WO2025004749A1 - ハロゲン化物固体電解質の製造方法、ハロゲン化物固体電解質、正極材料、および電池 - Google Patents

ハロゲン化物固体電解質の製造方法、ハロゲン化物固体電解質、正極材料、および電池 Download PDF

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WO2025004749A1
WO2025004749A1 PCT/JP2024/020790 JP2024020790W WO2025004749A1 WO 2025004749 A1 WO2025004749 A1 WO 2025004749A1 JP 2024020790 W JP2024020790 W JP 2024020790W WO 2025004749 A1 WO2025004749 A1 WO 2025004749A1
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solid electrolyte
halide solid
halide
halogen
producing
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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 CN202480043833.8A priority Critical patent/CN121420362A/zh
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Priority to EP24831619.2A priority patent/EP4738392A1/en
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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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  • the present disclosure relates to a method for producing a halide solid electrolyte, a halide solid electrolyte, a positive electrode material, and a battery.
  • Patent Document 1 discloses a halide-based solid electrolyte material.
  • Patent Document 2 discloses a halide-based solid electrolyte material as a solid electrolyte material that coats the surface of a positive electrode active material.
  • the method for producing a halide solid electrolyte according to the present disclosure includes the steps of: (A) halogenating a raw material containing a carbonate of at least one metal element selected from the group consisting of Li and M by heat treatment to obtain a halide solid electrolyte containing Li, M, and X; Includes.
  • the M is at least one element selected from the group consisting of metal elements (excluding Li) and metalloid elements
  • the X is at least one selected from the group consisting of F, Cl, Br, and I.
  • the manufacturing method disclosed herein makes it possible to obtain a useful halide solid electrolyte that is easily microparticulated.
  • FIG. 1 is a flow chart showing an example of a method for producing a halide solid electrolyte according to the first embodiment.
  • FIG. 2 is a flow chart showing an example of a method for producing a halide solid electrolyte according to the second embodiment.
  • FIG. 3 is a flow chart showing a modified example of the method for producing a halide solid electrolyte according to the second embodiment.
  • FIG. 4 is a flow chart showing an example of a method for producing a halide solid electrolyte according to the third embodiment.
  • FIG. 5 shows a cross-sectional view of a battery 1000 according to a fourth embodiment.
  • FIG. 1 is a flow chart showing an example of a method for producing a halide solid electrolyte according to the first embodiment.
  • FIG. 2 is a flow chart showing an example of a method for producing a halide solid electrolyte according to the second embodiment.
  • FIG. 3 is a flow chart showing a modified example of the method for producing
  • FIG. 6A is a graph showing an X-ray diffraction pattern of the halide solid electrolyte after the heat treatment and before the pulverization treatment in the production method of Example 1.
  • FIG. 6B is a graph showing X-ray diffraction patterns of the pulverized halide solid electrolyte obtained in Example 1 and the halide solid electrolyte obtained in Comparative Example 1.
  • the manufacturing method according to the first embodiment includes the steps of: (A) halogenating a raw material containing a carbonate of at least one metal element selected from the group consisting of Li and M by heat treatment to obtain a halide solid electrolyte containing Li, M, and X;
  • M is at least one element selected from the group consisting of metal elements (excluding Li) and metalloid elements
  • X is at least one element selected from the group consisting of F, Cl, Br, and I.
  • “Semi-metallic elements” are B, Si, Ge, As, Sb, and Te.
  • Metallic elements are all elements in groups 1 to 12 of the periodic table (except hydrogen) and all elements in groups 13 to 16 of the periodic table (except B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).
  • metalic elements are a group of elements that can become cations when they form inorganic compounds with halogen compounds.
  • the manufacturing method according to the first embodiment makes it possible to obtain a useful halide solid electrolyte containing Li, M, and X that is easily microparticulated. The reasons for this will be explained in more detail below.
  • the synthesized halide solid electrolyte containing Li, M, and X contains many holes formed by the release of carbon dioxide and has a high porosity.
  • a halide solid electrolyte powder that is high in bulk (i.e., low bulk density), fluffy, and easy to crush is obtained. Therefore, the obtained halide solid electrolyte has weak bonds between particles and is easy to crush, making it suitable for microparticulation.
  • the obtained halide solid electrolyte is also suitable for microparticulation into particles with a particle diameter of 1 ⁇ m or less.
  • the manufacturing method according to the first embodiment can produce a useful halide solid electrolyte that is easily microparticulated.
  • a halide solid electrolyte having a bulk density of 0.1 g/cm or more and 0.4 g/cm or less can be obtained.
  • a halide solid electrolyte having a porosity of 80% or more and 95% or less can be obtained.
  • M may include Ti and M1, where M1 is at least one element selected from the group consisting of metal elements (excluding Li and Ti) and semi-metal elements.
  • the above manufacturing method makes it possible to obtain a useful halide solid electrolyte containing Li, Ti, M1, and X that is easily microparticulated.
  • the heat treatment of the raw material may be performed at a temperature of, for example, 150°C or higher.
  • the heat treatment temperature may be, for example, 600°C or lower.
  • the halide can be synthesized before it hardens through sintering. Therefore, it is possible to manufacture a halide solid electrolyte that is easy to pulverize and can suppress contamination during pulverization.
  • the atmosphere for the halogenation treatment can be selected appropriately from any atmosphere suitable for the halogen-containing material used, such as air, a nitrogen atmosphere, or a reducing atmosphere.
  • the halogenation treatment of the raw material may be carried out, for example, by heat treating a thermally decomposable halogen-containing material.
  • the halogenation treatment of the raw material by heat treatment of the halogen-containing material having thermal decomposition properties, it is possible to simultaneously cause the halogenation of the raw material, the solid-phase reaction for synthesizing a halide solid electrolyte, and decarbonation. Therefore, it is possible to obtain a homogeneous solid electrolyte with excellent properties while reducing reaction residues such as oxides in a short time.
  • the halogenation treatment is carried out by heat treatment of the halogen-containing material having thermal decomposition properties, the reactivity (halogenation property) of the raw material is good and the productivity is also excellent.
  • the above (A) is (A-1) mixing the raw material with the halogen-containing material; (A-2) heat-treating the mixture containing the raw material and the halogen-containing material obtained in (A-1) to halogenate the raw material to obtain the halide solid electrolyte; may also include
  • a heat treatment for halogenation can be carried out on a homogeneous mixture of the raw material and the halogen-containing material.
  • the contact area between the raw material and the halogen-containing material can be increased. This promotes the halogenation of the raw material homogeneously, making it possible to obtain a halide solid electrolyte that is homogeneous and has excellent properties.
  • FIG. 1 is a flow chart showing an example of a method for producing a halide solid electrolyte according to the first embodiment.
  • an example of a production method in which the above (A-1) and (A-2) are implemented will be described as an example of the production method according to the first embodiment.
  • the raw material and the halogen-containing substance are mixed (S11).
  • the raw material contains a carbonate of at least one metal element selected from the group consisting of Li and M.
  • the halogen-containing substance is thermally decomposable.
  • the obtained mixture containing the raw material and the halogen-containing substance is heat-treated to halogenate the raw material (S12). This results in a halide solid electrolyte containing Li, M, and X.
  • M contains Ti and M1
  • the raw material contains a carbonate of at least one metal element selected from the group consisting of Li and M.
  • the carbonate is preferably a carbonate containing the cation that is the most abundant among the cations contained in the crystal lattice of the halide solid electrolyte to be produced, that is, a carbonate containing a cation with a high composition ratio (substance ratio).
  • the cation that is contained in the largest amount of substance among Li and M, or Li, Ti, and M1 is Li. Therefore, by making the Li source a carbonate, that is, by making the carbonate contain Li 2 CO 3 , the amount of carbon dioxide contained in the raw material can be increased.
  • a halide solid electrolyte with a higher porosity that is, a smaller bulk density
  • a halide solid electrolyte that is easier to pulverize and suitable for microparticulation can be realized.
  • the raw material contain Li 2 CO 3 as a carbonate
  • a powder of a halide solid electrolyte with a bulk density of 0.1 g/cm 3 or more and 0.4 g/cm 3 or less can be obtained.
  • the Li source may entirely be Li2CO3 , or a part of the Li source may be Li2CO3 .
  • the content ratio of carbonate in the raw material can be set in consideration of the pulverizability and productivity of the halide solid electrolyte to be produced.
  • a solid electrolyte having Li ion conductivity one that contains a large amount of Li, which is a carrier of ion conductivity, in the composition (crystal) often exhibits high ion conductivity. Therefore, in the case of a solid electrolyte having Li ion conductivity, Li cations are often contained most in the composition. Therefore, in the manufacturing method according to the first embodiment, Li 2 CO 3 is suitable as the carbonate contained in the raw material.
  • the raw material may contain compounds other than carbonates.
  • compounds other than carbonates In addition to carbonates, oxides, hydroxides, halides, and oxyhalides can also be used as raw materials.
  • Raw materials can be selected in consideration of their stability in the atmosphere and in the manufacturing process. Many of the compounds such as oxides listed above, other than halides that are easily evaporated, can be heat-treated normally without sealing. For example, the powder can be placed in a normal crucible and heat-treated.
