, the sample was dissolved. It was confirmed that a halide material with high ionic conductivity can be obtained in a short time by performing a mechanochemical process on a melt crystal (a composite of Li 3 AlF 6 and Li 2 TiF 6 structures).
  • the first compound in this example, Li 3 AlF 6 crystal
  • Li 3 AlF 6 crystal which is a complex cation halide
  • mechanochemical treatment together with the second compound in the mechanochemical step.
  • ionic conductive halide materials in a short time.
  • This halide has excellent bonding interface reliability and, for example, excellent atmospheric stability.
  • the manufacturing method of the present disclosure can be used as a solid electrolyte manufacturing method.
  • the halide material of the present disclosure can be used, for example, as a solid electrolyte for secondary batteries such as all-solid batteries used in various electronic devices or automobiles.

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WO2020158051A1 (ja) * 2019-01-28 2020-08-06 パナソニック株式会社 活物質、負極活物質、およびフッ化物イオン二次電池
WO2021186809A1 (ja) 2020-03-18 2021-09-23 パナソニックＩｐマネジメント株式会社 固体電解質材料およびそれを用いた電池
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