  • metal oxides such as Al 2 O 3 and TiO 2 can be used as oxide raw materials. Carbonates, hydroxides, and fluoride oxides of Al and Ti can also be used as raw materials.
  • M may be at least one selected from the group consisting of Ti, Al, Y, Ga, Dy, Ho, Er, Tm, and Yb. M may be at least one selected from the group consisting of Ti, Al, and Y.
  • M may contain Al. By including Al in M, a halide solid electrolyte having high ionic conductivity can be obtained.
  • M may be Al.
  • M1 may be at least one selected from the group consisting of Al, Y, Ga, Dy, Ho, Er, Tm, and Yb. M1 may be at least one selected from the group consisting of Al and Y. When M1 contains the above elements, a halide solid electrolyte having high ionic conductivity can be obtained.
  • M1 may contain Al. By including Al in M1, a halide solid electrolyte having high ionic conductivity can be obtained. M1 may be Al.
  • the raw material may be, for example, particulate. That is, the carbonates and the like that make up the raw material may each be particulate. This allows the halogenation of the raw material and the decomposition of the carbonate (i.e., the release of carbon dioxide) to proceed from the particle surface. This shortens the reaction distance and increases the reaction area. This reduces intermediate products in which the halogenation reaction or solid-phase reaction is insufficient, or reaction residues such as carbonates, making it possible to obtain a homogeneous halide solid electrolyte with excellent properties. Particulate raw materials have good reactivity (e.g., halogenation properties), so excellent productivity can also be achieved.
  • the average particle size of the raw material may be, for example, 0.5 ⁇ m or more and 20 ⁇ m or less.
  • the average particle size of the raw material is not limited to the above range, and any particle size and shape can be appropriately selected from the viewpoint of halogenation and solid-state reaction.
  • the smaller the particle size of the raw material the lower the temperature of the halogenation and solid-state reaction can be.
  • the raw material such as Li2CO3 may be a powder of primary particles (for example, a powder having an average particle size of 0.5 ⁇ m to 10 ⁇ m), a secondary particle body formed by aggregation of primary particles (for example, a powder having an average particle size of 20 ⁇ m to 100 ⁇ m), or a mixture of these or a pulverized product.
  • a powder of primary particles for example, a powder having an average particle size of 0.5 ⁇ m to 10 ⁇ m
  • a secondary particle body formed by aggregation of primary particles for example, a powder having an average particle size of 20 ⁇ m to 100 ⁇ m
  • a mixture of these or a pulverized product for example, a powder having an average particle size of 20 ⁇ m to 100 ⁇ m
  • the average particle size of the raw material is the median size of the raw material, and means the particle size (d50) corresponding to 50% cumulative volume, determined from the particle size distribution measured on a volume basis by the laser diffraction scattering method. The same applies to the average particle size of the halogen-containing material specified in this specification.
  • the halogen-containing material has thermal decomposition properties.
  • a fluorine-containing material that serves as a fluorine source is used as the halogen-containing material.
  • the thermal decomposition onset temperature of the halogen-containing material used may be, for example, 100°C or higher and 600°C or lower.
  • the halogen-containing material has stability in handling such as storage and mixing, and the obtained halide solid electrolyte can be prevented from becoming too hard.
  • the halogen element X may contain F or may be F. This makes it possible to obtain a halide solid electrolyte that is highly stable (e.g., has excellent electrochemical stability and heat resistance) and has high ionic conductivity.
  • the halogen-containing material may be, for example, particulate. This makes it easier for the halogen-containing material to thermally decompose. Therefore, by using particulate halogen-containing material, the raw material can be halogenated efficiently, and the halogen-containing material is less likely to remain in the finally obtained halide solid electrolyte.
  • the halogenation reaction can be controlled by the particle shape of the halogen-containing material. For example, by making the particles of the halogen-containing material finer, the temperature of halogenation can be lowered and the halogenation speed can be increased. In addition, by mixing the raw material containing carbonate with the halogen-containing material, homogeneous halogenation of the entire powder is possible.
  • the amount of halogen can be precisely controlled. Therefore, the synthesis of the desired halide solid electrolyte is made easier.
  • the halogen-containing material can be used in the amount necessary for halogenating the raw material, excess halogen gas emissions can be suppressed. This reduces the burden on the environment and also reduces the impact on corrosion of furnace materials, etc.
  • the halogen-containing material may have, for example, an average particle size of 0.5 ⁇ m or more and 500 ⁇ m or less, an average particle size of 0.5 ⁇ m or more and 150 ⁇ m or less, or an average particle size of 0.5 ⁇ m or more and 100 ⁇ m or less.
  • the halogen-containing material may have any particle size and shape.
  • the average particle size of the halogen-containing material may be larger than the average particle size of the raw material. This results in a state in which the surface area of the raw material is larger than that of the halogen-containing material, i.e., the surface exposed area (i.e., exposed area) of the raw material is large. This makes it easier for halogenation to proceed from the particle surface of the raw material, making it possible to obtain a homogeneous halide.
  • the average particle size of the halogen-containing material may be 5 ⁇ m or more and 100 ⁇ m or less, 5 ⁇ m or more and 20 ⁇ m or less, or 50 ⁇ m or more and 100 ⁇ m or less.
  • the average particle size of the halogen-containing material can be appropriately adjusted taking into account the temperature or reactivity of the halogenation. For example, by increasing the average particle size of the halogen-containing material, the heat treatment temperature for the halogenation process can be increased.
  • the halogen-containing material may contain an ammonium salt.
  • the ammonium salt starts to thermally decompose at a relatively low temperature (for example, about 150°C). Therefore, the ammonium salt is unlikely to remain as an unnecessary inorganic component in the finally obtained halide solid electrolyte, and the raw material can be halogenated by thermal decomposition at a low temperature. Therefore, by using an ammonium salt as the halogen-containing material, it is possible to suppress the remaining of unnecessary inorganic components derived from the halogen-containing material in the finally obtained halide solid electrolyte. In addition, since halogenation at such a low temperature is possible, the halide solid electrolyte can be synthesized without progressing sintering.
  • a halide solid electrolyte that is more excellent in pulverization and is easily microparticulated can be obtained. Furthermore, energy saving is achieved in the synthesis, and the temperature rise and fall time is also reduced, so productivity is improved. In addition, since synthesis at a low temperature is possible, the durability of the furnace material is improved, and the running costs and replacement frequency of the synthesis components are significantly reduced. As the halogen-containing material, only ammonium salt may be used.
  • the ammonium salt may contain NH 4 F.
  • NH 4 F is a highly decomposable fluorine source and can effectively act on the halogenation of the raw material. Therefore, NH 4 F can fluorinate the raw material without remaining in the solid electrolyte while thermally decomposing at a low temperature (e.g., about 150° C.) and at a high decomposition rate.
  • ammonium salts of other halogen elements such as NH 4 Cl and NH 4 Br, are also thermally decomposable and can be used as halogen sources in the same manner.
  • the halogen-containing material may contain a resin.
  • a resin as the halogen-containing material, the halogen-containing material can halogenate the raw material while being thermally decomposed at a relatively high temperature (e.g., about 450°C or higher and 600°C or lower). Therefore, the method including a resin as the halogen-containing material is suitable when it is desired to carry out the halogenation and solid-state reaction at a relatively high temperature (e.g., about 450°C or higher and 600°C or lower).
  • a resin used as a halogen-containing material is a fluororesin.
  • a fluororesin for example, polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF) can be used.
  • a fluororesin such as PTFE can halogenate a raw material while being thermally decomposed at a relatively high temperature (e.g., about 450°C or higher and 600°C or lower). Therefore, a method including a fluororesin as a halogen-containing material is suitable when it is desired to carry out halogenation and solid-state reaction at a relatively high temperature (e.g., about 450°C or higher and 600°C or lower).
  • the halogen-containing material may contain, for example, a material that does not substantially include inorganic components resulting from thermal decomposition by the heat treatment in (A) in the manufactured halide solid electrolyte, except for halogen elements.
  • the halogen-containing material used in the halogenation treatment is required to replace the halogen elements resulting from thermal decomposition by the heat treatment in (A) with the oxygen element of the raw material, while not allowing other components to be mixed as inorganic residues in the finally obtained halide solid electrolyte.
  • the inorganic components resulting from thermal decomposition by the heat treatment are not substantially included in the manufactured halide solid electrolyte, except for halogen elements" means that the content ratio of the inorganic components in the halide solid electrolyte is, for example, 0.5 mass% or less.
  • the halogen-containing material may contain multiple types of halogen-containing compounds.
  • both ammonium salt and fluororesin can be used as the halogen-containing material. This allows the temperature range in which the halogen-containing material acts as a halogen source to be widely controlled, so that the conversion of the raw material to a halide and the solid-phase reaction temperature can be controlled over a wide range. This makes it easier to obtain the desired halide solid electrolyte.
  • a raw material containing carbonate is mixed with a halogen-containing substance.
  • each material constituting the raw material is mixed uniformly with the thermally decomposable halogen-containing substance.
  • each material constituting the raw material and the halogen-containing substance may be mixed simultaneously, or the raw material may be mixed uniformly first, and then the raw material and the halogen-containing substance may be mixed.
  • the raw materials can be halogenated uniformly. This allows the synthesis of a homogeneous halide solid electrolyte.
  • organic materials and particle sizes such as acrylic beads of PMMA (polymethyl methacrylate) or PVA (polyvinyl alcohol), which are easily decomposable even at low temperatures, can be used.
  • the residues of organic and inorganic components can be detected by composition analysis such as EPMA.
  • a general electric furnace may be used for the heat treatment.
  • the atmosphere for the heat treatment may be selected as necessary, and the heat treatment may be performed in air, in an inert gas atmosphere (e.g., nitrogen gas or argon gas), or in a reducing gas (e.g., hydrogen or carbon dioxide).
  • the synthesized halide is usually obtained as a powder, but when heat treated at or above its melting point, it may be obtained as a molten body, a sintered body, or a block-shaped mass in which the powder has solidified.
  • the above-mentioned homogeneously mixed mixture is placed in, for example, an alumina heat-resistant container (sheath), and the mixture is fired in a firing furnace in any atmosphere.
  • a firing furnace for example, an inert gas such as nitrogen gas is flowed into the furnace, and gases generated during halogenation (e.g., ammonium, hydrogen chloride, carbon dioxide, etc.) are discharged while the mixture is heat-treated in the atmospheric furnace at a temperature of, for example, 150°C or higher and 600°C or lower for, for example, 1 hour or higher and 40 hours or lower, to synthesize a halide solid electrolyte.
  • gases generated during halogenation e.g., ammonium, hydrogen chloride, carbon dioxide, etc.
  • the gas inlet should be installed on the bottom side of the furnace, and the exhaust port on the top side (for example, on the ceiling side or above the side wall). This allows the reaction gas to be smoothly discharged outside the furnace by riding on the convection currents (from bottom to top) inside the furnace, reducing the amount of unwanted residual components that get mixed into the halide solid electrolyte.
  • the gas to be introduced may be heated before being introduced into the furnace. This prevents the temperature distribution in the sheath from becoming uneven. This allows the synthesis reaction of the halide solid electrolyte to occur uniformly, resulting in a more homogeneous halide solid electrolyte.
  • the furnace used for the heat treatment can be a known firing furnace (for example, an electric furnace) or an atmospheric firing furnace. Note that in order to remove the air and moisture between the particles deep inside the sheath and completely replace it with an inert gas, a vacuum replacement can be performed before the inert gas is flowed. This can reduce the effects of reactive components and moisture contained in the air. The vacuum replacement can be performed repeatedly.
  • the raw material contains a small proportion of material that is easily evaporated, it is not necessary to seal the raw material for heat treatment.
  • the mixture of raw material and halogen-containing material may be placed in a sheath, and if necessary, a lid (e.g., an alumina lid) may be placed on the sheath to prevent dust and foreign objects from falling, and then heat treatment may be performed. Therefore, unlike the heat treatment in the conventional manufacturing method using a halide raw material, in which the processing amount is limited by the size of a sealed heat treatment jig (i.e., heat treatment for causing a solid-phase reaction of the halide raw material), the heat treatment in the manufacturing method according to the first embodiment has excellent productivity and workability, and is extremely valuable industrially. According to the manufacturing method according to the first embodiment, a halide solid electrolyte with excellent ionic conductivity and stability (e.g., electrochemical stability and heat resistance) can be obtained by such a highly productive manufacturing method.
  • the sheath material does not have to be alumina.
  • heat-resistant containers made of various dense materials (e.g., relative density 98% or more), such as mullite and SiC, can be used for the sheath.
  • a material suitable for the sheath may be selected from the viewpoint of the reaction between the raw materials, halogen-containing materials, and halide solid electrolyte contained in the sheath and the sheath.
  • materials that are dense, heat-resistant, and have a small heat capacity can be used as the sheath material.
  • Various shapes such as cylindrical, prismatic, and gourd-shaped can be used for the sheath.
  • a rotary furnace such as a rotary kiln may be used, or the heat treatment may be performed by spraying the mixed powder as in spray drying.
  • the additives such as Na oxide and Ca oxide may be, for example, particulate.
  • the effect of the additive may vary depending on the particle form of the additive and the dispersion state in the raw material.
  • the particle size of the additive may be smaller than that of the oxide particles constituting the raw material.
  • the additive may be fine particles with a particle diameter of 0.1 ⁇ m or less and a BET specific surface area of 100 m 2 /g or more. Note that if coarse particles of Na oxide and Ca oxide are used or excessively added, an extra precipitated phase other than the solid electrolyte may be generated, which may reduce the ionic conductivity.
  • a halide solid electrolyte containing a first crystal phase and a second crystal phase it is possible to obtain a halide solid electrolyte with controlled properties such as density, strength, or electrical properties by, for example, changing the ratio of the first crystal phase and the second crystal phase by adjusting the raw materials.
  • the obtained halide solid electrolyte contains at least one selected from the group consisting of Na and Ca. That is, in this case, the halide solid electrolyte obtained by the manufacturing method according to the first embodiment contains, for example, Li, Al, and F, and further contains at least one selected from the group consisting of Na and Ca. With this configuration, a homogeneous halide solid electrolyte with excellent ion conductivity is obtained.
  • the halide solid electrolyte obtained by the manufacturing method according to the first embodiment may be substantially composed of Li, Al, F, Na, and Ca, or may be composed only of Li, Al, F, Na, and Ca.
  • the halide solid electrolyte is substantially composed of Li, Al, F, Na, and Ca
  • the ratio of the total amount of substance of Li, Al, F, Na, and Ca to the total amount of substance of all elements constituting the halide solid electrolyte is 90% or more. As an example, the ratio may be 95% or more.
  • the halide solid electrolyte obtained by the manufacturing method according to the first embodiment may further contain Ti.
  • the amount of oxygen as an impurity in the halide solid electrolyte obtained by the manufacturing method according to the first embodiment may be 0.5 mass% or less. According to the manufacturing method according to the first embodiment, a halide solid electrolyte with little oxygen contamination can be obtained.
  • the amount of oxygen as an impurity in the halide solid electrolyte may be, for example, 0.1 mass% or more.
  • Na and Ca when Na oxide and Ca oxide are added as additives to promote the reaction of raw materials, Na and Ca may not be detected as composition phases in X-ray diffraction measurement. Even in this case, the inclusion of Na and Ca in the halide solid electrolyte can be confirmed by a highly sensitive composition analysis (area analysis, etc.) such as an electron probe microanalyzer (EPMA).
  • the total content of Na and Ca in the halide solid electrolyte may be, for example, 0.0003 at. % or more and 0.15 at. % or less.
  • the content of Na and Ca can be determined by EPMA, etc.
  • the halide solid electrolyte obtained by the manufacturing method according to the first embodiment includes, for example, the first crystal phase and the second crystal phase, and further includes at least one selected from the group consisting of Na and Ca derived from the Na oxide and Ca oxide used as additives, for example, Na and Ca may be included in both the first crystal phase (i.e., Li 2 TiX 6 ) and the second crystal phase (i.e., Li 3 M1X 6 ).
  • Na and Ca may be included in the second crystal phase (i.e., Li 3 M1X 6 ) at a high concentration. It is considered that Na and Ca act strongly on Li 3 M1X 6 compared to Li 2 TiX 6 , and also give a secondary reaction promotion effect on Li 2 TiX 6.
  • the halide solid electrolyte to be manufactured is a solid electrolyte including the first crystal phase and the second crystal phase, it is desirable to add Na oxide and Ca oxide together.
  • the ratio of the first crystal phase to the second crystal phase is Li 3 M1X 6 >Li 2 TiX 6 , Na and Ca act particularly effectively.
  • the halide solid electrolyte obtained by the production method according to the first embodiment desirably satisfies at least one selected from the group consisting of the following (1), (2), and (3) in an X-ray diffraction pattern obtained by X-ray diffraction measurement of the halide solid electrolyte using, for example, Cu-K ⁇ radiation.
  • (1) There is no peak due to TiF4 .
  • (2) There is no peak due to LiF.
  • the halide solid electrolyte obtained by the manufacturing method according to the first embodiment is substantially free of compounds such as TiF 4 , LiF, and/or AlF 3 , and therefore has excellent characteristics and reliability.
  • a peak in an X-ray diffraction pattern is defined as a mountain-shaped portion having an S/N ratio (i.e., the ratio of signal S to background noise N) of 1.3 or more and a half-width of 5° or less. Therefore, the absence of a peak means that no mountain-shaped portion that is recognized as a peak as described above is confirmed.
  • the halide solid electrolyte obtained by the manufacturing method according to the first embodiment satisfies the above-mentioned configuration (1), that is, when there is no peak derived from TiF4 in the X-ray diffraction pattern, there is no peak within the range of the diffraction angle 2 ⁇ of 24° or more and 25° or less.
  • the halide solid electrolyte obtained by the manufacturing method according to the first embodiment may be particulate.
  • the halide solid electrolyte has a relatively soft property. Therefore, according to this configuration, a relatively soft particulate solid electrolyte can be realized. Therefore, such a compact of the halide solid electrolyte has high ionic conductivity, is excellent in stability, and can have any shape. Therefore, a compact of the halide solid electrolyte having such characteristics can realize a solid electrolyte layer of a battery having excellent characteristics and high reliability.
  • the size and shape of the halide solid electrolyte particles can be appropriately selected depending on the application.
  • Patent Document 1 discloses a halide-based solid electrolyte containing Li, Ti, M, and F.
  • M is at least one selected from the group consisting of Al and Y. It is described that all fluorides are used as starting materials for producing this solid electrolyte, and a halide solid electrolyte is synthesized by a mechanochemical reaction in which a strong crushing force is applied to the starting materials using a planetary ball mill and zirconia balls.
  • a raw material containing a carbonate (lithium carbonate as a specific example) is heat-treated to be halogenated, and the carbonate is decomposed to synthesize a halide solid electrolyte that is easy to crush and has excellent properties while desorbing carbon dioxide from the mixed powder. Therefore, the production method according to the first embodiment differs from the production method disclosed in Patent Document 1 in many respects in terms of raw materials, reaction mechanism, and production method.
  • the halide solid electrolyte obtained by the production method according to the first embodiment is easy to crush as described above, and therefore easy to finely pulverize.
  • the manufacturing method according to the first embodiment is superior to the manufacturing method disclosed in Patent Document 1 in that it is easy to pulverize, there is little contamination during pulverization, and it can produce a solid electrolyte with excellent properties such as ionic conductivity.
  • Patent Document 2 discloses a method for producing a halide solid electrolyte containing Li, Ti, M1, and F as a part of the positive electrode material.
  • M1 in the solid electrolyte described in Patent Document 2 is at least one selected from the group consisting of Ca, Mg, Al, Y, and Zr.
  • the production method according to the first embodiment has many differences from the production method disclosed in Patent Document 2 in terms of raw materials, reaction mechanism, and production method, as well as from the production method disclosed in Patent Document 1.
  • the production method according to the first embodiment is superior to the production method disclosed in Patent Document 2 in that it is easy to pulverize, so there is little contamination during pulverization, and it can produce a solid electrolyte with excellent properties such as ion conductivity.
  • the grinding process (B) is carried out, so that the halide solid electrolyte can be obtained with a particle size suitable for the application.
  • the halide solid electrolyte can be made amorphous, it is possible to improve the ionic conductivity and improve the softness of the particles of the halide solid electrolyte.
  • By improving the softness of the particles of the halide solid electrolyte it is possible to improve the density of the compact of the halide solid electrolyte. Therefore, according to the halide solid electrolyte obtained by the manufacturing method of the second embodiment, a compact that is dense and has high ionic conductivity can be formed.
  • FIG. 2 is a flow chart showing an example of a method for producing a halide solid electrolyte according to the second embodiment.
  • A a production method in which (A-1) and (A-2) are carried out as (A), which is an example of the production method described in the first embodiment, is described, in which (B) is carried out after (A-2).
  • the raw material and the halogen-containing substance are mixed (S21).
  • the obtained mixture containing the raw material and the halogen-containing substance is heat-treated to halogenate the raw material (S22).
  • S22 halogenate the raw material
  • M contains Ti and M1
  • M contains Ti and M1
  • a halide solid electrolyte containing Li, Ti, M1, and X is subjected to a pulverization process (S23).
  • S21 and S22 are the same as S11 and S12 described in the first embodiment, so detailed explanation will be omitted here.
  • the halide solid electrolyte synthesized by (A) above has an average particle size of, for example, 3 ⁇ m or more and 20 ⁇ m or less.
  • the halide solid electrolyte synthesized by (A) above is pulverized so that the average particle size is, for example, 0.1 ⁇ m or more and 2 ⁇ m or less.
  • the grinding process may be a dry process or a wet process using water or a solvent (e.g., ethanol, butyl acetate, etc.) as long as it can finely grind the halide to the desired particle size.
  • a solvent e.g., ethanol, butyl acetate, etc.
  • zirconia balls e.g., balls with a diameter of 1 mm to 30 mm
  • the halide solid electrolyte obtained in (A) above are placed in a ball mill container and ground for, for example, about 2 to 7 hours.
  • the halide solid electrolyte synthesized in (A) above has a small bulk density and is easily micronized, so it can be finely ground in a short time. Therefore, contamination from grinding media such as zirconia is also suppressed.
  • contamination depends on the grinding time and grinding force. Therefore, if the grinding sample is hard, for example due to sintering, contamination will also be affected by its hardness.
  • a polyethylene container, a container lined with fluororesin or zirconia, etc. can be used as the ball mill container.
  • the grinding process in (B) above may include, for example, mechanochemical processing.
  • the mechanochemical processing here is carried out to introduce distorted crystals or amorphousness into the crystals of the halide solid electrolyte.
  • the distorted crystals or amorphousness are mainly introduced into the surface layer of the particles of the halide solid electrolyte.
  • the specific means may be the same as the grinding process described above, for example, a ball mill is used. However, the grinding conditions may be strengthened or the time may be extended.
  • the equipment and media used for the mechanochemical processing may be the same as those used for the grinding process, and generally, the grinding and mechanochemical processing proceed simultaneously.
  • a ball mill container lined with zirconia is used, and zirconia balls are placed in a volume ratio of 10% to 60% to perform mechanochemical milling together with grinding.
  • the diameter of the zirconia balls is not particularly limited, and any size can be used. Typically, as described above, commercially available balls with a diameter of 1 mm to 30 mm are used, but balls with a smaller or larger diameter than these may also be used. The diameter of the balls used may be selected as desired depending on the desired particle size or degree of amorphization.
  • an appropriate amount of an additive that does not adversely affect the properties of the halide solid electrolyte such as ethanol, may be added. It is preferable that the additive can be removed by drying later.
  • the introduction of amorphousness into the halide solid electrolyte can be confirmed by the 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 1.5405 ⁇ and 1.5444 ⁇ ) as the X-ray source. Specifically, this can be confirmed by the fact that the peaks in the X-ray diffraction pattern of the halide solid electrolyte after the crushing process are broadened compared to the peaks in the X-ray diffraction pattern of the halide solid electrolyte before the crushing process. The peaks are broadened, meaning that the half-width is wider.
  • TEM transmission electron microscope
  • the manufacturing method according to the second embodiment includes a pulverization process
  • the halide solid electrolyte obtained by the manufacturing method according to the second embodiment includes, for example, an amorphous phase.
  • the amorphous portion of the halide solid electrolyte becomes even softer and has better deformability. Therefore, a compact of the halide solid electrolyte can be configured into a solid electrolyte layer of any shape with higher ionic conductivity and higher stability. Therefore, a compact of the halide solid electrolyte including an amorphous phase can realize a solid electrolyte layer of a battery with excellent characteristics and high reliability.
  • the halide solid electrolyte may be converted into a slurry for forming a coating film at the same time.
  • FIG. 3 is a flowchart showing a modified example of the method for producing a halide solid electrolyte according to the second embodiment.
  • the raw material and the halogen-containing substance are mixed (S31).
  • the obtained mixture containing the raw material and the halogen-containing substance is heat-treated to halogenate the raw material (S32).
  • M contains Ti and M1
  • the halide solid electrolyte obtained in S32 is subjected to a pulverization process and a slurry process (S33).
  • S31 and S32 are the same as S11 and S12 described in the first embodiment, so detailed explanation will be omitted here.
  • the grinding process is the same as the grinding process in S23 described as an example of the manufacturing method of the second embodiment.
  • a slurrying process is further performed.
  • the slurrying process is performed, for example, by adding an organic binder and a plasticizer, etc., dispersed in an organic solvent such as tetralin, to the halide solid electrolyte at the same time as the grinding process.
  • An example of the organic binder is, for example, styrene butadiene block copolymer (SBS).
  • SBS styrene butadiene block copolymer
  • An example of the plasticizer is, for example, bisbutyl phthalate (DBP) and butyl benzyl phthalate (BBP).
  • the obtained halide solid electrolyte slurry can be used for printing or coating.
  • the thickness of the coating film can be, for example, 10 ⁇ m or more and 100 ⁇ m or less, and this allows, for example, a slurry of a pulverized halide solid electrolyte containing an amorphous portion to be directly coated.
  • an organic binder, a plasticizer, etc. can be added in the pulverization process to prepare a slurry of the halide solid electrolyte, and the slurry can be used to form a coating film.
  • This allows the formation of a coating film of a halide solid electrolyte with excellent properties.
  • Such a coating film can be used, for example, in the manufacture of a coated cell.
  • a halogen-containing material is heat-treated to generate halogen gas, and the raw material is halogenated by contacting the halogen gas with the raw material.
  • the above (A) may be followed by the crushing process of (B) described in the second embodiment.
  • FIG. 4 is a flow chart showing an example of a method for producing a halide solid electrolyte according to the third embodiment.
  • raw materials are prepared (S41).
  • the raw materials and a halogen-containing material are placed in a predetermined position, and the halogen-containing material is heat-treated to bring the generated halogen gas into contact with the raw materials (S42).
  • This performs a halogenation treatment on the raw materials.
  • the halide solid electrolyte obtained in S42 may be subjected to a pulverization treatment (S43).
  • the raw material can be halogenated by the generated halogen gas without directly contacting the raw material with the halogen-containing material. Therefore, even if a halogen-containing material containing an inorganic component other than the halogen element (e.g., a material that emits fluorine gas when heated, such as CuF2 ) is used, it is not necessary to consider inorganic residues in the halide solid electrolyte to be manufactured. Therefore, the range of usable halogen-containing materials can be expanded.
  • a halogen-containing material containing an inorganic component other than the halogen element e.g., a material that emits fluorine gas when heated, such as CuF2
  • the raw material is placed on a fine-meshed nickel mesh, and the halogen-containing material, such as ammonium fluoride, is placed under the nickel mesh.
  • the halogen-containing material such as ammonium fluoride
  • the raw material and the halogen-containing material are placed without contacting each other.
  • halogen gas such as fluorine gas
  • the raw material and the halogen-containing material are as described in the first embodiment.
  • the heat treatment can be performed in air, but it is preferable to perform the heat treatment in a nitrogen atmosphere or a reducing atmosphere to prevent the nickel mesh from oxidizing.
  • the battery according to the fourth embodiment includes a positive electrode, an electrolyte layer, and a negative electrode.
  • the electrolyte layer is provided between the positive electrode and the negative electrode.
  • At least one selected from the group consisting of the positive electrode, the electrolyte layer, and the negative electrode includes a halide solid electrolyte that includes Li, Al, and F, and further includes at least one selected from the group consisting of Na and Ca.
  • the halide solid electrolyte can be manufactured, for example, by the manufacturing method according to the first embodiment, the second embodiment, or the third embodiment.
  • the halide solid electrolyte contained in the battery according to the fourth embodiment which contains Li, Al, and F and further contains at least one selected from the group consisting of Na and Ca, will be referred to as the halide solid electrolyte according to the fourth embodiment.
  • the halide solid electrolyte according to the fourth embodiment may be substantially composed of Li, Al, F, Na, and Ca, as described in the first, second, or third embodiment as an example of a halide solid electrolyte that can be manufactured by the manufacturing method according to the first, second, or third embodiment, or may be composed only of Li, Al, F, Na, and Ca.
  • the halide solid electrolyte according to the fourth embodiment may further contain Ti.
  • the halide solid electrolyte according to the fourth embodiment may be particulate.
  • the halide solid electrolyte according to the fourth embodiment may contain an amorphous phase, as described in the second embodiment.
  • the battery according to the fourth embodiment has excellent charge/discharge characteristics because it contains the halide solid electrolyte according to the fourth embodiment.
  • FIG. 5 shows a cross-sectional view of a battery 1000 according to a fourth embodiment.
  • the battery 1000 according to the fourth embodiment includes a positive electrode 201, an electrolyte layer 202, and a negative electrode 203.
  • the electrolyte layer 202 is provided between the positive electrode 201 and the negative electrode 203.
  • the positive electrode 201 may include a positive electrode material including a halide according to the fourth embodiment.
  • the positive electrode 201 contains a positive electrode active material 204 and a solid electrolyte 100.
  • the electrolyte layer 202 contains an electrolyte material.
  • the negative electrode 203 contains a negative electrode active material 205 and a solid electrolyte 100.
  • the solid electrolyte 100 includes, for example, the halide solid electrolyte according to the fourth embodiment.
  • the solid electrolyte 100 may be particles containing the halide solid electrolyte according to the fourth embodiment as a main component. Particles containing the halide solid electrolyte according to the fourth embodiment as a main component refer to particles in which the component contained most abundantly in terms of molar ratio is the halide solid electrolyte according to the fourth embodiment.
  • the solid electrolyte 100 may be particles made of the halide solid electrolyte according to the fourth embodiment.
  • the positive electrode 201 contains a material capable of absorbing and releasing metal ions (e.g., lithium ions).
  • the material is, for example, the positive electrode active material 204.
  • Examples of the positive electrode active material 204 include lithium-containing transition metal oxides, transition metal fluorides, polyanions, fluorinated polyanion materials, transition metal sulfides, transition metal oxyfluorides, transition metal oxysulfides, or transition metal oxynitrides.
  • Examples of lithium-containing transition metal oxides include Li(Ni,Co,Mn) O2 , Li(Ni,Co,Al) O2 , or LiCoO2 .
  • (A, B, C) means "at least one selected from the group consisting of A, B, and C.”
  • the shape of the positive electrode active material 204 is not limited to a specific shape.
  • the positive electrode active material 204 may be particles.
  • the positive electrode active material 204 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less. When the positive electrode active material 204 has a median diameter of 0.1 ⁇ m or more, the positive electrode active material 204 and the solid electrolyte 100 can be well dispersed in the positive electrode 201. This improves the charge and discharge characteristics of the battery 1000. When the positive electrode active material 204 has a median diameter of 100 ⁇ m or less, the lithium diffusion rate in the positive electrode active material 204 improves. This allows the battery 1000 to operate at a high output.
  • the positive electrode active material 204 may have a median diameter larger than that of the solid electrolyte 100. This allows the positive electrode active material 204 and the solid electrolyte 100 to be well dispersed in the positive electrode 201.
  • the ratio of the volume of the positive electrode active material 204 to the sum of the volume of the positive electrode active material 204 and the volume of the solid electrolyte 100 may be 0.30 or more and 0.95 or less.
  • the positive electrode material when the positive electrode 201 includes a positive electrode material including a halide according to the fourth embodiment, the positive electrode material may include the halide solid electrolyte according to the fourth embodiment as the solid electrolyte 100, or may include it as a coating material that coats the positive electrode active material 204.
  • the electrolyte layer 202 contains an electrolyte material.
  • the electrolyte material is, for example, a solid electrolyte.
  • the solid electrolyte may include the halide solid electrolyte according to the fourth embodiment.
  • the electrolyte layer 202 may be a solid electrolyte layer.
  • the electrolyte layer 202 may contain 50% by mass or more of the halide solid electrolyte according to the fourth embodiment.
  • the electrolyte layer 202 may contain 70% by mass or more of the halide solid electrolyte according to the fourth embodiment.
  • the electrolyte layer 202 may contain 90% by mass or more of the halide solid electrolyte according to the fourth embodiment.
  • the electrolyte layer 202 may consist of only the halide solid electrolyte according to the fourth embodiment.
  • the halide solid electrolyte according to the fourth embodiment will be referred to as the first solid electrolyte.
  • a solid electrolyte different from the first solid electrolyte will be referred to as the second solid electrolyte.
  • the electrolyte layer 202 may contain not only the first solid electrolyte but also the second solid electrolyte. In the electrolyte layer 202, the first solid electrolyte and the second solid electrolyte may be uniformly dispersed. A layer made of the first solid electrolyte and a layer made of the second solid electrolyte may be stacked along the stacking direction of the battery 1000.
  • the battery according to the fourth embodiment may include a positive electrode 201, a second electrolyte layer, a first electrolyte layer, and a negative electrode 203 in this order.
  • the solid electrolyte contained in the first electrolyte layer may have a lower reduction potential than the solid electrolyte contained in the second electrolyte layer. This allows the solid electrolyte contained in the second electrolyte layer to be used without being reduced. As a result, the charge/discharge efficiency of the battery 1000 can be improved.
  • the first electrolyte layer may contain a sulfide solid electrolyte in order to suppress the reductive decomposition of the solid electrolyte.
  • the electrolyte layer 202 may have a thickness of 1 ⁇ m or more and 1000 ⁇ m or less. If the electrolyte layer 202 has a thickness of 1 ⁇ m or more, the positive electrode 201 and the negative electrode 203 are less likely to short-circuit. If the electrolyte layer 202 has a thickness of 1000 ⁇ m or less, the battery 1000 can operate at high power.
  • the electrolyte layer 202 may have a thickness of 1 ⁇ m or more and 1000 ⁇ m or less.
  • the negative electrode 203 contains a material capable of absorbing and releasing metal ions (e.g., lithium ions).
  • the material is, for example, the negative electrode active material 205.
  • Examples of the negative electrode active material 205 are metal materials, carbon materials, oxides, nitrides, tin compounds, or silicon compounds.
  • the metal material may be a single metal or an alloy.
  • Examples of the metal material are lithium metal or lithium alloys.
  • Examples of the carbon material are natural graphite, coke, partially graphitized carbon, carbon fiber, spherical carbon, artificial graphite, or amorphous carbon. From the viewpoint of capacity density, suitable examples of the negative electrode active material are silicon (i.e., Si), tin (i.e., Sn), silicon compounds, or tin compounds.
  • the negative electrode active material 205 may be selected in consideration of the reduction resistance of the solid electrolyte contained in the negative electrode 203.
  • the negative electrode active material 205 may be a material capable of absorbing and releasing lithium ions at 0.27 V or more relative to lithium.
  • examples of such negative electrode active materials are titanium oxide, indium metal , or lithium alloy.
  • examples of titanium oxide are Li4Ti5O12 , LiTi2O4 , or TiO2 .
  • the shape of the negative electrode active material 205 is not limited to a specific shape.
  • the negative electrode active material 205 may be particles.
  • the negative electrode active material 205 may have a median diameter of 0.1 ⁇ m or more and 100 ⁇ m or less.
  • the negative electrode active material 205 and the solid electrolyte 100 can be well dispersed in the negative electrode 203. This improves the charge and discharge characteristics of the battery 1000.
  • the negative electrode active material 205 has a median diameter of 100 ⁇ m or less, the lithium diffusion rate in the negative electrode active material 205 improves. This allows the battery 1000 to operate at a high output.
  • the negative electrode active material 205 may have a median diameter larger than that of the solid electrolyte 100. This allows the negative electrode active material 205 and the solid electrolyte 100 to be well dispersed in the negative electrode 203.
  • the ratio of the volume of the negative electrode active material 205 to the sum of the volume of the negative electrode active material 205 and the volume of the solid electrolyte 100 may be 0.30 or more and 0.95 or less.
  • the negative electrode 203 may have a thickness of 10 ⁇ m or more and 500 ⁇ m or less.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a second solid electrolyte for the purpose of increasing ionic conductivity, chemical stability, and electrochemical stability.
  • the second solid electrolyte may be a sulfide solid electrolyte.
  • Examples of sulfide solid electrolytes are Li2S - P2S5 , Li2S - SiS2 , Li2S - B2S3 , Li2S - GeS2 , Li3.25Ge0.25P0.75S4 , or Li10GeP2S12 .
  • the negative electrode 203 may contain a sulfide solid electrolyte to suppress reductive decomposition of the solid electrolyte.
  • the negative electrode active material By covering the negative electrode active material with an electrochemically stable sulfide solid electrolyte, it is possible to suppress the first solid electrolyte from coming into contact with the negative electrode active material. As a result, the internal resistance of the battery 1000 can be reduced.
  • the second solid electrolyte may be an oxide solid electrolyte.
  • oxide solid electrolytes include: (i) NASICON-type solid electrolytes such as LiTi2 ( PO4 ) 3 or elemental substitutions thereof; (ii) Perovskite-type solid electrolytes such as (LaLi) TiO3 ; (iii ) LISICON-type solid electrolytes such as Li14ZnGe4O16, Li4SiO4 , LiGeO4 or elemental substitutions thereof ; ( iv) garnet-type solid electrolytes such as Li7La3Zr2O12 or elemental substitutions thereof ; or (v) Li3PO4 or its N -substituted derivatives; It is.
  • the second solid electrolyte may be a halide solid electrolyte.
  • halide solid electrolytes are Li2MgX4 , Li2FeX4 , Li(Al,Ga,In) X4 , Li3 (Al,Ga,In) X6 , or LiI, where X is at least one selected from the group consisting of F, Cl, Br, and I.
  • halide solid electrolyte is a compound represented by Li a Me b Y c Z 6.
  • Me is at least one selected from the group consisting of metal elements other than Li and Y and metalloid elements.
  • Z is at least one selected from the group consisting of F, Cl, Br, and I.
  • m represents the valence of Me.
  • Metalloid elements are B, Si, Ge, As, Sb, and Te.
  • Metal elements are all elements included in Groups 1 to 12 of the periodic table (excluding hydrogen), and all elements included in Groups 13 to 16 of the periodic table (excluding B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).
  • Me may be at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb.
  • the halide solid electrolyte may be Li3YCl6 or Li3YBr6 .
  • the second solid electrolyte may be an organic polymer solid electrolyte.
  • organic polymer solid electrolytes examples include polymer compounds and lithium salt compounds.
  • the polymer compound may have an ethylene oxide structure.
  • a polymer compound having an ethylene oxide structure can contain a large amount of lithium salt, and therefore can further increase the ionic conductivity.
  • lithium salt examples include LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3F3 , LiN ( SO2CF3 ) 2 , LiN (SO2C2F5)2, LiN(SO2CF3)(SO2C4F9), or LiC(SO2CF3)3 .
  • One type of lithium salt selected from these may be used alone. Alternatively, a mixture of two or more types of lithium salts selected from these may be used.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a nonaqueous electrolyte, a gel electrolyte, or an ionic liquid to facilitate the transfer of lithium ions and improve the output characteristics of the battery.
  • the non-aqueous electrolyte contains a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent.
  • non-aqueous solvents examples include cyclic carbonate solvents, chain carbonate solvents, cyclic ether solvents, chain ether solvents, cyclic ester solvents, chain ester solvents, or fluorine solvents.
  • cyclic carbonate solvents are ethylene carbonate, propylene carbonate, or butylene carbonate.
  • chain carbonate solvents are dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate.
  • Examples of cyclic ether solvents are tetrahydrofuran, 1,4-dioxane, or 1,3-dioxolane.
  • chain ether solvents are 1,2-dimethoxyethane or 1,2-diethoxyethane.
  • An example of a cyclic ester solvent is ⁇ -butyrolactone.
  • An example of a chain ester solvent is methyl acetate.
  • fluorine solvents are fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethyl methyl carbonate, or fluorodimethylene carbonate.
  • One type of non-aqueous solvent selected from these may be used alone. Alternatively, a combination of two or more types of non-aqueous solvents selected from these may be used.
  • lithium salt examples include LiPF6 , LiBF4 , LiSbF6, LiAsF6 , LiSO3CF3 , LiN ( SO2CF3 ) 2 , LiN ( SO2C2F5 ) 2 , LiN( SO2CF3 )(SO2C4F9), or LiC( SO2CF3 ) 3 .
  • One type of lithium salt selected from these may be used alone. Alternatively, a mixture of two or more types of lithium salts selected from these may be used.
  • the concentration of the lithium salt is, for example , in the range of 0.5 mol/L or more and 2 mol/L or less.
  • the ionic liquid may contain a lithium salt.
  • At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder to improve adhesion between particles.
  • binders are polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resins, polyamides, polyimides, polyamideimides, polyacrylonitrile, polyacrylic acid, polymethyl esters of acrylic acid, polyethyl esters of acrylic acid, polyhexyl esters of acrylic acid, polymethacrylic acid, polymethyl esters of methacrylic acid, polyethyl esters of methacrylic acid, polyhexyl esters of methacrylic acid, polyvinyl acetate, polyvinylpyrrolidone, polyethers, polyethersulfones, hexafluoropolypropylene, styrene butadiene rubber, or carboxymethylcellulose.
  • Copolymers may also be used as binders.
  • binders are copolymers of two or more materials selected from the group consisting of tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ethers, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene.
  • a mixture of two or more of these materials may be used as a binder.
  • At least one selected from the positive electrode 201 and the negative electrode 203 may contain a conductive additive to improve electronic conductivity.
  • Examples of the conductive additive include: (i) graphites, such as natural or synthetic graphite; (ii) Carbon blacks such as acetylene black or ketjen black; (iii) conductive fibers, such as carbon or metal fibers; (iv) fluorocarbons, (v) metal powders such as aluminum; (vi) conductive whiskers such as zinc oxide or potassium titanate; (vii) a conductive metal oxide such as titanium oxide, or (viii) a conductive polymer compound such as polyaniline, polypyrrole, or polythiophene.
  • the conductive assistant of (i) or (ii) above may be used.
  • the battery according to the fourth embodiment may be manufactured, for example, by preparing a material for forming a positive electrode, a material for forming an electrolyte layer, and a material for forming a negative electrode, and producing a laminate in which the positive electrode, electrolyte layer, and negative electrode are arranged in this order using a known method.
  • the synthesized halide solid electrolyte containing Li, M, and X contains many holes formed by the release of carbon dioxide and has a high porosity.
  • a halide solid electrolyte powder that is high in bulk (i.e., low bulk density), fluffy, and easy to crush is obtained. Therefore, the obtained halide solid electrolyte has weak bonds between particles and is easy to crush, making it suitable for microparticulation.
  • the obtained halide solid electrolyte is also suitable for microparticulation into particles with a particle diameter of 1 ⁇ m or less.
  • the M includes Ti and M1, M1 is at least one element selected from the group consisting of metal elements (excluding Li and Ti) and metalloid elements,
  • the halide solid electrolyte includes Li, Ti, M1, and X; The method for producing a halide solid electrolyte according to claim 1.
  • the above manufacturing method makes it possible to obtain a useful halide solid electrolyte containing Li, Ti, M1, and X that is easily microparticulated.
  • the halide solid electrolyte includes a first crystal phase represented by the following composition formula (1) and a second crystal phase represented by the following composition formula (2): The method for producing a halide solid electrolyte according to claim 2.
  • Composition formula (1) Li 2 TiX 6
  • Composition formula (2) Li 3 M1X 6
  • the M1 includes Al. 4. The method for producing a halide solid electrolyte according to claim 2 or 3.
  • the manufacturing method of Technology 5 makes it possible to obtain a halide solid electrolyte with high ionic conductivity.
  • the X includes F. 6.
  • the manufacturing method of Technology 6 makes it possible to obtain a halide solid electrolyte that is highly stable (e.g., has excellent electrochemical stability and heat resistance) and has high ionic conductivity.
  • the carbonate includes Li2CO3 ; 7.
  • the cation contained in the largest amount of substance among the constituent cations is usually Li. Therefore, according to the production method of Technology 7, by using Li2CO3 as the carbonate, it is possible to contain a large amount of carbonic acid in the raw material. Therefore, since the amount of carbonic acid contained in the raw material can be increased, it is possible to synthesize a halide solid electrolyte having a higher porosity, i.e., a smaller bulk density, after carbon dioxide is desorbed during the synthesis process. Therefore, it is possible to realize a halide solid electrolyte that is easier to pulverize and suitable for microparticulation.
  • the halogenation of the raw material and the decomposition of the carbonate proceed from the particle surface. This shortens the reaction distance and increases the reaction area. This reduces intermediate products in which the halogenation reaction or solid-phase reaction is insufficient, or reaction residues such as carbonates, making it possible to obtain a homogeneous halide solid electrolyte with excellent properties. Since particulate raw materials have good reactivity (e.g., halogenation), excellent productivity can also be achieved.
  • decarbonation, halogenation reaction, and solid-phase reaction can be caused to occur simultaneously by controlling the heat treatment conditions (control of the heat treatment temperature and heat treatment atmosphere, etc.). Therefore, a solid electrolyte with homogeneous and excellent properties can be obtained in a short time while reducing reaction residues.
  • the halogenation treatment is performed by heat treating a halogen-containing material that has thermal decomposition properties, the reactivity of the raw material (halogenation property) is good and the productivity is also excellent.
  • the temperature of the halogenation reaction and solid-phase reaction of the raw material and the progress of these reactions can be controlled according to the thermal decomposition temperature of the halogen-containing material selected. As a result, the desired halide solid electrolyte can be obtained.
  • the manufacturing method of technology 10 makes it easier for the halogen-containing material to thermally decompose, and increases the contact area between the raw material containing carbonate and the halogen-containing material. Therefore, according to the manufacturing method of technology 10, the raw material can be efficiently halogenated, and the halogen-containing material is less likely to remain in the finally obtained halide solid electrolyte.
  • the halogenation reaction can be controlled by the particle shape of the halogen-containing material. For example, by making the particles of the halogen-containing material finer, the temperature of halogenation can be lowered and the halogenation speed can be increased.
  • the (A) is (A-1) mixing the raw material with the halogen-containing material; (A-2) heat-treating the mixture containing the raw material and the halogen-containing material obtained in (A-1) to halogenate the raw material to obtain the halide solid electrolyte;
  • the method for producing a halide solid electrolyte according to Technology 9 or 10, comprising:
  • a heat treatment for halogenation can be performed on a homogeneous mixture of the raw material and the halogen-containing material.
  • the contact area between the raw material and the halogen-containing material can be increased. Therefore, according to the manufacturing method of Technology 11, the halogenation of the raw material can be promoted homogeneously. As a result, a halide solid electrolyte that is homogeneous and has excellent properties can be obtained.
  • the raw material can be halogenated by the generated halogen gas without directly contacting the raw material with the halogen-containing material. Therefore, even if a halogen-containing material containing inorganic components in addition to the halogen element is used, there is no need to consider inorganic residues in the produced halide solid electrolyte. This makes it possible to expand the range of halogen-containing materials that can be used.
  • the halogen-containing material includes an ammonium salt. 13.
  • Ammonium salts begin to decompose thermally at a relatively low temperature (for example, about 150°C). Therefore, ammonium salts are unlikely to remain as unnecessary inorganic components in the final halide solid electrolyte, and can be decomposed thermally at a low temperature to halogenate the raw material. Therefore, according to the manufacturing method of Technology 13, it is possible to suppress the remaining of unnecessary inorganic components derived from halogen-containing materials in the final halide solid electrolyte. In addition, since halogenation at such a low temperature is possible, a halide solid electrolyte can be synthesized without progressing sintering.
  • a halide solid electrolyte that is more excellent in pulverization and is easily microparticulated can be obtained. Furthermore, energy saving is achieved in the synthesis, and the temperature rise and fall time is also reduced, so productivity is improved. In addition, since synthesis is possible at a low temperature, the durability of the furnace material is improved, and the running costs and replacement frequency of the synthesis components are significantly reduced. In addition, in the conventional method of synthesizing a halide solid electrolyte by a solid-phase reaction using a halide raw material, a heat treatment of at least about 500°C to 600°C is required, for example.
  • the ammonium salt comprises NH4F . 14.
  • NH 4 F is a highly decomposable fluorine source and can effectively act to halogenate raw materials. Therefore, according to the manufacturing method of Technique 14, NH 4 F can halogenate raw materials while being thermally decomposed at a low temperature (e.g., about 150° C.) and at a high decomposition rate, without remaining in the solid electrolyte.
  • the halogen-containing material includes a resin.
  • the halogen-containing material can be halogenated while being thermally decomposed at a relatively high temperature (e.g., about 450°C or higher and 600°C or lower). Therefore, the manufacturing method of Technology 15 is suitable for cases where it is desired to carry out halogenation and solid-state reactions at a relatively high temperature (e.g., about 450°C or higher and 600°C or lower).
  • the resin includes a fluororesin. 16.
  • Fluororesins such as PTFE can be halogenated as raw materials while being pyrolyzed at relatively high temperatures (e.g., about 450°C or higher and 600°C or lower). Therefore, the manufacturing method of Technique 16 is suitable when it is desired to carry out halogenation and solid-state reaction at relatively high temperatures (e.g., about 450°C or higher and 600°C or lower).
  • the halogen-containing material includes a substance that does not substantially include inorganic components generated by thermal decomposition by the heat treatment in (A) in the halide solid electrolyte, except for halogen elements. 13.
  • the halogen-containing material is required to replace the halogen elements generated by the thermal decomposition by the heat treatment in (A) with anions such as oxygen elements in the raw materials, while other components are not mixed as inorganic residues into the finally obtained halide solid electrolyte.
  • examples of halogen-containing materials that do not substantially contain inorganic components, except for halogen elements, generated by thermal decomposition by heat treatment in the finally obtained halide solid electrolyte include substances in which inorganic components, except for halogen elements, generated by thermal decomposition by heat treatment are exhausted as gas.
  • the halogen-containing material includes a plurality of halogen-containing compounds. 18. The method for producing a halide solid electrolyte according to any one of claims 9 to 17.
  • both ammonium salt and fluororesin can be used as the halogen-containing material.
  • This allows for a wide range of temperature control over the temperature range in which the halogen-containing material acts as a halogen source.
  • This allows for a wide range of control over the conversion of the raw material to a halide and the solid-phase reaction temperature. Therefore, according to the manufacturing method of Technology 18, it becomes easy to obtain a desired halide solid electrolyte.
  • the manufacturing method of Technology 19 allows the raw material to be sufficiently halogenated.
  • the halide By performing heat treatment at a low temperature of about 150°C, the halide can be synthesized before the material hardens through sintering. This makes it easy to crush, and contamination during crushing can be suppressed.
  • a heat treatment temperature of, for example, 150°C or higher and 450°C or lower is suitable. This makes it possible to obtain a solid electrolyte that is excellent in terms of microparticulation and suppression of deterioration of characteristics.
  • the atmosphere for the halogenation treatment can be selected from any atmosphere suitable for the halogen-containing material used, such as air, nitrogen, or reducing atmosphere.
  • the manufacturing method of Technology 20 allows a halide solid electrolyte to be obtained with a particle size suitable for the application.
  • the halide solid electrolyte can be made amorphous, it is possible to improve the ionic conductivity and the softness of the particles of the halide solid electrolyte.
  • the density of the compact of the halide solid electrolyte can be improved. Therefore, the halide solid electrolyte obtained by the manufacturing method of Technology 20 allows the formation of a dense compact with high ionic conductivity.
  • the manufacturing method of Technology 21 makes it possible to obtain a halide solid electrolyte with even smaller bulk density. This makes it possible to obtain a useful halide solid electrolyte that is even easier to microparticulate.
  • This configuration results in a homogeneous halide solid electrolyte with excellent ionic conductivity.
  • the halide solid electrolyte is in particulate form. 24.
  • the halide solid electrolyte includes an amorphous phase. 25.
  • This configuration makes it possible to obtain a halide solid electrolyte with excellent characteristics and reliability.
  • This configuration provides a battery with excellent charge/discharge characteristics.
  • This configuration provides a battery with excellent charge/discharge characteristics.
  • X is F
  • M1 is Al.
  • Na 2 O powder and CaO powder were weighed out so that NaF was 0.04 mol% and CaF 2 was 0.01 mol% relative to [0.25Li 2 TiF 6 - 0.75Li 3 AlF 6 ].
  • the amount of NH 4 F powder required for fluorinating the raw materials was added . Specifically, an amount of NH 4 F that fluorinates all the raw materials in the reaction formula was used. The weighing of these starting materials was carried out in air.
  • the mixture containing the raw material, the halogen-containing material, and the additive was heat-treated (a step corresponding to the above (A-2)).
  • a high-purity (SSA-H) alumina crucible (diameter ⁇ : 36 mm, height: 40 mm) was used for the sheath, and about 3 g of the above mixture was placed in the crucible.
  • SSA-H high-purity alumina crucible
  • a spacer was placed on the outer edge of the upper surface of the sheath, and an alumina plate-shaped lid was placed on it to prevent foreign objects from falling.
  • the sheath with the lid placed on it was placed in the center of the firing furnace and heat-treated.
  • the sheath was placed on a small heat capacity tsuku made of mullite with a porosity of about 20%.
  • a tsuku with a length of 10 mm, width of 10 mm, and height of 10 mm was used, and three tsuku were placed under one sheath to float the sheath from the bottom of the furnace. In this way, the heater (radiation) heat and the inert gas were allowed to reach the bottom of the scabbard.
  • nitrogen gas was introduced as the inert gas at 2 L/min from the inlet at the bottom of the furnace and discharged from the exhaust port on the upper side of the ceiling. The gas continued to flow until the heat treatment was completed. The temperature of the heat treatment was 350°C.
  • raw materials containing lithium carbonate, an oxide, and a fluoride oxide, and a halogen-containing material (NH 4 F) as a fluorine source were used, and halogenation and desorption of carbonic acid from lithium carbonate were simultaneously performed by heat treatment.
  • the halide solid electrolyte powder synthesized in this way was a fluffy powder with a low bulk density because the carbon dioxide decomposed and escaped left holes.
  • the bulk density (apparent density) of the halide solid electrolyte obtained in this example was 0.24 g/cm 3.
  • the true specific gravity of the solid electrolyte in this example was about 2.8 g/cm 3.
  • the halide solid electrolyte powder obtained by such synthesis was easy to pulverize, and contamination during the pulverization process was also suppressed. In addition, it was easy to finely pulverize (for example, particle size 0.5 ⁇ m or less).
  • the halide solid electrolyte obtained by the above heat treatment was subjected to a pulverization process (a process corresponding to (B) above).
  • a dry pulverization process was performed. Specifically, zirconia balls (diameter: 15 mm) and the halide solid electrolyte obtained by the above heat treatment were placed in a ball mill (volume: 1 L) with a zirconia lining, and pulverized for 20 hours.
  • halide solid electrolyte The halide solid electrolyte of Example 1 synthesized as described above was evaluated for its crystal phase, ionic conductivity, electronic conductivity, average particle size, BET specific surface area, and bulk density. The crystal phase, ionic conductivity, average particle size, and BET specific surface area were evaluated for both the halide solid electrolyte after heat treatment and before and after pulverization. The halide solid electrolyte of Comparative Example 1 was also evaluated for its crystal phase. The halide solid electrolyte of Example 1 was also analyzed for trace components.
  • Crystal Phase The crystal phase was confirmed by powder X-ray diffraction measurement both before and after the heat treatment and the grinding treatment.
  • An X-ray diffractometer (MiniFlex600, manufactured by RICAKU) was used for the measurement.
  • Cu-K ⁇ radiation (wavelengths 1.5405 ⁇ and 1.5444 ⁇ ) was used as the X-ray source.
  • FIG. 6A is a graph showing the X-ray diffraction pattern of the halide solid electrolyte after heat treatment and before pulverization in the manufacturing method of Example 1.
  • FIG. 6B is a graph showing the X-ray diffraction pattern of the halide solid electrolyte after pulverization obtained in Example 1 and the halide solid electrolyte obtained in Comparative Example 1.
  • Li 2 TiF 6 corresponding to the first crystal phase and Li 3 AlF 6 corresponding to the second crystal phase were confirmed in the halide solid electrolyte synthesized in Example 1.
  • FIG. 6A Li 2 TiF 6 corresponding to the first crystal phase and Li 3 AlF 6 corresponding to the second crystal phase were confirmed in the halide solid electrolyte synthesized in Example 1.
  • FIG. 6A Li 2 TiF 6 corresponding to the first crystal phase and Li 3 AlF 6 corresponding to the second crystal phase were confirmed in the halide solid electrolyte synthesized in Example 1.
  • FIG. 6A Li 2 TiF
  • the ionic conductivity was calculated from the area, thickness, and impedance characteristics at room temperature of a compact sample obtained by putting a halide solid electrolyte powder into a mold with a diameter of 10 mm and applying a pressure of about 3 t/cm using a uniaxial hydraulic press. The impedance measurement was performed at room temperature while applying pressure. The impedance measurement was performed at a measurement frequency of 10 Hz to 10 MHz, a measurement voltage of 1 Vrms, and no DC bias. The deviation in the electrical length of the cable and the measuring jig was offset and evaluated.
  • the ionic conductivity before the pulverization treatment was 1.2 ⁇ S/cm
  • the ionic conductivity after the pulverization treatment was 6.3 ⁇ S/cm.
  • the electronic conductivity was calculated from the DC voltage and current characteristics.
  • the electronic conductivity of the halide solid electrolyte of Example 1 was ⁇ 1.0 ⁇ 10 ⁇ 9 ⁇ S/cm, which was a value that could be determined to have no electronic conductivity.
  • the average particle size is the value of the median diameter D50 obtained from the volumetric particle size distribution measured by a laser diffraction scattering type particle size distribution measuring device. Specifically, the powder of the halide solid electrolyte was dispersed in a 0.01 wt% aqueous solution of Na hexametaphosphate using a homogenizer, and then the particle size distribution of the halide solid electrolyte was measured using a laser diffraction scattering type particle size distribution measuring device (manufactured by Microtrac, product name: MT3100II). The value of D50 (i.e., cumulative 50% particle size) of the measured particle size distribution was regarded as the average particle size. For the halide solid electrolyte of Example 1, the average particle size before the pulverization treatment was 0.78, and the average particle size after the pulverization treatment was 0.58 ⁇ m.
  • the BET specific surface area was determined by a multipoint BET method using a nitrogen gas adsorption apparatus.
  • the halide solid electrolyte of Example 1 had a BET specific surface area of 2.98 m2 /g before the pulverization treatment and a BET specific surface area of 4.08 m2 /g after the pulverization treatment.
  • the bulk density of the halide solid electrolyte before the pulverization treatment was calculated from the apparent volume and weight of the halide solid electrolyte.
  • the apparent volume was obtained by placing the halide solid electrolyte in a quantitative container, and the weight of the halide solid electrolyte was obtained from the change in weight at that time (with or without the sample).
  • the trace components contained in the halide solid electrolyte were analyzed by EPMA. Specifically, the analysis was performed as follows. A sample (powder) of the halide solid electrolyte was attached to a conductive tape and fixed (the sample was fixed to a 5 mm x 5 mm area to form a solid), and the composition (quantitative) was examined by point analysis. Although not confirmed by X-ray diffraction measurement, it was confirmed that Na and Ca were contained in the halide solid electrolyte of Example 1. The Na content was 0.02 at. %, and the Ca content was 0.01 at. %.
  • Example 1 From the evaluation results of the halide solid electrolyte obtained in Example 1, it was found that the manufacturing method of the present disclosure produced a halide solid electrolyte having a high ionic conductivity of 6.3 ⁇ S/cm. This ionic conductivity was equal to or higher than that obtained by synthesis from a fluoride raw material, and the manufacturing method of the present disclosure produced a halide solid electrolyte with excellent properties.
  • the electronic conductivity was ⁇ 1.0 ⁇ 10 ⁇ 9 ⁇ S/cm, confirming that the resulting ionically conductive solid electrolyte had no electronic conductivity (i.e., had a negligible level of electronic conductivity).
  • Example 1 From the X-ray diffraction patterns shown in FIG. 6A and FIG. 6B, it was confirmed that the method of Example 1 can obtain a halide solid electrolyte containing Li 2 TiF 6 corresponding to the first crystal phase and Li 3 AlF 6 corresponding to the second crystal phase.
  • the halide solid electrolyte obtained in Example 1 before the pulverization treatment was confirmed to have only Li 2 TiF 6 and Li 3 AlF 6 crystal phases, and other precipitated phases such as Na and Ca were not detected.
  • FIG. 6B the X-ray diffraction pattern of the halide solid electrolyte after the pulverization treatment of Example 1 changed to a broad peak, and the progress of amorphization was confirmed.
  • the halide synthesized from the fluoride raw material by the manufacturing method of Prior Art 1, i.e., the manufacturing method of Comparative Example 1, and the halide of Example 1 finely pulverized in a short time had the same crystal quality including the amorphization level.
  • the halide solid electrolyte obtained in Example 1 had suppressed compositional variation compared to the halide obtained in Comparative Example 1.
  • the inclusion of impurities for example, zirconia derived from the pulverization medium (zirconia balls), was suppressed to a very low level of 20 ppm or less.
  • the Ti component evaporates as titanium fluoride and disappears from the halide because it is open. This causes the composition to fluctuate, and only a product with an ionic conductivity of less than 1 ⁇ S/cm can be obtained. In this case, a high heat treatment temperature of 500°C to 60°C is also required for synthesis.
  • a halide solid electrolyte containing Li, M, and X for example, a halide solid electrolyte containing Li, Ti, M1, and X, which is easy to pulverize and has excellent ionic conductivity, can be obtained with good productivity by a normal synthesis process (i.e., without sealing, etc., and in a synthesis environment in the atmosphere).
  • the method for producing a halide solid electrolyte according to the present disclosure can be used, for example, as a method for producing a solid electrolyte for secondary batteries such as all-solid-state batteries used in various electronic devices or automobiles.

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